12.

6 Thermal energy storage

Direct storage of heat in insulated solids or fluids is possible even at low temperatures, but energy can
only be recovered effectively as heat. Thermal energy storage (TES) is deally suited for applications such
as space heating, where low quality (temperature) energy is required. It has found wide use in many
industrial applications such as manufacture of cement, iron and steel, glass, aluminum, paper, plastics and
rubber and in food processing.
Following are 2 distinct thermal energy storage mechanisms.
(a) Sensible heat storage, based on the heat capacity of the storage medium
(b) Latent heat storage, based on the energy associated with a change of phase for the storage
medium (melting evaporation or structural change).
12.6.1 Sensible hea energy storage
Energy can be stored as sensible heat by virtue of rise in temperature of the storage medium, such as
water, liquid or solid.
Storage density (kJ/m3) is = Temperature difference (oC) * Specific heat (kJ/kg.oC) * Density of material
(kg/m3) =
This system is simple in concept, but has the disadvantage of cariable temperature operation and low
storage density. Sensible energy storage could employ one of the following devices.
(a)
(b)
(c)
(d)

Pressurized water storage

Organic liquid storage
Packed solid beds
Fluidized solid beds

There are 3 main ways of operating the accumulator, viz. variable pressure, expansion or displacement.
(a) Variable pressure accumulator : It is also called Ruths accumulator. When fully charged,
almost all its volume is filled with saturated hot water, with a small cushion of saturated steam
above it. In the discharge mode, steam is drawn off from the top and as the pressure in the steam
cushion decreases, some water flashes into steam.
(b) Expansion accumulator : It is shown in fig 12.22. When fully charged, the accumulator is
almost full of hot water with a small steam cushion, as in the variable pressure mode. As hot
water is drawn from the bottom during discharge, some water flashers to steam, which reduces
the pressure and temperature of saturated water and steam. All the water can be removed to the
flash evaporator with a reduction of pressure of about 30 per cent. The water from the last flash
evaporator is collected and stored.
(c) Displacement accumulator : It is always completely full of water. When fully charged, it contains
hot water at the desired temperature. When fully discharge, all the water cold. As shown in fig
12.23, hot water is injected at the top during charge and removed from the top during discharge.
Cold water leaves and enters at the bottom. Since hot water has lower density than cold water, it
will float at the top. A sharp temperature gradient or thermocline separates the hot and cold water.

During discharge, one of more flash evaporators are used to generate steam for peaking turbines.
The water drained from the evaporators and the condensate from the turbine are returned to the
accumulator as cold water. During charge, steam is mixed with cold water taken from the bottom
to raise the temperature to the desired level. Colde water equal in mass to the steam is returned to
the boiler inlet feedwater to generate more steam.
12.6.2 Latent heat energy storage
Energy is stored form of the latent heat caused by phase change either by melting a solid or vaporizing a
liquid. Energy release is accomplished by reversing the process, i.e. by solidifying the liquid or
condensing the vapour.
Storage density = latent heat * density
Since the latent heats are much larger than the specific heats, the energy storage density is larger than in
sensible heat storage. The system has the additional advantage of operating at constant temperature. It
also has the advantage of a wide choice of materials with different fusion and evaporation temperatures to
suit the peaking turbine.
Storage materials must pocess, in addition to proper phase transition temperature and high latent heat,
good thermal conductivity, containability, chemical stability, nontoxicity and low cost. No material meets
all these requirements, but some fluoride salts meet some of them. One of the most suitable salts for latent
heat storage is the 70% NaF-30% FeF2 eutectic salt, which has a fusion temperature of 680oC and the
highest storage density (of all salts) of 1500 MJ/m3. The following fluoride mixtures in table 12.4 are
chemically stable and can be contained in chromium nickle steel, suitable as storage for heat engines.
12.7 Chemical energy storage
The heat of reaction of reversible chemical reactions is used to store thermal energy during endothermic
reactions and to release it during exothermic reactions. Like latent heat energy storage, this form also
offers large energy storage densities. The following reversible reaction along with some others as given in
Table 12.5 have been suggested for energy storage.
CO + 3 H2

CH4 + H2O

For reaction from right to left at 298 K, 1 atm

Energy balance is
HR + Q = HP
( )

( )

( )

The reaction is endothermic and energy is absorbed. The revesr reaction from left to right result in Q = 250.3 kJ/gmol, i.e. energy is released and the reaction is exothermic . The endothermic reaction is called
reformation and the exothermic reaction is called methanation.

A schematic of a power plant with a chemical storage system is shown in Fig 12.24. During periods of
low demand, some heat from the primary heat source is deverted to the reformer (endothermic reactor) to
convert the products CH4 + H2O to the reactants CO + 3H2, which are stored in a vessel at high pressure,
about 70 bar, but at ambient temperature. During periods of high demands, these reactants are fed to the
methanator (exothermic reactor) where heat is generated to run a peak turbine. In the methanator the
reactants are converted to the products CH4 + H2O, which are stored in a separate vessel for later use in
the reformer during periods of low demand. A thermal turnaround efficiency of this system is estimated
as 85 to 90 per cent.
The two storage vessel and the two reactors operate at different pressures. Storage pressures need to be
high to minimize vessel size and cost and the reformer has to operate at low pressure to maximize the rate
of endothermic reaction.
12.8 Hydrogen energy
Hydrogen is widely regarded as the ultimate fuel and energy storage medium for future centuries. It can
be derived from water (by electrolysis) using any source of high quality energy and it can be combusted
back to water in a closed chemical cycle without any pollution. The potential of hydrogen for the storage
and cheap transmission of energy over long distances has led to the concept of hydrogen economy (Fig
12.25).
Hydrogen can be produced by the following methods.
1. Catalytic steam reforming of natural gas
2. Chemical reduction of coal (water gas reaction)

Or
3.
4.
5.
6.
7.

C + H2O

CO + H2

CO + H2O

CO2 + H2

Industrial photosynthesis
Ultraviolet radiation
Partial oxidation of heavy oils
Electrolytic decomposition of water
Thermal decomposition of water, utilizing thermochemical cycles. The electrolytic
decomposition of water (electrolysis) comprises two processes
Cathode :

2 H2O + 2e -

Anode :

2OH-

H2 + 2OH O2 + H2O + 2e -

According to Faradays law of electrolysis the mass of hydrogen m discharged maybe obtained from

Where A = atomic weight, I = electric current, t = duration of electrolysis, Z = valency and F = Faraday
constant = 96500 coulomb/kgm.

The overall reaction is

H2O

H2 + O2

- 237 kJ/kmol

Hydrogen maybe used as a primary fuel for peak power generation producing water in the reaction.
During off-peak hours hydrogen maybe produced by electrolysis of water with excess power available.
The hydrogen based power utility concept is shown schematically in Fig 12.26.
The main drawback of hydrogen is its extreme flammability and the problem of storing the gas inder
pressure. Liquefaction could simplify storage but it consumes a lot of energy
Methane maybe produced by reactions with hydrogen.
CO + 3H2 = CH4 + H2O
C + 2H2 = CH4
Methane maybe used by consumers as ordinary fuel, without being highly inflammable as hydrogen
Ammonia maybe more attractive as a fuel, which can be produced from hydrogen by combining it with
nitrogen, under 200-500 bar pressure and at 720K in presence of a catalyst (Haber process)
N2 + 3H2 = 2 NH3

Q = - 90kJ

Dissociating ammonia back into hydrogen and nitrogen can be done by passing the gas through a hot
tube. The advantage of storing ammonia, relative to storing hydrogen, are the following.
(a) Safer storage
(b) Energy density is higher
(c) Easier to liquefy
12.8.1 Storage of hydrogen
Hydrogen maybe stored as (i) compressed gas (ii)chemical compound (iii) liquid (iv) metallic hydrides
(i)
(ii)
(iii)

(iv)

Since the cost of liquefaction is high, the bulk storage of hydrogen can be made in the form of
compressed gas in underground caverns, where it can be stored like natural gas.
Hydrogen is chemical combination with other elements like methane and ammonia is more
amenable to storage.
Liquid hydrogen has a mass energy density three times greater than oil. Its use is attractive
for heavy surface transport and aircraft. For energy storage, liquid hydrogen is not so
attractive because of its low density. Ammonia and methane, as liquida, are more efficient in
this aspect.
The principal disadvantages of gaseous hydrogen as a storage medium is that it takes up lage
space, it is explosive and it is not leak-proof. Liquid hydrogen, highly cryogenic and
inflammable, is costly too. These drawbacks can be fought back if hydrogen is stored in
hydride form (Table 12.6). The aim is to select a hydride which can be thermally decomposed
in a reversible manner so that hydrogen maybe withdrawn or replenished from or to the

1.
2.
3.
4.
5.

vessel when necessary. Some of the desired features of a suitable hydride store are the
following :
High hydrogen content per unit mass of metal
Low dissociation pressure at moderate temperatures
Constancy of dissociation pressure during the decomposition time
Safe on exposure to air
Low cost.

The exothermic chemical reaction of hydride formation from metals (Me) and hydrogen (H2) is as
follows :

Low temperature FeTi hydride, with a low energy reuquirementt for hydrogen release, has been
developed by Brookhaven National Laboratory, USA. Magnesium-based high temperature hydride has
attracted interest because magnesium is a readily available and cheap metal. Both materials release
hydrogen endothermically, thus creating no safety problem. The mass energy densities (Wm) of hydrides
based on Ti Mg are the following :
FeTiH1.7

FeTiH0.1

516 Wh/kg

(1856 kJ/kg)

Mg2NiH4

Mg2NiH0.3

1121 Wh/kg

(4036 kJ/kg)

MgH2

MgH0.005

2555 Wh/kg

(9198 kJ/kg)

When hydride are used as hydrogen stores for heat engines or for domestic heaters, the waste heat
from them can be returned to the hydride. If the amount of waste heat is less than the heat nedded for
hydrogen release, then the waste heat energy can be stoered in the metal hydride with different release
temperatures maybe used for different applications such as heat pumps, central air conditioning and even
for renewable energy storage system.