international journal of hydrogen energy 35 (2010) 3817–3831

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Review

Metal hydride based heating and cooling systems: A review

P. Muthukumar*, M. Groll 1
Department of Mechanical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, India

article info abstract

Article history: Dry (solid) sorption systems are attractive competitors to wet (liquid) sorption systems in
Received 6 December 2009 providing useful cold and/or useful heat. Among the dry sorption systems, those based on
Received in revised form the absorption/desorption of hydrogen in/from metal alloys reveal advantageous features,
23 January 2010 and this has stirred up the interest of researchers already since the 1970s. In recent years,
Accepted 26 January 2010 many attempts have been made to develop metal hydride based heating and cooling
Available online 25 February 2010 systems. Of special interest was and is the possibility to utilize low temperature heat
(waste heat, solar heat) to drive those systems. Major applications are seen in air-
Keywords: conditioning and heat supply for buildings and in air-conditioning of automobiles. In
MHHP this paper, the research and development work on metal hydride based heating and
Cascading systems cooling systems is reviewed which has been published in the last three decades. Emphasis
Multi-staging is given primarily to cooling/air-conditioning. The objectives are to provide the funda-
Compressor driven systems mental understanding of metal hydride based heating and cooling systems and to give
useful guidelines regarding various design parameters. The operation principles of various
types of systems are explained and the importance of the metal hydride reaction bed heat
and mass transfer characteristics is stressed. Possible ways for improving the coefficient of
performance and specific cooling capacity are discussed. Besides a brief characterization of
many experimental and theoretical investigations, the worldwide status of the develop-
ment of metal hydride based heating and cooling systems is summarized in a tabular form.
ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1. Introduction working fluids and systems. Though not yet commercialized,

Thanks to rapid technological growth, the demand for cooling
and heating, more so the former in tropical countries, is rising
fast. Keeping in pace, the refrigeration technology has also
grown, mainly in the areas of improvement of energy effi-
ciency, waste heat utilization, and environment-friendly
metal hydride heating and cooling systems have also gained
importance and have potential for practical applications in
some niche areas.
Metal hydride heating and cooling systems operate similar
to conventional solid sorption systems, employing e.g. acti-
vated carbon/ammonia, silica gel/water, etc. as working pairs,

Abbreviations: BC, Bottom cycle; CD-MHHCS, Compressor driven metal hydride cooling system; CFC, Chlorofluorocarbon; COA,
Coefficient of amplification; COP, Coefficient of performance; CTBR, Capillary tube bundle reactor; DE, Double effect; DS, Double stage;
MFTR, Metal foam tube reactor; MHHCS, Metal hydride heating and cooling system; PMC, Porous metal hydride compacts; SCP, Specific
cooling power; SE, Single effect; SS, Single stage; TC, Topping cycle; U, Overall heat transfer coefficient; VRC, Vapour compression
system.
* Corresponding author. Fax: þ91 361 2690762.
E-mail addresses: pmkumar@iitg.ernet.in, pmuthukkumar@yahoo.com (P. Muthukumar).
1
Present address: Institut für Kernenergetik und Energiesysteme (IKE), University of Stuttgart, Germany.
0360-3199/$ – see front matter ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.01.115
3818 international journal of hydrogen energy 35 (2010) 3817–3831

the major difference being that hydrogen in a metal hydride/

a
hydrogen system is a non-condensable working fluid unlike
Qd (Td) Qm1 (Tm)
ammonia and water in the conventional systems. Therefore,
two reactors with metal hydrides of different characteristics A1 H2 B1
are needed, replacing the condenser/evaporator and gener- Qm2 (Tm) Qc (Tc)
ator/absorber of the conventional solid sorption system, as
described in Section 2. As illustrated there, the thermody- 1st half cycle
namic cycle of metal hydride heat pumps and refrigerators/ 2nd half cycle
air-conditioners is identical, as is the case for all respective Qm2 (Tm) Qc (Tc)
thermally or mechanically driven devices. Only the relation of
the low and medium temperature levels with respect to the
A2 H2 B2
ambient differs. Therefore, in the following, for heating Qd (Td) Qm1 (Tm)
systems (heat pumps) and cooling systems (refrigerators/air-
conditioners), the same abbreviation MHHCS (metal hydride b Qd
Qm1
based heating and cooling system) has been chosen.
P2
In this paper, research articles on theoretical and experi-
mental investigation of MHHCS are reviewed, and major B
results are summarized in a tabular form. Thereby various

ln P
aspects of the design and operation of these systems are dis- A Qm2
cussed, such as (i) selection of alloy pairs, (ii) heat and mass Qc
transfer aspects in the reaction bed, (iii) heat and mass P1

recovery, (iv) multi staging and thermal wave concept, (v)

compressor driven MHHCS (CD-MHHCS), and (vi) the devel-
opmental status.
2. Operating principle
In the literature, the following nomenclature has been widely
accepted. Single stage systems are those which operate
between two pressure levels. Double stage systems have two
pressure stages, respectively three pressure levels. The
distinction according to effects has been derived from cooling
systems. It means that in a single effect system, in one cycle
there is once cold generation, i.e. one cooling effect. In
a double effect system, there are respectively two cooling
effects, etc [1].
2.1. Single stage single effect system
Fig. 1 a and b shows the operating principle of a single stage
single effect metal hydride heat pump and its basic thermo-
dynamic cycle on the van’t Hoff plot, respectively. It
comprises two pairs of reactors, one with high temperature
hydride (A) and the other with low temperature hydride (B).
The device operates periodically with two half cycles. It can
operate with one pair of reactors only. Two pairs of reactors
are chosen, in order to have a quasi–continuous cold output,
i.e. cold generation (at Tc), in each half cycle. For heat pump
operation, useful heat (at Tm) is generated in each half cycle,
also in case of only one pair of reactors. During the first half
cycle, hydride A1 desorbs hydrogen at high pressure P2 by
taking up driving heat Qd at Td. The coupled hydride B1 absorbs
hydrogen from reactor A1 and the heat of absorption Qm1 is
released to the sink at Tm. Simultaneously, hydride B2 desorbs
hydrogen at low pressure P1 by taking up the useful cold Qc at
Tc. The desorbed hydrogen is absorbed by hydride A2,
releasing the absorption heat Qm2 at Tm. Then the reactors A1
and B1 are sensibly cooled down to Tm and Tc, respectively,
while the reactors A2 and B2 are sensibly heated up to Td and
Td Tm Tc 1/T
Fig. 1 – (a) Schematic of single stage, single effect MHHCS
operating with two pairs of reactors (A1,B1 and A2, B2).
(b) Thermodynamic cycle of a single stage, single effect
MHHCS on van’t Hoff plot.
Tm, respectively. Thus, the system completes its first half cycle
of operation. During the second half cycle, driving heat Qd at
Td is supplied to reactor A2 causing hydrogen to desorb at high
pressure P2, which is absorbed by reactor B2, releasing heat
Qm1 at Tm. Simultaneously, hydride B1 desorbs hydrogen at
low pressure P1 by taking up useful cold Qc at Tc, which is
absorbed by A1 releasing heat Qm2 at Tm. After sensible cooling
down of reactors A2 and B2 to Tm and Tc, respectively, and
heating up of reactors A1 and B1 to Td and Tm, respectively, the
system is ready for the next half cycle.
For a heat pump, the performance figure is called Coeffi-
cient of Amplification (COA), often also Coefficient of Perfor-
mance for Heating (COPh). For a refrigerator, the respective
performance figure is called Coefficient of Performance (COP
or COPc). In case of a single stage single effect system, these
coefficients are defined as (without consideration of sensible
heat losses):
Qm1 þ Qm2 Qc
COA ¼ ; COP ¼ (1)
Qd Qd
In terms of hydride properties, these coefficients can also be
written as:
DHA;a þ DHB;a DHB;d
COA ¼ ; COP ¼ (2)
DHA;d DHA;d
where, DH is the enthalpy of formation of the hydrides. The
subscripts A and B represent high and low temperature
hydride alloys, a and d represent absorption and desorption,
 international journal of hydrogen energy 35 (2010) 3817–3831 3819

respectively. The sensible heating and cooling of the thermal

a Qd Qm1
masses (hydrides and reaction beds) significantly reduces the 1st half cycle
performance of the system. The negative effect can be mini-
2nd half cycle
mized by internal heat recovery (see Section 5.2). The required A1
hardware comprises, besides four reactors, two hydrogen
valves, three or four fluid pumps, three or four thermal H2 H2
Qm3 Qm2
reservoirs/heat exchangers, and 16 fluid valves. Cooling C1 B1
Qc2 Qc1
temperatures from about 10  C down to about 50  C can be
obtained with single stage systems. H2 H2

2.2. Double stage double effect system Qc1 B2 C2 Qc2

Qm2 Qm3
H2
H2
Fig. 2a and b illustrates the schematic of a double stage double
effect MHHCS and its basic thermodynamic cycle on the van’t A2
Hoff plot, respectively. The unit comprises three different
metal hydrides (A, B and C), in two reactors each; they are
usually connected in a ‘‘star’’ scheme. This connection Qm1 Qd

scheme for reaction beds in double stage systems has been

first proposed by Suda [2]. Each hydride (reactor) is connected b Qd Qm3
on the hydrogen side with the other two hydrides (reactors). P3
The star scheme operates in two half cycles and allows quasi-
continuous heat and cold generation. In the first half cycle, C

hydride A1 desorbs hydrogen by taking up heat Qd at Td. It is
coupled with hydride C1 where the absorption heat Qm3 is
released at Tm. Hydride B2 desorbs hydride by taking up heat
Qc1 (useful cold) at temperature Tc. It is coupled with hydride
A2 where the absorption heat Qm1 is released at Tm. Simulta-
neously, hydride C2 desorbs hydrogen by absorbing heat
(useful cold) Qc2 at Tc. It is coupled with hydride B1 where the
absorption heat Qm2 is released at Tm.
After the first half cycle, there is an internal heat recovery
which takes place at closed hydrogen valves between the
reactors A1 and A2, between B1 and B2 and between C1 and C2.
At the end of this internal heat recovery (and additional
sensible heating or cooling of the respective reactors,
depending on the degree of internal heat recovery), the
starting temperatures for the second half cycle are: A1 at Tm,
A2 at Td; C1 at Tc, C2 at Tm; B2 at Tm, B1 at Tc. Then, the hydrogen
and fluid valves are switched on again and the second half
cycle with the following processes start: A2 desorbs by taking
up Qd at Td and C2 absorbs by releasing Qm3 at Tm; B1 desorbs
by taking up Qc1 at Tc and A1 absorbs by releasing Qm1 at Tm; C1
desorbs by taking up Qc2 at Tc and B2 absorbs by releasing Qm2
at Tm. It may become necessary to use four instead of three
temperature levels (i.e. Tm1 and Tm2 instead of Tm) to achieve
similar reaction kinetics in each reaction bed.
The COPs and COAs of the double stage double effect
system are
Qm1 þ Qm2 þ Qm3 Qc1 þ Qc2
COA ¼ ; COP ¼ (3)
Qd Qd
and in terms of hydride properties;
DHA;a þ DHB;a þ DHC;a DHB;d þ DHC;d
COA ¼ ; COP ¼ : (4)
DHA;d DHA;d
The design of the double stage double effect system requires
more hardware (besides six reactors, six hydrogen valves,
three or four fluid pumps, three or four heat reservoirs/heat
exchangers, and 24 fluid valves) when compared to a single
stage single effect system. Cooling temperatures similar to
ln P
Qc2
P2
Qm2
A
A
B
B
Qc1
P1
Qm1
Td Tm Tc 1/T
Fig. 2 – (a) Operation of double stage/double effect MHHCS.
(b) Thermodynamic cycle of a double stage, double effect
MHHCS on van’t Hoff plot.
those of a single stage single effect system can be obtained, i.e.
down to 50  C, but with significantly higher COP and specific
cooling power (SCP).
3. Selection of alloys
The performance of the MHHCS largely depends on the
properties of the metal hydrides selected. MHHCS should have
high COPs and high specific power outputs, in case of
refrigerator/air-conditioner, specific cooling power (SCP).
They should be compact in design, i.e. low mass and/or low
volume, have a long life and low performance degradation,
and they should be economic. Therefore, metal hydrides used
for MHHCS should respectively have suitable properties, e.g.
high enthalpy of formation, low specific heat, and high
hydrogen absorption capacity, high thermal conductivity and
fast reaction kinetics, favourable equilibrium pressures, low
hysteresis, flat plateau, simple activation process, minimum
degradation after cyclic operation, low cost, etc. There is
a plethora of metal hydrides which are potentially suitable
[1–5]. For MHHCS, usually intermetallic compounds of the
 3820
Table 1 – Status of metal hydride based heating and cooling pump systems: Experimental studies.
Ref. no Institute, Place Alloys used Type Mass (kg) Capacity COP/ SCPC SCPT Year
(high/low temperatures alloys) (kW) COA* W/kg W/kg

[12] Argonne National LaNi4.7Al0.3/MmNi4.15Fe0.85 R – 15 – – 1978

Lab., USA
[13] Solar Turbines LaNi5/MmNi4.15Fe0.85 R – 3.5 – – 1982
Int., USA
[14] Israel Inst. LaNi4.7Al0.3/MmNi4.15Fe0.85 R (PMH) – w1.0 – 900 (2 min) 240 (6 min) 1984
Tech., Technion, Israel

international journal of hydrogen energy 35 (2010) 3817–3831

[16] Kogakuin University, Japan LaNi4.65Al0.3/MmNi4Fe R 40 1.7 0.4 – 64 1984
[18] Ergenics Inc. USA LaNi4.5Al0.5 /(CFM)Ni5 R 32.4 2.3 0.33 – 142 1989
[19] KAIST, South Korea Zr0.9Ti0.1Cr0.9Fe1.1/Zr0.9Ti0.1Cr0.6Fe1.4 R 63 0.683 – – 272 1993
[20] Sanyo Electric LaNi4.6Mn0.3Al0.3/La0.6Y0.4Ni4.8Mn0.2 R 90 1.86 0.45 80 40 1995
Co. Ltd. Osaka, Japan
[21] SRISIA, Moscow, Russia LaNi4.6Al0.4/MmNi4.85Fe0.15 R 6 0.2 0.2 – 133 1996
[22] AEC Lab. Korea LaNi4.7Al0.3/MmNi4.15Fe0.85 R 10.2 – 0.2 – 1996
[23] IIT Madras, India ZrMnFe/MmNi4.5Al0.5 R 1.5 – 0.35 45 1999
[40] TED Inc., LaNi5 C (PMH) – – – 1500 (130 s) – 1997
New Mexico, USA
[41] TED Inc., Ca0.4Mm0.6Ni5 C (PMH) – – – 2200 (150 s) – 1998
New Mexico, USA
[35] IKE, University of HT: LaNi4.3Al0.4Mn0.3; LaNi4.4Al0.34Mn0.26; HP* 31 0.75 1.3* 1999
Stuttgart, Germany LaNi4.5Al0.29Mn0.21;LaNi4.7Sn0.3; R (MHTW) 0.36 0.6 20 10
LaNi4.75Al0.25; LaNi4.85Al0.15; LaNi5
LT: La0.555Co0.03Pr0.12Nd0.295Ni5;
Ti0.99Zr0.01V0.43Fe0.09Cr0.05Mn1.5
[42] KAIST, South Korea Zr0.9Ti0.1Cr0.55Fe1.45 C 8.4 0.29 – 291 2001
– (208 s)
[43] KAIST, South Korea Zr0.9Ti0.1Cr0.55Fe1.45 C 7 0.41 1.8 410 2002
(360 s)
[24] SRISIA, Moscow, Russia LaNi4.6Al0.4/MmNi4.15Fe0.85 R 3 0.15 0.33 – 100 2002
[39,40] IKE, University of LmNi4.91Sn0.15/LaNi4.4Al0.52Mn0.38/ HP* 45 1.63 0.86* 2002
Stuttgart, Germany Ti0.99Zr0.01V0.43Fe0.09Cr0.05Mn1.5 R (DS) 0.97 0.51 152 (15.5 min) 42 (56 min)
[46] HERA USA Inc., Ringwood, NJ Mm based alloys C 7 2 2.5 570 (1.5 min) 2006
[25] IRCE, Shanghai LaNi4.61Mn0.26Al0.13/La0.6Y0.4Ni4.8Mn0.2 R 11 0.085 0.26 15.3 2007
Jiaotong University, China
[26] Asian Design LaNi4.61Mn0.26Al0.13/La0.6Y0.4Ni4.8Mn0.2 R 11 0.24 0.3 18 2007
Center, Air Conditioning,
Shanghai, China
[27] IKE, University of LmNi4.91Sn0.15/ R (CTBR) 0.9 0.7 0.25 850 (95 s) 425 (190 s) 2009
Stuttgart, Germany Ti0.99Zr0.01V0.43Fe0.09Cr0.05Mn1.5

AEC, Air Conditioning & Environmental Control Lab, KIST, Seoul, Korea; C, compressor driven system; COP, coefficient of performance for cooling ; COA, coefficient of performance for heating; CTBR,
capillary tube bundle reactor; DS, double stage; HP, heat pump; IKE, Institute of Nuclear Technology and Energy Systems, University of Stuttgart, Germany; IRCE, Institute of Refrigeration and
Cryogenics Engineering, Shanghai Jiaotong University, PR China; KAIST, Korea Advanced Institute of Science and Technology, Daejeon, South Korea; MHTC, multi-hydride thermal wave; PMH, porous
metal hydride compact; SCPC, specific cooling power (W/kg of desorbing hydride, obtained during desorption period); SCPT, specific cooling power (W/kg of desorbing hydride, obtained during the
complete cycle); SRISIA, State Research Institute of Scientific and Industrial Association, Moscow, Russia; R, refrigeration; TED Inc., Thermal Electric Devices, Inc., Albuquerque, New Mexico, USA.
 international journal of hydrogen energy 35 (2010) 3817–3831
type AxBy (A ¼ hydride forming element, B ¼ not or hardly
hydride forming element) are employed. For high temperature
applications, the elemental hydride MgH2 (usually Ni doped) is
a good candidate. The AxBy alloys can be modified at will by
changing the alloy composition. Thereby metal hydrides with
tailor-made properties can be formed. Plenty of such alloys
have been synthesized, characterized and are recommended
for use in MHHCS, as indicated in Table 1.
4. Heat and mass transfer aspects
The absorption and desorption of hydrogen in metal hydrides
are exothermic/endothermic processes, i.e. associated with
release of heat from the reaction bed or uptake of heat into the
reaction bed. The operation of metal hydride based heating
and cooling systems is essentially determined by these heat
and mass transfer processes. Some key issues related to
reaction bed heat and mass transfer aspects are addressed in
the following sections.
4.1. General considerations
To effectively accommodate the heat transfer and also the
mass (hydrogen) transfer to/from and inside the hydride bed,
fast technical reaction kinetics is desired. Usually the intrinsic
reaction kinetics of metal hydrides is rather fast (an exception
is MgH2 at relatively low temperatures  300  C). Fast technical
reaction kinetics will avoid a limitation of the absorption/
desorption processes due to insufficient heat and mass
transfer which, in the case of absorption, would result in
heating up the reaction bed above equilibrium pressure or, in
the case of desorption, would result in reducing the pressure
in the reaction bed below the equilibrium pressure and thus
causing the reactions to come to a standstill. There are various
technical solutions for these problems. Usually hydrogen
supply to the reaction bed is made via a porous tube (typical
porosity of 1–5 mm) which extends all along the reaction bed
and guarantees that the applied pressure is instantaneously
available along the bed. Hydrogen has then to diffuse in
perpendicular direction only through a relatively small
hydride bed thickness. The thermal conductivity of metal
hydride powder beds (typical grain sizes are of the order of
1 mm after sufficient cycling) is usually small (order of 1 W/m K
or less). Therefore, the bed thermal conductivity is usually
enhanced, e.g. by introducing thermally well conducting
matrices, like highly porous Al foam or other Al or Cu struc-
tures [6–8]. An efficient technique is the mixing of hydride
powder with Al powder or graphite (e.g. expanded graphite)
with subsequent cold or hot pressing processes [9–11]. Ron
et al. [9] have developed porous metal hydride compacts (PMC)
by isostatic hot pressing of mixtures of metal hydride and
aluminum powders. They obtained an effective thermal
conductivity ke of about 23 W/m K. However, these highly
compacted pellets have a low diffusivity (about 1011 cm2). So,
one has to observe the mass transfer limitation. Groll and his
co-workers [10,11] observed that expanded natural graphite/
metal hydride compacts had a significantly improved effective
thermal conductivity ke up to over 10 W/m K, compared to
3821
their previously reported data with Al-foams as heat transfer
matrices (ke ¼ 7 to 8 W/m K) [6–8].
In the frame of development of a two-stage metal hydride
heat transformer, reaction beds with different heat conduc-
tion matrices to enhance the thermal conductance of the
reaction bed have been investigated by Groll and his co-
workers [1,7]. The reaction beds had diameters of 28–30 mm,
lengths of about 495 mm, and they were provided with
a central porous tube (6 m OD) for efficient hydrogen supply.
They were surrounded by a narrow gap annular heat
exchanger. Fig. 3a–d shows the employed heat conduction
matrices [7]: (a) porous Al-foam (porosity 90%, pore size 2 mm,
pressed into the reaction bed tube), (b) corrugated helical Cu-
band (0.2 mm thick, brazed to the tube wall), (c) perforated Al-
band (0.1 mm thick, slightly pressed into the tube), (d) upper
and lower tray of a Cu – cassette (0.2 mm wall thickness, 4 mm
cassette height, pressed into the tube). For comparison,
a reaction bed without heat conduction matrix was also
tested. The filling ratio of the metal hydride powder was about
50% of the open reaction bed volume. Desorption tests were
carried out by coupling two reaction beds filled with different
hydrides. The reaction beds at high equilibrium pressure
(about 16 bar) were filled with LmNi4.85Sn0.15 and heated with
water (inlet temperature of 70  C), the reaction beds at low
equilibrium pressure (about 0.5 bar) were filled with
LmNi4.49Co0.1Mn0.205Al0.205 and cooled with water (inlet
temperature of 20  C; the volume flow rate of 50 l/h). It was
shown that from the start of desorption, the cassette matrix
has the fastest reaction kinetics, followed by the other
matrices. The bed without matrix (‘‘tube’’) has a substantially
slower kinetics. The desorption reaction was completed
(hydrogen flow rate approaches zero) after about 5 min for the
cassette matrix, after about 6 min for the Cu-band matrix,
after about 7 min for the Al-foam matrix and for the Al-band
matrix. The time for complete desorption of the pure
powder bed was far beyond 20 min.
4.2. Reaction bed overall heat transfer
As already mentioned, the unrestricted flow of hydrogen
throughout the reaction bed and a high effective conduc-
tance of the reaction heat into and out of the reaction bed are
of utmost importance. Effective thermal conductivities of the
reaction bed of 10–20 W/m K can be obtained by various
techniques. However, it is the overall heat transfer coeffi-
cient (Utot), comprising external heat transfer to/from the
reaction bed (hext), conductance through the bed wall (kw),
contact conductance of the hydride to the bed wall (hint) and
effective thermal conductance of the bed (ke), which is
decisive [1,7].
Fig. 4a and b illustrates this interaction of various effects.
Internal wall heat transfer coefficients of hint up to 1000 W/
m2 K are possible, but not easy to achieve. External heat
transfer coefficients can be very high, if heat transfer
employs turbulent liquid flow; hext values of 2000–6000 W/
m2 K are possible. If a gas is used for external heat transfer,
this heat transfer (hext values of the order of 100–500 W/m2 K)
can become the critical point. Fig. 4a shows the influence of
the overall heat transfer coefficient on the reaction times for
absorption of 90%, 70% and 50% of the stoichiometric value,
3822 international journal of hydrogen energy 35 (2010) 3817–3831
Fig. 3 – Different heat transfer enhancement matrices [7]: (a) aluminum foam; (b) corrugated copper band; (c) perforated
aluminum band; (d) copper cassette.
calculated for a cylindrical reaction bed of 22 mm ID with two
hydrogen supply arteries on opposite ends of the tube
diameter, filled with LmNi5 in a 94% porous Al foam matrix
(effective thermal conductivity ke of 7.5 W/m K) [7]. It was
observed from Fig. 4b that an increase of Utot significantly
reduces the reaction times, e.g. by about a factor of 2 for
increasing Utot from 320 to 740 W/m2 K. Since the external
heat transfer coefficient hext is assumed to be rather high
(order of 5000 W/m2 K) in the discussed example, hint would
have to be increased well beyond 1000 W/m2 K to obtain Utot
values of over 700 W/m2 K. Fig. 4b shows the influence of hext,
hint and ke on Utot for a cylindrical reaction bed with 26 mm ID
and one central porous filter tube with 6 mm OD. It demon-
strates that very high ke are only desirable, if the other heat
transfer data are fitting. In case of liquid convective cooling,
hext can be made very high, and should be as high as possible,
as well as hint. In such cases, ke values of up to 20 W/m K or
even more can be desirable. This is no longer true, if hext
becomes relatively small, e.g. less than 1000–2000 W/m2 K,
and hint is limited to values well below 1000 W/m2 K. Then it
makes no sense to push ke beyond 10 W/m K. In case of gas
convection cooling (hext of the order of 250 W/m2 K), both hint
and ke are of minor importance. It may not pay off to increase
hint well beyond 1000 W/m2 K, and ke beyond 5 W/m K.
Fast technical reaction kinetics allows the design of fast
reactors with short cycle times for absorption/desorption of
hydrogen. This increases the specific power output (in case of
cooling, the specific cooling power, SCP), i.e. for a given small
hydride inventory a large cooling power can be obtained and
thus cost can be kept low.
5. Experimental and theoretical
investigations on metal hydride based heating
and cooling systems
A lot of experimental and theoretical works on the issue of
heat and mass transfer has been carried out over the years.
Besides extensive experimentation, detailed mathematical
modeling of the complex heat and mass transfer phenomena
in the reaction beds was performed. This comprises steady
state and transient analyses and the behaviour of coupled
 international journal of hydrogen energy 35 (2010) 3817–3831
Fig. 4 – (a) Influence of overall heat transfer coefficient on reaction time for hydrogen absorption [7]. (b) Influences of hext, hint
and ke on overall heat transfer coefficient.
reaction beds, as they are always present in MHHCS. In the
following sections, an overview is given on the investigations
of single stage single effect systems and also of the more
complex advanced systems, like thermal wave concept, multi
stage systems, cascading systems, and compressor driven
systems.
5.1. Single stage single effect systems
5.1.1. Experimental observations
In the late 1980s, Gruen et al. [12,13] initiated the development
of a chemical heat pump driven by solar or other low grade
heat sources at Argonne National Laboratory using LaNi4.7Al0.3
and MmNi4.15Fe0.85. The operating temperatures were 120  C
for input, 29–50  C for heat rejection, and 0–20  C for refriger-
ation with a cooling capacity of 15 kW. The heat pump reactor
was designed similar to a shell and tube heat exchanger with
3823
water flowing outside the tube bundle. Later, a similar kind of
metal hydride heat pump was developed by Solar Turbines
Inc. Research Laboratory in 1982 to provide a refrigeration
capacity of 3.5 kW with the operating temperatures of 93  C/
29  C/4.4–10  C (Th/Tm/Tc) using LaNi5/MmNi4.15Fe0.85.
A bus air-conditioning system with approximately 1 kW
cooling capacity was developed at Technion, Israel Institute of
Technology [14] using LaNi4.7Al0.3 and MmNi4.15Fe0.85 PMC,
both with 18% of Al. It was designed to run on waste heat
recovered from exhaust gases of a diesel engine. The cold
reactor was kept within the space to be air conditioned. For
a cooling time of 3 min, the SCP was between 565 and 700 W/
kg of desorbing hydride, and for 2 min cooling time, the SCP
increased to 680–900 W/kg of desorbing hydride. However,
upon cyclic operation, the rate of desorption from LaNi4.7Al0.3
into MmNi4.15Fe0.85 was reduced and a SCP of 200–240 W/kg of
desorbing hydride was observed (for complete cycle of 6 min
3824 international journal of hydrogen energy 35 (2010) 3817–3831
duration). Compared to conventional mechanical vapour
compression systems, this heat pump reduced the fuel
consumption of the bus by up to 30%.
Suda and his co-workers [15–17] developed a metal hydride
refrigeration system of 1.75 kW capacity using LaNi4.65Al0.3/
MmNi4Fe hydride pair. The four heat exchangers (reactors)
consisted of 18 reaction beds (25 mm dia and 360 mm length,
provided with aluminium foam of 92% porosity for heat
transfer enhancement) and each filled with 0.55 kg of
hydriding alloy. A total mass of about 10 kg hydride was in
each heat exchanger. Hydrogen was uniformly distributed
through a porous filter tube located at the centre of each
reaction bed. The system was tested at different heat source
temperatures from 110 to 150  C. The maximum reported COP
at 140  C was 0.4. The optimum cycle time of the system was
found to be 13 min. Later, they presented the dynamic
behaviour of MHHCS on van’t Hoff and PC plots [17].
Ergenics Inc. [18] fabricated and tested a waste heat driven
metal hydride air conditioner of 2.3 kW capacity for cooling
army shelters. The two hydride reactors were charged with
LaNi4.5Al0.5 as high temperature alloy and (CFM)Ni5 as low
temperature alloy, 16.2 kg each. The actual electrical power
consumption of the prototype was 1500 W, which was half of
the power consumption of a standard VCR unit of 2950 W.
Later, based on the test results of the prototype, a compre-
hensive design of a metal hydride air - conditioner was carried
out. In this system, the hydride reactors were alternately
heated/cooled by exhaust gas/ambient air. The metal hydride
heat exchanger matrices were compact coils of tubing con-
taining about 32.4 kg of metal hydrides for a cooling capacity
of 2.3 kW with a total weight of 75 kg and required only 387 W
of electrical power to run the system. The design was 17%
lighter and used only 13% of the power consumption of
a standard VCR unit.
Lee et al. [19] investigated the performance of an MHHCS
prototype using 2  14 Zr0.9Ti0.1Cr0.9Fe1.1  Zr0.9Ti0.1Cr0.6Fe1.4
cylindrical reaction beds (210 mm length and 19.1 mm inner
dia each), with total hydride with masses of 2 kg and 2.5 kg,
respectively. Internal aluminum fins of 2 mm thickness
were employed for improving the heat transfer character-
istics of the beds. Hydrogen was supplied at the centre
through a 5 mm dia 300 mesh size filter tube. The maximum
SCP obtained under the optimum operating conditions of
200  C/30  C/18  C was about 272 W/kg of desorbing hydri-
de(for total cycle time).
Imoto et al. [20] built a refrigeration system to generate cold
below 20  C using LaNi4.6Mn0.3Al0.3/La0.6Y0.4Ni4.8Mn0.2 pair
of total mass 90 kg. A heat source temperature range of 130 to
150 C was obtained from a solar collector. Cylindrical reactors
with internal aluminum fins were employed. The maximum
values of COP and cooling power of the system were 0.45 for
a cycle time of 25 min and 1.86 kW for a cycle time of 15 min.
The system was able to attain temperatures below 20  C with
a refrigeration capacity range of 900–1000 W and COP of 0.28 at
980 W. A maximum SCP of about 40 W/kg of desorbing alloy
for the whole cycle (corresponding to a cooling time of 7 min)
was reported.
Izhvanov et al. [21] developed a small capacity metal
hydride heat pump with heating and cooling capacity of 150
and 200 W using LaNi4.6Al0.4/MmNi4.85Fe0.15 alloy pair. They
employed two pairs of cylindrical reactors (32 mm dia and
560 mm length), each filled with 1.5 kg of respective hydride.
Corrugated Al foils were employed for heat transfer
enhancement. The estimated COP of the system varied from
0.17 to 0.2 at operating temperatures of 158  C/30  C/0  C. Kang
et al. [22] developed an MHHCS using LaNi4.7Al0.3 (mass of
4.5 kg)/MmNi4.15Fe0.85 (mass of 5.7 kg) hydride pair. Cylindrical
reactors made of Cu with 100 mm dia and 200 mm length were
employed. Internal Al fins were used for heat transfer
enhancement. The measured COP was about 0.2.
Ram Gopal and Srinivasa Murthy [23] carried out an exper-
imental study on MHHCS with the working pair ZrMnFe–
MmNi4.5Al0.5. They employed cylindrical reactors (OD 50 mm,
length 250 mm) made of Cu, into which a thick walled ceramic
filter tube was inserted (OD 40 mm). The metal hydride was
filled in the annular gap between Cu and filter tube, thus
forming a thin bed of 5 mm thickness. External heat transfer
was accomplished by a copper coil which was wrapped around
the reaction bed. Depending upon the operating conditions
(Td ¼ 110–130  C, Tm ¼ 25–35  C, Tc ¼10–20  C), the SCP was
between 30 and 45 W/kg of desorbing alloy for the whole cycle,
and the COP varied between 0.2 and 0.35. They also developed
a mathematical model for their experimental system [29]. The
numerical results showed reasonable agreement with the
experimental data. However, their model is suitable mainly for
thin beds and reactors of low thermal mass.
Chernikov et al. [24] demonstrated an MHHCS using
LaNi4.6Al0.4/MmNi4.15Fe0.85 alloy pair. They employed two
cylindrical reactors with a total of 3 kg (1.5 kg in each reactor)
alloy inventory. The reported average cold generation rate
was about 100 W/kg of desorbing alloy for the whole cycle at
operating conditions of 130/25/1.5  C with a COP of 0.33.
Qin et al. [25] developed an MHHCS with LaNi4.61
Mn0.26Al0.13/La0.6Y0.4Ni4.8Mn0.2 hydride pair using exhaust gas
from an automobile as a heating source. Two pairs of stainless
steel reactors (75 mm OD and length 500 mm) with alloy
masses of 2.75 kg each (filling density 3.38 kg/m3, effective
hydride bed thickness about 15 mm) were employed. A
stainless steel hollow sintered porous filter (porosity 2 mm) of
50 mm OD was fixed inside the reactor. Measured effective
thermal conductivities of the reactors (with copper matrices)
were in the range of 1.2–1.7 W/m K. Experiments were con-
ducted for a wide operating temperature range, viz. 120–
200  C/20–50  C/10 to 0  C. Heating oil and water were used
as high and low temperature heat transfer fluids. A maximum
cooling power of 639 W was achieved at the beginning of the
refrigeration period, while the average cooling power over the
refrigeration period was 238 W. The average cooling power of
the whole cycle was 85 W, and the system COP was calculated
as 0.26. Both the COP and cooling power increased with
heating temperature from 0.12 and 61 W at 115  C to 0.26 and
238 W at 150  C. According to the repeated tests, the operation
time was set as 800 s for preheating, 850 s for regeneration,
650 s for pre-cooling and 1300 s for refrigeration. They have
not employed any internal heat recovery.
Ni and Liu [26] tested an MHHCS working with a LaNi4.61
Mn0.26Al0.13/La0.6Y0.4Ni4.8Mn0.2 hydride pair. They employed
two pairs of stainless steel cylindrical reactors of 50 mm OD
and 500 mm length. Each reactor was filled with 2.75 kg alloy
(3 mm grain size). A large deviation between the static van’t
 international journal of hydrogen energy 35 (2010) 3817–3831
Hoff plots and the actual dynamic (ln P–1000/T ) curves was
observed. The reported lowest refrigeration temperature was
about 2  C at 150  C heating temperature. For the given oper-
ating temperatures of 150  C/30  C/20  C, the maximum COP
was 0.3 and cooling rate was 240 W. The COP and cooling rates
decreased from 0.3 to 0.22 and from 240 W to 185 W when the
heat source temperature decreased from 150 to 110  C.
Recently, Linder and Laurien [27] developed an MHHCS
system with LmNi4.91Sn0.15/Ti0.99Zr0.01V0.43Fe0.09Cr0.05Mn1.5
using two capillary tube bundle reactors (CTBR). These reactors
are designed similar to the ones described in Section 5.3.1 [33].
They observed fast reaction kinetics of about 95 s for desorp-
tion and 80 s for absorption. At the operating conditions of
130  C/35  C/15  C, the reported SCP was about 850 W/kg for
95 s cooling time (i.e. about 425 W/kg for the whole cycle).
5.1.2. Performance predictions
Transient hydrogen transport and heat transfer between the
paired reactors of MHHCS were studied by various researchers
[22,28–31]. Choi and Mills [28] presented a thermodynamic
analysis of metal hydride heat pumps for upgrading space-
craft waste heat. This model was used to select proper pairs of
metal hydrides. A transient coupled heat and mass transfer
analysis was also carried out for studying the dynamic
response of the system which employed Mg2.4Ni/LaNi4.9Al0.1.
The predicted cycle time was in the range of 10–12 min.
Ram Gopal and Srinivasa Murthy [29] predicted the
performance of an MHHCS working with ZrMnFe–
MmNi4.5Al0.5 for various operating conditions employing
a one-dimensional mathematical model in cylindrical co-
ordinates. They observed that there exists an optimum
value of bed thickness, effective bed thermal conductivity and
overall heat transfer coefficient for any given operating
temperatures.
Recently, Satheesh et al. [30,31] presented a numerical
investigation of an MHHCS working with a MmNi4.6Al0.4/
MmNi4.6Fe0.4 hydride pair. A cylindrical reactor of 27 mm ID
and 450 mm length was considered in the analysis. Their
computational results were in good agreement with the
experimental data reported by Ni and Liu [26]. The effects of
various operating parameters, such as temperatures of the
driving heat source and heat sink and the refrigeration
temperatures on the COP and SCP were investigated for both
constant reaction bed wall temperature and variable reaction
bed wall temperature convective boundary conditions. At
given operating temperatures of 373/298/288 K (TH/TM/TC), the
COP and SCP (for the cooling cycle) of a single-stage single-
effect metal hydride cooling system for constant wall
temperature boundary condition were found to be 0.62 and
96.2 W/kg, respectively, for 10 min cooling time (total cycle
time of 20 min). The computations reveal that the difference
in cycle times for the constant and variable wall temperature
boundary conditions was approximately 5 min. They also
observed a large deviation between the actual dynamic and
the static van’t Hoff plots [30].
5.2. Heat and mass recovery
The conventional wet vapour absorption systems (LiBr–H2O)
always have a solution heat exchanger to recover heat from
3825
the hot strong solution to the cold weak solution. The same
procedure can be applied in an MHHCS, through a more
complex technique, since the absorbents (the reactors) are
solid materials, which are sensibly cooled down/heated up.
Usually excess heat is recovered by transferring the heat from
the hot high temperature reactor after its desorption process
to warm up the high temperature reactor, which has just
finished its absorption process at a medium temperature
level. In addition to heat recovery, there is also the possibility
of mass recovery, i.e. making use of the heat of absorption/
desorption.
Kevin et al. [32] have carried out an extensive thermody-
namic study on the internal heat recovery by way of both
recovery of mass and direct recovery of sensible heat. They
found that by recovering first of mass and then of heat, the
COP could be increased by about 10–15%. The effect of heat
recovery was found to be much higher than that of mass
recovery. The heat recovery process can be made more effi-
cient by the so-called thermal wave scheme, which has been
adopted by Willers et al. [34,35] for metal hydride based
devices (see Section 5.3).
5.3. Advanced systems
As mentioned in Section 3, the inter-metallic compounds
allow to tailor their properties by variation of alloy composi-
tion, to meet the requirements of specific applications. So
a variety of hydrides is available which can be used for
advanced, e.g. for multi stage systems. Such complex systems
can be more easily realized as dry sorption systems with metal
hydrides than as conventional wet vapour absorption systems
with a limited number of working pairs. Systems allowing
vertical expansion, i.e., increasing the system pressure to
accommodate high temperature (high exergy) heat like in the
conventional multi stage–multi effect lithium bromide/water
absorption system, and horizontal expansion, i.e., increasing
the out-gassing range to utilize the high exergy of the heat,
like in the conventional GAX water/ammonia absorption
system, have been described, analyzed, built and tested (e.g.
[33–35]). The availability of a great number of suitable metal
hydrides also allows to realize the thermal wave concept,
which has been already developed earlier for wet sorption
machines.
5.3.1. Thermal wave concept
Dehouche et al. [33] developed a mathematical model of an
MHHCS employing a multi-hydride thermal wave concept.
The modeling was carried out for two different reactor
geometries, viz., a capillary tube bundle reactor (CTBR) and
a metal foam tube reactor (MFTR). The lengths and diameters
of the reactors were: CTBR: 500 mm  60 mm (260 capillary
tubes, 1 mm ID), MFTR: 1000 mm  10.5 mm OD  9.75 mm ID.
Fig. 5a and b shows the cross sections of the CTBR and the
MFTR reactors, respectively. The MFTR reactor had a lower
COPh of about 1.4–1.5 than the CTBR reactor with COPh y 1.6–
1.8. The COPc for the MFTR dropped sharply over the cycle, the
average was about 0.4–0.5, whereas the CTBR reactor had
a more uniform COPc of about 0.6. The average SCP (for whole
cycle) of the MFTR reactor was about 20 W/kg, that of the CTBR
reactor was about 28 W/kg.
3826 international journal of hydrogen energy 35 (2010) 3817–3831

Fig. 5 – Types of reactor cross-sections used for multi hydride heat pump [33].

Willers et al. [34,35] built a multi-hydride thermal wave
device for simultaneous heating and cooling using seven
metal hydrides on the high temperature side (Td ¼ 235  C) and
two metal hydrides on the low temperature side (Tc ¼ 18  C).
Fig. 6 shows a schematic and the thermodynamic cycle of the
device on a van’t Hoff plot [34]. The device consists of two
liquid loops which are coupled via a reversible two channel
proportionating pump. Excellent mass transfer and radial
heat transfer (combined with low axial heat transfer) inside
the reaction bed, good thermal contact of the bed material (Al-
foam) to the bed wall, and high external heat transfer coeffi-
cients are required for efficient and economic operation of the
multi-hydride thermal wave system. The relatively small
diameter reaction beds (length 880 mm, OD 30 mm) were
provided with axially arranged Al foam cylinders (20 mm long,
porosity 92%, pore size 1 mm, thermal conductivity about
8 W/m K) as thermal conduction matrix for each metal
hydride section. The gaps between the foam cylinders were
filled with hydride powders (thermal conductivity about 1 W/
m K), which reduced the overall axial conductivity to about
1 W/m K, while the radial conductivity is about 8 W/m K. This
anisotropic thermal conductance of the reaction bed in
connection with the special design of the annular gap
(0.5 mm) between the reaction tube and heat exchanger tube,
allowed the propagation of a sharp thermal and reaction front
along the length of each cylinder section of the reaction bed.
The cooling power of the device was about 230 W for coolant
outlet temperature 0  C and 500 W for coolant outlet

Fig. 6 – Operation of multi-hydride thermal wave system on van’t Hoff plot [34].
 international journal of hydrogen energy 35 (2010) 3817–3831
Th = 137°C
50
Tx = 113°C
20
H2 Pressure (Atm.)
10
5.0
2.0
1.0
V0.855Ti0.095Fe0.05
0.5
0.2
2.4 2.8 3.2
1000/T (K-1)
Fig. 7 – Thermodynamic cycle of crossed van’t Hoff system
on van’t Hoff plot [36].
temperature 10  C with an average of 360 W. The coefficient of
performance COPc was 0.60 at the cooling temperatures
between 0  C and 10  C [34].
The multi-hydride thermal-wave system offers significant
advantages, like modest hardware effort, low pumping
power, wide operating temperature range, and high internal
heat recovery of well over 50%. However, it has a rather long
cycle time and respectively low specific power output. But
with high efficient reaction beds, typical SCP of around
50–100 W/kg of total mass for the complete cycle and
100–200 W/kg of total mass for the desorbing cycle can be
obtained [34].
5.3.2. Crossed van’t Hoff systems
Libowitz et al. [36] described a novel MHHCS (crossed van’t
Hoff cycle, see in Fig. 7) in which the refrigeration alloy
contributes heat to the regeneration alloy, i.e., absorption heat
of the refrigeration alloy is utilized for desorbing hydrogen
from the regeneration alloy. The major advantage of this
configuration is that the theoretical COPs of the systems are
considerably higher than for conventional metal hydride
systems. The performances of systems with several metal
hydride pairs were analyzed. Among those pairs, LaNi5–
V0.855Ti0.0995Fe0.05 yielded the best theoretical COP of about 2.5
as compared to a COP of 0.72 for the conventional configura-
tion. However, taking into account the sensible heat losses,
these values are reduced to 0.83 and 0.64, respectively. So
there is still a substantial advantage in COP. However, an
additional heat transfer device, e.g. a heat pipe diode, is
required to transfer the absorption heat of the refrigeration
alloy to the regeneration alloy. Through this internal heat
3827
recovery one can also avoid to reject heat at very high
temperature.
5.3.3. Multistage systems
Willers and Groll [34] evaluated three different schemes of
metal hydride solid sorption devices for heat pumping and
cooling applications, viz. a single stage (SS), a double stage
(DS) and a thermal wave devices. The SS and DS devices show
reasonable performances, but they require comparably more
hardware effort, i.e., valves and pumps. Using high perfor-
mance reaction beds, e.g. capillary tube bundle reaction beds,
cycle times of about 5–10 min can be obtained with these
LaNi5 devices. This leads to high specific power outputs of 100–
200 W/kg (SS) or 150–300 W/kg (DS), referred to the total
hydride inventory of the device at operating temperatures of
115  C/35  C/3  C and 210  C/35  C/3  C, for the SS and DS
Tc = 5°C
systems, respectively. The maximum reported values of
calculated COPs for the SS and DS systems were 0.53 and 0.83,
respectively. Data for the thermal wave device have been
given in Section 5.3.1.
Ahmed and Srinivasa Murthy [37] outlined a two stage
3.6 system similar to that described in [34], employing LaNi4.6Sn0.4
as high temperature (225–175  C), LaNi4.7Al0.3 as intermediate
(175–60  C) and MmNi4.5Al0.5 as low temperature (60–5  C)
hydrides. The same star-scheme connection of hydride reac-
tors has been employed as described in Section 2.2. The
system can be operated as refrigerator or heat pump (or heat
transformer) based on the position of heat supplied as illus-
trated in Fig. 2a. The effects of operating temperatures on the
coefficient of performance, half-cycle time and specific alloy
output were studied in detail based on thermodynamics and
simple reaction kinetics equations. The performance of the
systems for a cycle time of 66 min and operating temperatures
of Th ¼ 480 K, Tm ¼ 443 K and Tc ¼ 278 K are COP ¼ 0.204 and
SCP ¼ 2.57 W/kg of total hydride mass for the whole cycle.
5.3.4. Cascading systems
Klein and Groll [38] analyzed the possibility of using a two-
stage metal hydride sorption system, with LmNi4.91Sn0.15,
LaNi4.1Al0.52Mn0.38 and Ti0.99Zr0.01V0.43Fe0.09Cr0.05Mn1.5 in
a cascading system as a topping cycle (TC) together with
a single effect (SE) or double effect (DE) lithium bromide/water
system as the bottoming cycle (BC). The system was designed
to operate at a driving temperature of 310  C, releasing heat
for driving a bottoming cycle at 125–130  C for DE-BC and at
95–100  C for SE-BC, and producing cold at 2  C. Fig. 8 shows
a photo of a cut-open reaction bed [38]. They employed 24
stainless steel reactors (8 reactors for each metal hydride),
having 27 mm ID with 1.5 mm thickness. Stainless steel
porous sinter metal tube of 3 mm ID (1.5 mm thickness, 1 mm
pore size) was used as filter. Aluminum foam with 92%
porosity was employed for heat transfer enhancement
(ke w 8 W/m K). The estimated cold production was about
1.8 kW and the heat generation was about 1.5 kW. The MHHCS
system COP and COA were about 0.73 and 0.97, respectively. If
a DE lithium bromide/water system is used as BC (COP ¼ 1.25),
the overall COP was estimated to be about 1.9. For an SE-BC,
the COP would be about 1.5. A respective system has been
built and experimentally investigated by Klein [39]. The major
experimental results obtained from an experimental run
3828 international journal of hydrogen energy 35 (2010) 3817–3831
Fig. 8 – Cut section of the reaction bed used in multi-
hydride reaction bed [38].
which lasted nearly 12 h and comprised 11 cycles are
COP ¼ 0.51 and COA ¼ 0.86. The discrepancy between experi-
mental results and predictions is explained by the experi-
mental conditions, mainly because the internal heat recovery
could not be accomplished in the expected /desired 5 min, but
took about 13 min. Coupled with a SE-LiBr/H2O-BC, this would
result in an overall COPtot ¼ 1.2. An estimate, taking into
account better thermal insulation and more suitable high
temperature thermostats as driving sources, shows that an
internal heat recovery time of 5 min is possible, and respective
performance data could thus be improved to COP ¼ 0.73,
COA ¼ 0.95, and COPtot ¼ 1.4 for SE-BC. The respective SCP
would be 22 W/kg. This low value would have to be signifi-
cantly improved by optimizing the reactors, in order to make
such a system economically interesting.
5.3.5. Compressor driven metal hydride cooling systems
(CD-MHHCS)
The performance of an MHHCS can be improved by employing
a low speed isentropic compressor in place of a regeneration
alloy. Performances of such systems are found to be attractive
and inline with commercial VRC systems. Kim et al. [40,41]
and Park et al. [42,43] have taken initiative steps to develop
such systems. The former initially carried out analytical
studies [40] which were followed by experiments [41]. The
reactors were Cu tubes (diameter 12.7 mm, length 165 mm)
with external fins for enhancing the outside heat transfer.
Experiments were carried out with reactors employing copper
coated PMC of LaNi5 and Ca0.4Mm0.6Ni5 [41]. Measurements
were carried out with single reaction beds (not coupled beds),
i.e. desorption was against vacuum and the respective
absorption was with hydrogen from a high pressure reservoir.
So the obtained reaction rates are definitely higher than
respective ones for coupled reaction beds. Both reactors
showed fast reaction rates. The SPC was about 1.5 kW/kg of
hydride (130 s cooling time) for the LaNi5 reactor, while the
reactor containing Ca0.4Mm0.6Ni5 hydride (150 min cooling
time) had a higher SCP of 2.2 kW/kg (due to high desorption
equilibrium pressure of Ca0.4Mm0.6Ni5). Life cycle tests with
LaNi5 were carried out (about 3000 cycles); the reduction in
cooling capacity was about 55%. It was shown that the copper
PMC not only provided very good thermal conductivity, but
also solved the problems of decrepitation and migration of
metal hydrides.
Park et al. [42] developed a CD-MHHCS using Zr0.9Ti0.1-
Cr0.55Fe1.45 (4.2 kg hydride). The compressor (oil-less type) was
operated between 1 and 18 atm. They employed a finned
reactor of 15 mm diameter. Cooling power was found to
increase by about 25% when the airflow was increased from
8 m3/min to 11 m3/min. The effect of room temperature beyond
24  C and the effect of airflow rate beyond 11 m3/min had no
significant influence. The maximum SCP of 0.29 kW/kg was
obtained under the optimum operating conditions cycle time
2.6 min and flow rate 11 m3/min. The same group [43] built an
experimental set up (using 3.5 kg of Zr0.9Ti0.1Cr0.55Fe1.45)
employing a commercial compressor and demonstrated the
practical applicability for air-conditioning applications. The
experimental results showed that the system could produce
a maximum SCP of 410 W/kg of alloy (6 min cycle time) at 6  C
cooling temperature and 7 m3/min airflow rate with a COP of
about 1.8.
Mazumdar et al. [44] presented a detailed mathematical
model of a CD-MHHCS working under static and transient
conditions. This analysis was carried out based on a model by
Kim et al. [40,41]. The model takes into account the transient
characteristics of the coupled metal hydride reactors with
external fins, reciprocating compressor and air-conditioned
space. For a cooling capacity of 1 kW, a reaction bed of cylin-
drical configuration (20 mm dia with internal radial aluminum
fins of thickness 0.15 mm, fin spacing 316 fins/m) was
selected. Two reactors were employed, both filled with
Zr0.9Ti0.1Cr0.55Fe1.45 hydride. The COPs obtained were in the
range of 1.7–2.2, depending on operating conditions, while the
maximum SCP obtained was about 0.16 kW/kg alloy (total
cycle). It was shown that in order to make these systems
commercially viable it is important to select suitable materials
with fast reaction kinetics.
Bedbak et al. [45] compared the performance of the system
using the well-established metal hydrides MmNi4.5Al0.5 and
Fe0.85Mn0.15Ti, and an assumed metal hydride of high hydrogen
storage capacity. Their studies revealed that the system perfor-
mance depends mainly on the temperature drops at the high
and low temperature reactors and on the compressor efficiency.
The calculated COPs may approach or even exceed those of
commercial vapour compression systems, if the parasitic losses
during thermal cycling are minimized by some form of heat
recovery during cycling; however, the technical and economical
feasibilities of such measures need to be evaluated further.
Magnetto et al. [46] developed a prototype of a CD-MHHCS
based air conditioning system for automotive applications. In
order to support the heat transfer rates required for rapid
hydrogen absorption and desorption, specially designed small
diameter (diameter 3.175 mm) ‘‘ring manifold’’ (shown in Fig. 9)
reaction tubes were employed. The individual ring manifold
 international journal of hydrogen energy 35 (2010) 3817–3831
Fig. 9 – Photographic view of ‘‘Ring Manifold’’ type reaction
bed [46].
hydride tubes were integrated (called hydride heat exchanger)
in the form of a circular disc of 203 mm diameter and 203 mm
long. Each heat exchanger was filled with 3.5 kg of Mm based
alloy. The hydride heat exchangers were designed for
a hydrogen inventory of approximately 27 g and a half cycle
time of approximately 1.5 min, resulting in a cooling capability
of approximately 2 kW. The 24 V fans were employed for
generating a maximum airflow rate of 7.4 m3/min. It was
anticipated that the system would capable of approaching 0  C
if the aluminum based heat exchangers were employed.
Performance tests were carried by varying the ambient
temperature from 21  C to 35  C and the respective reported
average cooling capacity were varied from 1545 W (COP ¼ 2.76)
to 2095 W (COP ¼ 2.57). It was observed during the cyclic tests
that the prototype delivered the consistent cooling perfor-
mance and achieved COP’s greater than 2.5 at all ambient
conditions. Since, the CD-MHHCS operates independently from
the engine (due to low electric consumption), it can be also used
for precooling. Simulations predict that 3 min of pre-cooling
using 3.5 kW average cooling power lowers the car cabin from
35  C to about 20  C. The authors claimed from their experi-
mental data that their prototype was superior to conventional
R-134a refrigerant cycles in terms of performance and
maintenance.
6. Summary of developments from
1978 to 2009
Table 1 lists the status of MHHCS developments. Interest in
metal hydrides for energy conversion applications rose espe-
cially in the wake of the second oil price crisis during 1978/
1979. There has been a steady, though slow development over
the following years. Since the imposition of international
restrictions on the production and use of chlorofluorocarbons,
the worldwide efforts to use metal hydride energy conversion
technology for MHHCS applications have been intensified.
7. Concluding remarks
A review of MHHCS thermodynamic analysis, mathematical
modeling and experimental development work is presented in
3829
this paper. Most of the investigators have addressed the
importance of improving the heat and mass transfer charac-
teristics of the hydride beds to achieve better performance. It
is observed that LaNi4xAlx with 0  x  0.75 is mostly used as
a high temperature alloy, while MmNi4xFex with 0  x  0.85
is used as low temperature alloy for heating/cooling systems.
In addition, Ti0.8Zr0.2CrMn or Ti0.99Zr0.01V0.43Fe0.09Cr0.05Mn1.5 is
used as low temperature alloy in the case of two stage
systems. The performance of the systems is largely based on
the amount of hydrogen transferred between the coupled
reactors and hence, attention is needed for improved/opti-
mized or novel hydriding alloys which have favourable prop-
erties, like high storage capacity, small plateau slope, small
hysteresis and moderate operating pressures.
The COPs of most investigated single stage MHHCS are
below 0.5. Since the late 1990s, lot of attention is given to CD-
MHHCS. They allow COPs well above 1.5. It is evident from the
recent experimental data reported by Magnetto et al. [46] that
performance (COP of above 2.5) of the compressor driven
metal hydride heat pumps are in comparable even better than
the conventional vapour compression systems. There was no
significant performance degradation observed during the
cyclic tests. The only battle neck is that the development of
low capacity hydrogen compressor. More such type of proto-
type developments leads to the possible commercialization of
this technology in automotive industry. Of course, cost of
hydride alloys are high; therefore the amount of alloy should
be minimized, which can to some extent be done by proper
design, and improved/optimized alloys should be developed.
MHHCS provide an environmentally safe technology. They
do not employ harmful or hazardous products such as CFCs,
and they contribute to a reduction of CO2 emissions. Due to
their attractive performance data and their obvious environ-
mental benefits, there is an increasing interest in the devel-
opment and use of MHHCS with low grade thermal energy
(waste heat or solar energy) utilization. Applications are
mainly discussed for air-conditioning in buildings and auto-
mobiles. Although the investment costs for MHHCS are high,
the environmental benefits are impressive, when compared to
conventional vapour compression systems. It is envisaged
that, in the long run, a CD-MHHCS system would be cost-
effective and would involve minimal maintenance, as it
would have few moving parts. If the costs of additional fuel
consumption, system maintenance, and environmental
issues are taken into account the CD-MHHCS seems to be
a very attractive option, particularly for automobile air-
conditioning applications [46].
In summarizing, there is an urgent need to develop cost-
effective technologies and to improve the system efficiency
(for both thermally driven and compressor driven MHHCS),
using fast reaction beds (e.g. metal hydride composites).
Advanced concepts, like thermal wave concept and multi-
staging should be further explored. Search for optimized
metal hydrides for MHHCS should also be given great atten-
tion. In this respect, the complex hydrides (e.g. aluminum
hydride) and composite metal hydrides (e.g. Mm based Mg
hydrides) deserve special attention; respective material
investigations are in progress. Especially Na(AlH4) and Na(BH4)
seem to be very promising alternatives. They are especially
investigated as hydrogen storage materials for mobile
3830 international journal of hydrogen energy 35 (2010) 3817–3831
applications, e.g. in connection with fuel cells. Their use for
thermodynamic devices has, however, not been considered so far.
Till today metal hydride systems are expensive, due to high
material cost and expensive fast reaction beds. So, the
commercial success of such systems in comparison with
liquid sorption systems and competing dry sorption systems
is not guaranteed. However, the potential to use low quality
heat, waste heat, and solar heat is a big advantage of the
MHHCS heat-driven systems besides their other environ-
mental benefits.
Acknowledgements
The authors express their sincere thanks to Mr. Marc Linder,
IKE, University of Stuttgart, Germany for his contribution.
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