Energy Sources, Part B, 1:8595, 2006 Copyright Taylor & Francis Group, LLC ISSN: 1556-7249 print/1556-7257 online

e DOI: 10.1080/009083190881481

Thermal Energy Storage and Phase Change Materials: An Overview

M. FATIH DEMIRBAS
Researcher of Energy Technology Trabzon, Turkey
The storage of thermal energy in the form of sensible and latent heat has become an important aspect of energy management with the emphasis on efcient use and conservation of the waste heat and solar energy in industry and buildings. Latent heat storage is one of the most efcient ways of storing thermal energy. Solar energy is a renewable energy source that can generate electricity, provide hot water, heat and cool a house, and provide lighting for buildings. Parafn waxes are cheap and have moderate thermal energy storage density but low thermal conductivity and, hence, require a large surface area. Hydrated salts have a larger energy storage density and a higher thermal conductivity. In response to increasing electrical energy costs and the desire for better lad management, thermal storage technology has recently been developed. The storage of thermal energy in the form of sensible and latent heat has become an important aspect of energy management with the emphasis on the efcient use and conservation of the waste heat and solar energy in the industry and buildings. Thermal storage has been characterized as a kind of thermal battery. Keywords thermal energy storage, phase change material, latent heat

Thermal energy storage (TES) can take the form of sensible heat storage (SHS) or latent heat storage (LHS). To store the same amount of energy, signicantly larger quantities of a storage medium are required for SHS in comparison to LHS. When LHS is used to store solar energy it can increase the thermal storage efciency. Phase change materials (PCMs) are materials that store energy in the process of changing the aggregate state from solid to liquid. PCMs are latent heat thermal storage materials. They use chemical bonds to store and release heat. The latent heat thermal energy storage (LHTES) method that is suitable for solar heating and air conditioning has received considerable attention due to its advantages of storing a large amount of energy as a phase transition at a constant temperature. The selection of the heat storage material as a PCM in the LHTES method plays an important role from the points of view of thermal efciency (Sar et al., 2004). Solar energy applications require an efcient thermal storage. The latent heat of melting is the large quantity of energy that needs to be absorbed or released when a material changes phase from a solid state to a liquid state or vice versa (Khudhair and Farid, 2004). The storage temperature or phase change can be improved by choosing the PCM in such a way that its phase change temperature optimizes the thermal gradient with respect
Address correspondence to M. Fatih Demirbas, P. K. 216, Trabzon 61035, Turkey. E-mail: muhammeddemirbas@yahoo.com

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Figure 1. Temperaturetime diagram for the heating of a substance (Source: Stritih and Novak, 2002).

to the substance with which the heat is being exchanged (Hassan, 1991). For example, with parafns and alkanes it is possible to vary the number of carbon atoms or form different molecular alloys, which allows a practically continuous variation of the phase change temperature within certain ranges (Zalba et al., 2003). Figure 1 shows the increase of internal energy when energy in the form of heat when it is added to a substance (Stritih and Novak, 2002). The well-known consequence is an increase in temperature (sensible heating) or change of phase (latent heating). Starting with an initial solid state at point O, a heat addition to the substance rst causes sensible heating of the solid (region OA) followed by a solid-to-liquid phase change (region AB), a sensible heating of the liquid (region BC), a liquid-to-vapor phase change (region CD), and a sensible heating of the vapor (region DE). The total amount of heat can be written in the following formula: Q=m
TA TO

Cps (T )dT + qt +

TC TB

Cpl (T )dT + qi +

TE TD

Cpv (T )dT .

(1)

Phase Change Material and Heat Storage

PCMs are latent thermal storage materials. They use chemical bonds to store and release heat. PCMs are materials that store energy in the process of changing the aggregate state from solid to liquid. Glaubers salt (sodium sulfate decahydrate), calcium chloride hexahydrate, and parafn wax are the most commonly used as PCMs in solar heating systems. PCMs perform best in containers that (when combined with the PCM) total 25.4 mL (one inch). Table 1 shows the main PCMs. The amount of solar heat energy that can be stored in one mole of CaCl2 6H2 O (calcium chloride hexahydrate) is estimated by envisioning a two-step storage sequence (Wilkins et al., 1992). First, heating calcium chloride hexahydrate from 293 K to 303 K, Heat energy (Q) = (change in temperature)(mass)(specic heat). Q = (10.0 K)(219.1 g/mole)(1.34 J/gK)(1 mole) = 2.94 J. (2) (3)

Thermal Energy Storage (TES PCM) Table 1 Main phase change materials
Parafns Parafn C14 Parafn C15 C16 Parafn C16 C18 Parafn C13 C24 Parafn C16 C28 Parafn C18 Parafn C20 C33 Parafn C22 C45 Parafn C23 C50 Parafn wax Oktadekan Inorganic compounds H2 O LiClO3 3H2 O KF4H2 O Mn(NO3 )2 6H2 O CaCl2 6H2 O LiNO3 3H2 O Na2 SO4 10H2 O Zn(NO3 )2 6H2 O Na2 CO3 10H2 O CaBr2 6H2 O Na2 HPO4 12H2 O Na2 S2 O3 5H2 O Na(CH3 COO)3H2 O Na2 P2 O7 10H2 O Ba(OH)2 8H2 O Mg(NO3 )2 6H2 O (NH4 )Al(SO4 )6H2 O MgCl2 6H2 O NaNO3 KNO3 KOH MgCl2 NaCl Na2 CO3 KF K2 CO3 Inorganic eutectics 58.7% Mg(NO3 )6H2 O + 41.3% MgCl2 6H2 O 66.6% CaCl2 6H2 O + 33.3% MgCl2 6H2 O 48% CaCl2 + 4.3% NaCl + 0.4% KCl + 47.3% H2 O 47% Ca(NO3 )2 4H2 O + 33% Mg (NO3 )2 6H2 O 60% Na(CH3 COO)3H2 O + 40% CO(NH2 )2 66.6% Urea + 33.4% NH4 Br Organic compounds

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Polyglycol E 400 Polyglycol E 600 Polyglycol E 6000 Dodecanol Tetradecanol Biphenyl HDPE Trans-1,4-polybutadiene (TPB) Propionamide Naphtalene Erythitol Dimetly-sulfoxide Capric acid Caprinic acid Laurinic acid Miristic acid Laksiol Palmitin acid Stearic acid Acetamid Propionamid

Second, converting the hexahydrate (at 303 K) to the dehydrate and water, CaCl2 6H2 O(s) CaCl2 2H2 O(s) + 4 H2 O(l) Q= Q=
Hreaction = Hreaction = Hformation, products Hformation, products Hformation, reactants . Hformation, reactants .

(4) (5) (6)

Q = (1402.9 kJ/mol)(1 mol) + (285.9 kJ/mol)(4 mol) (2607.9 kJ/mol)(1 mol) = +61.6 kJ. Total energy stored = 2.9 kJ + 61.6 kJ = 64.5 kJ. (7) (8)

Unlike conventional (sensible) storage materials, when PCMs reach the temperature at which they change phase (their melting point), they absorb large amounts of heat without getting hotter. When the ambient temperature in the space around the PCM material drops, the PCM solidies, releasing its stored latent heat. PCMs absorb and

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emit heat while maintaining a nearly constant temperature. Within the human comfort range of 293303 K, latent thermal storage materials are very effective. Additional research has led the development of PCM materials that may be designed for applications in the temperature range of just above 273398 K. By blending adjacent alkyl hydrocarbon chains, a mixture having a desired single melting temperature may be produced without a signicant decrease in thermal energy storage. Parafns are compounds that are, at room temperature, in shape of waxes. Chemically they are hydrocarbons with alkans Cn H2n+2 . The melting point increases with the increase of C atoms. The majority of organic nonparafns are acids. They can be characterized with the formula CH3 (CH2 )2n COOH. Their melting point is similar to those of parafns. Their downfall is that they are poisonous and the reason why they are more expensive than parafns. Inorganic compounds are known by the formula MnH2 O and have been studied for many years. They have relatively high latent heat but their melting-solidication processes are irreversible because of segregation. Eutectics are mixture of two or three compounds and are melted without segregation (Stritih and Novak, 2002). The thermal energy transfer occurs when a material changes from a solid to a liquid or from a liquid to a solid. This is called a change in state, or phase. Initially, these solidliquid PCMs perform like conventional storage materials; their temperature rises as they absorb solar heat. Unlike sensible heat storage materials, when PCMs reach the temperature at which they change phase, they absorb large amounts of heat without getting hotter (Demirbas, 2002). When the ambient temperature in the space around the PCM material drops, the PCM solidies, releasing its stored latent heat. PCMs absorb and emit heat while maintaining a nearly constant temperature. Within the human comfort range of 295305 K, latent thermal storage materials are very effective. Figure 2 shows the energy stored as a function of temperature in a combined water + phase change heat storage compared to a water-lled storage. They store 514 times more heat per unit volume than sensible storage materials such as water, masonry, or rock (Ghoniem and Klein, 1989). PCMs are usually more expensive than conventional heat storage materials. Relatively few of the solidsolid PCMs that have been identied are suitable for thermal

Figure 2. Energy stored as a function of temperature in a combined water + phase change heat storage compared to a water-lled storage (Source: Lambert DApote, 1998).

Thermal Energy Storage (TES PCM) Table 2 Melting points and heat of fusions of parafns with potential use as a PCM Compound Parafn Parafn Parafn Parafn Parafn Parafn Parafn Parafn Parafn Parafn C14 C15 C16 C16 C18 C13 C24 C16 C28 C18 C20 C33 C22 C45 C23 C50 wax Melting point (K) 277.7 281.2 294.2 296.2 316.2 301.2 322.2 300.7 340.4 337.2 Heat of fusion (kJ/kg) 165 153 152 189 189 244 189 23.5 189 173.6

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storage applications. Liquidgas PCMs are not yet practical for use as thermal storage. Sodium sulfate decahydrate (Glaubers salt), calcium chloride hexahydrate, and parafn wax are the most commonly used as PCMs in solar heating systems. PCMs are either packaged in specialized containers such as tubes, shallow panels, plastic bags, etc., or contained in conventional building elements (wall board, ceiling) or encapsulated as self-contained grains. Because the chemicals in some PCMs separate and stratify when in their liquid state, PCMs have not always resolidied properly. When temperatures dropped, they did not completely solidify, reducing their capacity to store latent heat. These problems have been addressed by packaging PCMs in thin or shallow containers, and by adding thickening and clumping agents. These types of PCMs, however, compare unfavorably with the newer generation of low-cost, highly efcient, linear crystalline alkyl hydrocarbons. Tables 25 show the melting points and the heat of fusions of parafns, inorganic substances, inorganic eutectics, and organic compounds with potential use as a PCM, respectively.

Thermal Energy Storage

Storage of thermal energy in the form of sensible and latent heat has become an important aspect of energy management with the emphasis on efcient use and conservation of the waste heat and solar energy in industry and buildings. Energy storage of all types plays an important role in energy conservation. In processes that are wasteful of energy, energy storage will result in saving premium fuels. Energy may be stored in many ways, e.g., mechanical energy, kinetic energy, and chemical energy, but because in so much of our economy it is produced and transferred as heat, the potential for storage of thermal energy warrants study in detail. TES deals with the storing of energy by cooling, heating, melting, solidifying, or vaporizing a material; the energy becomes available as heat when the process is reversed. Storage by causing a material to rise or lower in temperature is called SHS; its effectiveness depends on the specic heat of the material and, if volume is important, on the density of the storage material. Passive solar space heating systems commonly use dense materials, such as brick, concrete, and adobe, as thermal storage materials. Heat storage materials absorb heat through standard heat transfer mechanisms, e.g., radiation, conduction, and convection.

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M. F. Demirbas Table 3 Melting temperature and heat of fusion of inorganic substances with potential use as a PCM Melting temperature (K) 273.2 281.3 291.7 299.0 302.2 303.2 305.6 309.2 307.2 303.2 308.7 321.2 331.2 343.2 351.2 362.2 368.2 390.2 580.2 606.2 653.2 987.2 1073.2 1127.2 1130.2 1170.2 Heat of fusion (kJ/kg) 333 253 231 125.9 190.8 296 254 246.5 146.9 115.5 265 201 264 184 265.7 162.8 269 168.6 172 266 149.7 452 492 275.7 452 235.8

Compound H2 O LiClO3 3H2 O KF4H2 O Mn(NO3 )2 6H2 O CaCl2 6H2 O LiNO3 3H2 O Na2 SO4 10H2 O Zn(NO3 )2 6H2 O Na2 CO3 10H2 O CaBr2 6H2 O Na2 HPO4 12H2 O Na2 S2 O3 5H2 O Na(CH3 COO)3H2 O Na2 P2 O7 10H2 O Ba(OH)2 8H2 O Mg(NO3 )2 6H2 O (NH4 )Al(SO4 )6H2 O MgCl2 6H2 O NaNO3 KNO3 KOH MgCl2 NaCl Na2 CO3 KF K2 CO3

Table 4 Melting temperature and heat of fusion of inorganic eutectics with potential use as a PCM Melting temperature (K) 332.2 298.2 300.0 302.2 303.2 349.2 Heat of fusion (kJ/kg) 132.2 127 188.0 190.8 136 161

Compound 58.7% Mg(NO3 )6H2 O + 41.3% MgCl2 6H2 O 66.6% CaCl2 6H2 O + 33.3% MgCl2 6H2 O 48% CaCl2 + 4.3% NaCl + 0.4% KCl + 47.3% H2 O 47% Ca(NO3 )2 4H2 O + 33% Mg(NO3 )2 6H2 O 60% Na(CH3 COO)3H2 O + 40% CO(NH2 )2 66.6% Urea + 33.4% NH4 Br

Thermal Energy Storage (TES PCM) Table 5 Melting temperature and heat of fusion of organic compounds with potential use as a PCM Melting temperature (K) 281.2 295.2 339.2 299.2 311.2 344.2 373.2 418.2 352.2 353.2 391.2 289.7 Heat of fusion (kJ/kg) 99.6 127.2 190.0 200 205 190.0 200 144 168.2 147.7 89.8 85.7

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Compound Polyglycol E 400 Polyglycol E 600 Polyglycol E 6000 Dodecanol Tetradecanol Biphenyl HDPE Trans-1,4-polybutadiene (TPB) Propionamide Naphtalene Erythitol Dimetly-sulfoxide

As the materials cool at night or on cloudy days, they subsequently release the stored heat in the same fashion. Active space heating systems commonly use tanks of water or rock bins as a thermal storage material. Water, stored in plastic, berglass, or glass-lined steel containers, is the typical thermal storage medium in solar water heating systems. These heat storage materials deal with sensible heat. This means as they absorb heat, their temperature increases and they become warm to the touch. Heat storage is necessary in order to accommodate differences in the time between heat production and heat demand, which is gaining importance with the installation of decentralized power generation. The time scale varies from hours to months. Storage by phase changethe transition from solid to liquid or from liquid to vapor with no change in temperatureis another mode of heat storage, known as latent heat storage. The specic heat of solidication or vaporization and the temperature at which the phase change occurs are obviously of controlling importance. Both sensible and latent heat storage may occur in the same material (Gutherz and Schiller, 1991; Hawes et al., 1993). The thermochemical systems could eventually lead to an infrastructure in which waste heat from an industry can be accommodated and stored in chemical energy. The chemical energy be can transported to locations with heat demand and heat can be delivered at the required temperature level by means of a chemical heat pump. Figure 3 shows energy storage from solar and industrial sources. In this system, T1 shows the temperature of cool uid and T2 shows the temperature of hot uid. The overall efciency (o ) can be expressed as: o = Useful heat input to heat storage material . Input energy from the sun and industry (9)

Thermal efciency (t ) can be given as: t = T2 T1 T2 (10)

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Figure 3. Energy storage from solar and industrial sources (T2 > T1 ).

Upgraded low-quality heat can very well be used in heating and cooling systems. Upgrading can take place using a so-called chemical heat pump, operating in a continuous or batchwise mode. Reversible decomposition reactions of organic or inorganic substances are used to achieve the required temperature lift. Heat Q stored from a heat source at T1 temperature can be recovered by the transformation at a different temperature, T2 : At T1 temperature, At T2 temperature, AB + Q A + B. A + B AB + Q. (11) (12)

Underground Thermal Energy Storage Systems

Research in underground thermal energy storage systems (UTESS) started in the late 1970s. The purpose was to develop energy storage technology utilizing waste and renewable or ambient energy sources to supply space heating, space cooling, and process cooling to achieve signicantly improved efciency. Storage options that can be used in UTESSs can be grouped into three types: (1) storage in water, (2) storage in aquifers, and (3) storage in the ground (Paksoy, 1995): Waste heat or solar energy may be stored in underground earth pits using water as the storage medium. Pits have to be lined with polymer-based materials to prevent leakage from the storage. Earth pits can be partially or fully insulated. For a storage temperature above 368 K, a stainless steel liner was used (Zinko and Hahn, 1994). This storage can be used for both the short and long term in district heating system feeding fty dwellings. Heat storage in rock caverns was used for storing hot water. For the system to be economically viable the volume of the rock cavern should be 60,000120,000 m3 , large enough to feed a district heating system for at least 600 dwellings.

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Aquifer thermal energy storage (ATES) involves seasonal storage. ATES is a very promising technique for both heating and cooling purposes (Andesson, 1994). Aquifers are underground water reserves between consolidated (rock) or unconsolidated (gravel or sand) geologic formations. The natural temperature of aquifers can be slightly higher than the ambient temperature. An aquifer that is suitable for heat storage should have a permeable layer between two impermeable layers. In ATES applications, two hydraulically coupled wells are used. One well is used for storage and the other one is used as the source. Waste heat, solar energy, or just ambient heat can be stored in an ATES. Borehole or duct systems consisting of vertical heat exchangers are earth-coupled storage techniques. Examples of such heat exchangers are boreholes in which iron and plastic tubes in clay. The heat transfer uid is circulated through the space heating after passing through a heat pump. A system with many boreholes may be used to support large heat pumps.

The Storage of Hydrogen Energy as a Metal Hydride

The promise of hydrogen as an energy carrier that can provide pollution-free, carbonfree power and fuels for buildings, industry, and transport makes it a potentially critical player in our energy future. The acceleration of hydrogen technology development is appropriate and necessary. Another option is to use materials that absorb hydrogen into their crystal structure (metal hydrides) or incorporate it chemically (chemical hydrides) to hold the fuel until needed. In chemical hydride storage schemes, stable, relatively benign compounds such as boron, sodium, and calcium hydride are processed with water in a catalytic fuel reactor to generate pure hydrogen. An economy based on the extensive use of hydrogen would require the construction of waste facilities for the production, storage, and transportation of this fuel. Hydrogen gas is stored in a tank as a compound with metal alloy particles. The irontitanium alloy, FeTi, acts as a sponge to absorb the hydrogen, thus becoming a metal hydride (FeTiH1.6 ). Its physical appearance is like that of a ne silvery powder. The safest method for hydrogen storage is the metal hydride systems (Veziro lu, 1975; Williamson and g Edeskuty, 1986). When hydrogen combines with the metal alloy (in granular form or particles), an exothermic reaction occurs. The gas is thus stored in these metal particles until some heat is applied to release the hydrogen and build up the pressure in the tanks. This heat is obtained from the engine exhaust, which is ordinarily wasted in a conventional engine. When a metal hydride absorbs hydrogen, heat is given off. A hydride cold-start heater can be developed that instantly heats an automobiles catalytic converter when the car is started to dramatically reduce the overall exhaust pollution up to 80%. This technology can be used for other quick heat applications such as passenger compartment heating on cold winter days. The two low-temperature hydrides, FeTiH2 and LaNi5 H7 , hold hydrogen loosely and evolve it at low temperature. The high-temperature hydrides, MgH and Mg2 NiH4 , only release hydrogen at a high temperature because they have high binding entalpies (Dinga, 1988). The thermal compression of hydrogen using reversible metal hydride alloys offers an economical alternative to traditional mechanical hydrogen compressors. The hydrogen pressure in a metal hydride increases exponentially with increasing temperature. By employing successively higher-pressure hydride alloy stages in a series, high-pressure ratios can be generated. For example, a ve-stage hydride compressor will compress a

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1.43 atm inlet pressure to 346.94 atm, resulting in a compression ratio of 242.6 (Surmen and Demirbas, 2002). The metal hydrides provide a safe method for fuel storage in hydrogen-powered vehicles. Charging and discharging of the hydride tanks is a process that can be repeated an indenite number of times provided that the hydride material does not become contaminated.

Solar Heat Storage Systems

Solar energy is energy from the sun. It is a renewable energy source that can generate electricity, provide hot water, heat and cool a house, and provide lighting for buildings. The sun has produced energy for billions of years. Solar energy is the solar radiation that reaches the earth. There are a variety of different technologies used in order to take advantage of solar energy. Solar hot water heaters use the sun to heat either water or a heat transfer uid in collectors. An active system uses a solar collector that works with a pump, a heat exchanger and a number of large storage tanks. This type provides a highly efcient energy sources for large nonresidential buildings. These different types are (1) photovoltaic systems, (2) concentrated solar systems, (3) passive solar heating, (4) solar hot water, and (5) solar heating and cooling. Solar thermal technologies on the market now are efcient and highly reliable, providing solar energy for a wide range of applicationsfrom domestic hot water and space heating in residential and commercial buildings to swimming pool heating, solar-assisted cooling, industrial process heat, and the desalination of drinking water (Ayhan and Kaygusuz, 1998). Solar energy applications require a large energy storage capacity in order to cover a minimum of 12 days of demand. This is commonly achieved by sensible heat storage in large water tanks. An alternative is offered by latent heat storage systems, in which thermal energy is stored as latent heat in substances undergoing a phase transition, e.g., the heat of fusion in the solidliquid transition (Hamdan and Elwerr, 1996).

Conclusion
Energy storage in PCM has a lot of advantages over sensible systems because of the lower mass and volume of the system and the energy is stored at a relatively constant temperature and energy losses to the surroundings are lower than with conventional systems. Parafn waxes are cheap and have moderate TES density but low thermal conductivity and, hence, require a large surface area. Hydrated salts have a larger energy storage density and a higher thermal conductivity. In response to increasing electrical energy costs and the desire for better lad management, thermal storage technology has recently been developed. The storage of thermal energy in the form of sensible and latent heat has become an important aspect of energy management with the emphasis on efcient use and conservation of the waste heat and solar energy in industry and buildings. Thermal storage has been characterized as a kind of thermal battery.

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