United States Patent [19] [11] 4,292,189

Chen [45] Sep. 29, 1981

[54] THERMAL ENERGY STORAGE
COMPOSITION COMPRISING SODIUM FOREIGN PATENT DOCUMENTS
SULFATE DECAHYDRATE; SODIUM 50-90583 7/1975 Japan .................................. .. 252/70
CARBONATE DECAHYDRATE; AND 51-96788 8/1976 Japan ................................... ..252/7O
SODIUM TETRABORATE DECAHYDRATE
OTHER PUBLICATIONS
[75] Inventor: Johnson C. Chen, Philadelphia, Pa. Johnson, “Lightweight Thermal Storage for Solar
Heated Buildings”, Solar Energy, 19, pp. 669~675, 1977.
[73] Assignee: Pennwalt Corporation, Philadelphia, “Chemical Mixture Creates ‘Midnight Sun’", Chemical
Pa.
Week, Mar. 1, 1978, pp. 34—35.
[21] App]. No.: 61,590 Primary Examiner-Harris A. Pitlick
Attorney, Agent, or Firm-Robert G. Danehower
[22] Filed: Jul. 30, 1979
[57] ABSTRACT
[5 1] Int. Cl.3 .............................................. .. C09K 5/06 A thermal energy storage composition is disclosed that
[52] US. Cl. .................................................... .. 252/70 stores heat upon melting and releases heat upon solidi?
[58] Field of Search ................ .. 252/70; 126/400, 900, cation. It is composed of a mixture of sodium sulfate
126/430, 436 decahydrate, sodium carbonate decahydrate, sodium
[56] References’ Cited borate decahydrate and a thickening agent. Its good
heat transfer characteristics, relatively high latent heat
U.S. PATENT DOCUMENTS of fusion, low cost, and favorable melting point allow
2,677,664 5/ 1954 Telkes ................................. .. 252/70 this material to be particularly useful for space heating
3,720,198 3/1973 Lang et a1. 252/70X applications.
3,986,969 10/1976 Telkes .. . .. . _ . . . . . . .. 252/70

4,037,650 7/1977 Randall ........................... .. 252/70 X 3 Claims, No Drawings

 4,292,189 2
1
hydrate, sodium carbonate decahydrate, sodium borate
THERMAL ENERGY STORAGE COMPOSITION decahydrate and small amounts of a thickening agent.
COMPRISING SODIUM SULFATE This composition has a freeze-thaw range of 21° to 24°
DECAHYDRATE; SODIUM CARBONATE C. which makes it highly desirable for solar energy
DECAHYDRATE; AND SODIUM TETRABORATE 5 application.
DECAI-IYDRATE
DETAILED DESCRIPTION OF INVENTION
BACKGROUND OF THE INVENTION My phase-change energy storage system is based on a
This invention relates to a thermal energy storage combination of two inorganic salts together with nucle
composition with good stability and physical proper 10 ating and thickening agents. The two inorganic salts are
ties, especially useful for space heating applications sodium sulfate decahydrate, Na2SO4.l0H2O, also called
where it is incorporated in either active or passive ther Glauber’s salt and sodium carbonate decahydrate, N32.
mal energy storage systems. The objects of such storage CO3.10I-IzO.
systems are to provide operating ef?ciencies to thermal The sodium sulfate decahydrate is used at a concen
operations, to achieve energy savings, and to permit the tration ranging from about 30% to 50% by weight of
introduction of new, alternative energy sources, such as the composition. At concentrations outside of the indi
solar energy, that are characterized by intermittent cated range, the tendency to separate into undesirable
availability. Individual tailoring of each storage system layers increases considerably.
is required to match the requirements of each of the The sodium carbonate decahydrate is used at a con
potential applications. Current, commercial systems centration ranging from about 50% to 60% by weight
employ the speci?c heat capacity of water, rock, or of the composition. Concentrations of the sodium car
ceramics to store the heat. However, large volumes, bonate decahydrate exceeding about 60% by weight of
large temperature swings, and bulky, expensive heat the composition tend to promote layer separation.
exchange apparatus are required. The third component of my energy storage-release
Commercialization has recently begun of systems 25 composition is sodium borate decahydrate which is
- employing phase-change materials to store the heat. present as a nucleating agent. The sodium borate deca
These materials store signi?cant quantities of energy hydrate is used at a concentration ranging from about
upon melting. Conversely, this energy is liberated when 1% to 10% by weight of the composition. If less than
the liquid is solidi?ed. A number of these phase-change about 1.0% of Na2B4O7.lOHzO is employed, excessive
materials are disclosed in U.S. Pat. No. 3,986,969 such 30 supercooling is observed. Amounts of Na2B4O7.10H2O
as calcium chloride hexahydrate, sodium carbonate in excess of 10% are not required to prevent supercool
decahydrate, disodium phosphate dodecahydrate, cal ing and in fact have a deleterious effect on the melting/
cium nitrate tetrahydrate, sodium sulfate decahydrate freezing pro?le as well as the stability of the mixture.
and sodium thiosulfate pentahydrate. A preferred thermal energy storage composition con
v A candidate phase-change material that has received 35
sists essentially of the following principal ingredients in
research and development effort over several decades is the weight ratio indicated as follows: sodium sulfate
Glauber’s salt, sodium sulfate decahydrate. Its heat of decahydrate-40%, sodium carbonate decahy
fusion is high, its melting point is appropriate for many drate—55%, and sodium tetraborate—5%. This com
space heating applications, and its price is low; how position melts and freezes in the passive heating range
ever, Glauber’s salt suffers from loss of its water of 40 of 21°-24° C. with only gentle agitation being required
hydration, separation into an anhydrous sodium sulfate during phase transition to prevent supercooling or sepa
layer and a water layer, and a consequent loss of ability
to store heat. Another serious problem is its tendency to ration of components.
supercool, releasing thermal energy in large quantities When a thickener is used, the above principal ingredi
at undetermined times. Many modi?cations by way of 45 ents would be used in the same ratio but at slightly
additives and container con?gurations have been tried lower amounts. For example, if 4.75% of thickener is
in order to overcome these problems. Thus, the paten used in my composition, the concentrations would be;
tee in U.S. Pat. No. 2,677,664 disclosed and claimed the sodium sulfate decahydrate-48.1%,
use of borax as a nucleating agent to prevent supercool sodium carbonate decahydrate—52.4%,
ing in a thermal storage composition based on Glauber’s 50 sodium borate decahydrate—4.75%,
salt. The same patentee added a homogenizing or thick thickening agent-4.75%.
ening agent such as attapulgus clay to the same compo With addition of about 5% of thickening agent, no
sition in U.S. Pat. No. 3,986,969 in order to slow the rate separation is observed over a number of thermal cycles.
of separation. Below about 0.5% of thickening agent signi?cant bene
Use of thin tray containers allows convective cur 55 ?ts are not observed while above about 8% the stability
rents to help keep the components mixed. A rotating of the mixture and the melting/freezing pro?le are af
drum has been tried to prevent component separations. fected. The thickener can be one or more members
Both indirect and direct-contact thermal exchange ar selected from the group consisting of sawdust, wood
rangements have been demonstrated. Despite these shavings, sodium methyl cellulose, sodium ethylcellu
efforts, sufficient problems remain with phase-change 60 lose, starch, alginates, silica gel, diatamaceous earth,
candidates so that signi?cant commercial use of any of clay and ?nely divided silica. A preferred thickening
' them has not occurred. agent is fumed silica sold under the trademark CAB-O
SIL.
SUMMARY OF INVENTION Other additives may be used in my thermal energy
I have now discovered a phase-change thermal en 65 storage composition in small amounts which do not
ergy storage composition that considerably reduces the affect the stability of the mixture or the melting/freez
problems of supercooling and layer separation. My ing pro?le. Such additives are corrosion inhibitors such
composition consists essentially of sodium sulfate deca as sodium chromate, sodium dichromate and sodium
 4,292,189
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nitrite. Bactericides, fungicides and insecticides may be changer for heating and cooling. The solution was alter
also used to maintain the composition clean and sterile. nately and repeatedly cooled and heated so that the salts
Surface active agents are used in small amounts to dis crystallized and remelted over twenty times without
perse and suspend the various components of the ther change. The melt-fusion temperature range is 21°-24°
mal energy storage composition. These additives are C. with supercooling to 15° C. occurring when the
usually present at concentrations ranging from 0.005 to mixture is not gently agitated at the fusion temperature.
0.5 percent by weight. When the material is melted, additional slight agitation
The preparation of the mixture can be accomplished is applied for a few minutes to assist complete formation
in a number of ways. For convenience, the anhydrous of a solution. The storage capacity based on the heat of
salts of sodium sulfate and sodium carbonate can be fusion is 45 cal/g.
added with the sodium borate decahydrate to the calcu
lated amount of water with stirring. Gently warming EXAMPLE 2
the mixture facilitates dissolution. Addition of a small Anhydrous sodium carbonate (102 g) and borax (25
excess of water also facilitates dissolution and has no g) were mixed with 285 g of water to make a clear
adverse effects on performance. A small amount of 15 solution. Fume silica thickening agent Cab-o-sil (25.5 g)
thickening agent, such as Cabosil can be added if de was added to the sodium carbonate-borax solution
sired according to engineering considerations. Once all under high speed stirring (5000 rpm) to make a homoge
the ingredients are in solution, the liquid is introduced nous paste-like mixture. While still under high speed
into the thermal energy storage chamber. Conventional stirring, 88 g of ?ne anhydrous sodium sulfate powder
thermal energy storage equipment used in accordance 20 was added slowly in such a manner that agglomeration
with industry-wide accepted practices is suf?cient as did not occur. The stirring was continued for another 3
long as provision is made for slight agitation while the minutes after the addition of sodium sulfate was com
material is changing phase. Complicated high perfor plete. The resulting mixture was ready to be placed in
mance equipment is not required.
A preferred method of preparing my thermal energy 25 containers for storage and release of thermal energy.
storage composition requires that the sodium tetrabo EXAMPLE 3
rate decahydrate, anhydrous sodium carbonate and
water are stirred together to make a clear solution. The The mixture prepared in Example 2 was divided into
amount of water is that amount necessary to form so 50 g portions and placed in glass vials measuring 35” by
dium carbonate decahydrate and sodium sulfate deca‘ 1" diameter and sealed with air tight screw caps. Six
hydrate. vials were placed in a 1000 ml glass beaker filled with
This amount is 1.267 parts of water per part of anhy water. The beaker and content was placed in ice bath
drous sodium sulfate and 1.698 parts of water for each and on a hot plate alternatively allowing enough time
part of sodium carbonate. The thickening agent, if used, for the phase change material to freeze and melt respec
is then added with stirring, preferably high speed stir~ 35 tively. During the heating cycle, the water temperature
ring, to give a viscous mixture. In the next step of the in the beaker was never allowed to exceed 38'’ C. No
process, finely divided anhydrous sodium sulfate, hav separation of the composition occurred during 50 '
ing a particle size of about one micron in diameter, is freeze_thaw cycles.
added slowly to the viscous mixture during vigorous I claim:
stirring. Too rapid addition of the sodium sulfate will 40 1. A composition for storing and releasing thermal
cause agglomeration to take place. This method of prep energy consisting essentially of the following ingredi
aration insures homogenous distribution of the sodium ents expressed in percent by weight:
sodium sulfate decahydrate-about 30-50%,
sulfate throughout the matrix and prevents separation of
the composition during the heating and cooling cycles. sodium carbonate decahydrate-about 50—60%,
The best mode of practicing my invention will be 45 sodium borate decahydrate-about l—10% and
apparent from a consideration of the following exam a thickening agent——about 0.5 to 8%,
ples: wherein the composition melts and freezes within the
range of 21° to 24° centrigrade.
EXAMPLE 1 2. The composition of claim 1 in which the sodium
Anhydrous sodium carbonate, 2030 g, anhydrous 50 sulfate decahydrate is present at 40%, the sodium car
sodium sulfate, 1760 g, and sodium tetraborate decahy bonate decahydrate is present at 55% and the sodium
drate, 500 g, where added with stirring to 7210 g of borate decahydrate is present at 5 percent.
water. The mixture was stirred and heated to about 34° 3. The composition of claim 1 in which the thickening
C. until all of the salts were dissolved. The solution was agent is fumed silica at a concentration of 3 percent.
then poured into a chamber equipped with a heat ex 55 I‘! It i i i

65