Thermal Energy Storage

for Solar A--#cations: An

Overview

CharlesWyman

Solar Energy Research Institute

A Division of Midwest Research Institute

1536 Cole Boulevard

Gotden, Colorado 80461

Operated for the

U.S. Department of Energy
under Contract No. EG-77-C-01-4042
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1 >
SERI/TR-34-089
UC C A T E G O R Y : U C - 6 2

1 THERMAL ENERGY STORAGE FOR

SOLAR APPLICATIONS:
AN OVERVIEW

MARCH 1 9 7 9
. -

NOTICE 1
I
sponsored by Ule United Stater Government. Neither the
I ! United States nor the United Stater Departmnl of
Encrm, nor any of lh~lrcmplnycr.*. nnr on), of thbii
conlracton. mbconuacton, or their employees, makes
any warranty, cxpren or implied, or a n u m n any bgd
liability or rerpondbilily for the aEcuracy,complewneu
j,
or uvfulntb uf any information, apparatus, pmduct or
procen diwloocd, or rcpnvnQ that i u urc would not
i

Solar Energy Research lnstitute -

1536 Cole Boulevard
Golden, Colorado 80401

A Division of idw west Research Institute

Prepared for the
U.S. Departmentof Energy
Contract No. EG.77C.01.4042

~ ~ ~ TQF TD1S
I QDOCUMENT
H IQ

J
 PREFACE

This report was prepared a s part of Task 3407, Storage Technology Assessment, in t h e
Thermal Conversion Branch of t h e Solar Energy Research Institute (SERI), a Division of
Midwest Research Institute. The report reflects a current assessment of the status of
t hermal energy storage for solar applications. Comm ents by Ken Touryan, Frank Kreith,
Frank Baylin, and Robert Copeland, all of SERI, were valuable in improving the report.
The help of t h e Department of Energy and its support laboratories in t h e thermal storage
area is also acknowledged in re"iewing Section 6.0, DOE Storage Programs.

Frank Kreith
Branch Chief
Thermal Conversion Branch

Approved for:

SOLAR ENERGY RESEARCH INSTITUTE

Research Division
 TABLE OF CONTENTS

Page

Preface ....................................................... ii

Abstract ...................................................... 1

.
10 INTRODUCTION ............................................... 3

1.1 The Role of Storage ........................................ 3

1.2 Repurt Objectives and Organization ........................... 4

2.0 THE ECONOMICS O F SOLAR ENERGY STORAGE ................. 7

2.1 Selected Solar System Studies ............................... 7

2.1.1 Storage for Solar Home Heating ...................... 7
2.1.2 DedicatedStorageforSolar
Electric Power Plants ............................... 11
2.1.3 Analyses f o r Other Applications ...................... 22
2.2 The Cost of Stored Energy ................................... 24
2.2.1 The E f f e c t of Storage Utilization ..................... 25
2.2.2 The E f f e c t of Storage Efficiency ..................... 27

3.0 THERMALSTORAGEMETHODSANDMEDIA ..................... 29

Sensible H e a t Storage ...................................... 29

L a t e n t H e a t Storage ....................................... 36
Reversible Reaction Storage ................................ 39
3.3.1 Thermoche.mica1 Storage Reactions ................... 40
3.3.2 Chemical H e a t Pump Reactions ...................... 41
3.3.3 Thermochemical Pipeline Reactions .................. 47

4.0 STORAGE VESSELS AND HEAT EXCHANGERS .................... 51

4.1 Sensible H e a t Systems ..................................... 51

4.2 Latent H e a t Systems ...................................... 59
4.3 Reversible Reaction Systems ............................... 61

5.0 CHEMICAL STORAGE REQUIREMENTS .......................... 67

5.1 Equilibrium Considerations ................................. 67

5.2 Energy from Storage ....................................... 72

.
6 0 DOE STORAGE PROGRAMS ..................................... 85
 TR-089
SE?I@3
TABLE OF CONTENTS (cont'd)

DISCUSSION AND RECOMR/IENDATIONS ......................... 107

7.1 Sensible H e a t Storage ...................................... 107

7.2 L a t e n t H e a t s t o r a g e ....................................... 108
7.3 Reversible Reaction Storage ................................ 108
7.4 Thermal Energy Storage Applications ........................ 110
7.5 Recommendations ......................................... 111
 LIST OF TABLES
I

Table Page

2- 1 Eight Locations Used in Solar Home Heating Study 111 ................ 11

Relative Electricity Costs in 2015 for an

Autonomous Solar Electric Plant as a Function
of Collector Field Size and Associated Storage [71 ................... 16

2-3 Relative Electricity Costs in 201 5 for a

Hybrid Solar Electric Plant a s a Function of
..................
the Collector Field Size and Associated Storage [7] 20

3- 1 Selected Liquid Sensible Heat Storage Media. ........................ 31

3-2 Thermochemical Storage Reactions ................................ 41

3-3 Chemical Heat Pump Storage Reactions.. .......................... 47

3-4 Therm ochemical Pipeline Reactions ............................... 48

 LIST OF FIGURES

Page

Possible locations for energy storage in a solar thermal

electric power plant........................................ '5 .

Solar home heating system [ll ..................................... 8

Delivered heat cost as a function of storage capacity

alone. Units are in energy stored per temperature change
of storage media and area of collector [ll .......................... 10

Percentage of an autonomous electric power plant load

supplied by solar as a function of the collector mirror
area in solar mutliples. A minimum collector area of
2.63 solar multiples is required for autonomous
operation [7]..................................................... 13

Storage capacity for the autonomous electric power plant

of Figure 2-3 as a function of the collector mirror area
in solar multiples 171.......................... .................
.: 15

Percentage of a hybrid electric power plant load supplied

by solar as a function of collector mirror area in
solar multiples [71 ............................................... 18

Storage capacity for the hybrid electric power

plants of Figure 2-5 as a function of the collector
mirror area in solar multiples [71.................................. 19

Effect of storage duration on percent energy provided

by solar for various collector array weas in
Albuquerque [71 ................................................. 21

Possible utilization of last element of storage added

versus the storage duration to that point ........................... 26

Storage capacity per unit volume as a function of

temperature swing for selected liquid sensible heat
storage media .................................................. 30

Storage media costs in dollars per unit energy stored

as a function of temperature swing for selected liquid
sensible h e ~ storage
t mcdia....................................... 33
 LIST OF FIGURES (cont'd)

Page

Storage capacity per unit volume as a function of

temperature for selected solid sensible heat
storage media .................................................. 34

Storage media costs in dollars per unit energy

stored as a function of temperature for selected
301id c e r i ~ i h h ..................................
l ~~ i 3storage
t media 35

Storage capacity .per unit volume as a function of

temperature for sel'ected latent heat storage
materials. The molar composition of mixtures are shown
in pmenthesis .................................................... 37

Storage media costs in dollars per unit energy stored

as a func.tion of temperature swing for selected latent
heat storage materials. The fusion temperature is
in parentheses .................................................. 38

Chemical heat pump storage for sulfuric acid concentration/

dilution with the charging cycle represented by dashed lines
......................
(- -) and the discharging cycle by solid lines (-) 42

3-8 Chemical heat pump storage by ammonisted salt pairs for

heating applications w i t h the upper diagr8111Por charging
storage and the lower for discharging .............................. 44

3-9 Equilibrium pressures as a functiorl of temperature for a

variety of ammoniated salts [31:l .................................. 45

3-10 Chemical heat pump storage by ammoniated salt pairs for

cooling applications with the upper diagram for charging
storage and the lower for discharging .............................. 46

3-11 Transmission of therama1 energy by the therm ochemical

...................................
pipeline sulfur tsioxide reaction 49

4- 1 Dual medium thermal storage concept [171.. ........................ 52

4-2 Observed and calculated thermoclines a t various times

during storage discharging [I71 .................................... 54
 LIST OF FIGURES (cont'd)

Page

Observed and calculated thermoclines at various times

duringstoragecharging[17] ...................................... 55

Observed and calculated bed t e m p e r a t u r e profiles at

variolls bed locations during t w o s t o r a g e charging
and discharging cycles [I71 ....................................... 56

Prestressed cast iron vessel for pressurized water

storage: 1. upper cover; 2. axial tendons;
3. tangential tendons; 4. wedge; 5. liner, and
.........................................
6. t h e r m a l insulation [35! 57

Salt cavern leaching operation t o produce an

underground storage cavern [351 ................................... 58

Direct c o n t a c t system ,for heat transfer between

t h e l a t e n t heat storage medium and an immiscible
fluid[36] ....................................................... 60

~ q u i l i b r i u mpressure-temperature diagram for hydrates

of magnesium chloride and water [401 .............................. 62

Cavity converter-heat exchanger f o r SO3 decomposition

[411 ........................................................... 64

Details of converter-heat exchanger cavity for SO3

decomposition [411 .............................................. 66

Equilibrium convcrsion of SO3 as a function of

................................................
t e m p e r a t u r e [231 70

Equilibrium pressure for hydroxides as a function of

................................................
t e m p e r a t u r e [27] 71

Thermal energy storage system based on calcium oxide/

hydroxide with materials stored at high temperatures.
The charging cycle is shown by dashed lines and t h e
discharging cycle is shown by solid lines ............................ 74

Energy released as a function of t e m p e r a t u r e for calcium

oxide/hydroxide with m a t e r i d s stored at high
temperatures .................................................... 74
S=?I:*, TR-089
I \-,

LIST OF FIGURES (contld)

Page

Thermal energy storage system based on calcium oxide/

hydroxide with materials stored a t high temperatures
and with waste heat used t o evaporate water in a
chemical heat pump mode. The charging cycle is
shown by dashed lines and t h e discharging cycle
is shown by solid lines............................................ 75

Energy released as a function of temperature for t h e

cheniical 1 1 ~ pump
1 syotom shown in Figure 5-5 ..................... 75

Thermal energy storage system based on calcium oxide/

hydroxide with solids stored a t 390°C and water
condensed, stored, and vaporized using atmospheric
temperatures. The charging cycle is shown by dashed
lines and the discharging cycle is shown by solid
lines...........................................................
%
77

Energy released as a function of temperature for t h e

chemical heat pump system shown in Figure 5-7 ..................... 77

Energy released as a function of temperature for an

ammoniated salts chemical heat pump system with
storage of materials a t reaction temperatures.. ..................... 78

5-10 Thermal onergy s t n r ~ g esystem based on calcium oxide/

hydroxide with materials stored a t 256 C. The charging
cycle is shown by dashed lines and the discharging
cycle is shown by solid lines ...................................... 80

5-11 Energy released a s a function of temperature for the

calcium oxide/hydroxide system in Figure 5-10 ...................... 80

5-12 Ther m a1 erler gy storage system based on calcium oxide/

hydroxide in uhemica1 h e n t pump mode and with materials
stored a t 25OC. The charging cycle is shown by dashed
lines and t h e discharging cycle is shown by solid
lines........................................................... 81

5-1 3 Energy released as a function of temperature for 111s

chemical heat pump mode of Figure 5-12 ........................... 81

5-14 Energy released as a function of temperature for

ammoniated salts in the chemical heat pump mode
with all materials stored a t 25OC.. ................................ 82
 TR-089
S~?l@I

ABSTRACT

This report presents an overview of current technology and programs including some
economic studies in low, intermediate, and high temperature thermal energy storage for
solar applications and an assessment of key problem areas. Previous studies of the
economic role of storage for solar home heating and stand-alone electric plants are
examined first and factors which affect the economics of storage are discussed. Next,
the costs and storage capacities of representative sensible and latent heat storage
materials are summarized. Various modes of operation are also prcsented for thermal
storage by reversible chemical reactions, but this technology is at such an immature
stage of development that its economic and technical potential are not clearly
understood. Some new ideas in containers and heat exchangers are reviewed to illustrate
possible innovative approaches to reducing storage costs. A more detailed examination is
then made of reversible reaction storage, and gas-solid reactions are shown to have
desirable attributes for solar energy storage. However, there are problems with heat
transfer and heat exchange for these systems that must be solved to make such systems
more economically attractive. The DOE programs in thermal energy storage are
reviewed in light of this review, and recommendations are made for future program
directions which appear at this time to have the greatest potential impact on reducing
technical and economic barriers to thermal s t o r ~ g eutilization.
 SECTION 1.0

INTRODUCTION

1.1 THE ROLE OF STORAGE

Since solar radiation is an inherently time-dependent energy resource, storage of energy

is essential if solar is to meet energy needs at night or during periods of cloud cover.
Storage provides a reservoir of energy which can adjust for phase differences between
local solar energy supply and the load demand. For instance, in home heating the
maximum solar energy availability is during the middle of the day while the maximum
heating requirements are generally during the night-a difference of about 12 hours.
Storage allows an adjustment for this mismatch and solar home heating systems are more
economically a t tractive with storage than without because of the increased effectiveness
of equipment utilization [l, 2, 31. Storage is essential if solar is to meet a large fraction
of total energy needs for many such applications.

Energy storage is not a new technology and examples can be found throughout history.
For instance, the thick adobe walls used for the homes of the Pueblo Indians in the
American Southwest served as a means of thermal storage. The outside walls would
absorb energy during the hot days, but the interior would remain cool. Then the stored
energy would warm the living quarters during the cold desert nights. Thus, the thermal
storage provided by the building mass moderated the interior temperature against the
external extremes.

Due to the declining availability of inexpensive fossil fuels, energy storage is again
assuming an important role. Most alternate energy sources such as wind, solar radiation,
and nuclear power do not naturally provide energy in a pattern which matches the time-
dependent character of the load profile and it is necessary to store energy if the
particular energy resource is to service the rioncoincident portion of the load. The
example of the adobe walls provides just this ability to extend periods of energy excess
into times of deficiency.

The utility of energy storage is not restricted to solar applications. In fact, improve-
ments in energy storage technology can significantly alter the market in which solar
must compete [4. For instance, electric storage heating units are used in European
countries as "load leveling" devices [51. A thermal storage unit is charged by electric
resistance heaters when a lower off-peak electricity rate is offered. The heat is released
from storage at times when the electricity rates are higher. Consequently, the electrical
utility dernand curve is more uniform and a higher fraction of the load can be met with
less expensive electricity produced in nuclear or coal baseload plants rather than by oil-
fired peaking plants. Alternatively, the utility can use a central storage unit in a "peak
shaving" operation. A storage device is charged with excess power from a baseload plant
during off-peak periods, and the energy is released to the electrical grid during peak
demand periods. Again, more baseload plants can be used with a consequent reduction in
oil-fired peaking plants and associated high fuel costs. In both applications, less
expensive and more reliable storage lessens the reliance on oil imports, reduces the
consumption of scarce fuels, and cuts the price of generated electricity.

Since solar radiation can be converted into various forms of energy, storage is possible by
a variety, of means. Modern mechanical means include sophisticated flywheels, pumped
hydroelectric, and compressed air storage. Thermal energy may be stored as sensible
heat changes, latent heat changes, or changes in chemical bond energy. Batteries and
other electrochemical processes allow electrical energy to be converted into chemical
forms for storage and fuels such as hydrogen may be produced to store energy. Many of
these technologies are in their early stages of development, and only a few storage
subsystems are presently used in energy conversion systems.

Generally, the choice of the storage niedia is related to the end use of the energy supply
and the process employed to meet that application. For thermal conversion processes,
storage as thermal energy itself is most effective. For photovoltaic processes, storage in
a chemical form (batteries) appears more appropriate. In the case of some photochemi-
cal reactions, the conversion process itself forms the storage media directly. Alterna-
ti,vely, hydrogen can be produced electrically or thermally.

The location and type of energy storage in the overall system is riot always as well
defined as the above discussion suggests. For example, in a solar thermal electric plant,
steam is generated by concentrating solar collectors and is used to run a turbine. The
turbine powers a generator to produce electricity. If the system is to withstand
transients in insolation or produce power in the evening hours with solar energy, a
storage device must be integrated into the process. As shown in Figure 1-1, storage
could be provided as thermal energy between the collector and turbine, mechanical
energy between the turbine and generator, or chemical energy by a bullery (or potenti81
energy in a pumped storage unit) between the generator and the user. Since the turbine
and generator are less than 100% efficient, the closer the storage is located to the solar
source, the more storage capacity will be required for a given find output of electricity
provided all the storage units have the same efficiency. On the other hand, locating
storage near the source reduces the size of all subsequent plant components since they
are used for longer periods of time. Thus, better conversion efficiencies, lower capital
costs, and higher utilization of equipment result. The ultimate type and location of
energy storage generally depends on achieving the lowest delivered energy cost with the
highest value and satisfactory reliability, and it is necessary to examine the entire
system integrated into its specific application to arrive fit the optimum solution.

1.2 REPORT OBJECTIVES AND ORGANIZATION

The main objective of this report is to present an overview of economic factors which
effect the role of thermal energy storage for solar applications and important storage
technologies currently under development. A broad introduction to thermal energy
storage is provided. In addition, advanced thermal energy storage by reversible chemical
reactions is examined in some detail. Based on the review, problems are identified which
warrant further research and development to reduce important technical and economic
F i g u r e 1-1 . P O S S I B L E L O C A T I O N S FOR ENERGY STORAGE I N A SOLAR
THERMAL E L E C T R I C POWER PLANT
barriers t o s t o r a g e utilization. -The reader may consult t h e references at t h e end of this
r e p o r t f o r Inore details and o t h e r perspectives.

This report will examine only t h e r m a l energy s t o r a g e for solar applications. Section 2.0
reviews representative studies t h a t define possible economic contributions of thermal
s t o r a g e t o home heating a n d e l e c t r i c utility applications. In addition, o t h e r potential
uses f o r solar t h e r m a l s t o r a g e are outlined along with current ideas about t h e utility of
s t o r a g e and anticipated economic needs and problems. Section 3.0 then summarizes t h e
various classes of t h e r m a l s t o r a g e and t h e materials which a r e now being considered. In
addition, t h e c o s t s of representative materials are presented f o r sensible a n d l a t e n t h e a t
storage. Section 4.0 looks at problems in containment of s t o r a g e media and possible
solutions. H e a t exchanger problems and concepts a r e also outlined in Section 4.0.
Section 5.0 addresses t h e thermodynamic and kinetic limitations associated with
reversible chemical reaction thermal s t o r a g e s c h e m e s and t h e characteristics of t h e
energy delivered.

With t h e various important issues defined, Section 6.0 summarizes t h e DOE t h e r m a l

s t o r a g e programs supported by t h e Chemical a n d Thermal Branch of t h e Division of
Energy Storage Systems (S'I'OR), t h e Research arid Development Branch of t h e Division
of Solar Applications, a n d t h e Solar Thermal Branch of t h e Division of C e n t r a l Solar
Systems. The issues addressed by t h e various funded projects a r e emphasized. Then
Section 7.0 briefly discusses t h e various technologies. Problems a r e identified which t h e
a u t h o r believes warrant f u r t h e r research and development t o augment t h e DOE thermal
s t o r a g e program and address c r i t i c a l issues n o t currently being investigated.
 SECTION 2.0

THE ECONOMICS OF SOLAR ENERGY STORAGE

2.1 SELECTED SOLAR SYSTEM STUDIES

The capacity, type, and location of storage which minimize the delivered energy cost for
a given solar process depends on the solar availability, the nature of the load, the cost of
auxiliary energy, the reliability of the process components, the fraction of energy
required from solar, and the price of the system components. These factors must all be
weighed carefully for each application to arrive at the particular system design
(including storage duration) which minimizes the final delivered energy cost. In the
following discussion, summaries of particular cost optimization studies will be presented
for thermal storage in home heating and electric power generation. The optimum
technical and economic solutions involve particular assumptions about the controlling
factors and should not be taken as universally valid. However, these studies illustrate
the moderate amount of storage capacity generally thought to be economically
attractive for these applications. Results for other important thermal applications such
as solar air conditioning and process heat are not included in this report.

2.1 -1 Storage for Solar Home Heating

A study of active solar home heating was performed by Lbf and Tybout 11, a. The
following discussion will focus on the storage aspects of their work.

The system studied consists of flat-plate solar collectors tilted from the horizontal with
necessary pumps or blowers to transfer heat by water or air from the collectors to
storage. All the solar energy provided goes through the storage unit first as shown in
Figure 2-1. Since the storage unit is located inside the house, heat losses from storage
are to the house itself and do not penalize the solar heating efficiency when indoor
heating is desired. They are only true losses when there is no need for indoor heat.
Storage may be in a tank of water or rock bin depending on whether water or air
respectively is the heat transfer fluid. The stored energy could be used for either space
heating or hot water. A full-sized backup heating unit is provided since the authors
found it to be very costly per unit of energy.delivered to meet the total heating demands
by solar energy alone. Both the conventional heat source and the solar heating unit use
the same heat distribution system to serve the house heating needs.

A computer program was written to describe the performance of the home heating
system. To make the results easily adaptable to different systems, all the design
equations were written on the basis of one square foot of collector area. The program
requires that the collector temperature exceed the storage temperature by 10°F before
fluid is circulated between the storage device and the collectors. This is done to
overcome heat losses in the transfer process and to ensure that enough energy is
available to justify t.he electricity cost for operating the pump or blower. Since the
F i g u r e 2-1 . SOLAR HOME HEATING SYSTEM [ I ]
 collector t e m p e r a t u r e must exceed t h e storage t e m p e r a t u r e before fluid c a n be
'circulated profitably, i t is more difficult f o r t h e collector t o g e t t o a high' enough
t e m p e r a t u r e t o provide additional energy t o a charged storage device than t o add h e a t t o
a discharged s t o r a g e unit.

T h e objective is t o find t h e solar component sizes and t h e mixture of solar and

conventional fuel which minimize t h e cost of delivered energy. At t h e t i m e of t h e
referenced study, com mercial solar heating systems were not widely used and price
information was somewhat sketchy. In addition, t h e costs employed in t h e analysis w e r e
f o r 1961-1962 and since they are no longer applicable they will not be discussed in detail
here. However, t h e authors found t h a t changes in price levels did not significantly a f f e c t
t h e conclusions of t h e study and more r e c e n t work has substantiated t h e general s t o r a g e
requirement trends [3, 61. Therefore, t h e findings of Lbf and 'Qbout still have m e r i t in
'matching s t o r a g e requirements t o home heating needs.

The solar heating system performance was determined with t h e developed model for
eight different s i t e s within t h e United States. T h e locations shown in Table 2-1 w e r e
judged representative of a range of world climates. Cities in parentheses a r e locations
where a c t u a l d a t a was taken if t h e c i t y identified in t h e analysis is diffferent from t h e
a c t u a l monitoring stat-ion by a few miles. A full year of hour-by-hour horizontal s u r f a c e
solar radiation, atmospheric temperature, cloud cover, and wind'speed d a t a was selected
for t h e year t h e Weather Bureau advised t o be most typical for each location. This
information was used in t h e model.

T o keep t h e number of computer runs reasonable, e a c h of t h e seven design and demand

parameters was varied independently while maintaining all t h e others constant at levels
believed t o b e nearest their optimum. Each variable was optimized f o r a 28.5 MJPC-day
(15,000 B t u P F-day) and 47.5 MJPC-day (25,000 B ~ U P house. The influence of
F-day)
s t o r a g e capacity on energy cost is shown in Figure 2-2 f o r t h r e e of t h e cities studied.
The percent heating by solar with t h e s e designs is shown along t h e lines drawn. Since
only t h e s t o r a g e capacity was varied in Figure 2-2, t h e absolute costs shown on t h e
ordinate do not represent general least cost values. They were judged a d e q u a t e f o r t h e
relativc comparison made in t h e stl.rdy.

One observation from Figure 2-2 is t h e occurrence of t h e minimum delivered energy cost
for this study at .2 t o .3 M J of storage capacity per O C s t o r a g e t e m p e r a t u r e rise and m 2
collector area (10-15 Btul°F-ft2) f o r each of t h e s i t e s shown with a range of .2 t o
.4 M J 1 ° ~ - r n 2 (10 t o 20 B~UPF-ft2) f o r all s i t e s studied. This may be translated into
s t o r a g e mass by dividing t h e s e values by t h e h e a t capacity of t h e s t o r a g e material. Thus,
storage capacity varies q u i t e closely with collector area. However, Lbf a n d Tybout
found t h a t t h e optimum collector Rrea changes significantly with s i t e s (details a r e
available in References [I, 21). The somewhat fixed s t o r a g e capacity t o collector a r e a
r a t i o means t h a t t h e larger collector areas required in colder climates must b e
accompanied by m o r e storage t o m e e t t h e higher f l ~ l c t u a t i o nin solar insolation. Overall,
t h e increase in both s t o r a g e and collector c ~ p a c i t i e scauses t h e energy delivery cost t o
b e higher f o r colder c i t i e s such as Boston.
 Storage Capacity (MJ / OC-m2)

F i g u r e 2-2. DELIVERED HEAT COST A S A FUNCTION OF STORAGE CF.PACITY

ALONE. U N I T S ARE I N ENERGY STORED PER TEMPEV.TURE CHANGE
O F STORAGE M E D I A AND AREA O F COLLECTOR [ I ]
 TABLE 2-1

EIGHT LOCATIONS USED I N SOLAR HOME HEATING STUDY [ l ]

YEAR SITE CLIMATE CLASSIFICATION

1955 Mj ami T r o p i c a l Savannah

Albuquerque T r o p i c a l and S u b t r o p i c a l
Steppe

Phoenix T r o p i c a l and S u b t r o p i c a l
Desert

1955 S a n t a Maria M e d i t e r r a n e a n o r Dry Summer

Subtropical

1955 Charlcston Humid S u b t r o p i c a l

" 1960 Seattle-Tacoma Marine West C o a s t

1959 Omaha ( N o r t h Omaha) Humid C o n t i n e n t a l , Warm

Summer

Boston ( B l u e H i l l ) Humid C o n t i n e n t a l , Cool

Summer

Another important conclusion from this study is t h e moderate s t o r a g e capacity

required. A minimum s t o r a g e t e m p e r a t u r e of 2g0 c ( 8 5 ' ~ ) i s used since h e a t could not be
effectively supplied t o t h e house below this value. A maximum t e m p e r a t u r e of 93OC
(200°F) is specified t o prevent boiling of t h e water. If t h e s t o r a g e device could swing
through t h e full 6 4 ' ~ ( 1 1 5 ' ~ ) t e m o e r a t u r e range allowed between t h e s e limits, only
enough heat could b e stored at Albuquerque f o r about one winter day with t h e selected
storage capacity. In Boston, about t w o days h e a t could b e stored. In practice, even less
h e a t could be stored since a t e m p e r a t u r e swing of less than 6 4 O ~is expected in t h e
winter. In any event, s t o r a g e durations on t h e order of one week were definitely not
cost-effective in this study for t h e fixed collector s i z e as shown in Figure 2-2.

2.1.2 Dedicated Storage for Solar Electric Power Plants

The delivered energy cost has also been examined for one type of chemical s t o r a g e in a
high-temperature solar t h e r m a l e l e c t r i c power plant. Results obtained by Iannucci [71
augmented by those of Iannucci, Smith, and Swet [81 will be summarized since they
illustrate t h e interaction between storage capacity and t h e collector field size.
Furthermore, the studies have potential merit for other applications with simil.ar fixed
daily demand patterns.

The objective of the studies was to determine the economic role of storage for a stand-
alone solar electric plant-a plant which supplies all the electricity needs of an
electrically isolated community. The plant is powered either entirely by solar or by solar
with a fossil fuel backup. Thermal storage is provided by the S03/S02/02 reversible
chemical reaction (see Section 3.0 for more information on this reaction). Chemical
storage was chosen since the materials can be stored at low temperatures and the long-
term storage required for stand-alone plant operation can be provided. When the stored
energy must be released, the reaction is able to produce the high temperatures necessary
for the electric plant. Chemical storage also provides high energy storage densities.
However, for this choice of reaction, compressing; t h e g ~ s for
~ s storage could aversely
affect the economics.

Storage costs were estimated from the prices of the key components required. Power
related costs (reactors, compressors, etc.) were calculated based on the maximum
storage charge and discharge rates while energy related costs (chemicals, storage
vessels, etc.) were based on the required storage capacity. Although the storage
component costs were believed to be reasonable, chemical storage is still in the early
stages of development and significant uncertainties exist in the estimates. In addition,
less costly or more efficient chemical reaction storage systems could probably be
found. Therefore, the results are only an early indication of a possible economic storage
role at this point.

A computer model was constructed of the solar plant with chemical storage and fossil
backup (if one is specified). The model uses an entire year of hour-by-hour insolation and
load data. It determines how the load will be satisfied and how much energy is added to
or removed from storage. An hour-by-hour simulation is needed to examine the complex
interrelationship between the load, insolation, and storage.

The busbar energy cost (mills/k~h)in the first year of plant operation was minimized.
An optimization routine varies the plant component sizes, end consequently the amount
of fuel burned, to yield the lowest cost solution. Thus, A s t.he cnllectnr field size is
changed, the optimization program will determine the proper amount of storage
necessary for the hybrid solar/fossil plant to generate electricity at the lowest cost for
the consumer. A reasonable spectrum of fuel escalation rates was examined because the
cost of fossil fuel affects the optimum solar involvement significantly.

Two different modes of plant operation were considered. In the first, the goal was to
maximize the solar output of the plant with economic considerations taken as secon-
dary. The solar output as a percentage of the total energy demand by the load is shown
in Figure 2-3 with respect to the mirror area for a nominal 100 MWe plant in Inyokern,
California. The mirror area is specified in solar multiples where a solar multiple of one
is the mirror area required to produce 100 MWe at noon on a cloudless June 21. A solar
multiple of at least 2.63 must be provided to meet 100% of the load by solar and this
minimum mirror area is called the critical solar multiple (CSM). The value of the CSM
 Collector Area in Solar Multiples

figure 2-3. PERCENTAGE O F AN AUTONOMOUS ELECTRIC POWER PLANT LOAE

SUPPLIED BY SOLAR AS A FUNCTION OF THE COLLECTOR MIRF-OR
AREA I N SOLAR MULTIPLES. A MINIMUM COLLECTOR AREA OF
2.63 SOLAR M U L T I P L E S I S REQUIRED FOR AUTONOMOUS OPERATION [ 7 1
will change somewhat with storage efficiency. The value of 2.63 corresponds to a
storage efficiency of 65%. Figure 2-4 presents the storage capacity in hours of full plant
output for the plants of Figure 2-3.

For a mirror field of up to a solar multiple of 2.0, the storage requirements are modest.
However, the plant cannot meet the energy requirement by solar alone. The storage
requirements rise sharply beyond a solar multiple of 2.0 and peak at the highest storage
requirement near the critical solar multiple. For this collector area as well as any
additional area, the 100% solar goal is achieved. Further increases in collector area
result in a dramatic decrease in storage requirement until the minimum storage
requirements for a 100% solar plant are achieved at a solar multiple of 3.0 to 3.5. The
minimum storage duration must be adequate to last the longest time span without solar
i~lsulaliwlarid cannot be reduced with further increases in collector area.

The coupling of chemical storage requirements to collector area has interesting

consequences for the busbar energy costs (BBEC) shown in Table 2-2 for the year 2015
assuming a 7.5% fuel escalation rate. Two different collector area costs are shown in
this table. Only collector areas greater than the CSM are shown since less collector area
cannot provide 100% of the requirement with solar energy. The price rises sharply as the
collector field size approaches the critical solar multiple bemuse of the increase in
storage capacity requirements. Up to this point, no energy can be discarded at all in an
effort to attain the 100% solar goal. However, once a collector field greater than the
CSM is available, energy can be discarded and there are many ways to provide 100% of
raequirernent from solar energy. Thus, storage is traded off for more mirrors. It is this
freedom to discard energy which allows economic factors to control the 100% solar
solution.

Once the nliriirnum possible storage duration to provide 100% solar electricity is
attained, further incresses in collector area simply add to the field cost without
reduction in storage and the BBEC rises linearly. Consequently, the minimum BBEC for
this particular chemical storage system occurs at 3.5 solar multiples for a collector cost
of $60/m2 and 3.0 solar multiples for a cost of $120/m2. Thc fact that the optimized
collector area is close to the value for the minimum possible storage duration suggests
that storage is relatively expensive. Thus, the collector field will be sized greater than
the CSM for the storage system considered unless the field cost is extremely high in
which case the plant would probably not be built at all. However, if the storage system
cost is reduced, the optimum field size will decrease until the minimum sized field is
reached at the CSM for free storage. The cost of cncrgy will drop for a cheaper storage
system choice. The interaction of energy storage duration and collector field size are
discussed in Reference [91.

While the collector area is the most expensive item at the optimal cost solutions, it is
not the minimum possible for 100% solar. Thus, the increase in collector costs beyond
the CSM is more than offset by lower storage costs at the lowest BBEC. At the lowest
cost solution, decreasing the collector area slightly causes the storage duration to
increase quickly, but the added storage capacity adds so little to the electricity cost that
the BBEC rises slowly. However, the increased storage duration adds reliability to the
 a
w
g200 -
w

a
CI
C
(P
-
-n'
12
Y

.-*
(II

CI
-
0
(P

2 loo
0
a
m
-
2
0
G a
.c
0 -
E3
0
x
o A 1 b 7 ? I I 9 a I d
0 1 2 3 4 5
Collector Area in Solar Multiples

Figure 2-4. STORAGE C A P A C I T Y FOR THE AUTONOMOUS E L E C T R I C POWER PLANT

OF FIGURE 2 - 3 A S A FUNCTION O F THE COLLECTOR MIRROR
AREA 114 SOLAR M U L T I P L E S [71
 TABLE 2-2

RELATIVE ELECTRICITY COSTS I N 2 0 1 5 FOR AN AUTOFOMOUS SOLAR ELECTRIC

PLANT AS FUNCTION OF COLLECTOR FIELD SIZE AND A3SOCIAlXD STORAGE [7]

$60/m2 $ 120/m2
Percent Storage Storage Relative Re l a t ive
Satisfied Solar Receiver Charge Capacity Electricity Electricity
by S o l a r Multiple S i z e (MWt) R a t e (MWt) (Hours) Cost Cost
plant in the event of uncharacteristically long periods without sun. Therefore, i t may be
desirable to design the plant with somewhat less collector area and more storage than
t h e lowest cost solution.

The second mode of power plant operation was t o minimize t h e busbar energy cost
without regard t o solar involvement. Thus, a fossil fuel backup system was used t o
supplement the power provided by solar. This operation would likely be more in tune
with the strategy a utility would employ under ordinary market conditions. In this case,
a collector field with less area than the CSM is allowed.

A fuel escalation r a t e of 7.596 per year was assumed t o assure a solar involvement.
Figure 2-5 shows the percent solar energy provided as related t o the collector afea
measured in solar multiples. The result is similar t o Figure 2-3, but the percent solar
provided is 1 . e for
~ any collector area and i t asymptotically approaches the 100% solar
contribution instead of actually attaining that value. Figure 2-6 shows greatly reduced
storage requirements for the hybrid plant relative t o the 100% solar plant. The storage
capacity still peaks near the CSM but a t a value of only 4% of that seen in Figure 2-4.

In this study, the optimum hybrid power plant has a collector area less than the CSM.
The storage capacity also tends t o be low with values usually under 15 hours. The plant
now needs appreciable amounts of energy from a backup source. However, due t o the
lower collector area and storage needs, lower cost solutions result. For instance, a t a
solar multiple of 2.5, 90% of the energy is supplied by solar but a t a busbar energy cost
less than that for a pure solar plant. Table 2-3 presents the relative electricity costs for
the optimum hybrid plants with two different collector costs.

Once again, the freedom t o discard collected solar energy yields a much more economi-
cal solution. If enough storage is provided t o accept all of the available solar energy
throughout the year, a low utilizaton of the storage results in consequent high costs.
Thus, if a backup is available a t reasonable cost, i t is less expensive t o employ t h e
backup t o meet these infrequent demands than t o store all the captured energy for t h e
storage system used in this study. Allowing hybridization between solar and fossil energy
sources cnn greatly reduce the storage, and therefore costs, relative t o a 100% solar
solution.
\

A change in the pattern of insolation availability (storm duration) does not affect t h e
storage capacity for a hybrid plant a s much as one for autonomous operation [81.
Extended periods without solar occur infrequently while occulation occurs every night.
Thus, overnight storage requirements exert far more influence on the optimized storage
duration than extended outages for a hybrid plant. On t h e other hand, a stand-alone
plant must be able t o last the longest period without solar availability, even if it occurs
once in a year.

One of the more revealing studies by Iannucci shows graphically the low utilization of
long-term storage [7, 91. In Figure 2-7, t h e percentage of baseload electrical demand
satisfied by solar is plotted against storage duration in hours for an Albuquerque site with
various cullector field sizes expressed in criticel s o l ~ rmultiples. The tradeoff between
 1 2 3
Collector Area in Solar Multiples

Figure 2-5. FERCENTAGE OF A H Y B I ? I D E L E C T R I C POWER P L A N T L O A D S U P P L I E D

i3Y SOLAR A S A F U N C T I O N O F COLLECTOR MIRROR /.REA I N
SOLAR M U L T I P L E S [ 7 1
 Collector Area in Solar Multiples

F i g u r e 2-6 . STORAGE C A P A C I T Y FOR THE H Y B R I D E L E C T R I C POWER P L A N T S O F

F I G U R E 2-5 A S A F U N C T I O N O F THE COLLECTOR M l R R O R AREA
I N SOLAR MULTIPI-E!: 171
 . TABLE 2-3

RELATIVE ELECTRICITY COSTS I N 2015 FOR A EYBRID SOLAF- ELECTRIC PLANT

AS A FUNCTION OF TH3 COLLECTOR FIELD SIZE AND ASSOCIATED STORAGE [7]
\

$60/m2 $1 20/m2
Percent Storage Storage Relative Relative
Satisfied Solar Receiver Charge Capacity Electricity Electricity
by S o l a r Multiple S i z e (MWt) R a t e (MWt) (Hours ) Cost Cost
 Albuquerque

90.0 -

80.0 -
-
L
(0

70.0 -
>.
n

A = .73 Critical Solar Multiples

y.
o B = 1.00 Critical Solar Multiple
'
C = 1.46 Critic.31 Solar Multiples
D = 2.20 Critical Solar Multiples
E = 2.93 Critic.31 Solar Multiples

30.0 -

20.0 I I I I I I I I I I I 1 I I I I I I I I I I I I I I
1oU 10' 10' 1o3
Hours of Storage

Figure 2-7. E F F E C T O F STORAGE DURATION ON PERCENT INERGY PROVIDED

BY W L A R FOR V A R I O U S COLLECTOR AKRAY A ? E A S I N ALBUQUERQUE 171
collector field size and storage duration is obvious in this plot. For a given collector
field, there is an initially linear relationship between percent solar and hours of storage
up to enough storage to last overnight. Beyond 20 hours of storage, a point of rapidly
diminishing returns occurs because the storage utilization is so low. To gain a few
percent contribution by solar requires significant increases in storage beyond 20 hours.
The maximum useful storage duration is 845 hours to provide 100% solar for a collector
field size equal to the CSM. Similar trends in the storage-collector tradeoffs were found
for other cities [7, 91.

In summary, the work cited suggests that a significant storage capacity is potentially
desirable but that operation of a solar thermal power plant as an autonomous unit is not
as economically attractive as hybrid operation for the storage reaction selected. At
least enough storage capacity is required in an autonomous plant to last the longest
period without insolation and sufficient collector area must be available to assure that
the storage unit never completely discharges. The large storage capacity and collector
area necessary to meet these needs were more costly in the study 'than a backup fossil
fuel unit in the system and the utilization of the additional storage capacity and
collector area is so low that their cost cannot be justified by the fuel savings. However,
these results may not be universally applicable due to specific component costs used in
the study. A far less expensive or more efficient storage system, cheaper collectors, a
different alternative fuel than oil, or a different fuel price would probably alter these
conclusions; but the studies demonstrate that long-term storage should be inexpensive.
An analysis of the coupling between cost and efficiency goals illuminates the differences
between daily and seasonal storage [lo].

2.1 -3 Analyses for Other Applications

The study by Ltif and Tybout did not include sufficiently long storage durations to be
considered seasonal storage. In such a case, the amount of solar energy collected
exceeds the demand during the summer months, and a storage unit is charged with the
excess energy. In the winter months, the demand .by the load is greater than the amount
of solar energy collected, and the storage unit slowly discharges. S11ffici.entstorage
capacity is provided to prevent the storage unit from completely discharging at the end
of the winter before the net charge cycie begins again and no backup unit is required.
The storage capacity for seasonal operation is significantly greater than those discussed
by Ltif and Tybout, but the optimum collector field size would probably be less. As a
result, the cost of delivered energy could go through a second minimum for large storage
capacities provided storage is very inexpensive. A detailed systems study similar to that
of Iannucci is required to establish how the energy costs at that minimum relate to the
energy costs for the solutions investigated.

Although the study by Iannucci provides a valuable first step in defining the role of long-
term storage for electric utilities, an important question in the solar powered electric
plant study is whether it is realistic to consider building a stand-alone plant. It is more
likely that the'solar plant would be part of a grid composed of a mixture of nuclear, oil,
gas, and coal plants. Some of these plants would be used to meet short-term peak
electrical requirements while other baseload plants would supply the power demand
which is constant 24 hours a day. The baseload plants tend to be high capital cost, low
fuel cost nuclear or coal plants while the peaking units are usually low capital cost, high
fuel cost fossil plants. The location and function of a solar plant within this grid must be
defined by a system study which considers the entire network.

The optimum type and location of storage for electric power plants must also be defined
in the context of the entire grid. For example, storage could be located between the
electric generator and user in Figure 1-1, and the device could store excess power for the
entire mix of generating units-not just solar. Storage in this role would take excess
baseload capacity in off-peak hours and make that energy available in times of peak
demand, thereby, reducing the consumption of expensive fossil fuels. Pumped storage
units currently provide just this capability. If the solar plant generates excess electricity
during certain load periods, it could be stored in the grid storage unit for later distribu-
tion. However, as mentioned in Section 1.0, storage of excess solar energy as electrical
energy rather than thermal energy results in lower utilization of the turbines and
generators in Figure 1-1; and these units must be larger to produce the same amount of
euergy.

Other important solar applications exist besides home heating and electric power
generation. For example, industrial energy users consume 27% of the total U.S. energy
demand (20 quads) as process heat: About 22% (4.4 quads) is used at temperatures below
1 8 0 ' ~(350°F) and 30% (6.0 quads) below 290°C (550°F) [Ill. These temperatures are
considered accessible by current solar collector technology. However, storage is not
considered economically attractive now if an oil or gas backup is available because of the
large capital outlays required. For instance, if a plant runs 24 hours a day at a constant
load, it requires a t least three times as much collector area to service the entire load
with sixteen hours of storage as it does to supply energy just during daylight hours with
minimal storage and an oil backup. Therefore, the capital cost, which is substantial
anyway, is about three times as high. Industrial users with an oil or gas backup tend to
favor only enough storage to withstand transients in operation. When the cost of solar
energy becomes less than for the backup fuels, more storage will become attractive.

In order to accurately define the optimum role of storage in any application, detailed
system studies are required. However, some generalizations are possible based on the
studies cited. If the load requirements are generally constant over time and the
collected energy costs are marginal, it will probably be cheaper to use a backup energy
source than storage for long periods without solar since the stored energy requires extra
collector field as well as storage. If the demand is highest during sunny periods, this
argument still applies. In either case, storage will only have a potential economic role if
the cost of delivered energy is cheaper from solar collectors than from an alternate
source. On the other hand, if the load requirements and solar availability are out of
phase as in home heating, storage actually improves the system economics since it allows
better utilization of equipment.

Another exception occurs if the collector field lies idle frequently during periods of high
solar insolation such as hnme h e ~ t i n gsystems in the summer or five-day work week
process heat facilities on the weekends. In this case, storage could actually improve the
overall economics since extra solar energy can be delivered with the storage system
being the only additional cost. No increase in collector field size (and cost) is necessary,
and the size may in fact actually decrease since the stored energy could be used in place
of collected energy.

Hooper has suggested such a shift in collector area for home heating in northern latitudes
although, since the utilization of storage is low, the storage costs must be minimal for
this tradeoff to be economical C121. In a five-day week process heat application, the
above tradeoff is more likely to be attractive since the stored energy utilization could be
high. For example, 16 hours of energv could be stored over a cloudless weekend and used
on a Monday night for a plant operating 24 hours a day, five days a week at a constant
rate. Provided most weekends are cloudless, the utilization is high. The actual storage
utilization will depend on the plant operation and the weather patterns. The next section
will discuss the impact of storage utilization more fully.

2.2 THE COST OF STORED ENERGY

The total cost of a thermal energy storage unit can be determined from the cost of the
total storage capacity (energy related costs) and the cost of energy removal or addition
(power related costs).

Total Cost = Energy Related Cost + Power Related Cost (1)

Storage capacity costs include the costs of the storage medium, container, insulation,
and any other items used for the actual storage of heat. The power related components
are such items as heat exchangers, pumps, plumbing, heat transfer fluids, and any other
device needed to tranfer heat for the storage unit.

The total storage cost can also be related to the energy storage capacity and the power
capability from storage by:

Total Cost = (Jhergy Storage Capacity) (Storage Gipaci ty Cost) (2

+ (Power Capability) (Power Capability Cost)

The unit costs must be determined for the given storage capacity and power capability
since economies-of-scale can cause a decrease in unit price and changes in unit
configuration can result in discontinuities in the unit price [131.

In order to minimize the system cost given by Equation 2, the power capability and
energy storage capacity would be kept as small as possible and still provide adequate
energy transfer and the necessary storage duration time T:
, Energy Storage Capacity
T = Power Capability
For a device to provide long-term or seasonal storage, T will be generally very large.
The energy storage capacity will be much larger than the power capability, and the
energy related costs will generally dominate the total system cost of Equation 2.
Therefore, for a long-term storage device, it is necessary to find very inexpensive
storage materials, containers, and other capacity related items while the heat
exchangers and other power related components can be relatively expensive. On the
other hand, for a short-term storage unit which must only handle brief periods of cloud
cover (small T in Equation 3), the power related costs will generally dominate and the
power capability unit costs must be kept low to minimize the system cost. The unit
energy capacity cost can now be higher than for the seasonal storage without substantial
impact on the total cost. Of course, regardless of the cost breakdown, the total storage
system cost must be low enough to fit the appllcatfon.

2.2.1 The Effect of Storage Utilization

To conceptualize the impact of the total energy storage cost on delivered energy costs,
the energy in a storage device is broken down into fictitious elements according to
useage. A solar installation is considered in which the demand is regular and independent
of the season. With minor variations, the final conclusions should apply to any system,
however.

Initial blocks of storage cldded to the system are used nightly and during periods of cloud
cover, and substantial amounts of energy pass through these elements of storage.
Eventually, a point is reached where additional blocks of storage are only useful at
night. Once enough storage is available to last the shortest night, additional storage
elements are only discharged during longer nights in the year and cloudy periods which
follow sunny days. Storage blocks beyond those required to last the longest night are
used less since cloudy and sunny days rarely alternate in a regular pattern. This
diminishing utilization of additional storage elements continues until enough storage is
added to provide a 100% solar powered system. Any storage beyond that amount is not
used a t all. Figure 2-8 presents an idea pf how the storage element utilization might
change as elements are added.

The degree of utilization of storage discussed above has important consequences on the
price of the energy delivered from the storage subsystem. For example, suppose a price
of $3,/kWt-hr of capacity is projected for a thermal storage system. If 20% of that cost
will cover yearly charges for operation and maintenance, income taxes with straight
line depreciation, and the return on investment, the yearly cost of the unit is about
$0.60/kWt-hr. If the device is used 300 times per year to meet evening loads and periods
of cloud cover, the cost of the energy due to the storage unit price is about:
$0 .6O/kW+-hr-yr
= $0 .002/kWt-hr ($0.586Mtu) del ivered. (4)
300 useslyr

This cost is only that associated with storage and neglects the price of collectors
hardware, etc. rcquired to charge the unit. The cost is low enough that storage is not a
High

Low ,

Storage Duration
1

F i g u r e 2-E. P O S S I B L E U T I L I Z A T I O N O F L A S T ELEMENT OF S T I R A G E ADDED

VERSUS TI-1E STORAGE D U R A T I O N TO T H A T POIHT.
major cost barrier in many applications for such high utilization. If the cost of collectors
required to charge storage is low enough, the total delivered energy cost could be
at tractive.

If the storage block added to meet extended cloudy periods is examined, its utilization is
far less. Perhaps this fictitious block of storage would be used only four times per year.
With the same capital recovery factor as above, the cost of energy delivered from this
element is approximately:
$0 .60/kWt-hr-yr
4 useslyr - = $0. 15/kWt-hr ($43.95/NBtu) delivered. (5)

When the costs of collectors, hardware, etc., are added, the delivered energy cost for
this case is not promising. Furthermore, for a utility the costs must be divided by the
efficiency of thermal to electric generation to obtain the cost for electricity. Thus, if
the average number of uses of total storage capacity is low, it is critical to develop very
low cost storage subsystems such as aquifers with projected first costs of about
$O.Ol/kWt-hr capacity or less. In all cases, a complete study of the entire solar system
with storage is required to clearly establish the economics of the delivered energy.

2.2.2 The Effect of Storage Efficiency

The fraction of the energy used to charge storage which can be delivered to the load at
the required rate (efficiency) has important consequences on the delivered energy cost.
First, the amount of storage materials must be increased beyond the minimum theoreti-
cally required. For example, if 67% of the energy put into storage can be actually
delivered to the load, then 50% more storage capacity must be provided to allow for
these loses. Thus, the energy related cost is about 50% higher than if the same device
were 100% efficient.

The efficiency has perhaps more important consequences on the collector cost. To
provide the "lost" energy, the collector area must also be increased beyond the
theoretical minimum. Returning to the example above, the energy output from the
collector field to storage must be 50% greater than that from the storage device. As a
result, the collector field cost is higher than the minimum possible. The cost of the
energy from storage will be considerably higher in this instance since not only must the
minimum collector field and storage capacity be paid for, but the cost of the extra
components must be covered as well. As a result, low efficiency storage systems will
probably not provide competitively priced energy unless both collector and storage costs
are very low-an event not likely to occur in the immediate future-or excess energy
available at one time can be provided during periods of high demand, thereby reducing
collector size.

In considering energy storage costs, the penalty associated with the delivered energy
temperature must also be taken into account. If a process requires heat input at a
temperature T, the collector field must operate a t a higher temperature T + AT in order
to transfer heat to the process. However, if a storage subsystem is incorporated between
the collector and the load, allowances must be made for temperature drops between the
collector field and storage and between storage and the load. The collector field must
operate a t a higher temperature, perhaps at T + 2AT. To further complicate matters,
some storage media go through a continuous temperature drop as they are discharged
(sensible heat liquids) or must undergo a temperature decrease to release energy
(reversible chemical reactions).

The lowest storage temperature during discharge must be higher than that required by
the load while the collector field temperature must be above the highest storage
temperature required during charging. Consequently, the collector field will operate at a
temperature considerably higher than the load requirements. In each instance, an
increase in collector temperature results in a decrease in collector efficiency and the
field size (and cost) will increase accordingly. In some instances, it may be necessary to
use a collector designed for temperatures higher than the actual load requirements,
usually with a higher cost. Alternatively, if the heat is converted to work, the process
will operate with a lower efficiency. The magnitude of the effect of temperature on the
system cost and performance depends upon the nature of the collector efficiency or the
type of work cycle utilized.
 SECTION 3.0

THERMAL STORAGE METHODS AND MEDIA

Thermal energy is stored as a change in internal energy of a material through shifts in

sensible heat, latent heat, heat of reaction, or combinations of these. In general, it is
desirable to use materials which possess a large change in internal energy per unit
volume to minimize the space needed to store energy. To be economically competitive
in commercial solar systems, it is important to employ substances with a high internal
energy change per unit cost. Other properties such as vapor pressure, toxicity, and
corrosiveness also must be considered since they influence the price of material
containment in commercial systems. In this section, thermal storage methods, material
costs, and some of the important properties which influence thermal storage costs will be
reviewed for some presently considered thermal storage media. The equally important
questions of containment and heat exchange will be addressed later.

3.1 SENSIBLE HEAT STORAGE

Raising the temperature of a solid or liquid is the simplest way to store thermal energy.
Most thermal storage devices now in operation utilize sensible heat storage since current
technology is generally adequate for good system design. The amount of energy stored,
Q, is equal to the integral of the specific heat, C between the peak and minimum
P'
temperatures (temperature swing) experienced by the storage media:

The peak temperature T2 is fixed by the collector capabilities while the low temperture
T1 is determined by the temperature required by the load. The material chosen must be
thermally stable and undergo no phase change between the temperature extremes. The
substance should also have a high heat capacity, high density, and an acceptably low
vapor pressure. Finally, it must be inexpensive.

The energy storage capacities per unit volume of selected liquids for sensible heat
storage are shown in Figure 3-1 as a function of the temperature swing of the storage
media between the temperature limits of the liquid shown in Table 3-1. The heat
capacity data used to construct Figure 3-1 was quite accurate. However, an average
mass density was employed to give a feel for the volumetric energy storage capacities
since exact density data yields values which are only meaningful relative to a specified
lower operating temperature. For system design, more accurate data should be used.
But for the comparisons made here, this data should be sufficient.
 Water I

0 100 200 300 400 500 600

Temperature Swing (OC) .

Figure 3-1. STORAGE CAPACITY PER U N I T VOLUME AS A FUNCTION OF TEMPERATURE

SWING FOR SELECTED L I Q U I D SENSIBLE HEAT STORAGI MEDIA
 T a b l e 3-1

SELECTED LIQUID SENSIBLE HEAT STORAGE MEDIA

Heat
Temperature Capac ' t y
Medium FluLd Type Cost ( $ / k g ) Range ( "C)
-1
(Jkg K 1
-1
Comments

Water --- .OO 0 t o 374 4190 P r e s s u r e v e s s e l r e q u i r e d above 100°C.

Caloria Oil .30 -9 t o 316 ' 2300 Cracking o c c u r s a t h i g h t e m p e r a t u r e s

HT4 3 and may form v o l a t i l e p r o d u c t s lower-
The r m i n o l Oil .60 -18 t o 316 2400 i n g f l a s h p o i n t . May p o l y m e r i z e a t
55 high temperatures t o i n c r e a s e viscos-
Therminol Oil 2.03 -9 t o 343 2100 i t y . Nonoxidizing environment r e q u i r e d
66 a t high temperature.

Hitec Molten .59 150 t o 590 1550 Long-term s t a b i l i t y unknown above

Salt 550°C. S t a i n l e s s s t e e l o r o t h e r
expensive c o n t a i n e r s probably r e q u i r e d
Draw Molten .44 250 t o 590 1550 above 450°C. I n e r t atmosphere r e q u i r e d
Salt Salt a t h i g h t e m p e r a t u r e s . Heated l i n e s
required t o prevent freezing.

Na Liquid .90 125 t o 760 1300 Stainless s t e e l or suitable alternate

M e ta1 c o n t a i n e r s required. Requires s e a l e d
system. R e a c t s v i o l e n t l y w i t h w a t e r ,
oxygen, and o t h e r m a t e r i a l s .
Figure 3-2 shows the storage media capacity cost in dollars per M J of energy stored for
the same liquids. Prices are for 1978 and were determined for very large quantities of
materials from manufacturer's quotes for commercial fluids or from values given in the
Chemical Marketing Reporter [14. For the latter materials, commercial grades are
assumed to be acceptable without special purification. The price of water is for Denver
and may almost be considered as free. The cost of containers, heat exchangers, etc. are
not included in these comparisons.

Water appears to be the best sensible heat storage liquid available since it is inexpensive
and has a high specific heat. However, antifreeze must be added to water if the fluid
temperature can drop below O°C, and this adds significantly to the system costs. A heat
exchanger between storage and the heat transfer fluid for the collectors can eliminate
the need for antifreeze in the storage used but a t the expense of more equipment. Above
100°C, t h e storage tank must be able to contain water at its vapor pressure and the
storage tank cost not included in Figure 3-2 rises sharply with temperature beyond this
point. Water cannot be economically employed above its critical point of 374OC.
Organic oils, molten salts, and liquid metals circumvent the vapor pressure problems and
appear more desirable for high-temperature storage. Rut significant limitations in
handling, containment, storage capacities, cost, and useful temperature range are
evident for each as shown in Figures 3-1, 3-2, and Table 3-1 [15-171. Although these
fluids are used in commercial operations, the lifetime and cost requirements for solar
storage make them somewhat less desirable in this application.

The difficulties associated with the vapor pressure of water and the limitations of other
liquids con be avoided by storing thermal eriergy as sensible heat in solids. Many
inorganic solids are chemically inert even a t high temperatures. Larger amounts of solid
are generally needed than for water since the heat capacity of the solids is less as shown
in Figure 3-3. Figure 3-3 was prepared on the same basis as Figure 3-1 except that all
the temperatures are relative to a lower l i m i t of O'C. The cost of the storage media
alone per unit energy stored, although not as low as water, is still accept~blefor rocks as
shown in Figure 3-4. This figure was prepared on the same basis as Figure 3-2. In fact,
the cost of water and rocks are low enough that the storage costs are influenced more by
the price of containers, heat exchangers, and other auxiliary items than by the storage
materials themselves.

Direct contact between the solid storage media and a heat transfer fluid is desirable to
minimize the cost of heat exchange in a solid storage medium, and the storage volume
must be increased beyond that of Figure 3-3 by up to 50% to allow fluid passage. Thus
significant container volumes are required. While air is generally acceptable as a hcat
transfer fluid for rocks in low-temperature home heating systems, other fluids such as
high pressure helium or heat transfer oils are generally required in high-temperature
installations to provide adequate heat transfer capability [17, 181. The heat transfer
fluid must also be compatible with the solids, and the problems associated w i t h finding; a
fluid with low vapor pressure, high heat capacity, and low cost are similar to those for
storage in a liquid.
 Temperature Swing (OC)

F i g u r e 3-2. STORAGE M E D I A COSTS I N DOLLARS PER U N I T ENERGY STORED

AS A FUNCTION OF TEMPERATURE SWING FOR SELECTED L I Q U I D
S E N S I B L E HEAT STORAGE MEDIA
 0 100 200 300 400 500 600
Temperature (OC)

F i g u r e 3-3. STORAGE C A P A C I T Y PER U N I T VOLUME AS A FUNCTI(IR O F TEMPERATURE

FOR SELECTED S O L I D S E N S I B L E H E A T STORAGE M E D I A
I
 0 100 200 300 400 500 600
Temperature (OC)

Figure 3-4. STORAGE E.1EDIA COSTS I N DOLLARS PER U N I T ENEgGY STORED. A S A

F U N C T I O N OF TEMPERATURE FOR SELECTED S O L I D S E N S I B L E
'

HEAT STORAGE M E D I A
3.2 LATENT HEAT STORAGE

A substantial change in internal energy generally accompanies a phase change from solid
to liquid or from liquid to gas at a characteristic temperature. Such high energy storage
densities over a narrow temperature range make latent heat materials attractive for
thermal energy storage. Since a high volumetric energy storage density is essential, only
solid-liquid or possibly solid-solid transf orm ations with significant ent halpy changes are
of practical interest.

The literature on selection of low-temperature latent heat storage materials is extensive

with the representative summaries available in References [l9] and [20]. Material
requirements include low cost, high heat of transition, high density, appropriate
transition temperature, low toxicity, and long-term performance. Paraffin waxes [21]
and salt hydrates [I91 have been favored for low-temperature storage althn~~gh the
former are flammable while the latter are prone to liquid subcooling without crystalliza-
tion. The volumetric energy densities of these materials are higher than for water,
particularly for small temperature swings about the fusion temperature, as shown in
Figure 3-5. Constant densities and heat capacities have been used to prepare Figurc 3-5
and this figure should only be used for the purposes of comparison. The lower tempera-
ture limit of O°C was selected arbitrarily for the low-temperature materials. Some of
the volume advantage of low-temperature phase change materials relative to sensible
heat storage in water is sacrificed, however, in current systems since up to 50% more
volume is required than shown in Figure 3-5 to allow for passage of a heat transfer fluid.

Figure 3-6 presents the relative storage capacity costs for commercial paraffin wax and
sodium sulfate decahydrate, Once again, only the storage material cost is includcd in thc
plot. The price of sodium sulfate decahydrate is low enough to be attractive, but
containment by conventional methods causes the cost of an entire system to be higher
than for water. The transition temperature is also samewh~tlow for home heating
purposes, and large amounts of a heat transfer f l ~ l i r lwniild have to be oiroulatod through
the storage system. Continued work on improving the freezing process and developing
new heat exchange concepts may overcome some of these obstacles. The costs of the
other salt hydrates and paraffin wax are generally higher and these materials will likely
only be competitive with the price of water storage if very low cost heat e'xchangers and
containers are developed.

For higher temperatures, some generalizations are possible about latent heat materi-
als [221. Carbonates and possibly carbonatechloride systems are serious storage
candidates because their good corrosion chara.cteristi.cs make them inexpensive to
contain and their cost is reasonable. Nitrates and nitrites are good choices for
applications below 500°C since they are relatively noncorrosive and fairly inexpensive.
Chloride systems are cheap enough to be attractive but are more corrosive than the
previous compounds. Hydroxides as a group tend to be both more expensive and
corrosive. Fluorides offer rel.atively high heat storage densities, but they are often
expensive and their corrosive nature make the fluorides more expensive to contain than
the other salt systems discussed above.
 Temperature I O C )

F i g u r e 3-5. STORAGE C A P A C I T Y PER U N I T VOLUME A S A F U N C T I O N O F

'EMPERATURE FOR SELECTED L A T E N T HEAT STORAGE M A T E R I A L S .
TI.IE MOLAR C O M P O S I T I O N O F M I X T U R E S ARE StIOWN I N P f i R E N T H E S I S
 100 200
Temperature Swingi°CI

F i g u r e 3-6. STORAGE MEDIA COSTS I N DOLLARS PER U N I T DiERGY STORED AS A

FUNCTION OF TEMPERATURE SWING FOR SELECTED LATENT HEAT STORAGE
MATERIALS. THE FUSION TEMPERATURE I S I N PARENTHESES
Figure 3-5 presents the volumetric energy storage density for high-temperature storage
salts of the- types discussed. The lower temperature limit was arbitrarily chosen as
100°C to avoid confusion with the low-temperature materials. The density of the liquid
phase near the transition temperature of the material was used to transform the data of
Reference [221 to a volume basis for this plot because sufficient volume must be provided
to contain the lower density melt. Mixtures of salts were used in some cases.to provide a
lower transition temperature than the pure materials, and the densities were computed
assuming the compound volumes were additive. The composition of the mixtures by mole
percentage are shown in parenthesis on the plot. Since constant properties were used and
several approximation were employed to estimate properties, the plot should only be used
as a rough means to compare materials and not as a basis for engineering design.. The
two sharp increases in energy storage density exhibited by sodium hydroxide are due to a
solid-solid phase change within about 2 5 O ~of the solid-liquid transformation. Again, a
volume penalty must generally be assessed against the storage densities shown to allow
heat transfer for the phase change.

Figure 3-6 presents the storage media capacity costs as a function of the temperature
swing about the transition temperature shown in parenthesis. The assumption is again
made that commercial grade materials are acceptable. The costs of some of the salts
shown are competitive with the costs of sensible heat liquids for high-temperature
storage, but significant problems in containment, heat exchange and in some cases,
corrosion must be overcome to hake latent heat storage systems cost-effective. In
addition, extra charges may be necessnry to purify these materials to grades acceptable
for thermal storage.

3.3 REVERSIBLE REACTION STORAGE

Thermal energy may also be stored as the bond energy of a chemical compound and
energy can be repeatedly stored and released in the same materials by means of
reversible chemical reactions. Thermal energy from a source is absorbed under
conditions which favor significant conversions to a high enthalpy chemical species by an
endothermic forward reaction. The reaction can only proceed until the equilibrium
concentrations are reached. Then, the conditions are altered to favor high conversiorl by
the exothermic? reverse reaction to the low enthalpy species and energy is released. The
equilibrium concentrations of the species may be altered by: (1) changing the concentra-
tion (or pressure) of the chemical species and/or (2) changing the temperature of these
species.

The energy storage densities of reversible chemical reactions are generally higher than
for heat-of-fusion transitions. Chemical storage also has significant cost potential since
some of the materials could be available for as little as a few pennies per pound.
Chemical storage has the added advantage in that significant energy storage densities
are possible even at ambient conditions. However, as will be shown in Section 5.0,
careful heat exchange between products and reactants is required for some applications
to minimize sensible heat losses and provide efficient storage of energy.
A number of potential applications for chemical storage exist, particularly due t o t h e
capability to store energy a t ambient conditions. Long-term storage of energy is possible
with minimal loss of energy t o the environment during storage. Heat can be pumped
from the environment by some reactions. A transportable fuel could be produced in
sunny locations by a suitable reaction for use in cloudy sections of the country. .The
reactants might also be used a s a renewable fuel for automobiles.

Despite all the promise offered by chemical reaction storage, t h e technology is a t an

early stage of development and systems a r e not yet available for use in commercial
applications. Relatively little experience has been compiled in the laboratory, and no
significant scale demonstration units have been run. Research and development efforts
a r e therefore needed for most systems t o establish:

6 reversibility of reactions with minor degradation of t h e chemical species (and

catalysts, when required);

satisfactory kinetics, specificity, and conversions of the reactions;

acceptable heat transfer rates in cost-effective containers and/or heat

exchangers;

low cost storage and transportation (when required) of the chemical species;

no excessive corrosion;

oufficicnt cnargy storage densities; ~ I L I

acceptable storage efficiencies.

Reasonable cost projections will have t o await further research t o clarify the design of
storage systems.

3-3.1 Thermochemical Storage Reactions

Three operating concepts are currently considered for reversible reactions: thermo-
chemical storage, chemical heat pump storage, and thermochemical pipeline thermal
transport. Table 3-2 presents a few of the possible reactions considered suitable for
thermochemical storage [23-251. The heats of reaction are calculated at 2 5 ' ~ from
standard tables [261. Since a high energy storage density is important, only reversible
reactions with reactants and products which can be easily stored a s liquids and solids a r e
of practical interest, and some reactions obviously satisfy this criteria better than
others. Reactions which produce two distinct phases such as FI solid and a gas a r e
desirable since the separation of products t o prevent back reaction is facilitated. For
example, solid calcium hydroxide (slaked lime) will endothermically decompose t o solid
calcium oxide (quicklime) and water vapor if i t is heated to about 5 2 0 ' ~ a t one
atmosphere pressure. The water vapor is condensed for storage in a separate vessel.
 Table 3-2

THERMOCEIEMICAL STORAGE REACTIONS

React ion AH',ICJ T* ,K

When heat is required from storage, water and the calcium oxide are mixed, and the
exothermic reverse reaction of the two species produces energy [27-291. The operating
requirements for this reaction will be discussed in more detail in Section 5.0.

The "turning temperature" T* in Table 3-2 is defined as the temperature for which the
equilibrium constant is one and is approximated by the ratio of the standard enthalpy
change to the standard entropy change for the reaction [ 2 4 :

T* = AH"
-A so
At this temperature, the reactants and products will be present in approximately equal
quantities with the actual concentrations determined by the stoichiometry of the
> <
reaction. When T T*, the endothermic storage reaction is favored; while for T T*, the
exothermic reaction dominates.

3.3.2 Chemical Heat Pump Reactions

Figure 3-7 illustrates the chemical heat pump mode of operation in which a dilute
sulfuric acid solution is concentrated to 98% acid by using solar energy to evaporate
water. The water vapor is condensed for storage, and the heat of condensation can be
transferred to a load if it can be used fit. the condensation temperature or to the
 Buildings

F i c u r e 3-7. CHEMICAL H E L T PUMP STORAGE FOR S U L F U R I C A C I D CONCENTRATION/

D I L U T I O N W I T H THE CHARGING CYCLE REPRESENTED BY DASHED
L I N F S I--) F,ND THE D I S C H A R G I N G C Y C L E B Y S O L I D L I N E S ( - )
environment if it cannot. When heat is demanded from storage, energy stored in the
atmosphere can be used to evaporate the liquid water. Provided the temperatures of the
water and acid solution are properly regulated, t h e water vapor will condense in t h e
solution. Consequently, the heat of condensation a s well a s the heat of mixing can be
released t o t h e load, and energy is pumped from the environment. In principle, the total
energy released during charging and discharging of storage exceeds that supplied by t h e
sun because of the chemical heat pump capability, and if the energy can be used, the
collector field size is reduced relative t o a conventional storage system with potential
savings in cost. By interchanging t h e load and environment positions in Figure 3-7, the
chemical heat pump may be used for air conditioning a s well, and a higher utilization of
the solar system results.

Table 3-3 presents a number of reactions thought t o be suitable for chemical heat
pumping [23, 29-31]. The temperatures shown a r e the values typically considered
although other values are possible depending on the operating pressure. The reactions 'of
Table 3-2 generally could also be used in a chemical heat pump mode t o recover the heat
of condensation given off when the vapor is condensed, and the distinction between the
modes is quite arbitrary.

Some of the gaseous components in Table 3-3, such a s ammonia, a r e not readily liquified
,*atclose t o atmospheric pressures and ambient temperatures. Due t o the toxicity of the
gases, high pressure operation of the system is undesirable since there is a high
probability of gas rel.ease. For these compounds, i t is generally convenient t o employ a
second solid to store the vapor since an appropriate solid lowers the vapor pressure of the
gas a t a given temperature. For example, if MgC12'6NH3 is supplied heat a t about
1 2 0 ' ~( 2 4 8 ' ~ ) a s shown in Figure 3-8, i t decomposes as:

To store the ammonia gas, i t is reacted with CaClZm4NH3a t a temperature below 25O.C
(77' F):

The heat from this reaction is used for t h e load if possible or rejected t o the atmosphere
if not. When energy is to be released from storage, heat from the atmosphere is supplied
t o the CaC 12*8NH3a t about 5'C (41' F) t o drive off the ammonia by the reverse reaction
t o Equation 9. The ammonia is then absorbed by the MgC12'2NH3 in the reverse reaction
t o Equation 8 t o liberate heat for t h e load a t a ' temperature around 92'C (198'F).
Different temperatures can be used for both storage and release of energy t o meet
different ambient temperatures provided they are consistent with t h e equilibrium
requirements (Figure 3-9) and a differential pressure is provided between the two storage
vessels t o force t h e transfer of ammonia. Figure 3-10 illustrates the ammoniated salts
system with operating conditions altered t o provide air conditioning.

Metal hydrides have also been considered for operation in a manner similar t o that
described for the ammoniates. In these cases, hydrogen is driven between two metal
 Heat
Solar to
Heat Load
or
Atmosphere
Charging
MgCI, GNH,(s)
MgCI, 2NH,(s)
-
4NH3(g)
12O0C
+
- CaCI,
CaCI, * 8NH3(s)
25 OC
+
4NH3(s) 4NH,Zg) --t
e

7 I
L

Tank1 : Heat to
j~-
b Load Tank * 4
*Atmosphere
- Heat from

A ? w

Blischiarging
MgCI, ., 2$NH,(s) +
4NH3<g) -+ CaCI, 8NH3(s)-
Wl gCl, 6NH34s) CaCI, 4NH31sl + 4NH,dgl
-. 92OC 5OC

F i g u r e 3-8. CHEMICAL HEAT PLIRP STORAGE BY AMMONIZATED S A L T P A I R S FOR

I I E A T I N G A P P L I C A T I O N S W I T H THE UPPER DIAGRAM FOR CIiARGING
STORAGIE AND THE LObJER FOR DISCHARGING
 MnCI,
MgCI,
- 2NH3=MgCI,

2NH,-MnCil, NH, + NH,

NH, + NH, 7
UI
111
aJ
MgCI, 6NH3=MgC12 2NH3 + 4NH3 8,
MnCI, 6NH,=MnCI, 2NH, + 4NH3
CaCI, ~NH,-C~CI, 4NH3 + 4NH3
200 -

150 -

([1
a
Y
-
100 -
fn
fn
2
a

50 -

I 1 I I I I A
0
250 300 350 400 450 500 550 600
Temperature (K). c3
T0
CO
F i g u r e 3-9. E Q U I L I B R I U M PRESSURES A S A F U N C T I O N O F TENPERATURE FOR A \O

V A R I E T Y O F AMMONIATED S A L T S [ 3 1 1
Solar
Heat+
-
+
- Tank 1
Heat
to
Atmosphere
.

-
I A >

Charging
MgCI, 6NH3(s)-* CaCl, @'4NH3(s) 4NH3(g) +
MgCI, 2NH3(s) + 4NH,(g) CaCI, 8NH3(s)
-135OC 30OC

Tank I Heat to
Atmosphere

Discharging
MgCI, 2NH3lSl + 4NH3(g)--, CaCI, 8NH3(s).-
MgCI, a 6NH3(s) CaCI, ~NH,(s)+ 4NH3(g)
-115OC 15OC
F i g u r e 3-10. CHEMICAL F E A T PUb!P STORAGE BY AMMONIATED S A L T P A I R S FOR
COOLING A P P L I C A T I ' O N S W I T H T H E UPPER D I A G R A M FOR CHARGING
STORAGE AND THE LOWER FOR D I S C H A R G I N G
 Table 3-3

C a M I C A L HEAT PUMP STORAGE REACTIONS

React ion Temp. ,K

Ammoniated Salt Pairs

Hydrated Salts

Concentration Dilution

compounds. However, the metals are usually expensive and small quantities of material
are employed in a thermally driven heat pump without storage capacity. The sysle~liIs
not considered as a cost-effective storage device [22, 231 and it will therefore not be
considered further. More details on the metal hydride heat pump system without storage '

are available in Reference 1321.

3.3.3 Thermochemical Pipeline Reactions

Significant enthalpy changes also accompany a number of reactions involving one or more
gaseous reactants which are not easily condensed. Since the energy storage density is
low, these reactions are not considered as attractive as the preceeding for thermal
energy storage although some workers have proposed using massive underground caverns
or compressing the reactants/products for storage of the gaseous materials. Most
applications utilize the reactinn products for transmitting thermal energy over long
distances in a thermochemical pipeline (chemical heat pipe) operation. The endothermic
sulfur trioxide decomposition reaction, for example, is driven catalytically at the energy
source (Figure 3-1 1) as [23, 331:

This reaction occurs a t about 900°c. The gaseous reaction products exchange heat with
the reactants and are transmitted at lower temperatures to a remote load site where the
reverse exothermic reaction proceeds catalytically, liberating energy at about 550°c:

The products of this reaction are sent back to the source to repeat the cycle. A number
of reactions considered for thermochemical pipeline applications are listed in Table 3-4
along with their standard heats of reaction [23, 24, 34. AV of the tabulated reactions
must be triggered catalytically to avoid the necessity of separating the materials prior to
transit.

THERMOCHEXICAL PIPELINE REACTIONS

-----

React ion A H ~ k~
, T*, K.
 Exothermic Reactor
H y h Temperature
Endothermic Reactor
w i t h Catalyst -0%
.\
w i t h Catalyst
So2+1/2O2

'k
/ Solar Heat Source
Return

F i g u r e 3-11. T R A N S M I S S I O N OF THERMAL ENERGY BY THE THERMOCHEMICAL

P I PEL I N E SULFUR T R I O X I D E R E A C T I O N
 SECTION 4.0

STORAGE VESSELS AND HEAT EXCHANGERS

It is obvious that the cost of the storage media and the container could constitute a
significant portion of the energy related costs in Equation 1 and must be kept to a
minimum. In addition, power related costs are frequently a substantial portion of the
total system costs since heat exchangers and associated heat transfer equipment are
generally very costly. Therefore, it is important to consider the design of low cost
containers and heat exchangers as well as the selection of low cost materials for
storage. In this section, attention is focused on a few of the concepts which are aimed at
lowering the cost of heat exchange and containment. Most are in early development
stages and require extensive.effort to achieve that goal.

4.1 SENSIBLE HEAT SYSTEMS

In order to charge and discharge storage, it is necessary to circulate a heat transfer fluid
between storage and either the energy source or the load. For liquid storage media, the
storage fluid frequently can be used directly for heat transfer. If practical considera-
tions such as freezing of the liquid prevent this, the storage liquid can be brought into
thermal contact with an auxiliary heat transfer fluid via a conventional heat exchanger,
although a t additional expense. Alternately, a second fluid that is immiscible with the
storage media can be bubbled through the storage container, and direct contact heat
exchange thereby achieved between the heat transfer fluid and the storage media.
Research is in progress on such a system for heating and cooling applications.

Solids are often desirable storage media according to the criteria outlined in the
preceding section. Some of the solids for sensible heat or chemical reaction storage are
in particulate form, and heat transfer through these materials is slow. In addition, the
thermal conductivity of many of the solids considered for storage, including phase change
materials, is low. To achieve useful heat transfer rates in a shell and tube heat
exchanger, very high surface-to-volume ratios must generally be utilized. Even if the
storage material costs are low, the heat exchanger costs usually make such a _system
uneconomical.

For solid sensible heat storage media, current practice is to put the heat transfer fluid in
direct contact with the storage media. Numerous examples of such systems are
available, but one of the more interesting is a dual media unit being considered for
application to commercial power plants of 100 MWe and larger size [ l a . The concept
originally employed a mixture of sand and granite to reduce the amount of more
expensive organic oil, Cdoria HT43, used in storage. However, t h e addition of solids
facilitates temperature stratification in the storage vessel. For the device pictured in
Figure 4-1, oil is circulated from the bottom of the storage vessel, through a heat
exchanger to pick up heat, and back to the top of the storage tank. A fairly sharp
temperature transition or thermocline will occur naturally between the hot and cold
regions in the storage bed, and this thermocline will move downward through the bed
Receiver --b

Rock and Heat

Transfer Fluid

Condensate
Retur.1+
Temperature Temperature

F i g u r e 4-1. EUkL MEDIUFl THERMAL STORAGE CONCEPT ! I 7 1

during charging. If the oil flow direction is reversed during extraction of heat, t h e
thermocline wiil move upward through the bed. A constant discharge temperature is
produced from storage as a result of this temperature stratification.

An analyses of the dual medium thermal storage unit has been developed t o aid in
engineering design [ i n . Assuming the system can be modeled in terms of unidimen-
sional, unsteady flow conditions the temperature of the oil can be predicted from the
energy balance:

.while t h e solid temperature can be predicted from the relation:

f is the packed bed void fraction by volume, p L the liquid density, ps the solid density,
c the liquid specific heat, c the solid specific heat, vL the actual fluid velocity, h
P
tR&heat transfer coefficient b e b e e n the liquid and solid, AIV the arealvolume ratio for
heat transfer, TL the fluid temperature, Ts the solid temperature, t the time, and x t h e
axial distance down the tank. For constant physical properties, velocity, and boundary
conditions, the Shumann-Hausen analytical solution can be used t o solve these equa-
tions. A variable mesh numerical integration method has also been developed in
Reference [I71 t o allow variation of properties with temperature and velocity and permit
the use of arbitrary boundary and initial conditions.

Figure 4-2 and 4-3 show the numerically calculated and the observed thermocline for
discharging and charging of t h e storage unit respectively. The surface-to-volume ratio,
A/V, was adjusted in the model until the predicted and actual thermocline slopes
matched a t a value of about 40 ft-l. It was also necessary t o increase the solid heat
capacity above the actual value for the calculated thermocline velocity t o match the
observed value. Based on these adjusted parameters, temperature histories were
calculated a t various locations in the bed for two charge-discharge cycles. The results
a r e presented in Figure 4-4 along with t h e pilot plant data. Due t o t h e nature of the
thermocline, an essentially constant outlet temperature is provided by t h e pilot plant
unit until i t is almost completely charged or discharged.

Inexpensive containment of liquid sensible heat storage media is a major challenge in

reducing system cost. For high-temperature thermal storage in water or other liquids
with significant vapor pressures a t the storage conditions, a low-cost pressure vessel is
required. A vessel made of inexpensive cast iron blocks held together by axial steel
tendons as shown in Figure 4-5 offers one solution. Underground solution caverns created
in salt domes may be an economical way t o contain high pressure water or other liquid
storage media (Figure 4-6).
 Feet
0 10 20 30 40
r I I 1 I I 1 600

300 -

-
0
-
250 -
2
3
+
! Q,
i
E -
e -
- OBSERVED
- 400
200 -- 124 ~t.-'I
AIV 178.71~1-'
-
---- A/V = 393.6m-I 1120 ~ t ~ l l
I
I I 1 1 I L
0 2 4 6 8 10 12
Distance from Bottom of Tank [Meters)

F i g u r e 4-2. OBSERVED AND CALCULATED THERMOCLINES A T V A R I O U S T I R E S

D U R I N G STORAGE D I S C H A R G I N G [ I 7 1
 Feet
0 1 20 30 40
600

300

--
---- A/V=78.7m-'124~t.-'l
CALCULATED

-
2 500 &
Q,
3 250 23
C, C,

2 E
Q, Q,

E P
P F

400
200

0 2 4 6 8 10 12
Distance from Bottom of Tank [Meters]

F i g u r e 4-3. OBSERVED AND CALCULATED THERMOCLINES A T V A R I O U S T I M E S

D U R I N G STORAGE CHARGING [ 1 71
 400
14:OO 16:OO 18:OO 20:OO 22:OO
Clock Time 1hr.l

F i g i ~ r e4-4. OBSERVED AND CALCULATED 6ED TEMPERATURE PKUFlLES AT

VARIOUS BED LOCATIONS DURING TWO STORAGE CHARGING AND
DISCHARGING CYCLES [ I 71
F i gure 4-5. PRESTRESSED CAST I R O N VESSEL FOR P R E S S U R I Z E D L i A i E R
STORAGE: 1 . UPPER COVER; 2 . A X I A L TENDOilS;
3 . T A N G E N T I A L TENDONS; 4 . WEDGE; 5 . L I N E R , AND
6 . THERMAL I N S U L A T I O N [ 3 5 ]
-
7
Brine solution out
For long-term energy storage an inexpensive container is essential. Perhaps the most
promising prospect is using a confined underground aquifer for storing water at lower
temperatures. Aquifers are natural geological formations which contain and conduct
water and are abundant in many parts of the world at depths from a few meters to
several kilometers. Confined aquifers are surrounded by essentially impermeable
formations and contain water under pressure. The flow rate of water through the aquifer
is low enough that long duration storage of hot or chilled water looks feasible. Both the
storage medium and its containment are provided by the aquifer, and the system costs
are limited to drilling the well and outfitting it with heat exchanger equipment, pumps,
and associated piping. At this time, the use of aquifers for storage is in its early
development stages. More work must still be done to establish their technical,
environmental, and economic feasibility, particularly when integrated into a solar
system.

4.2 LATENT HEAT SYSTEMS

Heat transfer in latent heat storage materials is complicated by the phase change that
occurs during storage or release of energy. During extraction of energy from storage,
the liquid freezes on the heat transfer surfaces and an immobile layer of solid material
continually grows as it gives up the heat-of-fusion. The layer of solid material often has
a low thermal conductivity, and as it grows, heat transfer is impeded. In most opera-
tional latent heat storage devices, heat transfer to the load or energy source is through
the container vessel walls. In order to provide adequate heat transfer through the frozen
material, a high surface area to volume ratio is required for the combined container-heat
exchanger. As mentioned in Section 3.0, the cost of such units can be substantial. Up to
50% or more extra volume must be provided to allow passage of a heat transfer fluid, and
a good deal of the volume advantage offered by latent heat storage is sacrificed. Volume
changes during the phase change can further complicate system design and add to system
costs. Plastic containers show some promise for lower cost containment heat transfer
for low-temperature home heating use with salt hydrates. Containers that can withstand
the corrosiveness of high-temperature latent heat storage salts are far more costly.

One way to lower the cost of heat exchange is to eliminate the need for containers
between the latent heat material and the heat transfer fluid. A direct contact low-
temperature latent heat storage unit is illustrated in Figure 4-7. This device uses a heat
transfer fluid which is immiscible in the storage medium and lower in density. The fluid
enters the bottom of the storage unit and rises through the latent heat material,
transferring heat and stirring the storage media as it moves. The heat transfer fluid
coalesces in a pool at the top of the storage vessel and is then pumped back to the energy
source or load prior to returning to the bottom of the storage vessel. In order for the
heat transfer fluid to coalesce properly, the viscosity apparently
. <, :(*.,.,:.-: must be below 4.5 cp
.a"

for the salts used for storage [36]. This requirement restricts t h choice ~ of heat transfer
fluids. It is also critical that the latent heat material freeze' to a slurry and not into a
solid block if heat transfer is to be made possible. A similar high-temperature system
using fluoride salts for storage and liquid lead for heat transfer has been proposed [3q.
Considerable worlc m u ~ still
t be undertaken to dem0nst.r~ te the merits of this approach.
 Pump-

Heat

F i g u r e 4-7. D I R E C T CONTACT SYSTEM FOR HEAT TRANSFER BETWEEN THE

LATENT HEAT STORAGE MEDIUM AND AN I M M I S C I B L E F L U I D [ 361
Another approach to direct contact heat transfer in latent heat storage media relies on
forming a pebble-like storage material. A heat transfer fluid can then be passed directly
through a packed bed of the material. For instance, if crystalline polymer is crosslinked
in a controlled manner either by radiation or by chemicals, the amorphous regions will
crosslink more readily than t h e crystalline areas. The material now releases its heat-of-
fusion upon being raised above the crystalline melting point even though i t still remains
in . a solid rubbery state. High density polyethylene pellets have been chemically
crosslinked in this fashion and the product retains about 98% of the initially.high heat-of-
fusion of the polymer. The crosslinked polymer melts between temperatures of 120' c
and 1 4 0 ' ~ . More importantly, the crosslinked pellets will not fuse after releasing their
enthalpy of melting, and a packed bed of the material can be formed [381. Alternatively,
materials such a s paraffin wax can be encapsulated for use in a similar storage
configuration 1391. Both of these materials tend t o more expensive than conventional
latent heat storage substances but a substantial savings in the cost of the heat exchange
system. is possible. Therefore, the final system cost is potentially lower.

4.3 REVERSIBLE REACTION SYSTEMS

Storage of solar energy in reversible chemical reactions is in the early stages of concept
development and the problem of providing an inexpensive means of heat transfer has not
been adequately dealt with. As a class, gas-solid reactions show promise for chemical
storage but posses the inherent problem of poor heat transfer through the solids. Many of
the current devices under development for low-temperature storage of energy in solid
reaction materials for home heating and cooling use shell and tube type heat exchangers
for both containment and heat transfer in a manner similar t o heat-of-fusion systems.
The storage materials a r e placed on the shell side, and due t o t h e low conductivity of the
packed bed, the tubes have to be placed close together t o obtain satisfactory heat.
addition and withdrawal rates. The cost of these heat exchanger containers is high and is
usually far more than the price of many of the storage materials.

In an alternate concept, the solids are placed permanently in t h e solar collector

itself [401. Radiation is directly absorbed by the container for the solids, and water is
released from a MgC12'4H20 reactant by t h e endothermic forward reaction:

For a solar collector able t o supply heat a t 1 2 0 ' ~( 2 5 0 ° ~ ) ,this decomposition reaction
occurs a t point D on the equilibrium pressure-temperature diagram in Figure 4-8. The
water is condensed in a separate vessel a t a slightly lower pressure (to promote water
vapor movement) and a t a temperature slightly above the home heating load value, point
C in Figure 4-8. If t h e load demands heat, this enthalpy of condensation is given off t o
the load; otherwise, i t must be rejected to the atmosphere.

When t h e load demands energy from storage, t h e system is run in a chemical heat pump
mode. Energy from the atmosphere is used t o evaporate the water (point A in
Figure 4-8), and the water vapor reacts with the salt in the collector according t o the
exothermic reverse reaction:
 Temperature @]

F i g u r e 4-8. E Q U I L I B R I U M PRESSURE-TEMFERATURE DIAGRAM FOR HYDRATES

OF MAGNESIUM CHLORIDE AND WATER [401
This reaction occurs a t point B on the equilibrium curve. The energy released by the
reaction is sent to the load. Of course, this device may also be used for air conditioning
by reversing the position of the load and environment while discharging storage. A
pressure of about one kPa (.01 atm) is required to operate this system, and the device
must be carefully sealed to insure long-term operation.

Some of the reactions discussed in Section 3.0 involve either just gases or gases and
liquids for thermal energy transmission. A heat exchanger-reactor-receiver is being
developed to handle these types of reactions and in particular, the S03/S02/02chemical
heat pipe reaction [41]. A diagram of the system is shown in Figure 4-9 with the details
more clearly visible in Figure 4-1 0. SO3 flows into the receiver cavity through a spiral
counterflow ceramic heat exchanger that heats the SO3 up to a temperature close to that
in the reaction chamber. The SO3 dissociates on the catalyst dispersed on the cavity
walls while simultaneously absorbing solar energy to drive the endothermic reaction. The
dissociated gas then exits through the counterflow spiral heat exchanger and releases its
sensible heat to the inflowing SO3. By exchanging heat, the gases may be transmitted
more efficiently at lower temperatures. This device is still in the early stages of
development, and considerable work is still required to make it operational and establish
its utility in a solar application.
F i g u r e 4-9. C A V l T i CONVERTER- HEAT EXCHANGER FOR S O 3 D E C O M P O S I T I O N I411
Inlet, Outlet

Figure 4-1 0. D E T A I L S 01; CONVERTER-HEAT EXCHANGER C A V I T Y FOR SO3

DECOMPOSITION [411
 SECTION 5.0

CHEMICAL STORAGE REQUIREMENTS

In this section some of the thermodynamic, kinetic, and heat exchange requirements of
reversible chemical reactions will be discussed. Particular attention will be focused on
the requirements and limitations of chemical reactions for efficient thermal storage.
The aim of this analysis is to indicate which chemical reaction systems hold promise for
solar storage and what important issues must be addressed to facilitate commercial
implementation of this promising storage technology. The thermodynamic constraints on
heat transfer for sensible, and latent heat systems will not be included since these issues
have been addressed elsewhere [13].

5.1 EQWLIBRIUM CONSIDERATIONS

The free energy change for a reversible reaction AG can be expressed in terms of the
equilibrium constant K as:

The free energy change can also be related to the enthalpy and entropy changes of the
reaction by:

AG = A H - TAS (17)

If the equilibrium constant has a value of one, the free energy change is zero, and the
reactants and products will be present in approximately equal quantities depending on the
reaction stoichiometry. Thus, Equation 17 can be solved for an l1averagel1or l1turningl1
temperature.T* required to make AG = 0:

Generally, AH and AS are approximated by their standard values as presented in

Equation 7 to simplify the analysis.

A high energy storage density is very desirable in chemical storage, and a high enthalpy
change AH is therefore important in Equation 18. Furthermore, to provide energy
storage for a variety of solar applications, it is necessary that reactions exist for a range
of temperatures. Examining Equation 18 reveals that to get appreciable enthalpy
changes A H for low-temperature heating and cooling or industrial process heat
applications, the entropy change AS must be large.

In approximate terms, a high entropy change is associated with a transition from a highly
ordered state to a highly disordered state. A solid would provide the ordered structure,
particularly if it is crystalline, while a gas would be considered disordered. Therefore,
reactions in which a solid (ordered structure) decor~iposesto form one or more gaseous
compounds (disordered structure) seem to provide the high entropy change required to
allow a high enthalpy change a t lower temperatures.

Examination of Tables 3-2 and 3-3 reveals that the lower temperature reactions are
essentially all gas-solid type reactions. Furthermore, this class of reactions spans a
widescale of temperatures while gaseous and liquid reactions tend to occur mainly a t
higher temperatures. Since the enthalpy changes associated with gas-solid reactions are
large and the products can be stored as liquids or solids, sizeable energy storage densities
are possible as well. The decomposition products can also be readily separated to
prevent back reaction during storage, and no elaborate separation step is required prior
to storage. It is evident from these considerations that of the various reversible
reactions, the gas-solid reactions as a class appear to provide the most promise for solar
energy storage. However, their performance must be clearly demonstrated.

Another important consideration in the selection of a storage reaction is the manner in

which the forward and reverse reactions are driven. For example, a general reversible
dissociation reaction can be written as:

where kf is the forward rate constant and kr is that for the reverse reaction. If these
components are all gaseous, the equilibrium expressinn for the reaction is:

To cause the endothermic forward reaction to proceed to an appreciable extent, the

equilibrium constant should be much greater than one. Therefore, the forward rate
constant kf should be much greater than the reverse constant kr. Either rate constant. is
generally @ven by an Arrhenius expression of the form,

where ko is the frequency factor (a constant), E is the activation energy of the reaction,
R is the gas constant, and T is the absolute temperatr~re. Since Ef> Er, a high-
temperature will favor the forward endothermic reaction. On equilibrium grounds, the
free energy change must be negative, and the temperature T must be greater than the
turning temperature T*.

Once energy has been stored by the endothermic forward reaction, energy can be
released by the exothermic reverse reaction. In this case, the equilibrium concentration
of A must be much higher than that of R or S in Equation 20; the equilibrium constant K
must be much less than one. By lowering the system temperature, kf will decrease much
more rapidly than kr. At a low enough temperature, their ratio, which is equal t o the
equilibrium constant, will be much less than one as desired. Thus, the system tempera-
ture must be less than the turning temperature T* t o yield t h e positive free energy
change required for a K less than one.

The change in temperature necessary t o shift the equilibrium conversion significantly for
gaseous reactants may be several hundred K. For example, in Figure 5-1, the equilibrium
fraction of SO3 converted t o SO and O 2 is plotted against temperature for two
T
pressures. To proceed from 90% o t h e SO3 converted t o SO2 and O2 a t the receiver t o
10% of the SO3 converted t o SO2 and O 2 after energy release a t one atmosphere pressure
would require that t h e temperature be dropped from about 1200 K a t the solar receiver
t o less than 800 K during release. As discussed in Section 2.0, such a large temperature
drop could impose a significant penalty on collector operating efficiency and cost. In
addition, lhe reverse reaction will proceed more slowly than t h e forward reaction, and a
larger reactor will be needed t o release t h e energy. Alternatively, if the pressure were
increased significantly in the system during the energy release stage, the energy could be
released a t a temperature closer t o t h e endothermic value. However, this will require a
compressor in the storage loop with significant parasitic power requirements likely.

For a gas-solid reaction, substances A and R in Equation 19 a r e solids while S is a gas. In

such cases, activities are used in Equation 20 in &ace of concentrations for the solids
while t h e partial pressure of the gas is used in t h e same expression. Furthermore, the
activities of the solids are approximately equal t o one leading t o the simple result:

where ps is the equilibrium pressure of the gas S. Therefore, a s long a s the pressure of
the gas B l e s s than ps , the endotheric forward reaction will proceed t o completion
while if the gas pressur&3s greater than ps , the exothermic reverse reaction will take
place. e¶

The equilibrium curves for gas-solid reactions involving magnesium oxide and calcium
oxide are shown in Figure 5-2. For a water vapor pressure of one atmosphere, the
calcium hydroxide will decompose if heatcd above 520'~ since t.he equilibrium pressure
is above one atmosphere. On the other hand, if t h e system is cooled below 520°C, any
calcium oxide in the system will now hydrate since the equilibrium pressure is below one
atmosphere. Thus, in principle, the direction of t h e reaction can be reversed with small
changes in temperature.

U~~fortunately, thcrc may be some kinetic limitations t o the use of gas-solid reactions
with small temperature swings. The rate of reaction is influenced by variables such as
the temperature, extent of reaction, and the difference between the equilibrium pressure
and t h e system gas pressure. To rapidly react t h e gas with t h e solid in the exothermic
reverse reaction of Equation 19, i t may be necessary for the equilibrium pressure t o be
considerably below the system pressure. Thus, a s noted from equilibrium plots such as
Figure 5-2, i t would be desirable t o lower the solid temperature. However, lowering the
temperature also lowers t h e r a t e constant decreasing the reaction rate. A compromise
 Temperature [Kt

Figure 5 - 1 . E Q U I L I B R I U b l CONVERSION OF SO3 AS A FUNCTION OF

TEMPERATURE 1231
 Temperature, K

F i g u r e 5-2. E Q U I L I B R I U M PRESSURE FOR HYDROXIDES A S A F U N C T I C N OF

TEMPERATURE [ 2 7 1

R e p r i n t ~ dh y p e r m i s s i o n of t h e American S o c i e t y of H e a t i n g , X e f r i g e r a t i n g ,
and A i r - c o n d i t i o n i n g E n g i n e e r s , Inc.
between these two extremes must be made. Diffusion of the gas through the solid can
further co'mplicate matters with the net result that the rate exhibited by some gas-solid
reactions may become extremely low. More work is required to understand the exact
nature of the reactions, quantify it, and determine its effect on reactor design and the
temperature swings required.

One intriguing possibility can arise from the unusual equilibrium characteristics of the
gas-solid reactions. Calcium hydroxide could be decomposed by a solar collector at a
temperature of about 440°C (825OF) to produce water vapor with a pressure of about
0.07 atm. The water could then be condensed at 38OC (lOO°F) where the water vapor
pressure is slightly below 0.07 atm. If a sizeable source of waste heat were available
above 100°C (212OF), it could be used to produce steam at 100°C and one atmosphere
pressure. The steam could then be reacted with the dehydrated calcium oxide to produce
temperatures c l o ~ eto 630°c (!368OF), a temperature above 111e orlginnl collector
ternp~rnt11rP.

5.2 ENERGY PROM STORAGE

In the analysis that follows, it is assumed that as much as possible of the energy from
storage should be available at essentially the same temperature as generated by the
collectors. Even if the temperature requirements of the load are well below the
collector temperature over a large portion of the process, the size of the heat
exchangers and other components will be minimized for the large temperature difference
available. If the storage unit produces a significantly smaller temperature difference,
than a larger heat exchanger is needed to accommodate the storage unit and an
additional cost penalty is accrued against storage. In addition, subsequent process units
may have to be designed to handle lower temperatures than are optimum. It is further
assumed that energy produced at a temperature below that of the collector during the
charging of storage is not very useful, and it is far more desirable to release energy from
storage only upon demand. For various applications, it may be desireable to relax some
or all of these restrictions with some simplifications in the storage design requirements,
but a detailed system design is necessary for each application to identify the tradeoffs.
Such studies are beyond the scope of this report.

For the purposes of this discussion. the reversible re~ction

is employed as an example since good thermodynamic data is available and the reaction
has significant potential for high-temperature thermal storage. Complete reaction is
assumed to occur. The transition

is used to allow storage of the water. Arbitrary operating conditions are employed for
these examples. Other conditions could be used with little change in the conclusions. A
continuous operation is assumed for the different operating schemes discussed to
illustrate the effect of the mode of storage operation on the energy delivery temperature
and the storage characteristics calculated are therefore based on enthalpy changes. For
batch operations, the internal energy change should be quite similar, and the general
conclusions will still apply.

The first operational mode is based on storing all materials at high temperatures. The
storage and release reactors are assumed to operate at a water vapor pressure of one
atmosphere, and water is condensed for storage. Hydrated lime, Ca(OH)2, is contained at
5 2 0 ' ~(968OF) until it can be dehydrated with solar thermal energy. The CaO produced
by reaction 23 is also stored a t 5 2 0 ' ~while the water must be cooled to 100°c ( 2 1 2 ~ ~ )
and condensed as shown in Figure 5-3. To release the stored energy, the 100°C water
and 520°C CaO are mixed in a suitable reactor to produce heat.

Figure 5-4 presents the energy released in M J per kg of Ca(OH)2 required during both
charging and discharging of storage as a function of temperature for the operational
scheme discussed. The energy released at temperatures below 5 2 0 ' ~is that necessary to
cool down and condense the water during charging of storage while the energy released
at 520°c is due to the hydration reaction during discharge. The COP (coefficient of
performance) in Figure 5-4 is defined as the ratio of the total energy delivered from
storage to the solar energy input, and since the total amount of solar energy needed to
charge the storage system at 520' c is equal to the total energy output of 1.45 MJ/kg,
the maximum COP is equal to one. However, only 48% of that energy output is released
during the discharge of storage at the input temperature of 520°C. The other 52% of the
solar energy into the system is released at temperatures below 520°C while the system is
being charged. In fact, about 38% of the total solar energy input is available a t 100' c
during the charging phase. One should note that the effective specific heat shown in
~ i g u r e5-4 is simply the total energy storage capacity divided by the total required
temperature swing to produce it. The value shown is less than sensible heat storage in
liquid water although the temperature distribution is certainly far different.

The energy "wasted" in the previous case is the result of cooling the water vapor from
5 2 0 ' ~to 100°c and condensing i t at 100°c. If the temperature of this energy is too low
to be useful at any other location in the process, the energy must be simply discharged to
the environment. The value of this energy is not as high as the input energy even if used,
particularly since a high-temperature collector was required to capture it. In some
cases, it may be possible to use waste heat available a t slightly above 100°C to improve
the energy distribution. This energy could be used to evaporate the water during
discharge of storage, and the water vapor at 100°c can be added to the CaO stored a t
5 2 0 ' ~ . Thus, heat is pumped from a low-temperature waste stream in the process to the
high-temperature point where stored energy is released as shown in Figure 5-5.

A diagram of the amount of energy released from storage is plotted against its release
temperature in Figure 5-6 for the chemical heat pump system described. Again, the
energy released below 520°c is that associated with cooling down and condensing the
water vapor during the charging of storage. Although the total energy input is again
equal to t.he total energy output, the solar energy input is only equivalent to the energy
 TR-08 9
s:?l%j
QSOLAR

Reactor 1

r----
I .
Receiver
520 OC 1H 2 0 ( I )
I
i 1 I
I I QCOND I
I
r

Ca(OH),(s) H,O(I)
520 OC 100 OC

H,O(I)
Reactor
520 OC

QSTORE

F i g u r e 5-3. THERMAL ENERGY STORAGE SYSTEM BASED ON C A L C I U M O X I D E /

HYDROXIDE W I T H M A T E R I A L S STORED A T H I G H TEMPERATURES.
THE CHARGING CYCLE I S SHOWN BY DASHED L I N E S AND THE
DISCHP.RGING CYCLE I S SHOWN BY S O L I D L I N E S

% Solar Delivered a t 520°C = 4a0/0

M a x i m u m COP=i.Oo
Effective Specific Heat = 0.83

Temperature (OC)

F i g u r e 5-4. ENERGY RELEASED AS A FlJNCTIOPl O F TEMPERATURE FOR CP.LCIUM

O X I C E / E Y D R O X I D E W I T H M A T E R i A L S STORE9 A T H I G H TEYPERATURES
F i g u r e 5-5. THERMAL ENERGY STORAGE SYSTEM BASED ON C A L C I U M O X I D E /
HYDROXIDE \ / I T 3 M A T E R I A L S STORED A T H I G H TEMFERATURES
AND W I T H WASTE H E A T USED TO EVAPORATE WATER I N A C H E M I C A L
HEAT PUMP MODE. THE CHARGING CYCLE I S SEObIN BY CASHEC
L I N E S AND T H E D I S C H A R G I N G CYCLE I S SHOWN SY S O L I D L I N E S

2.0 1

;C
r
1
i
I
I
I
I
i
; i
%TORE
.-C:
3 1.0
C
.O

OO
/ Solar Delivered a t 520°C = 85%
Maximum COP = 1.37 I
Effective Specific H e a t = 1.14

0.0 I f I ! I
. . . . .. . . . _.
0 100 200 m 400 : 500 .' . .. ' .

Temperature (OC)

F i g u r e 5-6. ENERGY RELEASED A S A F U N C T I O N O F TEMPERATURE FOR THE

C H E R I C A L HEAT FUMP SVSTEPI SHOWN I N F I G U R E 5 - 5
o u t p u t shown a b o v e 100°C s i n c e t h e w a s t e s t r e a m energy is used t o e v a p o r a t e t h e w a t e r
at 100°c. Thus, t h e coefficient of performance is 1.37. However, only 85% of t h e solar
energy used t o c h a r g e s t o r a g e is delivered at 520°C. Overall, t h e t o t a l energy released
yields a n "effective s p e c i f i c heat" of 1.14, a value somewhat above t h a t of water.

Of course, t h e r e is a good probability t h a t energy will not b e available at 1 0 0 t~o ~

vaporize t h e water. However, t h e reaction and its operating conditions were both chosen
q u i t e arbitrarily. If t h e atmosphere t e m p e r a t u r e w e r e 7OC ( 4 4 O ~ ) w
, a t e r would condense
at 1.0 k P a (0.01 atm.) pressure or more. Therefore, t h e s t o r a g e charging reaction could
t a k e place at a t e m p e r a t u r e somewhat g r e a t e r t h a n 3 9 0 ' ~ (734OF) corresponding t o a n
equilibrium pressure of 1.0 k P a in Figure 5-2. T h e energy evolved during condensation of
t h e w a t e r vapor at 7OC would now b e given off t o t h e environment as shown in Figure 5-7
a n d l'storedl' there. When energy is required from storage, t h e w a t e r would b e vaporized
at a t e m p e r a t u r e slightly below 7OC using t h e "stored1' heat in t h e atmosphere t o give a
water vapor pressure below 1.0 kYa. Thus, from t h e e q ~ ~ i l i b r i ~C ~I I r~nV Pnf Figure 5-2, t h e
reaction of t h e calcium oxide stored at 3 9 0 ° c and t h e w a t e r vapor would produce h e a t a t
a t e m p e r a t u r e below 390°C and t h e input and output t e m p e r a t u r e s could be very
similar. Figure 5-8 presents t h e results of this case graphically, and when compared t o
Figure 5-6 shows t h e energy distribution to b e very similar. For convenience, all
subsequent calculations consider operation of t h e system at 520°C as a n example
although different conditions may b e required i n p r a c t i c e without a major change in t h e
conclusions.

As a n independent check on these results, t h e energy released per weight of t o t a l

m a t e r i a l is shown as a function of t e m p e r a t u r e in Figure 5-9 f o r a n ammoniated salts
s y s t e m using t h e coupled reactions 25 and 26.

T h e thermodynamic d a t a available for t h e l a t t e r t w o reactions is f a r less reliable than

f o r t h e previous pair, and c r u d e e s t i m a t e s must b e made t o calculate t h e energy
requirements. T h e f i r s t energy s t o r a g e reaction occurs at 135OC ( 2 7 5 ' ~ ) for a n ammonia
pressure of one atmosphere. T h e second reaction is r~sedt o s t o r e t h e ammonia and t a k e
place at about 32OC (90°F) at one atmosphere ammonia pressure. Both salts a r e stored
at t h e i r reaction t e m p e r a t u r e s , and t h e energy available below 1 3 5 ' ~ is again t h a t
associated with t h e cool down and reaction of ammonia (reaction 26) f o r storege, This
s y s t e m m u s t b e o p e r a t e d in a chemical h e a t pump mode if t h e gaseous ammonia is t o b e
s t o r e d with t h e solid C a C 1 2 by reaction 26. Although t h e t o t a l possible chemical h e a t
pump coefficient of performance is higher than for calcium oxidelhydroxide, t h e percent
energy delivered at t h e s t o r a g e generation t e m p e r a t u r e is only slightly better than
before.

S o m e additional penalty must b e assessed against s t o r a g e system efficiencies t o account

f o r t h e r m a l losses of t h e materials s t o r e d at high-temperatures. Considering t h e final
 Receiver
I 390 OC 1H:O(l)
I

4 I H201

a
~ E V A P

Reactor
Ir
Evaporatgr
i
390 OC
II

F i g u r e 5-7, THERMAL ENERGY STORAGE SYSTEM B A S E D ON C A L C i U M O X I D E / -

H Y D R O X I D E W I T H S O L I D S STORED A T 3Y0°C AND \4ATER COFIDENSED,
STORED, AND ' j A P O R I Z E D U S I N G A T M O S P S E R I C TEMPERATURES.
THE CHARGING CYCLE I S SHOWN BY CASHED L I M E S AND THE
D I S C H A R G I N G CYCLE I S SHOWN 3Y S O L I D L I N E S

-
-
QSTORE

-
-
QCOND

- YU Solar Dslivered a t 390°C = 87O/n

M a x i m u m COP = 1.42
.QcoND Effective Specific Hear = 1.28

0 I I I I I I I
0 100 200 300 400
Temperature ("C)
F i g u r e 5-8. ENERGY R E L E A S E D A S A F u N C T I O N O F TEMPERATURE F13R T H E
CHEP!ICWL HEAT 2\84? SYSTEM SHQWN 1% F I G U R E 5-7
 -

% Solar Delivered at 135OC = 91°/o

Maximum COP = 1.92
- Effective Specific Heat = 2.13

0.0 I I 1 1 I I A

0 20 40 60 80 100 120 140

Temperature (OC)

F i g u r e 5-9. ENEFGY RELEASED AS A FUNCT1O:q OF TEMPERATLRE FOR AN AMMONIATED

SALTS CHEMICAL HEAT PUtlP SYSTEM W I T H STORF.GE OF MATERIALS A T
REACTION TEMPERATURES
total efficiency, complexities of operation, and temperature drops between the storage
and release conditions, chemical reactions with material maintained at the high
temperatures appear less desirable for thermal energy storage than latent heat-of-fusion
materials. The only advantage offered by the reactions is a generally higher energy
storage density at the elevated temperatures. This advantage is slight for many of the
reactions. However, if the reactants and products could be stored at temperatures close
to ambient, the thermal losses and container corrosion problems in storage would be
substantially reduced, and chemical storage would offer substantial advantages.'

The simplest way to get the products to ambient conditions is to let them give off their
sensible heat either to the load if it can be used at the available temperatures or to the
surroundings if it cannot. If calcium hydroxide is stored a t 25OC, it can be dehydrated a t
one atmosphere pressure by heating it up to 520°c. (Figure 5-10.) The calcium oxide
and water vapor produced at 520°C are then cooled down to 25OC (or any other low-
temperature) for storage. When energy is required from storage, the cool water and
calcium oxide react in much the same way as for hydrated lime production, and energy is
drawn off at 520° C. The calcium hydroxide is then cooled down from 520°C to 2 5 ' ~ .

Figure 5-11 presents the distribution of released energy with respect to available
temperature for the operational scheme just described. The small amount of energy
shown a t 5 2 0 is~ that
~ released during the discharge reaction while the larger quantity
of energy released at 100°C arises from condensing the water for storage. The sloping
lines in the figure represent the energy released in cooling down the calcium oxide and
water to 25OC after charging storage as well as the energy available in cooling down the
calcium hydroxide after the discharge reaction. As shown in the figure, only 14% of the
solar energy added to the system is available at the original input temperature of
520°C. If the energy is useful at all temperatures, then a coefficient of performance
equal to one results although the wisdom of using a 520' C collector to generate so much
low-temperature energy could be questioned.

As discussed previously, evaporation of the water by waste heat (or ambient heat if all
other conditions are altered) increased the temperature of the energy delivered. If this
chemical heat pump mode is adopted again to heat the stored water from 25OC to 100°C
and vaporize it using waste heat as shown in Figure 5-1 2, the energy distribution is as
shown in Figure 5-13. The chemical heat pump operation makes it possible to deliver
44% of the input solar energy near the 520°c temperature. It is theoretically possible to
obtain 30% more energy from the storage system than the energy used to charge it
although most of the energy is no more useful in the process than the 'lwastel' heat used
to evaporate the water. Figure 5-14 presents similar results to those discussed above for
the ammoniated salts system of Equations 25 and 26. Sixty-nine percent of the solar
energy used to charge storage is available now during discharge at the higher tempera-
ture.

From the preceding results, it is apparent that the sensible heat changes associated with
heating and cooling the reactants and products is significant. For home heating or other
applications in which energy is useful over a wide spectrum of temperatures, the
operational schemes can be adjusted only slightly from the simplistic ones discussed
 TR-08 9
SE?I*

r----
I
I I
I I
I I
I

Ca(OH1, CaO(s1 HzO( I )

25 OC 25 OC

4
HzO( I 1

I Cooler Reactor
520OC

QCOOL~
QSTORE
F i g u r e 5-1 0. THERMAL ENERGY STORAGE SYSTEM BASED ON CALCIUM OXIDE/
HYDROXIDE WITH MATERIALS STORED A T 2S°C. THE CHARGING
CYCLE I S SHOWN BY DASHED L I N E S AND THE DISCHARGING
CYCL.E TS SHOWN RY SOLID L I N E S

% Solar Delivered at 520°C = 1496

Maximum COP = 1.00
5'
Effective Specific Heat = .99

0
0 100 200 300 400
Temperature (OC1

F i g u r e 5-11. ENERGY RELEASED AS A FUNCTION OF TEMPERATURE FOR THE

CALCIUM OXIDE/HYDROXIDE SYSTEM I N FIGURE 5 - 1 0
 H*OIgl
Cooler
1 I1

F i g u r e 5-12. THERMAL ENERGY STORAGE SYSTEM BASED ON CALCIUM O X I D E /

HYDROXIDE I N CHEMICAL HEAT PUMP MODE AND WITH M A T E R I A L S
STORED A T 25OC. THE CHARGING CYCLE I S SHOWN BY DASHED
L I N E S AND THE DISCHARGING CYCLE I S SHOWN BY S O L I D L I N E S

-
-
-
.
2
-I
2.0

r- -
r
.-
z-
U
-
3
U
Y
31
-
2
1.0 -

- -;a;I1
- QCOND
Solar Delivered a t S20°C = 4496 .-5 '
-
Maximum COP= 1.30
Effcctivo Spooifio Heat - 1.29 ?I
r1
1

0,
0 100 290 300 400 500
Temperature laCl

F i g u r e 5-13. ENERGY RELEASED AS A FUNCTION OF TEMPERATURE FOR THE

CHEMICAL HEAT PUMP MODE O F FIGURE 5 - 1 2
-

-
- -
ig l
I
1" I

YLO I

-
940 Solar Delivered a t 135C%= 69%
Maximuni COP = 1.79
-
ZI
m
I
73 1
Effective Specific Heat. = 2.20 2I
Q,
.I I

I / I I I I I
0 20 40 60 80 100 120 140
Temperature (OCl

F i g u r e 5-14. ENERGY RELEASED AS A FUNCTIOR OF TEMPERATURE FOR

AMMONIATED SALTS I N TtlE CHEMICAL HEAT PUMP MODE
WITH ALL MATERIALS STORED AT 250C
above t o take advantage of unique heat pumping capabilities, and more energy can be
obtained in principle from t h e system than was applied by solar. In these cases, the
sensible heat is used more effectively. It is possible that t h e energy distribution curves
such as in -Figure 5-13 may match t h e load requirements for high-temperature
processes. However, t h e operational schemes described a r e not generally satisfactory
for applications where significant value is placed on high-temperature heat but little if
any value is placed on low-temperature heat.

Dramatic improvements in high-temperature energy delivery capabilities a r e possible if

t h e energy storage and release reactions a r e carried out in continuous reactors with heat
exchange. For example, t o charge storage, t h e calcium hydroxide at 25OC could be first
passed through a countercurrent heat exchanger and then into a reactor where solar
energy would drive the reaction a t 520°C. The calcium oxide and water vapor would be
separated at t h e reaction temperature t o prevent subsequent back reaction, and then the
two products would flow back through the heat exchanger t o give up their sensible heat
t o t h e incoming calcium hydroxide. More sensible heat is available for heat exchange in
the products than required by the reactants, and assuming the reactants could be heated
t o close to 520°C in the heat exchanger, about 1.46 M J of solar energy is needed per kg
of calcium hydroxide t o charge storage.

Two possiblilities can be devised t o use the energy from storage. First, liquid water and
calcium oxide at 2 5 ' ~ a r e passed through separate passages in a countercurrent heat
exchanger and a r e mixed in a continuous reactor t o produce a temperature of 520°C.
Energy is taken from the reactor a t 520' c by t h e load, and t h e calcium hydroxide
produced flows back through the countercurrent heat exchanger t o give up i t s sensible
heat t o t h e incoming reactants. More energy is now needed t o heat t h e reactant t o
520' c than is available in the products, and the energy available from t h e reactor is
0.879 M J per kg of Ca(OH)2. Thus, just over 60% of the solar energy required t o charge
storage is available at 520°C assuming effective heat exchange is possible. Although this
is not completely satisfactory, i t is a dramatic improvement over t h e 14% level observed
in Figure 5-1 1 for the same concept but without heat exchange. The energy delivered a t
5 2 0 ' ~ in t h e heat exchange system is shown graphically by t h e dashed line in
Figure 5-11. The energy "wastedM at other temperatures is not shown since t h e data
available t o perform the more detailed analysis required t o determine t h e profile is
sketchy:

T h e second route ,employed t o release the stored energy combines t h e chemical heat
pump mode with t h e heat exchange system t o make up for t h e "wasted" heat. Water is
heated up from 2 5 O ~t o 1 0 0 and~ ~vaporized using heat available above 100°C. The
vaporized water and the cool calcium oxide then pass t h r o ~ ~ gseparate
h passages in a
countercurrent heat exchanger. These materials a r e mixed in a reactor where they give
up heat a t 520°C for t h e load. The calcium hydroxide formed passes back through t h e
counterflow heat exchanger t o give up i t s heat t o the incoming reactants. Somewhat
more sensible heat is available in cooling down t h e calcium hydroxide than is required t o
heat up t h e oxide and water vapor; and 1.410 M J of energy is released t o t h e load per kg
of calcium hydroxide produced assuming complete heat exchange is possible. Thus, as
shown by the dashed line in Figure 5-13, about 97% of the solar energy needed t o charge
storage is available a t t h e input temperature (520°c). The dashed vertical line in
Figure 5-14 shows the result of combirled heat exchange and heat pumping for ammoni-
a t e d salts. An essentially 100% efficiency is predicted.

The analysis used here is cursory in nature and neglects some of the practical considera-
tions which must be addressed for real systems. For instance, some drop will be required
in the energy release temperatures if the heat for vaporizing water during discharging of
storage is pumped from the' heat sink used during charging. The exact amount of this
shift depends on the reaction kinetics and reactor design tradeoffs. The temperatures of
t h e heat source and sink for heat pumping depend on the application and location, and the
system operating temperature must shift to fit the equilibrium requirements for these
temperatures. Furthermore, reactions other than calcium oxidelhydroxide and
ammoniated salts are available, and the operating temperatures will be altered for
different systems. To be complete, studies must be done of an integrated solarlstorage
system. However, in the final analysis, the basic conclusion should still remain: heat
exchange and chemical heat pumping are necessary for chemical storage a t ambient
temperatures if a reasonable fraction of the solar energy used to charge storage is t o be
delivered a t a temperature close to t h ~ oft the collector. Heat exchange decreases t h e
amount of sensible heat losses while chemical heat pumping counteracts t h e losses that
a r e apparently unavoidable if materials a r e t o be stored a t ambient conditions. For gas-
solid reactions, substantial research and development are required t o economically and
efficiently provide these capabilities.
 SECTION 6.0

DOE STORAGE PROGRAMS

This section summarizes major r e c e n t projects in t h e r m a l energy s t o r a g e funded by t h e

Department of Energy primarily through t h e Chemical a n d Thermal Branch of t h e
Division of Energy Storage Systems (STOR), t h e Research and Development Branch of
t h e Division of Solar Applications (R&D), and t h e Solar Thermal Branch of t h e Division of
C e n t r a l Solar Systems (Solar). Since t h e r e are a substantial number of programs in
t h e r m a l storage, only a brief t a b l e of c o n t r a c t titles, contractors, funding organizations,
and project summaries is presented here. If a project is monitored by an agency other
than t h e funding organization, a n o t e appears in parenthesis below t h e funding agency.
Only t h e programs which have possible application t o solar energy s t o r a g e a r e included.
Further details a r e available in publications prepared by t h e branches funding t h e
research 139, 421 and t h e laboratories administering t h e programs [43, 44 or by direct
correspondence with t h e s e agencies. A more detailed summary a n d evaluation of
t h e r m a l energy s t o r a g e projects for low-temperature applications is being prepared by
Dr. F. Baylin at t h e Solar Energy Research Institute, and a preliminary report will b e
released soon.

The summary has been checked by t h e various laboratories monitoring t h e programs prior
t o publication. The projects a r e broken down according to t h e mode of thermal s t o r a g e
(sensible, l a t e n t , o r chemical heat) as f a r as possible and studies which span more than
one mode are listed as a general category at t h e end. An a t t e m p t is m a d e t o f u r t h e r
subdivide t h e s e headings according t o t h e issues addressed although many of t h e
programs actually cover more area than this breakdown suggests.
PH0.J E C T T1Y'I.E
S u h s ~ ~ r l i a cWastc
e H e ; ~ tS t o r a g e , A u h ~ t r -Ilni
~ versi ty
I<xl~cri~nanr;i L StuJy ( J . C. Warnla!:, I?. J.
blolz)
Fcasibi.Li t y Study f o r Desert Reclamatlon
A q ~ t i f e rCooliless S t o r a g ? a t Industries
.I FK A i r p u r t
1.c11g I ) u r ; ~ c i oEa
~ ~rtll S t o r a g e 93eorgt Washi.ngtsn
of S o l a r Energy Vtliversity
(S. W. Yuan,
A . El. HLoom)
Iln~lergl.<n~nd
S t o r a g e of Sol.ar U n i v e r s i t y of Hotiston
I:~lr:rgy iK. E . Coll.ins)
Lawrence Berkeley
Labora ~ o r y
( C . F. Tsarig)
Rock Red Asc~imtili~cors I J n i v e r s i t y of
Mi~r~rescta
( M . Kizz)
PROJECT S U ~ R Y
STIJK i a c t i v e l 'Cest ; ~ q u i f e rthernrnl s t o r a g e concept and pruvide
d a t a f o r cal. i b r a t ion of ~ n a t l - ~ e ~ n a t i cmodels
al
d e s c r i b i n g t r a n s p o r t oE he;it i n g r o ~ ~ n water.
tl
STOK (complete) Ex[)lore f e i t s l b i l i t y of cool.ing . l V K A i r p o r t i.n
tlle sulslner, wit11 water s t o r e d i n an a q ~ ~ i f ein c
the winter.
STOH (complete) I:valuete a n a l y t i c a l l y long-tern1 eiirtli s t h r a g e of.
s o l a r energy f o r space and I ~ a twater l ~ e i i t i n gir~rd
t l r t e c ~ nne
i t h e economics of 1)rolnis iny c o n c e p t s .
S o l a r (STOR mon.) E s t a b l i s h E e : l s i b i l i t y of Iii.gl~-tel~ll)erature,l~i.gli
(active) p r e s s u r e s t o r a g e of t l l e r n ~ a l energy i n deep
s a l i n e a q u i f e r s o r so11~ti.011c a v e r n s c r e a t e d i.n
s a l t domes by t l i e o r e t i c a l s t u d i e s and survey oE
potential sites.
STOK ( a c t i v e ) Study ~actthematiciilly and ~ ~ n d c r s t a ntdh e hydcudy-
n a ~ n i c and t l ~ a r ~ ~ lbehavior
al of iin a q u i E e r when
used f o r hot o r c l r i l l e d water s t o r a g e , e s t i m a t e
t h e energy s t o r a g e a n d r e t r i e v a l e f f i c i e n c y , and
s u g g e s t ope.i~min~ arrangements.
STOK (complete) I n v e s t i g a t e tlre t e c h n i c a l and eco~iomic feasibi1.-
i t y of s t o r i n g l a r g e amounts o f t l l e r ~ ~ r aenergy l
a t t e ~ ~ l p e r a t u r e st o 5 0 0 ° C o v e r p e r i o d s of up t o
s i . ~months u s i n g ~ r a t i v ee a r t h o r coclc , cunduct
s t u d i . c s t u establ.islr t h e performance clrar:icter-
i s t i c s of l a r g e rock bed accum~il;rtorsa t v a r i o r ~ s
I I O W C ~ a ~ i d t e m l ~ e r a t u r e l e v c l . ~ , and a s s e s s the
r.iateria1 and e ~ i v i r o n m e ~ i t nprobl.cms l ;~ssociatetl
wLtl1 opercicion of such l a r g e u n i t s .

PROJECT TITLE
A. SENSIBLE HEAT STORAGE ( c o n t ' d )
1. I n Ground S t o r a g e ( c o n t ' d )
S t o r a g e of Cold Water i n
Groundwate: A q u i f e r s Eor
Cooling Purposes - Phase I
2. S t o r a g e A n a l y s i s and Design
Computer Modeling and Exper-
i m e n t a l Measurement of Thermal
S t r a t i f i c a t i o n i n Water Tanks
Develop and Apply T h e o r e t i c a l
Model of FLOWS t r a t i f i c a t i o n
i n S o l a r Systems
S t r a t i f i c a t i o n s and Seasonal
Storage Studies
S e r i e s - P a r a l l e l S o l a r Augmented
Rock Bed I k a t Pump
CONTRACTOR
(INVESTIGATOR) FUNDING AGENCY PROJECT SUMMARY
Texas A 6 M Research STOR ( a c t i v e ) Study and e v a l u a t e c o l d water a q u i f e r s t o r a g c
Foundation system f o r a i r c o n d i t i o n i n g , monitor water
(D. L. Reddell) movement and temperature p r o f i l e s t o v e r i f y
e x i s t j n g numerical models, and e v a l u a t e s t o r a g e
efficiency.
U n i v e r s i t y of Alabama R6D ( a c t i v e ) E v a l u a t e and improve one dImensLonal s t r a t i f l c a -
i n Huntsville t i o n code f o r TRNSYS type programs and o b t a i n
(S. T. Wu) d e t a i l e d e x p e r i m e n t a l d a t a f o r u s e 1.n v a l i d a t i o n
of t h r e e dimensional t r a n s i e n t codcs under
development by Argonne 1,aboratory.
Argonne National. R6D ( a c t i v e ) . Develop a d e t a i l e d t h r e e d i m e n s i o n a l t r a n s i e n t
Laboratory s i n g l e f l u i d computer code w i t h a two dimen-
(E. 1-11. L i n , W. T. Sha) sional. o p t i o n f o r modeling thermal s t r a t i f Lca-
t i o n and hydrodynamic and h e a t flow i n l i q u i d
h e a t s t o r a g e t a n k s , v a l i d a t e t h e model, optiinize
h e a t s t o r a g e and s o l a r system d e s i g n s and param-
e t e r s f o r s t r a t i f i c a t i o n , and expand t o multi-
f l u i d systems l a t e r .
Argonne N a t i o n a l STOR ( a c t i v e ) Determine t h e b e n e f i t s of s t r a t i f i e d tliermal
Laboratory s t o r a g e and e v a l u a t e t h e economics of sensona.1
(J. G. Asbury, thcrmal energy s t o r a g e .
R . 0. Mueller)
California S t a t e R6D ( a c t i v e ) Define t h c performance advantages and dlsadvao-
University t a g e s of a s o l a r rock bed thermal s t o r a g e l h e a t
(E. F. Sowell) punp subsystem Ln a s e r i e s - p a r a l l e l c o n f i g u r a -
t i o n by computer modeling and s i m u l a t i o n and
deve1:sp t h e concept t o t h e p o i n t where . i t can he
considered f o r d e t a i l e d d e s i g n i n i n s t a l l . a t i o n s .
 CONTRACTOR
(INVESTIGATOR)
A. SENSIB1.E HEAT STORAGE ( c o n t x
2. Storage Analysis and Destgn (coolt'd)
Heat 'CransFer Properties of Sol1 C>l.or;~doS t a t e
University
( D . Kempar)
Rock Bed Storage f o r cool in^ Dynatech RbU
Company
(E. C. Cuyer)
Conceptual Ceslgn of Tl~ecmal General. E l e c t r i c Co.
Energy (TES) Systems f o r !Near- (E. V . IlaLl)
Term E l e c t r d c U t l l l t y
Appl l c a t i o n ~
Thermal Enecgy Storage i n J e t Prop1.11.sior.
s o Lids Laboratory
. .
( li I1 T~.urncr)
Storage FLuld Evaluation Martln-I.larLett;l: Corp.
( T . It. Ilaato~i)
C e r ~ t r a lReceiver P r e l l n ~ i n s r y McDoi~~iel.L-Do~~gl
es
Dcslgn - Exter~tledT e s t i n g of. (R.. W . IlaLLet)
Storage F l u i d s and Flow Loop
Experiment
FUNDING ACENCY
KCID ( i n A ~ . a t r . n g )
R&D ( c o n ~ p l e t e )
STOR ( a c t i v e )
STOK (co111p1.ete)
Solar (active)
Solnr (actl.ve)
PRO.IECT SUhYAHY
Investigate soil l ~ e a t tr;insfer ~,ropc?rties
L n c l ~ ~ d t n gwater mlgratlon and heat f l u x 111
small-scale e x p e r i m e ~ i t s , eva1.11;lte t l ~ ce f f e c t s o l
n ~ o i s t u r e on heat t r a n s f e r , I.nvcstlp,ilte use of
b a r r i e r s f o r 1no1s t t i r e c o n t r o l , and c~~itlcrtake ;I
small-scale field stcicly of these effects.
S t u d i e s a r e dl rected toward in-ground t l ~ e r m a l
energy s t o r a g e and e a r t l ~source heat Immp ap11li-
cations.
l n v e s t l g a t e and qt1a11tLFy on a r e g l o n a l l e v e l t l ~ e
c o s t s ant1 p e r f o r m : ~ ~ ~ of
c e uslng rock beds c l ~ i led l
by n i g h t a i r o r a l r from all evaporallve c o o l e r
a s an a l r c a n d i t t o n i n g system.
Examine the Field O F proposed concepts f o r
thermal en.>rgy storilge syslelns a ~ ~ sde l e c t ,
conceptuallp deslgn, and analyze the most prorlr-
l s l n g f o r near-term e l e c t r l c 11111 i t y appl l r a -
t ions.
Assess f e a s l . b i l i ty and problems in s t ~ ~ r n gofc
tl~ccm;~l energy i n hollow s t e e l ingots and plpcs
s ~ ~ r r o u n d eby
d an inexpensive sol1.d and e s t i m a t e
c l ~ e cconn~n.ic ~ ~ e r f o r ~ n aof
~ ~ cthe
e sys telna w11e11
i n t e g r a t e d wit11 a baseload power p l a n t .
Provlde engtneeri ng and cl~emlr;~L dnta on c l ~ ; t ~ ~ g c s
e n l~ydrnrarbon o i l wit11 l~igh-Lemperatl~rer~xpo-
s u r e i~ndd c f l n c treatlnellt of tlie f111ld t o c x t ~ 1 1 1 1
I t s l i f e 111 t l ~ e r ~ n ns lt o r a g e a p p l l c a L l o r ~ s .
Provide dnt:! on f1ul.d n t a b l l l t y , c:omp;~tlbll t l : y ,
and s ~ ~ r f a c fe( ~ ol.ng
l t o perm1 t 1.11.1lds c l ~ ? c t t o n
f o r tlicr~n:~l.
s t o r a g e appl i c a t Lolls.
 CONTRACTOR
PROJECT TITLE (LNVESTIGATOK)
A. SENSIBLE HEAT STORAGE ( c o n t a d )
2. Storage Analysis a~itlDesign ( c o n t ' d )
P r e d i c t Lon of Performance of Pen~isylvanlaS t a t e
S o l i d S e n s i b l e Ileat Thermal Univcrslty
Storage Units (ti. , W . Schnlldt)
llybrid Tllcrmal Storage wit11 Rockwell I n t e r n a -
Water t innal
(M. Moriarty)
Multlmedla Storage Santlla L a b o r a t o r i e s ,
A 1 huquerque
(C. E. Ilackett)
'L'hermocl lne Storage Sandla I.ahocatorles,
Albc~querclue
( C . E. Ilackett)
Molten Sa 1 t High l'en~pera- Sar~diaLal~oratorle!;
t u r e Storage Medla 1. lver~nore
( V . P. Burolla)
FllNDING ACENCY PROJEC'I SUHEIARY
-1 Uetermtne para~ncLers wl~lclt c l r a r a c t e r i z e trans-
i e n t heltavior 01 s o l i d s e n s i b l e Iteat s t o r a g e
u n l ~ s , d e t e r ~ n l r ~ ethe t r a ~ l s l e n t response of
s i n g l e and two Elelid 11nit s , optlmlze the 11nlt s
t o provide maxlm~~m ~ ~ o s s i h l e~llcrmal s t n r a g e
c a p a h l l l t y , and evnlctate t h e nccitracy of Lire
predicLed r e s t ~ l t shy e x p e r l n ~ e n t n lt e s t s .
RSD (complete) Survey s t a t e - o f - t h e - a r t oE l ~ y b r l d water tank
with e a r t h o r irock thermal s t o r a g e , e s t a h l l s h
four t o s i x storilgc concept deslgcls, o b t a l n d a t a
from t h r e e hybrld l n s t a l l a t t o n s v j s l t e d , develop
ant1 checkout Ilyt.rld s t o r a g e colnpclter s u h t o c ~ t i n e ,
s e l e c t candldnte l ~ y h r i d desi.gns, and s l m c ~ l a t e
y e a r l y performance of these cotlcepts OII a c o w
p l e t e system model SIICII a s 'TKNSYS.
Solar (active) Minimize t l i i c k ~ ~ e sof s tl~ermocline reg Ion, reduce
convect lve c ~ ~ r r e l i twbi.cl~
s degrade tl~er~noc:l l ne,
and minimize t h e amount of expensive 11e:ir trans-
f e r E1ui.d r e q e ~ i r e d in mu1tlme~ll.a s t o r a g e con-
c e p t s t o be a p p l i e d t o near-term p r o J c c t s .
Solar (actlvc) Mlnilnlze t h l c k r e s s of thermocline reglon and
reduce convective c u r r e n t s wl11cl1 dcgradc 1 liermo-
c l l n e i n one tank system f o r a p p l l c a t l o n t n
I .~rge-
tlenr- term pro J c c r s s u c l ~a s the Shena~~tlonl~
s c a l e enperl~nenl.
S o l a r (complete) Study m o l t e ~ is:ii r/rock ~ n a t e r i n l I n t c r n c t l o ~ ~ .

PROJECT TITLE
A. SENSIBLE HEAT STORAGE (cont_*d)
2. Storage Analysis and IJcsign ( c o n t ' d l
O i l Stabllity/Compati.~I,1ity
Thermal S t a b i l i t y of l o c k s
S o l a r Space lleating Systems
Using Annual lieat Storage
Annual C o l l e c t i o n and Storage
of S o l a r neated water f o r
l l e a t l ~ i gof Buildings
CONTRP.CtOR
(INVESTIGATOR) PUNDLNC ACBNCY PROJECT SUMMARY
Sandla' L s b o r a t o r l e s , Solar (active) Evaluate 11Igl1 temperature c y c l i n g s L a b l l l t y of
Livermrz proposed lieat t r a n s f e r o i l s s u c l ~ ax c a l a r l a
(V. P. B ~ r u l l a ) HT43, thermlnol 6 6 , Sun 2 1 , and o t h e r s and study
c o ~ n p a t i h i l l t yand i n t e r a c t i o n of thefir 011s wlth
v a r i o l ~ sn e t a l s , rocks, and santl.
Sandla Laboratories Solar ( i n i t i a t e d ) Eval.uate the thermal s t a b i l i t y of rocks under
LI.verm>r,s Iligh temperature c y c l l n g with e~nphasIs oli
(V. P. B - ~ r o l l a ) e f f e c t s cf c y c l i n g on rock s t r c ~ ~ g t h .
Univerai :y >f Toronto RCD ( a c t i v e ) Explore I.l~crmcilc11aracterlstl.cs of l a r g e under-
(F. €2. timoper) ground €.torage t a ~ ~ k s expand , computer tank
performar,ce s1n111 l a t i o n nnd heat l o s s model t o
inc111de s o i l l a y e r i n g and exa~nlne square cor-
nered tamks, colnl)are model. ~ ~ r e d l c t i o ntso r e a l
d a t a , determine relntions11i.p hetween pr1111ary
weatlier variables and ol)t.Imum an1111n1.s t o r a g e
con€l g u r a t lon, mid clevcl.op a noncomputer a lgo-
r i t l ~ mand deslgn procedure t o c a l c ~ ~ l a toptim~~m
e
or1 a l i f e - c y c l e
system s h e and c o ~ i f l g c ~ r a t i o n
cost basis.
University aF V i r g i n i a R6D (comp1.etc) Ilesign a~ad c o n s t r u c t n l a r g e t r i c k l e r o l l e c t o r -
( J . T. Beard) s t o r a g e mu1 suhsystem, develop and v a l l d a t e
computer d i g i t a l and analog heat l o s s ~notlcls l o r
t h e lieat l o s s fron~ l a r g e stc)rage pools, p r e J l c t
pool performance wit11 t h e model and co~npare t o
experlmental mensure~nents, and develop design
c o n s i d e r n t l o n s and reco~nrnend;~L
Ions For a f u l l -
s c a l e ann 131 s t o r a g e pool.
 CONTRACTOR
PROJECT TITLE IINVESTLCATOR) FUNDING AGENCY PROJECT SUMMARY

A. SENSItlLE HEAT STORAGE ( c o n t ' d )

2. g o r a g e Analysis and Design ( c o r ~ t ' d )

Rock Red Storage with Heat I l a Associates, Znc. R I D (actlve) Analyze t l ~ e p l ~ y s l c a l r e s t r a l nLs lnvolved In
Puinp ( J . E . Anderson) c o ~ ~ l ~ l l an n g e l e c t r l c a l heat ptrmp t o a cnllven-
t i o ~ ~ arock l hell sturclge a i r system wl t t ~cur-
rently available flat-plate solar collectors,
o b t a i n n ~ n e t l ~ o df o r s i z i n g , l o c a t t ~ l g , and
a r r a n g i n g t l ~ e components f o r optlm~lm. cost-
effective performance, develop a c o n t r o l s t r a -
tegy wl~lch optimizes the ~)erformanceof a c a ~ s t -
e f f e c t i v e lieat pump/solar system, and determine
optimum deslgns f o r new and r e t r o f i t applica-
t i o n s including l i f e - c y c l e c o s t l ~ i g a ~ ~optlm\~md
o p e r a t i o n s t r a t e g i e s If Justified.

3. Vessel Construct&

The Developmellt of a Gas
Backup lleating Water Tank
Properly I n t e g r a t e d with
S o l a r Iieated Domestic Water
Storage Tanks
Altns Corporation H I D (active) 0eslg11, h u l l d , and t e s t a gas f i r e d l ~ c n t pLpe
(F. cle Winter) hackup h e a t e r m o ~ l ~ ~ t on
c d top of arid 111tc.yr.11
w i t l ~a s o l a r heated domestic water tank.

Thermal Energy Storage Groz University of S'TOR (complete) Assess the f e n s l b i l i t y a n d economics of t l ~ e
Using P r e s t r e s s e d Cast Teclluology prestressed c a s t i r o n v e s s e l developed a s n
lrtln Vessels (PCIV) (P. V . G i L I i , G . Reckman) ntbclear r e a c t o r p r e s s u r e v e s s e l f o r t l ~ e r a a l .
energy storilge i n t l ~ e r m a lpower s t a t i o n s .

I)evclopment of an llnproved 'Indepe~idel~t i.l.ving, R I D (actLve) Deslgn a water tank wit11 a foam core sa~~dwlcl~ecl
Water Tank f o r Dliermal Inc. between a r i g i d f 1 b c r g l a s s s t r t ~ c t ~ ~ roa~l ~ t s i d e
Icnergy Storage (W. T. Iludson, l a y e r : I I I ~ a FLexLble moisture bot~ntl;~ryl a y e r
I.. W. H e l ~ f l e l d ) I n s i d e , lay i ~ p a prototype tank hy ha1111 For
t c s t l n g , and atla1 y z e l~ow p r o d ~ ~ c t t o~netIlods
n can
lower I I I I ~t coti t s .
PROJECT TITLE
3. Vessel Construct l o n (cont'd)
blemhrnne I,l.nc Foundat I o n
Systems f o r I . i q r l i d T h e r n ~ a l
Energy S t o r a g e
L i g l r t w e j g l ~ t3 o n c r e t e
M a t e r i a l 8 an:! S t r u c t l l r u l
Systems f o r Water Tanks
f o r T h e r m a l Energy Stora(~,e
4. lleat Transfer t o Storage
1,nvest l g a t I o n o f F k t h o d s
t o T r a ~ i s f e rl i e a t Prom S o l a r
Licl111d I l e a t i n g C o l l e c t o r s t o
I l e a t S t o r a g e Tanks
D i r e c t Contact I.lqr~td-
L i q t t i d l l e a t F:xcl~angcrs
f o r S o l a r l l e o t e ~ lorld
C o o l e d Hu.1LdLrrgs
FUNDING AGENCY PR0.I ECC SIJMYAHY
U r t i v e r s l t y o f Nehrnska R6D (act.l\;e) S l ~ r v e y~ n e ~ n b r al ~l ~ e i e ds t o r a g e dev11:es. cleterlnlne '
(li. C. Rnurne] lnos t c o s t - e f r c c t i v c m a t c r l n l / e n c l o s ~ ~ r ta?l t e r ~ i i u -
tlves for tlrrer. specl.Eietl s t o r a g e vnlumes,
i n v e s t l g a t e and a n a l y z e a1 t e r ~ ~ n t metl~orlr; e fa~r
Itcat t rsnsrer, i d e n t i f y bent l ~ c n t n x c l i n ~ ~ g c r
d e s i g ~ i s , ei,nluate v a r i . o ~ ~ sties l g n s 11ro1noti n g
t e m p e r a t u r e f i t r a t l f l c n t l o ~ i , ~ ) r c ? ~ a and
rc 11t1l i z e
c o s t modcls, and c o ~ r s t r c l c tsmall-fica1.e rnotlcls o f
s e v e r a l p r o ~ n i i s i n gt l e s i g n s f o r t e s t Ing.
N e s t lnghouse E l e c t r l c AhD ( a c t i v z ) S e l e c t ~ n n t e r i a l s , p r o c e s s e s , ant1 d e s l j i n f i f o r
Corporation two-layer, s t n ~ c t u r a l , and l n s u l a t l np, Foa~ncd
(It. W. Du-kmanJ c o n c r e t e m o d r ~ l a r u r i l t s a11d s ~ ~ b s c n l500 ~: galloll
t a n k s ; f a b r l . c a t e and t e s t s u h s c a l e 1nod111arIIIII t s
and t a n k s ; d e s i g n , c o ~ l s t r u c t , and t e s t a 2 ,O(j0
g a l l n n p r o t o t y p e tank; a n a l y z e s t r ~ ~ c t ~ ~ and r n l
t l ~ e r n i a l p e r f o r m a ~ ~ c ep; r o v i d e e c o ~ l o mcl a n a l y s i s ;
and make recnm~nendatLolls l o r o p t i ~ n l z aIto n o f t h e
Altas Corporatio~~ RSI) ( c o m p l e t e ) Compile d a t a on c,onimerclally n v a l . l . a h l e I~ent.
( Y . d e Winter) t ransler f l u i d s and h e a t e x c l ~ a r ~ g e,r s d e v e l o p
computer s i m o l n t Lon progralas and anal.yze o p t i ~ n r ~ n ~
I r e a t t r a ~ ~ f eand r f l o w r a t e s , o p t t ~ n l z es t r ~ t c t l ~ r n l
d e s i g n and c.perat l . o n o l p a r a m e t e r s f o r s t ? l e c t e d
l ~ c n t e x c l ~ i l ~ r g c r s , and i n v e s t l g a t e d r a l n down
systems f o r I r e e z e p r o t e c t i o n .
C o l o r a ~ l oS t a t e Fi11d l l r l t ~ t d s i1n1111scLhlewit11 w a t e r ~ I I IwLI:II ~
I1nl.versit.y s u l t a b l e p r c p e r t l e s ; o ' b t a l n r x ~ ~ c r i ~ ~ ~ Ie~ cn! ; itt n l
(.I. C . Ward) t r a n s f e r d a t a f o r t l ~ c s c I11111ids i l l an e l l g l a s s
p l l o t p l a n t ; desll:r~, c n n s t r ~ ~ cand t L ~ ~ s t1a la
f111.l-scale d i r e c t c o n t a c t 1lrl11id-1Iq11ld I w a t
ewe-ltn~~ger; eva1.uat.e 1111i.t I n c o n t r o l l . c l l s y s l : t * ~ l ~ ;
s ~ r dc o n n e c t 11n1t t o s o l a r honcic f o r t e s t 1.n.g.

, '0. LATENT l l E M STORAGE
I. System I)cvelopmenc
Fa1 t H y d r a t e Thermal e n e r g y
Storage S y s t e ~ ~ f ol r Space
I l e n t i . n g and A l r Cottdl t t o l l i n g
Developnlent o f a P l ~ a s eCltangc
Thermal E ~ t c r g yS t o r a g e l l n i t
U t l l l z l u g Modifled Anltydro~~s
Sod 111mI l y d r o x l d e
D e v e l o p n ~ e n t o f l n t e r m e ~Late
l U n l v e r s l t y o f Delaware
I ' e ~ n p c r a t u r e Thern:aJ Energy
S t o r a g e Systems
M o l t e n - S a l t T l i c r a a l Energy
S t o r a g e Systems
A r tech C ~ ~ r p o r a t i o ~ i
( F . Ordwny)
CALMAC Manu fat: t ~ ~ r i n g
a r p o r a t lo11
( C . I).E l a ~ % r a c k c ~ t )
C,OIIS cock 6 Wescot t,
Enc.
(R. M. Cohen)
4.1. R. I~lc~szynskl.)
i ~ r s tt lu t e oE C a s
~ecllll0loJ:y
CJ. I ) u l l e n ,
13. C. Mnru)
PUNDlHG AGENCY PKOJEC'I' SUNMARY
K6D ( a c t l v e ) Des l g n , d c v c l o l ) . artd del.1ver a t l t e r m a l e n e r g y
storage sy s teln 11slltg 1 . 0 ~tempera
- t ~ ~ r pllnse
e
clrange s n l t l t y d r a t c s package11 i n p l a s t l c - t r a y s
f o r b o t h h e a t i n g irnd c o o l l n g a p p l l c a t l o n s .
R6U ( a c t i v e ) I)evelop and f n h r i c a t e t h r e c ' €1111-sca1.e l a t e n t
h e a t t l ~ e r m a lenergy s t o r a g e s c ~ l ~ s y s t e ~fnosr t l t r e c
d l f f e r c n t tclnycrc.ture a p p l l . c a t l o n s , nleasttrc and
t e s t tt1el.r p e r f o r m a n c e c h a r a c t e r l s t l c s , d e v e l o p
o n s l ce f 1 L l i n g iiqc~lpment and p r o c e d u r e s , a~id
p r e p a r e d o c ~ ~ m e n t n t i orne q u l r e d t o use s ~ t h s y c r t c ~ n s
i n l a r g e r systems.
STOR .(complete) Measure r e l e v a n t t l t c r m o p l t y s l c a l p r o p e r t t e a o f
m o d l f l.ed a n l t y d r c i u ~ c a u s t l c soda l a t e n t ltua t
s t o r a g e m e d l ~ ~ md; e s i g n a s t o r a g e t ~ n i tt r t i l . i z l n g
a ~ ~ a l y t l c a n1ode.t
l d e v e l o p e d prev.lorrsly; colt-
s t r u c t , t e s t , a d anal.yze a 1 / 1 0 sca1.e stor;tgc
u n l t ; make a p r e . l i m l ~ t a r yd e s i g n of 3.1 GJ caltac-
i t y u ~ tt l f o r Sanein I . n b r ) r a t o r i e s SI'E'L'F.
R6D (STtrK matt. ) L d e ~ t t l f y s r ~ i t a h l e~ n a t c r i a l sf o r t l t e r ~ n a l s t o r a g e
(active) 111 t h e t e ~ n p c r a t l l n t r range 100°C t o .30U°C, c o l n p l l e
p e r t i n e n t t l ~ e r n ~ o p l t y s k c adl a t a a s f a r S I; posslhlc
f r o m e x l s t l n g I l . O e r a t u r e , d e t e r n ~ l n em l s s i r ~ gtl;itn
a s r e q u l . r c d , and b l ~ l l dand t e s t a scal.c lnotlel o f
a s t o r a g e system u s i n g s c l e c t e t l m a t c r l a l .
S'TOll . ( a c t i v e ) D e t e r ~ n l n e t l l c t e c l ~ n l c a l r e i i s i l ) l l j t y o f 11s1ng
i . n o r g a n l c s a l t s f o r phase cliange tlterrnal energy
s t o r a g e above JOO°C, clevel.oo n ~ n a t l ~ e l nla. ct n l
lnotlel t o p r c d l c t systeltl beliavl.or, and t l e s l g n n
large-scale p r o t o t y p e (IOO kwht t o 1000 kWht)
s t o r a g e system f o r C u r t h e r t e c l ~ n l . c a l . and 6 x 0 -
nolnlc c v ; l l u ~t i o n
 CONTRAC'POR
PROJECT TITI,E ( LNVESTICATOR) FllNOING AGENCY PROJECT SUMMARY

B. e r IlEAT STORAGE (cont'd)

I. System llevelopment ( c o n t ' d )

Research on S o l a r Energy Sub- Nortll Caroline St:lte R60 (coml>lete) Analytlca l l g model, deslgtl, develop, a i d t e s t
systems U t l l i z l . n g tile 1,atetir Univers Lty prototype storage stlhsyste~ns wlllclt utll1.z.e
lleat of Phase Cl~angeof Cercaln ( J . A. Railey) mixtiires of paraff l n s i d e n t i f led a s ef f e c t l v e
Organic M a t e r i a l s- I'l~asc I Z and inexpeiisive i n a previous study.

2. New Concept~_l)evclopntei~t

Solid-So l i d Pliase Change Rescnrcll CE.I,MAC Maniifac t u r l ng STOK ( c o t ~ ~ p l e t e ) Design and iiilrricate a sodiim s ~ i l f a t epebble bed
and Tccl~nolcgy Corporat ton module f o r e v a l u a t i o n by NASA Lewis Research
(C. D. Mar.Crac:ken) Center.

ImmlsctbLe Fluid Ileat-of- S'I'OR ( a c t lve) Eval.uate Eeast.bllJ.ty of t l l r e c t c o n t a c t lieat

Fusion S t o r a g e System t r a n s f e r betwcer~ aqueous s a l t phanc change
m a t e r l a l aml iinmlsclhle heat t r a i t s f e r Plulcl,
improve ki~ovledge and understandlng of heat and
mass transE3r i n these systems, and build a t ~ d
o p e r a t e small-scale systems.

Electrot1 Beam C r o s s l l n k i r g of Unlverslty of Dayton STOR ( I n i t t a t lng) Develop e l e c t r o ~beam

~ tecltniqlle f o r crosslLnkl.~lg
Polyethylene ( I . 0 . SaLyer) lllgll densit,y polyctllylene t o a Pornrstal1l.e
s t o r a g e materla.1 wl~lclt I s l e s s ex1)enslve tllan
t h e clicml.cal1 y c r o s s 1 lnketl polyetlry lene dcvel-
oped by Elons~nto.

Sodirtm S t ~ l f n t eDecaliydratr Unlvcrslty oE S'SOR (act.lve) Develop a s t 3 r a g e concept I-or off-peak e1actrlc:-
Ellxttires a s n Low-Temperature Delaware l t y s t o r a g e llstr~g (:lai~her's s a l t mixtttres 111
Phase Change Storage Material ( C . Fryslngcr) cliuh c o n t a i n e r s supplied hy I)iipor~t f o r low-
(Mel.tlng Point 55OF) temperatiire s t o r a g e ( 5 0 ° F t o 5 S ° F ) .

PROJECT TITLE
B. I.ATENT IIEAT STORAGE ( c o n t ' d )
2. New Concept Uevclo,pment ( c o n t ' d )
Macroencapsu1.a t l n n of Ileat
Scorage P l ~ a s eChange Ftaterlals
Tnermal Energy Storage by
Means of Ileat-of-Solut loft
Two Component Thermal
H a t e r i a l Study
Develop Rolling Cylinder
':I~crmal Storage System
Laboratory S t u d l e s of
Act lve Ileat Excl~angeSystelns
CONTRACTOR
( LNVESTIGATOR)
Dcw Chemical Co.
(C. A . I.ane)
Franklin I n s t i t u t e
Research 1.a hoca tori.es
(ti. Kar~fmann,
D. Kyllonen)
G2ncral E l e c t r i c Co.
(b. T . 'I'weedle,
E . M. Hcl~al.ik)
Gcnernl E l e c t r l c Co.
(C. S. Ilcrrlck)
FUNDING AGENCY PROJECT SUPIMAItY
S'I'OR ( a c t Lvc) Sc l e c t pllnse change aild encapfi~il:~tton
1 1 1 a 1 c r1s.
t~
s ti~dy enc:ipscilatl~~n,t e s t encnpsril;~te~l111ntvr1-
a l s , and dcslgn and evolllate economlcu of r c s l -
tlential-sized s t o r a g e systems.
STOR (complete) Develop a c o ~ ~ ~ p a clow t . c o s t , low m a l n t e ~ ~ a n c e
prototype thermal s t o r a g e devtce hased oli Latent
h e a t of crystnll.l.zat1011 of s o l u t e s f r o ~ s S ; I ~ I I -
r a t e d aqlieotls s o l ~ ~ t i o na1111
s determine p e r l o r ~ i r
anc:e of a prototype thermal s t o r a g e devlce.
RhU (complete) Develop l a t e n t llent s t o r a g e s ~ ~ h s y s t e must l l.lz l ng
a packed bed of cncapsulntrd par;lf€ln s p l ~ e r e sns
a s t o r a g e m o t e r l a l with water a s a heat t r a ~ ~ s f e r
' Eluld alld h ~ i l l d an11 t e s t a small-sca1.e proto-
type.
R60 ( STOR moil. ) Ai~alyze and t e s t s t o r a g e material.' t l ~ c r a n l .per-
(nctlve) form;lnce, scl.ect c o l ~ t a l n e rm n t e r l a l s c~)mp;rt1 h l e
witli ~ > l ~ s change
sc material., s y ~ ~ t l ~ e s n
i z matlie-
e
Inat l c a l ~nodcl. dcscr i bing t l ~ e r m a l I)chavl.or of
r o l l l n g c y l l ~ ~ d e system,
r nnd design ;11111 con-
s t r u c t a protntype w111.t. Clauber's s a l t wi.1 1 he
used For storage.
SI'CJR (octl.ve) S e l e c t mcd 1 n ;311rl Itlent l fy cant1 Ida t e 11c;lt i!x-
cllangc concepts f u r cles ign, f i ~ blrc : ~ t 1011, ;IIIII
tesclng.
 CONTRACTOR
PROJECT TITLE (INVESTIGATOR) FUNDING A G E N C I'ROJEC'l' SUMMARY

B. LA'CENT tIEAT STORAGE (conte&

2. New Concept Deve1.npme11t ( c o n t l d )

Laboratory S t u d i e s of Active Honeywell SC

' OR ( a c t i v e ) S e l e c t me.Jl.a and LdCnt l f y candld;cte heat cx-
Heat Exchaagc Systems (R. T. LeFrols) change concellts f o r d e s l g n , f n b r i . c a t t n n , and
t e s t ing.

Form-Stable C r y s t a l l i n e Honsanto Kcseerc.1 STOR ( c o m p l e t ~ ) Develop a f o r m s t a h l e crystall.lnc! pol y e t l ~ y l e n e

Polymer P e l l e t s f o r Corporation and demonstrate f e a s i b i l t t g f o r a thermal energy
Thermal Energy Storage ( I . 0 . Salyer: s t o r a g e hcd materl.al 11scCu1 In the 120°C t o
140°C telnperccture range.

Enerey Storage Holler Naval Researck. STOR ( a c t i v e ) Study energy s t o r a g e a t abotrt 14OOoC I,y l a t e n t
Tank Laboratory heat-of-fusion of natural.Ly occurring sa1.L.s w l t l ~
(T. A. Chubh: evaporatioo/condensatLon of a f l u i d f o r Ileal:
t r a n s f e r t-3 and from t h e s a l t s wl~l.cha r e seal.ed
i n containers.

Thernlal Energy Storage To Ue Determined STOR (initiating) Assessment study.

System UtlEl.zing FloLdirecl 12/78
Q\ Bed lleat Exchangers

3. Phase Change Materials i; Buildings

Encapsulation of Phase Change Brookhaven Nettonal STOR (complete1 Develop t?cllnlqt~es f o r incorporat inp, I'CM's
Flatcrlals LII Concrete Flasonry I.abora tory (phase change m a t e r i a l s ) i n t o c o n c r e t e b ~ ~ l l d i n g
Cons t r ~ t .~1 c~ 1 (El. Sansonc) m a t e r i a l s , c l ~ a r a c t e r i z e mechanical., pl1ys1r.a1,
and c l ~ e m l c a l properties, and d c t e r ~ n l ~ l eeco-
nomics.

Thermocrete and Thermotl Le
Building Components witl.
J s o t l ~ e r n ~ allent
l Storage
Suntek Resenr-b STOR (complete: Denlonetrate tlre f e a s l b i l i t y of devel.oplng h u i ld-
Associates ing components w l t l ~ isotllermal heat s t o r a g e
(D. Cl~al~roudCD through the case of a phase change matc?rl.al.
suspended i n a cvncretc mat rlx.

PROJECT TZTLE
8 . LATENT IIBAT S T E E (cont'd)
3. Phase Change I.lnterla1 Selection ( c o ~ i t ' d )
Engineering Design f o r Thermocrete
C e n t r a l S t o r a g e U n i t s f o r Low-
Temperature S o l a r A p p l i c a t i o n s
It. Phase Change Materl.al S e l e c t i o n
Sodium S u l f a t e Decahydrate (Glauber's
S a l t ) a s Pledlum-Temperature Phase
Change Thermal S t a r a g e Materlal
Alloy T l ~ e r n ~ aStorage
l Media
Thersopl~yslcaLP r c p e r t i r s and
Hehaviora 1 C l a a r a c t e r i s t i c s of
Phase Change H a t c r l a l s
1avest.Lgartlon of W'etal Fluor lde
Thermal Energy S t @ r ; ~ gMaterials
e Corporat.Lon
CCNTRACTOK
(INVESTIGATOR) CUNUZNG AGENCY PROJECT SUMMARY
S L ~ I IR~ C SC
C ~~
I~ C I I RbD (terminated) Develop M.1 .T. c n t n p ~ ~ t c rprogram f u r t h e r wl~lch
AE s o c i a t e s models b e l ~ a v l o r I I ~ tl~ermocr e t c (phase cl~ange
( C . TI lford) ~ n a t e r l a l s InJected i n modt~lar foamed cemctlt
s t o r a g e u n i t s ctmted wit11 rubher), s11n11laLe
system perl.ormance ancl s i z e components wlth the
model, analyze cost o f e a c l ~ f inn1 izecl tlcsign,
and f a h r l c a t e and t e s t two prnmisl.ng small-scale
l ~ e a ts t o r a g e su1)systerns.
Universl ty of Delaware STOR (complete) ReporL p r l o r research on material, d e s c r t h e
(N. Telkes, P. Kando) preparaLlon of the mlxcure, document he 1000-
c y c l e performance exoerlment, nntl pcrforn~exper-
iments to'amplify above and reproduce c y c l l ~ ~ p , .
University of Delaware S'lOK ( a c t l v c ) Survey p r o p c r t l e s of f r ~ s l h l ea l l o y s f o r use a s
( C . E. Rirclicnall) , Latent heat thermitl s t o r a g e 1nedl.a ahove 2CI0°C
i and menstace the heat of t r a n s f o r n ~ n t i o n , specl f l c
h e a t , and volr~n~echange on trnnsformat Lon of
s e l e c t e d hlnary a l l o y s .
Oak Ridge Nat iotial. STOR (complete) Complle a l l s t oC cor~~pounds and n ~ l x t ~ ~ rS eI I sI C -
Lsboratory a h l e f o r Lsotltcrmal heat s t o r a g e w l t h l ~ i9 0 ° C t o
(S. Cantor) 250°C range hased on p ~ ~ h l i s h e dda t a and Lnbora-
t o r y evaluat lolls a ~ ~develop
d IaboraLory t o o l s
f o r rapidly evaluntlng cl~emlcal beliavlor ;#lid
t l ~ e r ~ n apcrforn~ance
l of phase cltangc ~ n a t e r l n l s .
Penliwal t STOR (complete) Asse~nhl.~ :tnd e v a l u a t e propert l e s of metal f 1 1 1 c r
rirles f o r t l ~ e r m a l s t o r a g e a p p l i c a t Ions, ~ i e t c r -
(L. 1.. Eichelherger) mlnc f ~ ~ t u ra ev n i Lahi1 l t y of metal. f l u o r i d c s f o r
p o t e n t i a l slgnl.Clcant markets, and e s t l . ~ n a t e t h e
€utut.c c o s t s of t l ~ ef l ~ l r ~ r l d eI sf ~ n i ~ ~ i ~ ~ f a (011: t ~ ~ r e d
a large scale.
PROJECT TITLE FUNDING AGENCY PROJECT SlfMMARY

8. LATENT IIEAT STClRAGE (cont'd)

4. Phase Charge ElaLerlal Selection ( c o n t ' d )

The llsc of S o l i d - S t a t e Phase Vi.1 Lanova. I l u i v e r s i t y STOR (complete) Find new s1111stances capahle of s t o r i ~ ~thermitl g
T r a n s i t i o n s f o r TltermaL Energy (A. L e f f l z r ) energy by s o l i d - s t a t e pliase t r a n s 1 t i o n s .
Storage

5. e a s e Change Analysis and T e s t i n g

Stud1e.s of S a l t Ilydrate Desert Re ;eacch NSF (STOK man.) 'I'o study nucleation and growtl~of hydrate s a l t
I
Nucleation. and C r y s t a l .;rowth Instltttte (complete) c r y s t a l s with application t o t l ~ e r ~ n a lenergy
,
( J . Ilalle-:t) storage.

Heat T r a n s f e r Aspects of S o l a r I J n i v e r s L t ~ of lloustort S o l a r (STOR rnnn.) Dcvelop crmpr~taLLottal t e c t ~ n i q u e s a11tl analytical

Energy Systems - Develoment
of Design ?rocedures f h r Thermal
Storage i n Holten S a l t 5
(N. Shamsmndar) (active) models t o j t t d y h e . ~ t t r a n s f e r c l ~ a r a c t e r i s t l c sof
molten s a l t s ; a s c e r t a i n the l ~ l f l i ~ e ~ of ~ r esuper-
s
c o o l i n g , volr~me cl~anges, i m p u r i t t e s , and f o u l tng
on s o l i d i f i c a t i o n ; and o b t a i n design a ~ i d per-
f ormance d a t a t o ctteck r e s t l l ~ s .

C r y s t a l St ructures of S a l t Oak Ridge Naclonal STOR (complete) Determine c r y s t a l s t r u c t ~ ~ r e of

s phase change
Hydrates and Nucleators Labora t o r ) materials an11 n u c l e a t o r s by neutron d i f f r a c t Con
( W . K. n u ~ l n g ) experiments t o understand c r y s t a l nctclent 1011
pltenomenon.

Experimental Thermal T-nsport
S t u d i e s i n Welting-Freezing System
Oak Ridge National STOK ( a c t t v e ) Assess a computer model f o r tlterm.11 energy
Laboratory s t o r a g e in pl~nse change m a t e r i a l s , c o l l e c t
(R. Ileal) f~rndamental heat t r a n s f e r d a t a d u r l l ~ g melting
and f r e e z l n g of v a r l o ~ ~msa t e r i a l s , and provldc. A
f a c i l i t y fcbr Lest ing of proposed PCFI n ~ ; ~ t e r i a l s .
 PROJECT TITLE FllNDlNC AGENCY PROJECT SUMtlARY

B. LATENC HEAT STORAGE (cont'd)

5. P l ~ a s cChange Analysis and T e s t i n g ( c o n t ' d )

Thermal Cycling F a c i l l . t y f o r Oak Ridge National STOK ( a c t l v e ) B111.l.d a thermal c y c l l n g f a c i l i t y f o r test1.11g

T e s t i n g Prototype TKS Units iabora tory prototype thermal energy s t o r a g e (TES) compo-
[ R . Kedl) nents a11d h ~ ~ i l dYO t e s t loops - one For a
1lq11id tl~ermal.t r a n s p o r t f l u i d and the o t h e r f o r
a i r a s the thermal t r a n s p o r t F1ul.d.

Ha t h e ~ n o t l c a lModel Lng of Oak Ridge National STOR ( a c t i v e ) Develop a tl!ne-depcndcnt computer s l m ~ ~ l a t i o n

Movin~Boundary Problems 1,aboratory d e s c r l b i ng thermal t ric~lsport i n a me1 t l ~ig-
(A. Solomon) f reeeing system f o r a p p l i c a t i o n t o thermal
s t o r a g e hy phase c l ~ a ~ i gme a t e r i a l s .

C. REVE3SIBLE REACTION STORAGE

\O 1. Thennocl~emicnl A.enction Storage

S o l a r Enerfjy Storage by Atomics l n t e r n a t l o n a l STOR (complete) Delermlne the chemlcal character l s t l c s of

Reversl.hle Cl~emlcalReactions (T. 11. Springer) CaO/Ca(011)2 r e a c t ion experimentnlly and a ~ i n l y z e
f l u i d i z e d hed and moving-solids concepts f o r
t e c l i ~ i l c a land economic f e a s l b l l i t y .

Development of Uperat l o n a l Universl ty of llouflton S o l a r (STOR mon.) Develop and demonstrate a r e v e r s i b l e cl~cmlcnl
Chemical Cycles f o r the (U. E . Wentwortl~) (actlve) r e a c t l o n cyclc bascd on nmmonit~m hydrogen sul-
Storage of S o l a r Energy f a t e wl~lch ran be used f o r s o l a r energy s t o r a g e
and regenernllon In c o n j ~ ~ n c t i owith
n e l e c l r lc.11
power g e ~ i e r a t i o n s)~slems In the 450°C t o 'i0O0C
range.

PROJECT TITLE
C. REVERSIBLE REACIION STORAGE 'jcont'd)
1. Thermochemicnl Reaction Storage
The Chemical S t o r a g e of
Thermal Energy
Tl~ermochemicalE n e r ~ y
Storage Systems
Chemical Energy Storage f o r
Solnr Ther~nalConversiou
2. Chemical Ilea t Pump Devcloym=nt
The Cl~emical.Ilent Pump
(Ilydrated S a l t Heat Ptlmp)
CONTRACTOR
(CNVESTICATOP.) FUNDING AGENCY PROJECT SUHMARY
I cont'd)
L a w r e ~ ~ cBerkeley
e Synthesize and e v a l u a t e cliemtcal flow filleets f o r
Laboratory processes employing SO3 o r metl~ane/steam re-
(A. S. Foss, S. Lynn) a c t i o n s , look f o r CIMIE i g c ~ r a t l o n s tltat promlse a
high energy s t o r a g e ef Fictency , and compare
processes 0 0 fiensihle and l a t e n t heat s t o r a g e .
Hartin E h r i e t h STOR (complete) Demonstrate tecltnical. f e a s i b i l i t y of rrsing
Corporation paired amnonlated s a l t s f o r thermal energy
(F. A. J a e g e r , s t o r a g e , o b t a i n k i n e t i c and property d a t a on
W . T. ltowerton) v a r i o u s ammonlated s a l . t a , demonstrate r e v c r s i -
b i l i t y and r e p e a t a b i l i t y over a nt~mher of
c y c l e s , develop a computer s l ~ n u l a t l o n of an
ammoniated s a l t r e a c t o r , and compare c o s t of an
ammoniated s a l t system wit11 conventional s t o r a g e
systems.
Rocket Research Corp. STOR, S o l a r , NSF S e l e c t r e a c t i o n s wl~lch~may be useft11 i n r e v e r s i -
(D. Hustable. (STOR mon.) b l e chemical r e a c t i o n energy s t o r a g e , evalltate
R. D. Smith) (active) s e l e c t e d r e a c t i o ~ t son thermodynalnic and k i n e t i c
SRndCa Livermore Lab. grounds, make a preliminary design and model of
( J . J . Iannucci] energy s t o r a g e systems based on t h e s e r e a c t i o ~ ~ s ,
and study the technical and ecol~omicf e a s i b l 11ty
of extendD ng the concept t o baseload power
generation.
Chemt c a l Energy Study e x p e c l m e ~ ~ t a l land
y a n a l y t i c a l l y a cllam.ical
Specinlists h e a t pump based on vapor I~ydratlnltof s a l t x f o r
( I A . Grelner) h e a t lng and cool.ing of restclences and provide
hackgrollnd f o r design and f a b r l c n t l r ~ nof n pre-
prototype storng'e r ~ ntj.
PROJECT TITLE PUNDlNG AGENCY PROJECT SUMMARY

C. ECERSIBLE REACTION STORAGE ( c o n t ' d )

2. Chex~lcallleat Pump Development ( c o n t ' d )

Ele thanol-Based Single- EIC Corporatlon STOR ( a c t i v e ) Flnd combinations of lnorganlc s a l t s u b s t r a t e s

S u b s t r a t e lleat Pump for
S o l e r Thermal Storage
(P. O ' D . Offenhartz) and methariol t h a t a r e thermodynamlca l l y and
k i n e t l c a l l y s u i t a b l e f o r c l ~ e ~ n l c a lhent pump
thermal energy s t o r a g e and use tile d a t a obtained
t o des lgn and ~ n a l y a evnrlous s t o r a g e con€l g ~ ~ r a -
t l o n s a s a b a s i s f o r consLruction and t e s t l n g of
a prototype u n i t f o r residential a p p l l c a t l o n s .

S o l a r Cooling Using Paired Mariin Marietta RCD (STOR mon.) E s t a b l i s l ~ f e a s l b i l i t y of c o n s t r ~ r c t i n g chemlcnl

Ammonlated S a l t Reactioris Cor?oratlon (active) lieat pump based upon paired ammo~ilates, perform
(F. A. J a e g e r ) and v e r i f y engineerJ.r~g a n a l y s i s and d e s l g n , a ~ i d
deslgn prototype system.

S ~ r l f u r i cAcid/Water I n t e -
g r a t e d Chemlcal Energy Storage
Kocltet Rescarcli Corp.
(E. C. Clark)
STOK ( a c t i v e ) Determine feas.ibilit\y of using n ~ r l f ~ ~ ar cl tcd and
water a s cl~emlcal s t o r a g e medla, g e n e r a t e hnsic
deslgn concepts, e s t l m a t e systetn c o s t s , s e l e c t a
concept f o r d e t a l l e d s l z l n g and s c a l lng analy-
s i s , design a ~ ~corlstruct
d a s c ~ b s c a l edemonstra-
ti011 system, cond~rct t e s t s t o v c r l f y perforulr
atice, and provide recommendati.ons f o r p l l o t
p l a n t deslgn.

3. Tliermocl~emicol P i p e l i n e Development

C.l.csed-Loop Chemical Sys terns
f o r Energy Storage arid
Transmission (Chemical lleat
Pipe)
General E l e c t r i c Co.
(11. B. Vakll)
STOR (complete) I d e n t i f y and e v a l r ~ a t e teclinical f e a s l b i l i t y and
c o s t of most promlsirig ol)tions of the cl~emicnl
heat pipe f o r Unlted S t a t e s n p p l l c a t i o n s , par-
t.lclrlarly i n t r a n s p o r t lng tlier~nal energy over
l a r g e dl s t a n c e s .

Cycllc Cata1.y t i c S o l a r
Energy Storage Systcrns
University o f llouston
.
( J T. Kl c l i a r ~ l s o ~ i )
S o l a r (S'TOR Inon.) Optl.mlze process s t a g e s of tile EVA-ADAM chemlci~l
(cocnplete) hent ptpe cortcepts for s o l a r a p p l i c a t tons aritl
d e t e r m l ~ ~steam
e reformtt~g-11.q11idsodlr~m r e c e l v c r
1)roccss par;lmctc?rs t o e s t a b l i . s l ~rallge of temper-
a tclres, p r e s s u r e s , and compos l t ions t o he CII-
countered by reforming c a t a l y s t s .
 CONTRACTOR
PROJECT TITLE (INVESTIGATOR) FUNDING AGENCY PROJECT SUMMARY

C. WVERSIBLE REACTION STORAGE (cont'd)

4. Generic Research

K i n e t i c s of D i s s o c i a t i v e University 0.: STOH ( a c t i v e ) Perform l i t e r a t r ~ r e study of thermal decomposi-

Cllemical React i o n s i n C a l i f o r n i a a t Davis t i o n reac:ions; s e l e c t cliemical systems f o r
Storage Systems (Z. Munir) continued experimentation; d e s i g i ~ , f a b r i c a r e ,
, and check out e x p e r l ~ n e n t a l a p p a r a t ~ ~t so o h t a i n
k i n e t i c , d a t a ; g a t h e r experimental r e a c t i o n r a t e
d a t a ; and develop d e t a i t e d unilerst;inding of
kinetics.

Development of Ammoniated H a r t i n Mariea t a STOR ( a c t i v e ) Determine r e a c t i o n r a t e s , h e a t s of r e a c t i o ~ i ,and

S a l t Themochemlcal Energy Corpora t i o n bulk den.sity f o r s e l e c t e d ammoniates; d e s i g n ,
Storage Systems Phase 11- (F. A. Jaegee) f a b r i c a t e , and t e s t a subscale r e a c t i o n system;
and upgrade system performance computer models.

Heat T r a n s f e r I n v e s t i g a t i o n Martin M a r i e t t a STOR (completeb Determine packed bed thermal c n n d u c t l v i t y ,

i n Chemical Systems f o r Corpora t i o n f luid-to-sclid Iieat t r a n s f e r c o e f f i c l e r ~ t s , and
Thermal Storage Colorado S t a t e Univ. h e a t t r a n s f e r c o e f f i c i e n t s between tlie Iled
( C . Prenger) s o l i d s and the gas and tubes immersed 111 t h e
bed.

Development of a Long-Life, Rocket Research Corp. STOR ( a c t lve) Evaluate experimenta1l.y t h e a h i l i t y of c ~ i r r e ~ ~ t i y

High-Temperature C a t a l y s t (E. Schmidt) a v a i l a b l e commercial c a t a l y s t s t o function i n
f o r the S02/S03 Energy t h e s O ~ / S O ; s t o r a g e system and develop new, more
Storage System d u r a b l e c a t a l y s t s i f necessary.

O. GENERAL TllERnAL STORAGE

1. Storage S t u d i e s and Models

Commercial F e a s i b i l i t y c.f Argonne National STOR ( a c t i v e ) l d e n t l f y near-term cost-ef f e c t i v e thermal s t o r -

Thermal Energy, Storage La horatary age t e c l ~ ~ i o l c g l e ss,p e r l f y c o s t / p e r f ~ ~ r m n n cge o a l s
( J . G. Ashury:~ f o r advaliced systems, and c o ~ n ~ n e r c i a l i z a t i ~ m
s t r a t e g i e s , and recommend fitnrage RCI).
PROJECT TITLE
D. GENEMI. TIIERHI\I. STORAGE (con't'd)
I. S:orage Strrdles and Models ( c o n t ' d )
Developing and Upgrading of
S o l a r System Therral. Energy
Storage S i m l ~ l aion
t Models
A3aly s l e of Advanced .Tl~crma1
Energy Storage Subsystems For
S i ~ l a rHent I ng and . C o o l l . ~ g
Evaluation of Self-Drivzr~
Ileat Transport Schemes
Research on Energy Storage
f o r S o l a r Thermal Conversion
FUN1)ING AGENCY 'PROJECT SUMMARY
Bcelng Con~puler Acquire and .' e v a l r ~ a t e a l l n v a l l a b l c tller~ilal
SEr v l c e s , Inc. energy s t o r a g e colnoonent n~odels, ~ ~ p g r a t l eand
.
(.I Kulin) valldatc? the models, and f i t a ~ ~ d a r d l xancl
l i n e the hest motlels a s compatlhle system
e fitrcnlrr
3 l h r n r y sodules 111 an o v e r a l l s t o r a g e component
I lnkage peograln (ASSI.:SS).
E I C Corporotlon Westgn and c o n s t n r c t an o v e r a l l l ~ e a t l n g ond
(P. O'D. Offenhartz) c o o l i n g model; c o n s t r u c t s e n s i b l e , phase change
and reverslble reaction storage s~rl~systcm
models; examine e l c c t r t c , h e a t pump with s t o r a g e
and absorption and Rankine c y c l e a i r cariditi.or~-
i n g with s t o r a g e ; c o n s t r u c t a chemical Ileat pclmp
s t o r a g e model; t e s t the models; makc sim111;itl.nn
runs o n . published designs; and make adtlit lonal
.sj.mulntions on t h e most promlstng tlesigns.
Franklin I n s t i t u t e R6D (complete) Survey, a n a l y z e , ant1 compare on b a s l s of tecllnl-
Researcl~Labs c a l f e a s l b l l 1 t y , perFor~nance c a p a b i l i t y , cost-
( C . P. Wacl~tell) m e f f e c t l v e n e s s , and s a f e t y a l l ~ ? o t e ~ i t l aslc l f -
d r i v e n Iteat t r a n s p o r t methods and recornmcnd
.which systems, i f any, deserve f u r t l ~ e rdevelop-
ment.
Xerox E l e c t r o - O p t l c a l NSF (S'POR won. j Provide idcnt'lf lcattoll, def l n l t ion, and concrp-
SysLe~ns (complete) t c ~ a ldesign of I~nl)rovcd s e n s i b l e . and l a t e n t Ilcnt
(3. A. C a r l s o r ~ , s iorage sys tems. and c o m ~ ~ o ~ r e. s~~i~t h s y s t e , n sf o r
J . L. Clayton) t e ~ ~ ~ p e r n t ~ tof
r e s lt1)CI0F. t o 6 0 0 ° F and 900°F t o
1 100°F.
, .

PROJECT T1TI.X
D . GENERAL TllERMAL STORAGE ( c o n t a d )
2. System Devclopme~~t
Thermal Storage f o r Iligi-way
Vehicle Propulsion
Development of I n t e r m e d B a t e
Temperature Thermal Energy
Storage Systems
Analysis and Development oE
a S o l a r Energy Regenerated
Desiccant Crop Drying
Facility
Thermal. S t c r a g e f o r lligiway
Vehicle Prcpulslon
Thermal S t c r a g e f o r llighway
Vehl.cle Prcpulslon
CONTRACTOR
(INVESTIGATOR)
Ar gonne Na t i u n a I.
I.ahora tory
( A . A. C l ~ l l e n s k a s )
University ol Delavae
( J . R . Moszynski)
Lockheed M i s ~ l e s
aod Space Company
(D. V . M e r r l f i e l d )
Sigma Researcll Corp.
(E. I). 'daters)
Therlno E l e c t r o n Corp.
(D. Morgan)
FUNDING AGENCY PROJECT SUdMARY
STOK ( a c t l v c ) Develop e i f e c t lve thermal energy s t o r a g e f o r
matlng with a heat engine t o provide a velll.cle
propulsion, system.
RQD (STOR moll.) I d e n t i f y s u i t a b l e s t o r a g e processes and mate-
(active) r i a l s f o r s o l a r d r i v e n a i r c o n d i t i o n i n g tliermal
s t o r a g e between 90°C and lRO°C, s e l e c t one
combinat ion f o r f u r t h e r development, determine
r e l e v a n t propert l e s of the s e l e c t e d lieat trails-
f e r m a t e r i a l , v e r i f y i t s c o m p a t i b i l i t y wit11 t h e
proposed c o ~ ~ t a l n m e nm t a t e r i a l , and c o n s t r u c t a.
f u l l y instrumented prototype f o r t e s t i n g accord-
i n g t o NBSfASIIRAE t e s t standards.
STOR (complete) Develop a d demonstrate a c o s t - e f f e c t i v e r e g e l r
e r a t e d d e s l c c a n t drying system whicll has more
than double t h e energy e f f i c i e n c y of conveli-
t i o n a l sy:;tems and wl~ich can be operated on
e i t h e r s o l n r energy o r conventional f u e l s .
STOR ( a c t l v e ) Perform c o ~ c e p t u a ldesign of l a t e n t heat s t o r a g e
fiystems f o r S t i r l i n g engines.
STOR ( a c t lve) Perform co:bceptual design of l a t e n t h e a t s t o r a g e
systems f o r St.1rllng engines.
PNKOJEC'CTITLE
I). GENERAL THERMAL STOMGE (cont'd)
3. Design Information,
A llandbook and Guide f o r
Thermal Energy Storage
Appllcatlons i n S o l a r
Heating and Cooli-
Systems
Technological Da tiibases
f o r Energy Storage
FUNDING ACENCY PROJECT SllMMhRY
Argonne National RCD ( a c t l v e ) Prepare a s e t of handbooks conta Lnir~g d e s c r i p -
Laboratories t i v e and nt11nerlcnL l n f o r a a t l o n oil t l ~ ec h a r a c t e r -
(F.. Cole) i s t i c s and ccl~plicatlons of thermal energy s t o r -
age by water, rocks, phase change, I ~ y h r i d , and
advanced systems f o r a c t l v e h e a t i n g anti cooll.ng
a p p l i c a t i o n s and ' I n l . t i a l l y prepare a p r a c t f c a l
design and i n s t a l . l a t i o n rnant~al f o r water ti111ks
and rock beds.
Lawrence Livennore STOR ( a c t i v e ) C r e a t e b l b l l o g r a ~ h l c and e v a l ~ ~ n t e drnater1al.n
( T . M. Quick) p r o p e r t y databases f o r energy s t o r a g e systellls,
N i t i o n a l Bureau c r e a t e s t o r a g e te=linology c l ~ a r a c t elrz n t lon d a t a
of Standards b a s e s , and develop remc~te a c c e s s t o datahflses
f o r cornparalive a r a l y s t s and decision~saki.ng.
 SECTION 7.0

DISCUSSION AND RECOMMENDATIONS

In this section, the thermal storage technologies are briefly discussed and some
recommendations for future research directions are made. The assessment is based on
information assembled in preparing this report. Since storage is not a prime source of
energy, storage concepts must be evaluated in the context of a final application with
appropriate component costs, backup fuel costs, etc. to clearly define the best storage
choice for any given system. Furthermore, the climatic conditions may significantly
alter the economic storage role for different locations. Due to the interactions between
the system, storage, the climate, and backup fuel costs, the analysis is complex, and a
considerable variation of storage needs is anticipated. Therefore, the generalizations
offered here should be used only as a guideline, and a detailed analysis should be made to
define specific storage system needs.

7.1 SENSIBLE HEAT STORAGE

For low-temperature storage, it is probably impossible to develop less costly sensible

heat storage materials than water and rocks. The greatest need is to minimize the cost
of containers, insulation, heat exchangers, and other equipment associated with use of
these common storage materials. Currently, the DOE supported studies summarized in
aquifers, ground storage, low-cost tanks, and direct contact heat exchange are directed
toward reducing these costs. Studies are also in progress to evaluate the benefits of
stratified water tanks and understand their performance for design purposes. The
fundamental basis for design of sensible heat storage systems is well in hand for
conventional mixed tanks and rock bins, and predictions of their performance based on
fundamental principles have been quite successful. The design knowledge for storage
concepts such as aquifers, solar ponds, and stratified storage is far less satisfactory and
considerable research work must still be done to achieve confidence in performance
predictions.

For high-temperature sensible heat storage, the, commercially available liquids are
generally expensive, and containment of water at elevated pressure is also expensive.
For short-term storage durations with large temperature swings, these options may have
acceptable .economics. However, they are not attractive for long-term storage.
Moreover, many of these liquids degrade at high temperatures, and .fluid must periodi-
cally be added to the system with additional costs. Some of the materials require
stainless steel vessels thereby driving the cost up further. Research directed toward
improving the lifetime of sensible heat storage fluids could be useful. In addition, new
fluids could be developed which are more suitable for high-temperature thermal energy
storage provided the projected costs of s ~ c hspecialty fluids and their containers would
be acceptable.
Approaches such as underground caverns and prestressed cast iron. vessels offer some
promise of reducing containment costs, and innovative research is needed in this area.
Solid materials are economically more attractive for high-temperature storage than the
fluids mentioned and their volume requirements are comparable. However, research and
development are needed to find heat transfer fluids which can be used in direct contact
with the solids over long time periods. The effect of temperature cycling on solid
integrity and on the interaction of the solid and a storage vessel must be studied as
well. Although some work has been initiated in these areas, they deserve more emphasis
because of the short-term potential. Finally, low cost containment is still desirable for
these storage materials.

7.2 LATENT HEAT STORAGE

Materials which undergo a phase transition at an essentially constant temperature are

conceptually attractive for thermal energy storage. Under DOE support, studies have
been and are being undertaken to identify storage materials to satisfy a range of
temperatures. Low-cost materials are available for a number of thermal energy storage
applications. Some continued work is required to examine the ability of these materials
to withstand thermal cycling and determine their corrosiveness.

The price of providing adequate heat transfer is a significant part of the total storage
system cost for latent heat materials. Innovative research and development are required
to overcome this cost barrier. Programs in immiscible fluid heat transfer, encapsulated
materials, and form-stable materials have been funded by DOE to reduce the cost of low-
temperature heat-of-fusion storage. A system which utilizes phase change materials
contained in plastic "chubs" is projected to cost less than a rock bed for low-temperature
storage although excessive air circulation rates may be required because of the low phase
change temperature. The ability of the system to withstand long-term cycling must still
be established.

Projects on active heat exchangers which prevent buildup of the frozen layer have
recently been initiated for high-temperature latent heat storage. Continued efforts are
required to improve the understanding of heat transfer in latent heat systems and apply
that knowledge to reduce storage system costs, particularly for high-temperature
storage. The economics of each new system should be carefully evaluated in a total
system context before spending significant funds on research to be certain the concept
has sufficient merit to warrant further development. In addition, promising latent heat
storage systems should be subjected to long-term cycling to ascertain their reliability.

7.3 REVERSIBLE REACTION STORAGE

Thermal energy storage by reversible chemical reactions offers very high. energy storage
densities. In principle, storage of energy is possible at ambient or near ambient
conditions, and tank size and insulation requirements can be minimized. Chemical heat
pump reactions also offer a reduction in solar collector area with a potential cost
 savings. Overall, thermal storage by reversible chemical reactions has a possibly
significant storage role, and increased research and development is worthwhile.
Reactions have been identified which have potential for thermal energy storage, and as a
class, gas-solid reactions have a number of significant advantages for solar energy
storage as discussed in Section 5.0. However,' there are significant problems in heat and
mass transfer in gas-solid reactions. Storage by reversible gas-solid chemical reactions
is both new and complex, and limited experience has been assembled in the design and
operation of storage devices. Most systems under current development are for heating
and cooling applications and require extensive heat exchanger surface area at significant
cost. Thus, even though the heat pumping capability may reduce the collector area, the
total system economics may not be encouraging. Furthermore, the actual coefficient of
performance has not been evaluated for chemical heat pumps, and a real reduction in
co1,lector area has not been established. In addition, the source of a number of problems
in the use of reactants such as magnesium hydroxide is not understood.

Substantial further research is necessary to understand the complexities and limitations

of reversible chemical reactions and develop the most cost-effective means of storage
for the final application. Fundamental analyses are needed to understand the heat, mass
transfer, and kinetics of gas-solid reactions to aid in effective reactor design. Particular
attention should be devoted to high-temperature gas-solid reaction systems to determine
whether the energy can be delivered at temperatures which are acceptable for the
projected end use and if the efficiencies are acceptable.

Other reactions besides the gas-solid type may be suitable for solar energy storage, but
important questions must be satisfactorily answered to clearly establish their role. For
instance, catalyzed reactions are attractive because no material separation step is . .
necessary. However, gaseous components are involved in known reactions, and they must
be compressed for storage. The cost and parasitic power requirements for compression
must be carefully evaluated. For some systems such as the S03/S02/02 reaction,
atmospheric oxygen might be used in the system to eliminate the compressor power
requirements, but the feasibility and environmental acceptability of this concept must be
demonstrated.

Noncatalyzed liquid reactions such as the NH4HS04 reaction mentioned in Section 3.0 are
attractive because they could avoid the solid heat transfer problems, but separation of
the gases produced may be too complex to achieve satisfactory economics. The likely
acceptability of toxic substances must also be assessed early in each program to be
. certain the technology can be adopted later. In all storage systems, careful analyses are
required to establish the parasitic power requirements, energy delivery efficiencies, and
energy delivery temperatures dnce sufficient knowledge is available to be certain the
concepts are useful in the context of an entire solar application. These analyses should
be performed early in a project before extensive development effort is expended, and
concepts which cannot deliver energy at competitive costs with alternate storage
systems should be abandoned.
7.4 THERMAL ENERGY STORAGE APPLICATIONS

In addition to developing more cost-effective storage devices based on the various

thermal storage technologies, gods must be developed in cooperation with projected
users to guide technology selection. Studies have been performed to provide guidelines
for the economically optimum amount of storage and other requirements for some
applications. Those analyses must be updated as new solar and storage technologies
become available to be certain that an integrated system is, in fact, economically
attractive. Specific storage requirements such as charge rates, discharge rates,
temperatures, reliability, storage durations, and cost criteria must be determined for
important solar applications, particularly those to be commercialized in the near future.

General requirements should be specified along with economic tradeoffs to allow storage
workers to examine the v~riousavailable technologies and select t h e best technology for
further major development at R pace consistent with the identified application. The
results can also be used to identify important problem areas for immature concepts, and
research directed toward resolving these problems. Efforts have begun in this area for
solar thermal power applications, but far more work is needed for a l l applications [451.

Cost data on specific?storage devices is a step in identifying useful storage concepts, but
does not provide a total picture of their utility. A total systems study is required to
identify the merit of a particular storage concept to a given application. For example,
suppose a new system looks promising because the storage costs are low. However, only
about 50% of the solar energy charged to the storage system can be delivered to the load
from storage. Relative to a storage device operating at close to 100% efficiency, the
less efficient storage system would require mare collectnr area to providc the "lost"
energy. Since solar collectors generally are significant in the total system cost, the
extra collector area could offset the price savings offered by storage. Even if the
storage system is essentially free, the total dclivered energy r h c t in the entire solar
system could be higher than for more costly, but also mnre efficient, ~toragcdevices.
Furthermore, the inefficient storage unit might deliver energy a t temperatures far lower
than from the solar collectors and at unsatisfactorily low rates. Only a study of the
integrated solar/storage system will clearly establish these deficiencies and whether thc
tradeoffs necessary are cost-effective.

As part of the system studies for storage, a definitive investigation of soaoonal storage
of energy would be beneficial. The studies cited in Section 2.0 indicate that less than
two days' storage provides the lowest cost energy for home heating. However, otReP
workers have indicated that for Northern l~titudes.seasonfil ntnrnge is more attruclivc
for home heating because the storage unit can be charged up more readily in times of
high insolation than in times of low insolation. Thus, as storage capacity is added to a
system, a second minimum may occur in the delivered energy costs. If possible, both
optimums should be found for every important application and its projected locations
whet1 systems studies are done; and their relative economics established for various
scenarios (fuel escalation rates, discount rates, etc.). The result would allow a clearer
definition of the merits of seasonal versus short-term storage for important applications.
7.5 RECOMMENDATIONS

The following points summarize the most important recommendations presented

previously in the order discussed:

Research and development programs aimed at providing low cost containment

and heat exchange for water and rocks should continue since these materials
are attractive for low-temperature storage in solar home heating systems.

More effort is required on research and development of low-cost storage

systems for specific intermediate- and high-temperature solar applications.

Heat transfer in solid materials, including direct contact methods, requires

considerable research and innovation if storage in heat-of-fusion materials and
gas-solid reactions is to become economically attractive. Inexpensive
containment methods also deserve study because such methods could alleviate
the need for reducing the cost of the heat transfer process. This type of
research should take precedence over continued identification and studies of
storage materials.

For thermal energy storage by reversible chemical reactions, the temperature

distrih~~tionof the energy delivered from storage, the parasitic power
requirements, the energy storage densities, total system requirements, and
required shifts in temperature for reaction should be carefully assessed for
competing technologies to deter mine their effects on energy delivery costs.
Based on such studies, the reaction classes should be identified to decide which
of these warrant further research and development for solar applications.
Other aspects such as toxicity must also be evaluated.

Specific target applications and their requirements must be identified with

major efforts directed toward developing specific storage technologies to meet
these targets over appropriate time spans. Technologies which offer little
promise of ever satisfying the identified targets should be eliminated arid the
effort devoted to those with the greatest potential for both near- and far-term
applications.
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16. Fried, J. R.,. "Heat Transfer Agents for High-Temperature Systems," Chemical
Engineering, May 28, 1973.

17. Hallet, R. W.; Jr. and Gervais, R. L., "Central Receiver Solar Thermal Power
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SG?! @!I

DISTRIBUTION LIST

30. of Cooies Distribution

1 Department of Energy:
DOE, SERI S i t e O f f i c e
Contracting Officer
A t t n Y C h a r l e s H. S k i n n e r

Chicago O p e r a t i o n s O f f i c e
I n t e r i m Program D i v i s i o n
A t t n : X. E. J a c k s o n

D i v i s i o n of S o l a r Technology
O f f i c e of A s s t . D i r e c t o r
f o r Administration
A t t n : R. H. Annan

O f f i c e of A s s t . S e c r e t a r y
f o r Conservation & S o l a r
..'
Applications
A t t n : R. S c o t t

O f f i c e of S o l a r , Geothermal,
E l e c t r i c & S t o r a g e Programs
A t t n : N a r t i n Adams

D i v i s i o n of Energy Technology
Administration
Xttn: S . Hansen

D i v i s i o n of D i s t r i b u t e d
s o l a r Technology
O f f i c e of t h e D i r e c t o r
A t t n : k. San $ j a r t i n

D i v i s i o n of C e n t r a l S o l a r
Technology
Of £ i c e of t h e D i r e c t o r
A t t n : H. Coleman

D i v i s i o n of Energy S t o r a g e
Systems, ETS
o f f i c e of t h e D i r e c t o r
B t t n : G. P e z d i r t z

D i v i s i o n of P l a n n i n g h Energy
T r a n s f e r , ETS
O f f i c e of t h e D i r e c t o r
Attn: L e s l i e Levine

Wind Energy Systems

X t t n : L . Divone

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