Application of Hydrogen Storage Alloys

Chapter 5.3.4
Application of Hydrogen Storage
Alloys
Hydrogen storage alloys have unique and interesting characteristics such as a
higher hydrogen storage density than that of the liquid hydrogen state, and
reversible exothermic hydriding and endothermic dehydriding with fast reaction rates. Cyclic hydriding-dehydriding treatment induces pulverization of the
alloy because of relatively high volume changes of the alloy by the treatment
[106]. The pulverization means the reduction of the alloy particle, resulting in
increasing surface area and reaction rate while decreasing heat conductivity
among the particles. These phenomena should be taken into account in
application [107]. Many interesting phenomena can be observed as surface and
volume effects of the alloy reacting with hydrogen [107e112].
The high hydrogen storage capacity of the alloy is applied to the nickelmetal hydride (Ni-MH) rechargeable battery as commercial products. The
Ni-MH battery is widely used in various scales. A small size of the Ni-MH
battery is used for daily electric commodities, and the larger Ni-MH batteries are used for hybrid vehicles such as the Toyota Prius and Honda Insight.
Much larger sizes of the Ni-MH batteries with megawatt (MW) capacity are
used for power peak-cut and/or peak-shift of power grid, and indispensable for
the efficient use of unstable renewable energy [113].
As is well known, the density of electric capacity of the Ni-MH battery is
lower than the lithium (Li) ion battery. However, the Ni-MH battery is not
flammable and has a high chemical stability compared with the Li ion battery.
This is the main reason that many hybrid vehicles are adopting the Ni-MH
battery in order to avoid firing of vehicles in accidents. Use of the Li ion
battery is strictly controlled or even inhibited by mailing or air transport, as is
well known.
The reversible heat reactions of the alloy can be applied as a metal hydride
(MH) heat pump. Unique MH freezer/water cooling systems are applied to the
cultivation of strawberry in agriculture and water temperature control in fish
breeding. The MH freezer technology is found markedly effective in cutting
carbon emission and in saving energy compared with conventional freezing
technologies using Freon gas [114].
Science and Engineering of Hydrogen-Based Energy Technologies. https://doi.org/10.1016/B978-0-12-814251-6.00014-9
290
Copyright © 2019 Elsevier Inc. All rights reserved.
Application of Hydrogen Storage Alloys Chapter j 5.3.4
291
In this section, typical examples of application of hydrogen storage alloys
are demonstrated in terms of the Ni-MH battery and an MH freezer system
combined with waste heat.
NICKEL-METAL HYDRIDE RECHARGEABLE BATTERY
Typical rechargeable batteries for power storage are sodium-sulfur (NaS),
redox flow (RF), Li ion and Ni-MH, and lead (Pb) cells. Typical costs per
kWh of each battery are about US$400/kWh for NaS, US$ 2000/kWh for Li
ion, US$ 1000/kWh for Ni-MH, and US$ 500/kWh for Pb batteries,
respectively. No cost for the RF battery is given because large-scale RF
batteries are still at the test stage. The RF battery, using vanadium ions for
positive and negative electrodes, is attracting a strong battery at
US$ 600e700/kWh. NGK Insulators, Ltd. has applied the NaS battery to
MW class power storage. The NaS battery is used rather for industrial use
because the battery is operated at 573K. For residential use, the Li ion battery
with 7 kWh is commercialized. Typical features of the Ni-MH battery, such
as high chemical stability and high cyclic charge-discharge durability under
high current and load use, are confirmed by many commercialized hybrid
vehicles in and outside Japan. The high diffusivity of H atoms inside the
negative electrode of hydrogen storage alloys enables the high current
density, and the rare earthebased hydrogen storage alloys used for the
negative electrode are responsible for high chemical and cyclic stabilities.
Large-scale Ni-MH batteries are used for power storage and control in
transportation and residential use because of their high safety and reliability
under high load. Kawasaki Heavy Industries, Ltd. has developed Ni-MH
rechargeable batteries with high capacities for power storage and control
(Fig. 5.47).
FIGURE 5.47 Applications of the nickel-metal hydride (Ni-MH) rechargeable batteries GIGACELL (Kawasaki Heavy Industries, Ltd.) to power storage and control systems for monorail
trains of Tokyo Monorail Co., Ltd. (left), and to power smoothing of a wind power system in Akita
Prefecture, Japan (right) [115].
292 Science and Engineering of Hydrogen-Based Energy Technologies
Many applications using the Ni-MH rechargeable battery are demonstrating prominent results in transportation use such as light rail vehicles,
trains, and hybrid vehicles; and in residential use, such as smoothing of
fluctuating Renewable Energy (RE) supply. Many companies are constructing
and demonstrating smart communities or towns where the Li ion and the NiMH battery are widely used for power storage and grid control.
APPLICATIONS OF METAL HYDRIDE AS A FREEZER SYSTEM
[114,116]
Operating Principle of a Metal Hydride Freezer [116]
In an MH freezer system, a pair of hydrogen storage alloys for high and low
temperatures are used as shown in Fig. 5.48. In this system, waste heat
from outside is needed to drive hydrogen in hydrides. A hydride of a high
temperature alloy, Ma, desorbs H2 gas by absorbing waste heat Qa at TH. The
desorbed H2 gas is transported to another low temperature alloy, Mb, to form a
hydride MHb at room temperature TM. This exothermic hydriding reaction
releases heat Qb, which is not used in this case. Then MHb desorbs H2 gas by
absorbing heat Qb from the surroundings, resulting in reducing temperature of
air or water from TM to a lower temperature. The H2 gas desorbed from MHb
is transported back to Ma to form a hydride. By implementing this cyclic H2
gas reaction between the alloys Ma and Mb, the temperature of the
surroundings of Mb cools.
Using this system, different types of the MH freezer can be operated in
temperature ranges below 243 K, or at 273e278 K, respectively. The temperatures can be selected and adjusted for freezing foods (meats/fishes) or for
FIGURE 5.48 Principle of a metal hydride (MH) freezer system with high and low temperature
hydrogen storage alloys, Ma and Mb, respectively.
Application of Hydrogen Storage Alloys Chapter j 5.3.4
293
cooling agricultural products such as vegetables and fruits above freezing
temperatures. An MH freezer system can be used not only for freezing, but
for the production of cold water at temperatures above freezing. The latter
temperatures are important to control water temperature for agriculture and
fish cultivation. These technologies have been examined in various ways over
10 years at the city of Saijo, Ehime Prefecture, Japan, by the cooperation
among Tokai University, Japan Steel Works (JSW), Ltd., the Ministry of
Economy, Trade and Industry (METI), and Saijo City, Ehime Prefecture.
Fig. 5.49 shows a plan of an MH freezer system using a high-temperature
heat source of waste heat from an industry or an incinerator, and a lowtemperature heat source of ground water.
Hydrogen Storage Alloys for a Metal Hydride Freezer
Fig. 5.50(A) and (B) show the pressure isotherms of the developed hydrogen
storage alloys, TieZreMneVeFe and TieZreCreFeeNieMneCu for highand low-temperature alloys, respectively. The amount of hydrogen transferred
to drive heat reactions was over 100 cc/g-alloy at these conditions: dehydriding at 433 K and 1.0 MPa, and hydriding at 313 K and 0.075 MPa,
respectively. The reduction of the maximum hydrogen storage capacity was
found to be less than 2% after 10,000 hydridingedehydriding cycles.
Conventional
Output into Environment
Hydrogen
Storage Alloy
Hydriding
(exothermic reaction)
Dehydriding
(endothermic reaction)
253 k – 278 k
Refrigerator
Freezer
and
Air Conditioner etc
Waste Heat utility
50 % at 276K
45% at 253K
(25% at 253K by a Long Heat transport)
FIGURE 5.49 Utilization of high-temperature waste heat sources of industry and ground water,
respectively, for the operation of a metal hydride (MH) freezer.
294 Science and Engineering of Hydrogen-Based Energy Technologies
FIGURE 5.50 Pressure isotherms of the TieZreMneVeFe (A) and the TieZreCreFeeNie
MneCu and (B) for high- and low-temperature hydrogen storage alloys, respectively (JSW, Ltd.).
Application of Hydrogen Storage Alloys Chapter j 5.3.4
295
FIGURE 5.51 A metal hydride (MH) freezer system (left) with control unit and two freezer
rooms. Two freezer rooms (right) for 243 K and for 273e278 K with a volume of 67 m3,
respectively.
Fig. 5.51 show a whole MH freezer system and two freezer rooms,
respectively. Each room has a volume inside 67 m3. The temperature of each
room was designed for food preservation.
The amounts of hydrogen storage alloys in MH tanks were 137 kg 2 and
120 kg 2 for high- and low-temperature heat reactions, respectively. The time
for a cyclic operation of the alloys was around 2000 s. At temperature 283 K
outside, the temperature inside a room fell to below 243K within 4 h. Realizing
a temperature as low as 243 K, the low temperature alloy is cooled until 290 K
using ground water. And then the alloy is cooled further using a hydrocarbon
cooler (5.5 kW) until 283 K. Endothermic reactions by dehydriding of the low
temperature alloy realizes a freezer temperature of 243 K after these two steps.
If a groundwater or cold heat source has a temperature less than 290 K, such an
additional cooler is not needed to realize 243 K. The durability of the alloys is
very stable at cycles over 30,000e50,000 over 3 years’ use.
Energy Consumption and CO2 Reduction
The energy consumption is less than 30% that of a conventional
chlorofluorocarbon-type freezer, because the MH system utilizes hightemperature waste heat from industrial facilities and low temperature of
groundwater. The extra energy is required for an additional hydrocarbon
cooler and for electric fans to circulate air inside the rooms. This system reduces the CO2 emission over 70% compared with a conventional CFC system.
The MH freezer system is a prominent result of eco-technology, or
environment-friendly green technology.
This system was also examined to produce cold water for strawberry
cultivation and fish breeding. In that system, the effects of CO2 reduction and
energy saving were over 80%. Thus the combination of an MH freezer and
high temperature waste heat is a prominent way for energy saving and CO2
reduction for freezing/cold food preservation, and environmentally friendly
agriculture and fish breeding.
296 Science and Engineering of Hydrogen-Based Energy Technologies
CONCLUSION
Hydrogen storage alloy has highly interesting features as shown here. Many
types of the alloy have been developed so far, however only limited numbers
of the alloy are practically used such as rare earth base type MmNi5,
magnesium-base type Mg2Ni, and titanium base type FeTi. Some alloys with
specific compositions have been developed and used for a certain purpose as
shown for the MH freezer system. The cost of the alloys was relatively high,
however mass production of the nanostructured FeTi alloy was accomplished,
and this reduced the cost by a third compared with those of conventional alloys
[117]. This may accelerate use of the alloy for safe hydrogen storage in a large
scale; for example, hydrogen fuel stations for fuel cell vehicles and effective
control of fluctuating electric generation by renewable energy. Many more
extended applications of the alloy are expected.
CONCLUDING REMARKS
Traditionally, hydrogen production has been using fossil fuels, but in recent
years technologies that can be manufactured with renewable energy have been
developed and expected to be high. Fossil fuels are used for most of the
hydrogen produced, but hydrogen production by renewable energy is expected
to develop in the future. Hydrogen production that does not emit carbon dioxide is an important development item because it can reduce the impact on
global warming. Hydrogen production including electrolysis will become
mainstream in the future.
In addition, demonstration projects of fuel cell vehicles have been carried
out many times in Europe, America, and Asia in the 21st century. As a result,
fuel cell vehicles were sold and fuel cell buses also began to run on ordinary
roads. Production volume of these fuel cell vehicles surely grows, and it seems
that it will occupy a part of mainstream automobiles in the future.
In addition, hydrogen refueling stations have been under construction since
2015 in Japan, and now more than 100 hydrogen stations have been built. It is
planned that 160 places will be built in 2020 and about 900 stations will be
constructed by 2030. Hydrogen energy technology is definitely beginning to
penetrate society.
Because concern about global warming due to carbon dioxide has
increased, a technique of reacting hydrogen with carbon dioxide is attracting
attention as hydrogen utilization technology. Although this is a challenging
study, it will be developed as a technology to be incorporated into the chemical
process.
Furthermore, the use of hydrogen storage alloy is promoted as an energy
stockpile. Hydrogen energy plants using storage alloys have been commercialized in recent years. Hydrogen storage is a technology that enables clean
energy on a yearly basis, and it can be regarded as a distinguishing technology.
Application of Hydrogen Storage Alloys Chapter j 5.3.4
297
In this way, hydrogen energy technology is beginning to penetrate into
society and has made remarkable progress. In the future, further growth in this
field will continue.
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