Composite Materials for Thermochemical

Energy Storage Applications-A Study

Introduction
● Demand for energy is increasing everyday on a global level.
● However the supply of fossil fuels is limited and is depleting continuously.
● Renewable Energy Resources are the one people look for to cater to their
demands.
● One such form of energy is Solar Energy.
● However it is available only during day time and so requires proper storage
techniques.
● Thermal Energy Storage systems are most promising for the same
● Conventional Heat Storage Systems are Sensible Heat Storage and Latent
Heat Storage.
● Upcoming energy storage systems include Thermochemical Energy Storage.
What is Thermochemical Energy Storage?
● Operates via reversible chemical reaction.
● Energy is stored after a dissociation reaction and then recovered in a
chemically reverse reaction.

C+heat⇄A+B

● Stages of TCES: Charging, Storing, Retrieval

● Major advantage of using TCES is that its energy storage density is about 15
times of SHS and about 6 times LHS.
● Also it could store and transport energy without heat loss.
● Apart from this thermochemical energy storage allows us to store energy for a
longer period.
Types of Materials being used
● Salt Hydrates ex: MgSO4.7H2O, CaCl2, MgCl2
● Metal Hydroxides ex: Mg(OH)2, Ni(OH)2
● Metal Oxides ex:Co3O4, MgO, CaO
● Carbonates ex:CaCO3
● Sorption Materials ex: solid-gas sorption materials which include zeolites,
silicalgels, halide-ammonia and activated carbon ammonia.
Salt Hydrates
● These storage materials are charged by heat induced dehydration of the salt
hydrate or by desorption of an adsorbate from the porous adsorbent.
Thereafter, the stored heat is released as the heat of hydration of the salt or
as the heat of adsorption. Ex: CaCl2.6H2O ⇄CaCl2+6H2O
● Major Constraints:
○ Formation of hard crust due to agglomeration of partially hydrated salts.
○ Dehydration leads to a mixture of lower hydrates with an average water content
○ Rehydration did not lead to a thermodynamically stable product.
○ Low melting point.
○ Swelling [1]
○ Aggregation or pulverization [1]
○ Formation of gel like substances
Metal Oxides
● Thermochemical Energy Storage in the case of oxides is based on the
transition reaction between multivalent ions. Ex: Fe2+/Fe3+ or Co2+/Co3+.[2]

Fe2O3 → 4Fe3O4 + O2 (515.23 J/g )

2Co3O4 → 6CoO + O2 (826.67 J/g )

● Major Constraints:
○ Too high reaction temperature.
○ High material costs
○ Low enthalpies
Metal Hydroxides
● Mg(OH)2, Ni(OH)2 , LiOH.2H2O (with a storage density of 1440 kJ/kg) were
some of the most promising candidates for thermochemical energy storage.

● Major Constraints:
○ Low hydration rate
○ Low thermal conductivity
○ Low rate of heat and mass transfer
Carbonates
● Among carbonates, the cyclic reversible conversion between CaO and
CaCO3 also known as calcium looping process with high energy density of
around 3.2 GJ/m3 is a promising technique for energy storage.

● Major Constraints:
○ Major drawback is sintering-coalesce into a solid or porous mass by means of heating. Cao
particles progressively deactivate due to sintering-induced morphological changes during
repeated carbonation , calcination cycles.
Need For Composites
● Salt hydrates, metal oxides and hydroxides had many limitations such as low
melting point, low hydration/dehydration rate, agglomeration etc. To overcome
these difficulties, composite materials were brought into picture.

● Normal salt hydrates, oxides or hydroxides when mixed or were impregnated

with porous materials like zeolites, silica gel, vermiculite, attapulgite, activated
carbon, metal organic framework,molecular sieves. showed enhanced
properties such as increased water sorption capacity which in turn increased
the hydration energy of the composites and many more.
Composite Material
● These are materials made from two or more constituent materials with
significantly different physical or chemical properties which remain separate
and distinct within the finished structure.
● They can be categorized into two major types
1. structural composites with outstanding mechanical properties.
2. functional composites with various outstanding physical, chemical or
electrochemical properties.
Composites based on zeolite
• Zeolites are crystalline aluminosilicates of alkali or alkali earth silicates such as
sodium, potassium, and calcium. Due to high water sorption capacity and a porous
structure, zeolites can be used a host matrix material.
• MgCl2.6H2O with total dehydration heat of 2890J/g is considered as a suitable TCHS
material. However, the heat stored was not fully utilized due to agglomeration. Wide
pore zeolites namely Faujasite Na-X (Na), Mordenite (Na), 13X, and Faujasite Na-H
were used.
• The composite was prepared by incipient wetness method.
• Increasing the concentration of salt lead to decrease in heats of water sorption.
• The results were different for mordenite composites for which heat of hydration
increased with increasing salt content.
Composite based on vermiculite
• Vermiculite is a naturally occurring hydrous phyllosilicate mineral which expands on heating.
• Ca(OH)2/CaO hydration-dehydration reaction have been used for storing thermal energy beyond 450C because
of its high storage density of 1300kJ/kg. However, Ca(OH)2 exhibits agglomeration and pulverization during
subsequent cycles of hydration/dehydration.
• Mg(OH)2 with an energy storage density of 1044J/g is yet another TCM material for energy storage at high
temperatures.
• Using vermiculite along with Mg(OH)2 not only provided chemical stability to the salt but also reduced the
decomposition temperature making it a potential candidate for medium temperature heat storage.
• Using expanded vermiculite with SrBr2.6H2O as host matrix was beneficial in the sense that it not only
increased the water holding capacity of the solution but also the mass-energy storage density and the enthalpy of
reaction.
• CaCl2 was impregnated with vermiculite and encapsulated with ethanol and water.
Vermiculites allows the salt to swell or shrink without changing the crystal structure of the material, salt maintain its
density and improves the water holding capacity of the salt.
Composite based on silica gel
• Silica gel can be defined as a coherent, rigid three-dimensional network of contiguous particles of colloidal
silica, which can be prepared by the polymerization of silicic acid or by the aggregation of particles of colloidal
silica.
• A composite based on strontium bromide and silica gel for solar energy storage application. The stability of the
salt was maintained over 14 successive sorption/desorption cycles which proves that the confinement effect of
the pores of silica gel.
• Dongsheng Zhu et. al. tested calcium chloride with silica gel sorbent for low-grade heat storage. It was observed
that the water sorption capacity of the composite reached around 0.73 g/g of dry sorbent while that of pure silica
gel is only 0.15 g/g of dry sorbent.
• Yuri I. Aristov et. al. synthesized a composite named SWS-8L by impregnating calcium nitrate (Ca(NO3)2) into
the pores of mesoporous silica gel KSK. It was found that the isosteric heat of water sorption for the composite
(47 kJ/mol) was higher than the heat of evaporation of water (44 kJ/mol).
• Silica gel impregnated with potassium formate (KCOOH) and DSC analysis revealed that this composite had an
energy storage density of 457 kJ/kg.
Preparation Methods
● For the synthesis of the salt-porous-carrier composites two different
procedures are applied:

Impregnation method:-

Two types: wet(solution used in excess of pore volume).

dry or incipient wetness(solution just fills pore volume).

The preparation of mixtures of zeolite,binder (PTFE, AI(OH)3 or graphite) and,

additive (SIC, Si3N4 or Graphite). [3]

Calcium chloride impregnated in vermiculite (V). [4]

Preparation Methods
Soaking:-

To obtain the nano-composite, a poly(methyl methacrylate) (PMMA) poly(2-

hydroxyethyl methacrylate) (PHEMA) film with PMMA and PHEMA domains
was soaked into a pyridine/m-xylene/perhydropolysilazane (PHPS) mixture
and calcinated at 90 °C under steam.[5]

solid-state reaction (SSR) process:-

Stoichiometric amounts of precursor powders: calcium carbonate (CaCO3 ⩾

99.5% purity), manganese dioxide (MnO2 purity ⩾ 99.9% purity), and the
appropriate dopant compounds were mixed in isopropyl alcohol and ball-
milled for 48 h.[6]
Special Methods of Preparation
Sol-gel Method [7]

It is one of the most widely used processes to prepare novel metal oxides as well
as mixed oxide composites. This method has potential control over the textural
and surface properties of the material. Sol gel undergoes the following steps
before delivering the final metal oxide:

1. Hydrolysis-to produce metal hydroxide solution

2. Condensation-converting hydroxides to three dimensional gels
3. Drying Process
Characterization Techniques
Characterization includes methods used to identify, isolate or quantify chemicals
or materials or to characterize their physical properties. Some common
characterization techniques include:

● TGA-Thermogravimetric Analysis
● DSC-Differential Scanning Calorimetry
● XRD-X ray Diffraction
● X-Ray Fluorescence (XRF)
● SEM-Scanning Electron microscopy
● BET- Brunauer Emmett Teller
● ICP-OES- Inductively coupled plasma optical emission spectroscopy
ANALYSIS OF CHARACTERIZATION TECHNIQUES

 Experiments and curves obtained:

TGA and DSC experiments on 7 mg encapsulated CaCl2 and simultaneous mass curve obtained.
 DSC analysis of zeolite/MgSO4
X-ray diffraction patterns for Mg(OH)2/vermiculite composites and anhydrous and partially hydrated
Ca(NO3)2/SiO2 composite as well as pure Ca(NO3)2.2H2O.
SEM images of vermiculite/Ca(OH)2 samples
CaCl2 content of ACF-A, SC-A determined by electronic weighing method and ACF-B, SC-B determined by
ICP method. Comparison of result between weighing method and ICP.
Some Common Instruments used for
Characterization
● TGA/DSC1 (Mettler Toledo) to analyze heat fluxes and changes in sample
mass during hydration and dehydration experiments.
● Rubotherm magnetic suspension balance- a widely used thermo gravimetric
instrument.
● Siemens Kristalloflex D5000 with Cu-K1 radiation for XRD analysis.
● Ultra high resolution S4800 instrument for SEM.
● Nitrogen adsorption-desorption isotherms were measured at 77K by using a
ASAP2420 (Micrometrics) instrument.
References
[1] Calabrese L, Brancato V, Palomba V, Frazzica A, Cabeza LF, Assessment of
the hydration/dehydration behaviour of MgSO4∙7H2O filled cellular foams for
sorption storage applications through morphological and thermo-gravimetric
analyses, Sustainable Materials & Technology. 17 (2018) , 250-260.

[2] Block T, Knoblauch N, Schmücker M,The cobalt-oxide/iron-oxide binary system

for use as high temperature thermochemical energy storage material,
Thermochimica Acta. 577(2014),25-32

[3] PINO L, ARISTOV UY, CACCIOLA G, RESTUCCIA G,Composite Materials

Based on Zeolite 4A for Adsorption Heat Pumps, Adsorption. 3(1996), 33-40.
[4] Gaeini M, Rouw A.L., Salari J.W.O, Zondag H.A., Rindt
C.C.M,Characterization of microencapsulated and impregnated porous host
materials based on calcium chloride for thermochemical energy storage, Applied
Energy. 212(2018), 1165-1177

[5] Synthesis of poly(methyl methacrylate)/silica nano-composite by soaking of a

microphase separated polymer film into a perhydropolysilazane solution.

[6] Imponenti L, Albrecht J.K., Kharait R, Sanders D.M,Redox cycles with doped
calcium manganites for thermochemical energy storage to 1000 °C, Applied
Energy.230(2018), 1-18.

[7] Block T, Schmu¨cker M, Metal oxides for thermochemical energy storage: A

comparison of several metal oxide systems, Solar Energy. 126(2016), 195-207.