i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 5 0 5 e1 7 5 1 4

Available online at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/he

Liquid metal activated hydrogen production from

waste aluminum for power supply and its life cycle
assessment

Shuo Xu a,b,c, Xiao-Hu Yang a,b,c, Shou-Sheng Tang a,b, Jing Liu a,b,c,d,*
a
Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing
100190, China
b
Beijing Key Laboratory of Cryo-Biomedical Engineering, Technical Institute of Physics and Chemistry, Chinese
Academy of Sciences, Beijing 100190, China
c
School of Future Technology, University of Chinese Academy of Sciences, Beijing 100049, China
d
Department of Biomedical Engineering, School of Medicine, Tsinghua University, Beijing 100084, China

article info abstract

Article history: Hydrogen energy draws increasing concerns as a kind of renewable and clean energy.
Received 9 April 2019 Liquid metal (LM) activated AleH2O reaction is recently emerging as an alternative for real-
Received in revised form time hydrogen production. In this study, the energy consumption and environmental
20 May 2019 impact of this newly emerging method are evaluated via the life cycle assessment (LCA),
Accepted 22 May 2019 which indicates that the utilization of waste Al could significantly relieve the energy and
Available online 13 June 2019 environmental issues. In addition, conceptual experiments were conducted to verify the
feasibility of hydrogen generation from waste Al, and to disclose the hydrogen generation
Keywords: performances of Al samples in different forms. To balance the cost of LM and reaction
Hydrogen production efficiency, the optimum mass ratio of LM to Al were explored, and the reusability of LM was
Waste Al demonstrated. Further, a SWOT analysis is adopted to interpret the Strengths and Weak-
Life cycle assessment ness of such hydrogen production method, and to evaluate the Opportunities and Threats
Liquid metal it confronts. Overall, waste Al could provide an energy-saving and environmentally
SWOT analysis friendly approach to produce hydrogen, which is expected to exploit a new way towards
the green hydrogen era.
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

terminal applications [6]. However, as an intermediate energy,

Introduction
Increasingly severe issues on air pollution and the shortage of
fossil fuel are motivating human to explore and utilize clean
and sustainable energy, such as solar energy [1], wind power
[2], hydro-energy [3] and nuclear energy [4,5]. Most renewable
energy is converted to electricity first and then provided to
electricity cannot be stored and released efficiently, and thus
fails to satisfy all of the terminal power supply requirements,
especially in those situations where conventional fossil fuel is
used, such as transportation. Hydrogen is considered to be a
rather promising energy carrier in the near future to replace
fossil fuel, owing to its intrinsic favorable properties, such as

* Corresponding author. Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China.
E-mail address: jliu@mail.ipc.ac.cn (J. Liu).
https://doi.org/10.1016/j.ijhydene.2019.05.176
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
17506 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 5 0 5 e1 7 5 1 4
high gravimetrical energy density, high conversion efficiency
to electricity, cleanness and carbon emission free [7e11].
So far, many methods have been developed to produce
hydrogen, mainly including the reforming of hydrocarbon
fuels [12,13], water electrolysis [14,15] or photolysis [16,17],
biomass [18,19], hydrogen-involved chemical reactions
[20,21]. Among them, the first method is dominating the cur-
rent hydrogen market, mainly benefitting from its low-price
and technology maturity [22]. However, in the viewpoint of
raw materials, this method essentially relies on the fossil fuel
consumption. Water electrolysis/photolysis is thought to be a
long-term solution for hydrogen production, profiting from its
inexhaustible source and completely closed cycle, and many
researches have proceeded to promote the electrolysis effi-
ciency and the photolysis rate [23e25]. The storage and
transportation of hydrogen remains a big challenge due to the
fact that it is flammable, explosive, and of low volumetric
energy density [26,27]. Although many efforts have been
devoted to the compression and liquefaction of hydrogen, the
high cost still reserves to be an obstacle, and hydrogen may
cause the problems of hydrogen embrittlement and hydrogen
corrosion [28e31]. Some new solid hydrogen storage methods,
such as metal hydride materials [32] and the physisorption of
hydrogen in porous structures [33e37], are also under
research and development.
As an alternative, hydrogen can also be indirectly stored
and transported by reactive metals, such as Zn [38,39], Mg
[40e42] and Al [43,44], and then released via certain hydrogen
evolution reactions with water or hydrocarbons, and thus
realizing real-time and on-demand production and utilization
of hydrogen energy. Al is considered to be the most promising
candidate as energy storage material for its abundant reserve
in the earth crust and high energy density [45]. Besides, Al can
be fully recycled from the byproduct of the hydrogen evolu-
tion reaction (mainly Al(OH)3) by electrolysis process. An
inevitable problem encountered in the use of Al is that a dense
oxide layer readily forms on the surface of Al, which protects it
from being further oxidized but hinders the AleH2O reaction
for hydrogen evolution at the same time [46]. Acidic or alka-
line media could dissolve the passive film, but also causes
corrosion problem [47]. Alloying Al with certain low melting
point metals, such as Ga [48,49], Bi [50,51], Sn [52] and Zn [53],
can effectively activate the AleH2O reaction. The common Al-
based alloys are prepared by melting at high temperature
[54,55] or ball-milling [56,57], which are energy-intensive, and
the alloys are easy to get aged. Recently, a new conceptual
liquid-phase hydrogen production method was proposed by
the authors’ lab [58e62]. A typical room temperature liquid
metal (LM), Ga-based alloy, was used directly for the activation
of the AleH2O reaction. The hydrogen generation mode and
the effects of various reaction conditions on the hydrogen
generation performances were explored. This method can
realize straightforward and simple production of hydrogen,
and eliminate the time- and energy-consuming alloying
treatment or milling process.
In the viewpoint of life cycle, the production of hydrogen
from the AleH2O reaction is essentially energy intensive and
accompanied with high carbon emission, mainly because
elementary Al is usually extracted from alumina by electrolysis
process. Whereas, if waste Al is used, the cost of hydrogen
production can be dramatically reduced, and a fully use of Al
resource can thus be realized. Takehito et al. [63] had ever
proposed a hydrogen production process from waste Al and
NaOH solution in 5 mol/L, wherein, Al powders with particle
size of 180e425 mm and purity of 99 wt% were prepared for
experiments. Ho et al. [64] treated waste Al cans via ball-milling
with additives in argon atmosphere, and then obtained a high
hydrogen generation rate in low alkaline concentration solu-
tion. As for waste Al foils recovered from packages, they should
be immersed in nitric acid to remove the polythene film in
advance, and then ball-milled [65]. Setiani et al. [66] compared
the reaction model of hydrothermal reaction with commercial
Al power and waste Al from capacitors, respectively. The re-
sults showed that the non-Al materials in the wasted Al had no
impact on the reaction mechanism.
In this paper, a more simplified waste Al-based hydrogen
production process with the assistance of liquid metal and
solar energy was proposed and experimentally demonstrated,
and its superiority is reflected via a life cycle assessment
(LCA). Waste Al was directly used for hydrogen production,
without any energy-intensive preprocessing. Liquid metal
(Ga-In-Sn) alloy was used to activate the hydrogen evolution
reaction, and solar energy was utilized for heating the
aqueous solution, thus accelerating the reaction rate. Such a
hydrogen generation routine could improve the availability of
waste Al, and provide a possibility for real-time and green
hydrogen production.
Conceptual construction of the waste Al based
energy supply system
Production and utilization of Al
Aluminum is widely used in industry and human's daily life,
such as transportations, aerospace, architecture, commod-
ities and electronic products, and other fields. The annual
global primary Al production increased from 39.5 million tons
(Mt) in 2008 to 64.3 Mt in 2018 [67], with an average annual
growth rate about 5%. Therein, China has the highest Al pro-
duction and utilization proportion, about 50% of the whole
world, as shown in Fig. 1. Besides primary Al, the reuse of
secondary Al is also predictable. There are primarily two
technical routes to recycle nonferrous metal scraps, namely
the remelting method and solid state extrusion [68e71]. The
former requires high energy consumption, and causes metal
loss due to the increase of chemical reactivity at high tem-
perature. Moreover, the melting and combustion of polymer
impurities may lead to the liberation of harmful gases. The
latter is still in the experimental stage, and many operation
parameters need optimizing. To date, the recycle of Al is
insufficient, and a large amount of waste Al is directly land-
filled, especially the Al foil products. In China, the Al foil
production in 2017 is 3.65 Mt [72]. Those Al foils are widely
used for package of tobacco, food, medicine, cosmetics and
commodities, etc. The recycle of those lightweight and
scattered-distributed Al foils is difficult in practical operation.
Many of those Al foils are thrown as garbage, which is a huge
waste of resources. In fact, such waste Al can be fully used by
releasing its chemical energy to produce hydrogen.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 5 0 5 e1 7 5 1 4 17507

Fig. 1 e Annual Al production (million tons), from 2008 to 2018. (The total Al production in China includes the primary Al and
secondary Al.) (Data source: The data of global annual primary Al production in December 2017 come from [73]; The rest data
come from [67]).

Waste Al based energy supply system
Fig. 2 shows the conceptual construction of the liquid metal
activated waste Al-based energy supply system. The core of
the system is the well-known hydrolysis reaction of Al, i.e.
2Al þ 6H2 O/2AlðOHÞ3 þ3H2
Here, daily waste Al and tap water or sea water are used as
the reactants, both of which are available and low-cost. Since
a dense passivation layer is readily formed on the surface of Al
and hinders the reaction, LM (typically gallium and its alloys)
is used to break this passivation layer and then activates the
reaction from three aspects [74]. First, Ga atoms diffuse into Al
grain boundaries, and AleGa solid solution alloy forms
accompanied by the atom exchange at the interface. Al gets
activated as its lattice structure is distorted. Second, inter-
metallic compounds, like InxSny, diffuse into Al internal
together with LM and distribute along the Al grain boundaries,
(1) which shifts the electrode potential of Al more negatively,
thus facilitating the anodic activation. Third, owing to
different electrode potentials of different metals, Al and other
metals constitute galvanic corrosion cells, which accelerates
the anode corrosion of Al. The activation effect and corre-
sponding hydrogen evolution mode can refer to our latest

Fig. 2 e Conceptual construction of the LM activated waste Al based energy supply system. Daily waste Al and tap water or
sea water are used as reagents, LM for activation and sunlight for heating. Generated H2 is converted to electricity by Proton
Exchange Membrane Fuel Cell (PEMFC) or actuates the combustion gas turbine.
17508 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 5 0 5 e1 7 5 1 4
work [59,61]. Generally, high temperature is conductive to
promoting the hydrogen evolution rate so that solar energy
can be utilized to heat the reagents. Generated hydrogen can
be directly used for combustion gas turbine [75] or Proton
Exchange Membrane Fuel Cell (PEMFC) which has a high effi-
ciency over 50% [76]. Theoretically, 9 kg Al can produce 1 kg H2,
and the heating value of 1 kg H2 is 142 MJ, namely 39.44 kWh
[77]. Assuming that a PEMFC has an efficiency of 50%, thus
approximately 19.72 kWh electricity can be obtained by 9 kg
waste Al. Such a system can be easily constructed in a resi-
dential district, a school or a factory to centrally utilize the
waste Al daily generated there.
Evaluation of the system
LCA was adopted here to evaluate the proposed process and
conventional electrolysis of water method. LCA is a technique
to assess environmental impacts associated with all the
stages of a product's life from raw material extraction through
materials processing, manufacture, distribution, utilization,
repair and maintenance, and disposal or recycling [78]. The
life cycle of hydrogen generation from the AleH2O reaction is
illustrated in Fig. 3. Here, Al could be obtained from three
sources, namely bauxite, recycled Al(OH)3, and waste Al. The
dominating energy consumption arises from the production
process of Al. The electricity cost for the recycle of LM is
assumed to be 2 kWh/kg H2 (detailed in Supplementary Ma-
terial). The emission of carbon dioxide mainly occurs in the
refining and electrolysis process.
Although Al is the most abundant metal element in the
earth crust, free element Al is hardly found in nature. Gener-
ally, the industrial and daily used Al is extracted from bauxite
based on HalleHe
roult process [79]. Such an extraction pro-
cess mainly includes the mining and refining of bauxite, the
decomposition of Al(OH)3, and the electrolysis of Al2O3 dis-
solved in cryolite. The major energy consumption stems from
the electrolysis process which happens at 940e980  C, about
13 kWh for 1 kg Al with purity of 99.9%, and the corresponding
electrochemical reaction is given by Eq. (2):
Fig. 3 e The life cycle of hydrogen generation from AleH2O reaction.
2Al2 O3 þ 3C/4Al þ 3CO2 (2)
In this process, carbon is consumed and it is estimated that
12.7 kg carbon dioxide is released for the production of 1 kg Al
[80]. The unit energy consumption for producing 1 kg Al from
bauxite is estimated to be 21.24 kWh [81]. Thus, the energy
consumption and carbon emission required for the produc-
tion of 1 kg H2 is 21:24 9 ¼ 191:16 kWh and 12:7 9 ¼ 114:3 kg
CO2, respectively.
As known from Eq. (1), this hydrogen generation reaction
produces Al(OH)3 at the meantime. Thus, the recycled Al(OH)3
could be calcinated into Al according to Eq. (3):
2AlðOHÞ3 /Al2 O3 þ3H2 O (3)
And then Al2O3 is electrolyzed into Al, while the mining
and refining process of bauxite are eliminated. The corre-
sponding energy consumption and theoretical carbon emis-
sion of this recycling method is respectively 17:04 9 ¼ 153:36
kWh/(kg$H2) [81] and 11 kg CO2/(kg$H2).
Al can also be recycled from the recyclable scraps con-
taining Al or its alloys, which is called secondary Al. Much less
energy is consumed (0:39 9 ¼ 3:51 kWh/(kg$H2)) [81] in pro-
cessing the scrap since the electrolysis process with high en-
ergy consumption and high carbon dioxide emission is
eliminated. If the waste Al is used directly for hydrogen pro-
duction, no additional energy is consumed and no carbon di-
oxide is released.
Typical characteristics of the aforementioned methods are
summarized and tabulated in Table 1. The conventional water
electrolysis method for hydrogen production, which seems to
be a long term source because it does not rely on fossil fuel, is
selected for comparison. It is clear that producing Al from
bauxite and recycling Al(OH)3 for hydrogen production is
accompanied with large energy consumption and high carbon
emission, while the use of waste Al is much more advanta-
geous, with zero carbon emission and extremely low energy
consumption. Given that the converted energy from 1 kg
hydrogen is 19.72 kWh, the energy output-input ratio of
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 5 0 5 e1 7 5 1 4 17509

Table 1 e Energy consumption and carbon emission accompanied with production of 1 kg H2.
Al source Production processes of Al Energy consumption Carbon emission
(kWh/kg H2) (kg CO2/kg H2)a
Bauxite Bauxite mining and refining, electrolysis 196.16 114.3
Recycling Al (Al(OH)3) Calcinations, electrolysis 158.36 11b
Waste Al (smelting) Scrap processing 5.51 0
Waste Al Direct use 2 0
Water electrolysis e 51.22c 0
a
The carbon emission refers only to the carbon dioxide emission in the Al electrolysis process.
b
The carbon emission in the cycle of Al(OH)3 refers to the theoretical value.
c
Calculated by a superior reported water electrolysis efficiency of 77% [77].

hydrogen generated from waste Al reaches up to 19.72/
5.51 ¼ 357.89%, which is over 9 times that of water electrolysis,
namely 38.5%.
Experimental verification of the system
Materials
LM alloy used here is prepared by melting 68 wt% Ga, 22 wt%
In and 10 wt% Sn together at 200  C. To verify the feasibility of
hydrogen generation from waste Al, we collect several kinds
of Al discarded in daily life, including Al alloy sheet for con-
struction, Al radiator, Al wire for gardening, Al foil for food
cooking, Al foil for medicine package and Al can for food
package. A certain amount of Al samples and LM are placed in
a glass reactor which is filled with 0.4 mol/L NaCl solution
(simulating sea water here). The reactor was placed in a
thermostat water bath whose temperature was set as 30  C,
which simulates the auxiliary heating by solar energy. When
interfacial wetting occurs between Al and LM after direct
contact, Al would be activated to react with water, releasing
hydrogen. Generated gas flows through a drying tube, and
then its volume is measured by the displacement of water.
The photos of Al samples in the reaction process are taken
with a camera (EOS 80D, Canon, Japan). The effect of mass
ratio of LM to Al on the hydrogen generation performances is
explored with the same kind of Al samples, namely Al sheet.
In the recycle trial of LM, reaction mixtures after the reaction
are separated via a centrifuge (Anke TDL-40B, Anting Scientific
Instrument Factory, Shanghai, China). After one reaction cycle
ends, the reaction mixtures are transferred into the centrifuge
tube, and then separated by being centrifuged in 3000 r/min
for 1 min.
Results
We collected several kinds of wasted Al materials in daily life,
like Al alloy sheet for construction, Al radiator, Al wire for
gardening, Al foil for food cooking, Al foil for medicine pack-
age, and Al can for food package. As presented in Fig. 4a, Al
samples are passivated in water and remain unreacted. As
shown in Fig. 4b, the hydrolysis reaction is triggered imme-
diately with the addition of LM. Therefore, it is feasible to
produce hydrogen from wasted Al recycled from daily life.
Nevertheless, there is a layer of organic coating covering on
the surface of Al for some package materials (No. 5 and No. 6
in Fig. 4), which decelerates the AleH2O reaction to some
extent. It is suggested that Al samples taken from package
should be processed in advance to weaken the impact of
protective coating, like being grinded or being immersed in
specific organic solvent.
To figure out the hydrogen generation performances of
diverse Al materials, hydrogen generation experiments were
conducted on Al materials in four forms, including Al powder
in micro scale, Al foil with a thickness of 15 mm, Al plate with a
thickness of 1 mm, and Al bar with a diameter of 3 mm. The
ratio of LM to Al is fixed as 1:2. The hydrogen productivity,

Fig. 4 e Hydrogen evolution modes with recycled Al in different forms. (a) Raw materials. (b) The hydrolysis reaction mode of
various Al materials activated by LM. 1-Al alloy sheet for construction; 2-Al radiator; 3-Al wire for gardening; 4-Al foil for
food cooking; 5-Al foil for medicine package; 6-Al can for food package.
17510 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 5 0 5 e1 7 5 1 4

namely the ratio of actual hydrogen yield to the theoretical

hydrogen yield with equal Al input, is adopted to evaluate the
hydrogen production capacity of Al materials. As displayed in
Fig. 5, Al foil and Al plate possess the fastest hydrogen gen-
eration rate because of their large specific areas. The hydrogen
productivity of Al plate reaches up to 100%, and the value is
95% for Al foil. It is to be noted that Al foil is inclined to detach
from LM and then floats in water resulting from its large
buoyancy. To guarantee the better contact between Al foil and
LM, Al foil should be crushed into grains with LM together in
advance. Al powders disperse in the solution and are unable to
realize highly effective contact wetting with LM. Thus, the
productivity of Al powders is quite low. As for Al bar, the
penetration rate of LM into inner Al is extremely slow, which
sharply decreases its reaction velocity. Above all, Al samples
with laminar structures, like Al foil and Al plate, are appro-
priate for fast hydrogen generation, while Al samples with
compact crystal structures, like Al bar, only work for slow Fig. 6 e The hydrogen yields under different mass ratios of
hydrogen generation. To make Al powder activated, it should LM to Al.
be ball-milled with activators [53].
To reduce the input cost of LM, proper ratio of LM to Al
should be explored. Al plate was used here. As shown in Fig. 6, with the largest density sinks to the bottom, the lightest
when the mass ratio of LM to Al is no less than 1:4, the electrolyte float on the top, and Al(OH)3 remains at the middle
hydrogen productivity always reaches 100%. The hydrogen segment. Then the LM could be removed directly from the
generation rate is rather stable with a ratio of 1:1 or 1:2, and bottom. Recovered LM is reused to trigger the AleH2O reaction
the rate rises as the ratio decreases. When the ratio is 1:4, the in the same condition. This process was cycled for ten times.
hydrogen generation rate is fast in the early stage, and slows As recorded in Fig. 7, the hydrogen productivity reaches 100%
down in the late stage. When the ratio is as low as 1:8, the in approximately 30 min every time, and the hydrogen gen-
reaction ceases as the hydrogen productivity reaches about eration rate keeps stable after the introduction period. It
67%. As for the Ga-In-Sn activated AleH2O reaction, the opti- proves to be feasible to activate the AleH2O reaction with
mum mass ratio of LM to Al is around 1:2 according to recycled LM.
experiment results.
In addition, the hydrogen generation performance with
recycled LM is also explored. In the first cycle, LM and 0.2 g Al Discussions
plate are added into NaCl solution with a mass ratio of 1:1.
After approximately 30 min, a hydrogen productivity of 100% The above experimental results proved the feasibility of
is achieved. And then the LM is separated from the reaction hydrogen generation from waste Al in this method. Moreover,
mixture by centrifugation. After centrifuged in 3000 r/min for the material cost could benefit from the study on the effect of
1 min, the reaction mixture is separated into three layers. LM ratio of LM to Al and the recyclability of LM.
According to the LCA result, the energy consumption and
carbon emission of hydrogen production from LM activated
AleH2O reaction mainly lie in the acquisition process of Al.
The reutilization of waste Al possesses great superiority. But
the transportation cost has not been quantified. As a matter of

Fig. 5 e Hydrogen yield curves over time with recycled Al in Fig. 7 e Hydrogen production performances with recycled
different forms. LM alloys.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 5 0 5 e1 7 5 1 4
Table 2 e The SWOT analysis of the proposed hydrogen production approach.
Strengths
 Al could be activated by directly contacting LM, eliminating
energy-intensive pretreatments, like ball-milling or melting.
 This method with simple process flow could realize in-time
and on-demand hydrogen generation.
 The reuse of waste Al is energy-saving and carbon dioxide-free.
Opportunities
 The increasing energy demand and environment problems
urge the development of renewable and clean energy.
 Most countries have distributed encouragement
policies for hydrogen energy.
 A large amount of waste Al is directly discarded.
fact, waste Al is obtained in daily life, thus its transportation
cost could be ignored. However, as the smelting of Al proceeds
in factory, the bauxite should be transported in, and the Al
product should be transported out. Then the transportation
cost of primary Al or recycled Al from Al(OH)3 must be counted
in, which reinforces the superiority of the usage of waste Al.
Experiments verify that wasted Al could react with water
when activated by LM, and this is an effective and convenient
way to produce hydrogen on site. The hydrogen productivity
could be customized by adjusting the dosage of Al or water.
Nonetheless, there are several issues to address. Al plates
from construction materials, radiators, and other usage oc-
casions, as well as Al foils, could directly react with water at a
high rate when activated by LM. Al packages are usually
covered by a layer of plastic film, which impedes the hydro-
lysis reaction of Al. Measures should be taken to remove the
passive coating, like grinding or chemical dissolution.
As for the AleH2O reaction, the ratio of LM and Al is a
significant factor to the hydrogen generation performance. It
affects the exposing rate of Al activation site and the effective
contact of Al and water. After the interface wetting between
LM and Al occurs, the passive film on Al surface would be
broken, and the active sites of Al would be exposed. However,
with the proportion of LM increasing, the LM is apt to cover on
the Al surface, thus decreasing the effective contact of Al and
water. When the ratio of LM to Al is rather higher, only Al
granules floating to the surface of LM could react with water
and release hydrogen. Therefore, the induction period be-
comes shorter when the ratio of LM to Al decrease from 1:1 to
1:4. But from another perspective, as the LM amount de-
scends, the diffusion depth of LM drops down, and less acti-
vation sites of Al are exposed. As a result, when the ratio of LM
to Al reduces to 1:8, the reaction could not process completely,
and some unreacted Al residues could be observed after the
reaction finished.
In the recycle trials, the reuse of LM has no impact on the
hydrogen generation performance, but the mass of LM was
found to reduce approximately 0.01 g in each experiment. It is
inferred that the loss mainly lies in two terms, including the
hydrolysis of gallium, and the mass loss caused by the
transfer process. As known from former research [82], the
hydrolysis of gallium in neutral electrolyte processes as Eq. (4):
2Ga þ 4H2 O / 2GaOOH þ 3H2 [
17511
Weaknesses
 The quality of waste Al is uneven, making the
control of hydrogen generation rate difficult.
 The activator, LM, is costly, and
its recovery rate is to be improved.
Threats
 Mass-produced hydrogen from the reforming
of hydrocarbon fuel is low-cost and
occupies the majority of market.
 The investment in wind energy and
solar energy researches is ever-increasing.
The depletion rate of LM could be evaluated by the
hydrogen generation rate. Experiments verify that 0.03 g in
10 g LM is consumed when placed in 0.4 M NaCl solution for
48 h. Thus, the majority of LM loss is ascribed to the separation
and transfer process. It calls for further researches to develop
efficient and easily-operated recovery method of LM.
To comprehensively evaluate this hydrogen production
technology from waste Al in terms of internal factors and
external factors, a SWOT analysis is conducted as in Table 2.
SWOT analysis is a strategic tool to identify Strengths,
Weaknesses, Opportunities and Threats of an object or a
technology. Such an analysis could assess its performances
and competitive position, thus facilitating to formulate
reasonable development plans, and to catch opportunities
and defense threat. Here, we analyze the strengths and
weakness of this hydrogen generation approach, and discuss
the opportunities and threats it meets in current social cir-
cumstances. This analysis manifests its promising prospect
and challenges, and indicates the further research
orientation.
Conclusion
Liquid metal activated AleH2O reaction provides possibility
for in-time and on-demand hydrogen production. As can be
seen from the life cycle assessment of hydrogen production
from Al, the reuse of wasted Al could largely reduce the energy
consumption and environment cost of this process. Then
experiments prove that it is practicable to produce hydrogen
from waste Al. Among Al materials in various forms, Al
samples with laminar structures are preferred with high
hydrogen productivity and hydrogen generation rate. Al
packages are generally coated by a layer of organic film. Thus,
the film should be removed before the reaction to gain a
higher hydrogen generation efficiency. Al powders could not
be activated until they are ball-milled with activators. To
lower the cost of LM, the optimum mass ratio of LM (Ga-In-Sn
here) to Al in this method is recommended to be 1:2. In addi-
tion, even if LM is recycled for ten times, the hydrogen gen-
eration performances are not degraded. However, it is
insufficient to achieve the high-efficiency separation and
recycling of LM. According to the SWOT analysis, the
(4) strengths and social opportunities would promote further
17512 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 5 0 5 e1 7 5 1 4
development of this hydrogen generation method. Mean-
while, more endeavors should be devoted to overcome the
weakness, and to meet the competition against other renew-
able and energy sources.
Acknowledgement
This work is partially supported by the NSFC Key Project under
Grant No. 91748206, the Dean's Research Funding and the
Frontier Project of the Chinese Academy of Sciences.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.ijhydene.2019.05.176.
references
[1] Kabir E, Kumar P, Kumar S, Adelodun AA, Kim KH. Solar
energy: potential and future prospects. Renew Sustain
Energy Rev 2018;82:894e900. https://doi.org/10.1016/j.rser.
2017.09.094.
[2] Vargas SA, Esteves GRT, Maçaira PM, Bastos BQ, Oliveira FLC,
Souza RC. Wind power generation: a review and a research
agenda. J Clean Prod 2019;218:850e70. https://doi.org/10.
1016/j.jclepro.2019.02.015.
[3] Rehman S, Al-Hadhrami LM, Alam MM. Pumped hydro
energy storage system: a technological review. Renew
Sustain Energy Rev 2015;44:586e98. https://doi.org/10.1016/j.
rser.2014.12.040.
[4] Abram T, Ion S. Generation-IV nuclear power: a review of the
state of the science. Energy Policy 2008;36:4323e30. https://
doi.org/10.1016/j.enpol.2008.09.059.
[5] Suman S. Hybrid nuclear-renewable energy systems: a
review. J Clean Prod 2018;181:166e77. https://doi.org/10.1016/
j.jclepro.2018.01.262.
[6] Varun, Bhat IK, Prakash R. LCA of renewable energy for
electricity generation systemsda review. Renew Sustain
Energy Rev 2009;13:1067e73. https://doi.org/10.1016/j.rser.
2008.08.004.
[7] Dawson JK. Prospects for hydrogen as an energy resource.
Nature 1974;249:724e6. https://doi.org/10.1038/249724a0.
[8] Balat M. Potential importance of hydrogen as a future
solution to environmental and transportation problems. Int J
Hydrogen Energy 2008;33:4013e29. https://doi.org/10.1016/j.
ijhydene.2008.05.047.
[9] Edwards PP, Kuznetsov VL, David WIF, Brandon NP.
Hydrogen and fuel cells: towards a sustainable energy future.
Energy Policy 2008;36:4356e62. https://doi.org/10.1016/j.
enpol.2008.09.036.
[10] Ball M, Wietschel M. The future of hydrogen e opportunities
and challenges. Int J Hydrogen Energy 2009;34:615e27.
https://doi.org/10.1016/j.ijhydene.2008.11.014.
[11] Marchenko OV, Solomin SV. The future energy: hydrogen
versus electricity. Int J Hydrogen Energy 2015;40:3801e5.
https://doi.org/10.1016/j.ijhydene.2015.01.132.
[12] Khojasteh Salkuyeh Y, Saville BA, MacLean HL. Techno-
economic analysis and life cycle assessment of hydrogen
production from natural gas using current and emerging
technologies. Int J Hydrogen Energy 2017;42:18894e909.
https://doi.org/10.1016/j.ijhydene.2017.05.219.
[13] Seyitoglu SS, Dincer I, Kilicarslan A. Energy and exergy
analyses of hydrogen production by coal gasification. Int J
Hydrogen Energy 2017;42:2592e600. https://doi.org/10.1016/j.
ijhydene.2016.08.228.
[14] Tang C, Zhang R, Lu W, Wang Z, Liu D, Hao S, et al. Energy-
saving electrolytic hydrogen generation: Ni2P nanoarray as a
high-performance non-noble-metal electrocatalyst. Angew
Chem Int Ed 2017;56:842e6. https://doi.org/10.1002/anie.
201608899.
[15] Patel CRP, Tripathi P, Vishwakarma AK, Talat M, Soni PK,
Yadav TP, et al. Enhanced hydrogen generation by water
electrolysis employing carbon nano-structure composites.
Int J Hydrogen Energy 2018;43:3180e9. https://doi.org/10.
1016/j.ijhydene.2017.12.142.
[16] Christoforidis KC, Fornasiero P. Photocatalytic hydrogen
production: a rift into the future energy supply.
ChemCatChem 2017;9:1523e44. https://doi.org/10.1002/cctc.
201601659.
[17] Guo L, Chen Y, Su J, Liu M, Liu Y. Obstacles of solar-powered
photocatalytic water splitting for hydrogen production: a
perspective from energy flow and mass flow. Energy
2019;172:1079e86. https://doi.org/10.1016/j.energy.2019.02.
050.
[18] Sivagurunathan P, Kumar G, Mudhoo A, Rene ER,
Saratale GD, Kobayashi T, et al. Fermentative hydrogen
production using lignocellulose biomass: an overview of pre-
treatment methods, inhibitor effects and detoxification
experiences. Renew Sustain Energy Rev 2017;77:28e42.
https://doi.org/10.1016/j.rser.2017.03.091.
[19] Liu W, Cui Y, Du X, Zhang Z, Chao Z, Deng Y. High efficiency
hydrogen evolution from native biomass electrolysis. Energy
Environ Sci 2016;9:467e72. https://doi.org/10.1039/
C5EE03019F.
[20] Boran A, Erkan S, Eroglu I. Hydrogen generation from solid
state NaBH4 by using FeCl3 catalyst for portable proton
exchange membrane fuel cell applications. Int J Hydrogen
Energy 2018. https://doi.org/10.1016/j.ijhydene.2018.11.033.
[21] Bhosale R, Kumar A, AlMomani F, Gupta RB. Solar
thermochemical ZnO/ZnSO4 water splitting cycle for
hydrogen production. Int J Hydrogen Energy
2017;42:23474e83. https://doi.org/10.1016/j.ijhydene.2017.02.
190.
[22] Turner JA. Sustainable hydrogen production. Science
2004;305:972e4. https://doi.org/10.1126/science.1103197.
[23] Tang C, Zhang R, Lu W, He L, Jiang X, Asiri AM, et al. Fe-
Doped CoP nanoarray: a monolithic multifunctional
catalyst for highly efficient hydrogen generation. Adv
Mater 2017;29. 1602441, https://doi.org/10.1002/adma.
201602441.
[24] Meng F, Cushing SK, Li J, Hao S, Wu N. Enhancement of solar
hydrogen generation by synergistic interaction of La2Ti2O7
photocatalyst with plasmonic gold nanoparticles and
reduced graphene oxide nanosheets. ACS Catal
2015;5:1949e55. https://doi.org/10.1021/cs5016194.
[25] Wang Y, Yu Y, Li R, Liu H, Zhang W, Ling L, et al.
Hydrogen production with ultrahigh efficiency under
visible light by graphene well-wrapped UiO-66-NH2
octahedrons. J Mater Chem 2017;5:20136e40. https://doi.
org/10.1039/C7TA06341E.
[26] Mazloomi K, Gomes C. Hydrogen as an energy carrier:
prospects and challenges. Renew Sustain Energy Rev
2012;16:3024e33. https://doi.org/10.1016/j.rser.2012.02.028.
[27] Sharma S, Ghoshal SK. Hydrogen the future transportation
fuel: from production to applications. Renew Sustain Energy
Rev 2015;43:1151e8. https://doi.org/10.1016/j.rser.2014.11.
093.
[28] Abdalla AM, Hossain S, Nisfindy OB, Azad AT, Dawood M,
Azad AK. Hydrogen production, storage, transportation and
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 5 0 5 e1 7 5 1 4
key challenges with applications: a review. Energy Convers
Manag 2018;165:602e27. https://doi.org/10.1016/j.enconman.
2018.03.088.
[29] Schmidt MS. Containing hydrogen deflagrations. J Loss
Prevent Proc 2018;55:450e6. https://doi.org/10.1016/j.jlp.2018.
04.011.
[30] Moradi R, Groth KM. Hydrogen storage and delivery: review
of the state of the art technologies and risk and reliability
analysis. Int J Hydrogen Energy 2019;44:12254e69. https://doi.
org/10.1016/j.ijhydene.2019.03.041.
[31] Abe JO, Popoola API, Ajenifuja E, Popoola OM. Hydrogen
energy, economy and storage: review and recommendation.
Int J Hydrogen Energy 2019;44:15072e86. https://doi.org/10.
1016/j.ijhydene.2019.04.068.
[32] Rusman NAA, Dahari M. A review on the current progress of
metal hydrides material for solid-state hydrogen storage
applications. Int J Hydrogen Energy 2016;41:12108e26.
https://doi.org/10.1016/j.ijhydene.2016.05.244.
[33] Sethia G, Sayari A. Activated carbon with optimum pore size
distribution for hydrogen storage. Carbon 2016;99:289e94.
https://doi.org/10.1016/j.carbon.2015.12.032.
[34] Dündar-Tekkaya E, Yürüm Y. Mesoporous MCM-41 material
for hydrogen storage: a short review. Int J Hydrogen Energy
2016;41:9789e95. https://doi.org/10.1016/j.ijhydene.2016.03.
050.
[35] Ramimoghadam D, Gray EM, Webb CJ. Review of polymers of
intrinsic microporosity for hydrogen storage applications. Int
J Hydrogen Energy 2016;41:16944e65. https://doi.org/10.1016/
j.ijhydene.2016.07.134.
[36] Balderas-Xicohte
ncatl R, Schlichtenmayer M, Hirscher M.
Volumetric hydrogen storage capacity in metaleorganic
frameworks. Energy Technol 2018;6:578e82. https://doi.org/
10.1002/ente.201700636.
[37] Ilbeygi H, Kim IY, Kim MG, Cha W, Kumar PSM, Park D-H,
et al. Highly crystalline mesoporous phosphotungstic acid:
a promising material for energy storage applications.
Angew Chem Int Ed 2019. https://doi.org/10.1002/anie.
201901224.
[38] Steinfeld A. Solar hydrogen production via a two-step water-
splitting thermochemical cycle based on Zn/ZnO redox
reactions. Int J Hydrogen Energy 2002;27:611e9. https://doi.
org/10.1016/S0360-3199(01)00177-X.
[39] Xiao L, Wu SY, Li YR. Advances in solar hydrogen production
via two-step water-splitting thermochemical cycles based on
metal redox reactions. Renew Energy 2012;41:1e12. https://
doi.org/10.1016/j.renene.2011.11.023.
[40] Frankel GS, Samaniego A, Birbilis N. Evolution of hydrogen at
dissolving magnesium surfaces. Corros Sci 2013;70:104e11.
https://doi.org/10.1016/j.corsci.2013.01.017.
[41] Grosjean MH, Zidoune M, Huot JY, Roue
L. Hydrogen
generation via alcoholysis reaction using ball-milled Mg-
based materials. Int J Hydrogen Energy 2006;31:1159e63.
https://doi.org/10.1016/j.ijhydene.2005.10.001.
[42] Liu J, Wang H, Yuan Q, Song X. A novel material of
nanoporous magnesium for hydrogen generation with salt
water. J Power Sources 2018;395:8e15. https://doi.org/10.
1016/j.jpowsour.2018.05.062.
[43] Wang HZ, Leung DYC, Leung MKH, Ni M. A review on
hydrogen production using aluminum and aluminum alloys.
Renew Sustain Energy Rev 2009;13:845e53. https://doi.org/10.
1016/j.rser.2008.02.009.
[44] Huang XN, Gao T, Pan XL, Wei D, Lv CJ, Qin LS, et al. A review:
feasibility of hydrogen generation from the reaction between
aluminum and water for fuel cell applications. J Power
Sources 2013;229:133e40. https://doi.org/10.1016/j.jpowsour.
2012.12.016.
[45] Shkolnikov EI, Zhuk AZ, Vlaskin MS. Aluminum as energy
carrier: feasibility analysis and current technologies
17513
overview. Renew Sustain Energy Rev 2011;15:4611e23.
https://doi.org/10.1016/j.rser.2011.07.091.
[46] Mahmoodi K, Alinejad B. Enhancement of hydrogen
generation rate in reaction of aluminum with water. Int J
Hydrogen Energy 2010;35:5227e32. https://doi.org/10.1016/j.
ijhydene.2010.03.016.
[47] Yang BC, Chai YJ, Yang FL, Zhang Q, Liu H, Wang N.
Hydrogen generation by aluminum-water reaction in acidic
and alkaline media and its reaction dynamics. Int J Energy
Res 2018;42:1594e602. https://doi.org/10.1002/er.3953.
[48] Ziebarth JT, Woodall JM, Kramer RA, Choi G. Liquid phase-
enabled reaction of AleGa and AleGaeIneSn alloys with
water. Int J Hydrogen Energy 2011;36:5271e9. https://doi.org/
10.1016/j.ijhydene.2011.01.127.
[49] Godart P, Fischman J, Seto K, Hart D. Hydrogen production
from aluminum-water reactions subject to varied pressures
and temperatures. Int J Hydrogen Energy 2019;44:11448e58.
https://doi.org/10.1016/j.ijhydene.2019.03.140.
[50] Fan MQ, Xu F, Sun LX, Zhao JN, Jiang T, Li WX. Hydrolysis of
ball milling AleBiehydride and AleBiesalt mixture for
hydrogen generation. J Alloy Comp 2008;460:125e9. https://
doi.org/10.1016/j.jallcom.2007.05.077.
[51] Zhang F, Edalati K, Arita M, Horita Z. Fast hydrolysis and
hydrogen generation on Al-Bi alloys and Al-Bi-C composites
synthesized by high-pressure torsion. Int J Hydrogen Energy
2017;42(49):29121e30. https://doi.org/10.1016/j.ijhydene.2017.
10.057.
[52] Xiao F, Guo Y, Li J, Yang R. Hydrogen generation from
hydrolysis of activated aluminum composites in tap water.
Energy 2018;157:608e14. https://doi.org/10.1016/j.energy.
2018.05.201.
[53] Fan MQ, Xu F, Sun LX. Studies on hydrogen generation
characteristics of hydrolysis of the ball milling Al-based
materials in pure water. Int J Hydrogen Energy
2007;32:2809e15. https://doi.org/10.1016/j.ijhydene.2006.
12.020.
[54] Wei C, Liu D, Xu S, Cui T, An Q, Liu Z, et al. Effects of Cu
additives on the hydrogen generation performance of Al-rich
alloys. J Alloy Comp 2018;738:105e10. https://doi.org/10.1016/
j.jallcom.2017.12.152.
[55] Qiao D, Lu Y, Tang Z, Fan X, Wang T, Li T, et al. The superior
hydrogen-generation performance of multi-component Al
alloys by the hydrolysis reaction. Int J Hydrogen Energy
2019;44:3527e37. https://doi.org/10.1016/j.ijhydene.2018.
12.124.
[56] du Preez SP, Bessarabov DG. Hydrogen generation by the
hydrolysis of mechanochemically activated aluminum-tin-
indium composites in pure water. Int J Hydrogen Energy
2018;43:21398e413. https://doi.org/10.1016/j.ijhydene.2018.
09.133.
[57] Guan X, Zhou Z, Luo P, Wu F, Dong S. Effects of preparation
method on the hydrolytic hydrogen production performance
of Al-rich alloys. J Alloy Comp 2019;796:210e20. https://doi.
org/10.1016/j.jallcom.2019.05.053.
[58] Zhang J, Yao Y, Sheng L, Liu J. Self-Fueled biomimetic liquid
metal mollusk. Adv Mater 2015;27:2648e55. https://doi.org/
10.1002/adma.201405438.
[59] Yuan B, Tan SC, Liu J. Dynamic hydrogen generation
phenomenon of aluminum fed liquid phase GaeIn alloy
inside NaOH electrolyte. Int J Hydrogen Energy
2016;41:1453e9. https://doi.org/10.1016/j.ijhydene.2015.10.
044.
[60] Yang XH, Yuan B, Liu J. Metal substrate enhanced hydrogen
production of aluminum fed liquid phase GaeIn alloy inside
aqueous solution. Int J Hydrogen Energy 2016;41:6193e9.
https://doi.org/10.1016/j.ijhydene.2016.03.020.
[61] Lu JR, Yu WB, Tan SC, Wang L, Yang XH, Liu J. Controlled
hydrogen generation using interaction of artificial seawater
17514 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 7 5 0 5 e1 7 5 1 4
with aluminum plates activated by liquid GaeIn alloy. RSC
Adv 2017;7:30839e44. https://doi.org/10.1039/C7RA01839H.
[62] Tan SC, Gui H, Yang XH, Yuan B, Zhan SH, Liu J. Comparative
study on activation of aluminum with four liquid metals to
generate hydrogen in alkaline solution. Int J Hydrogen
Energy 2016;41:22663e7. https://doi.org/10.1016/j.ijhydene.
2016.10.090.
[63] Hiraki T, Takeuchi M, Hisa M, Akiyama T. Hydrogen
production from waste aluminum at different temperatures,
with LCA. Mater Trans 2005;46:1052e7. https://doi.org/10.
2320/matertrans.46.1052.
[64] Ho CY, Huang CH. Enhancement of hydrogen generation
using waste aluminum cans hydrolysis in low alkaline de-
ionized water. Int J Hydrogen Energy 2016;41:3741e7. https://
doi.org/10.1016/j.ijhydene.2015.11.083.
[65] Ho CY. Hydrolytic reaction of waste aluminum foils for
high efficiency of hydrogen generation. Int J Hydrogen
Energy 2017;42:19622e8. https://doi.org/10.1016/j.ijhydene.
2017.06.104.
[66] Setiani P, Watanabe N, Sondari RR, Tsuchiya N. Mechanisms
and kinetic model of hydrogen production in the
hydrothermal treatment of waste aluminum. Mater Renew
Sust Energ 2018;7:10. https://doi.org/10.1007/s40243-018-
0118-8.
[67] Worldal.com. 2019. https://market.cnal.com/. [Accessed 3
April 2019].
[68] Wan B, Chen W, Lu T, Liu F, Jiang Z, Mao M. Review of solid
state recycling of aluminum chips. Resour Conserv Recycl
2017;125:37e47. https://doi.org/10.1016/j.resconrec.2017.
06.004.
[69] Go€ kelma M, Meling I, Soylu E, Kvithyld A, Tranell G. A
method for assessment of recyclability of aluminum from
incinerated household waste. In: Chesonis C, editor. Light
metals 2019. The minerals, metals & materials series. Cham:
Springer; 2019. p. 359e65. https://doi.org/10.1007/978-3-030-
05864-7_168.
[70] Capuzzi S, Timelli G. Preparation and melting of scrap in
aluminum recycling: a review. Metals 2018;8:249. https://doi.
org/10.3390/met8040249.
[71] Baffari D, Reynolds AP, Li X, Fratini L. Influence of processing
parameters and initial temper on Friction Stir Extrusion of
2050 aluminum alloy. J Manuf Process 2017;28:319e25.
https://doi.org/10.1016/j.jmapro.2017.06.013.
[72] Ecns.cn. http://www.chinanews.com/ny/2018/12-06/8694595.
shtml. [Accessed 6 December 2018].
[73] ChinaIRN.COM. http://www.chinairn.com/news/20180914/
115053102.shtml. [Accessed 14 September 2018].
[74] Xu S, Zhao X, Liu J. Liquid metal activated aluminum-water
reaction for direct hydrogen generation at room
temperature. Renew Sustain Energy Rev 2018;92:17e37.
https://doi.org/10.1016/j.rser.2018.04.052.
[75] White CM, Steeper RR, Lutz AE. The hydrogen-fueled internal
combustion engine: a technical review. Int J Hydrogen
Energy 2006;31:1292e305. https://doi.org/10.1016/j.ijhydene.
2005.12.001.
[76] Barbir F, Go
mez T. Efficiency and economics of proton
exchange membrane (PEM) fuel cells. Int J Hydrogen Energy
1997;22:1027e37. https://doi.org/10.1016/S0360-3199(96)
00175-9.
[77] Koroneos C, Dompros A, Roumbas G, Moussiopoulos N. Life
cycle assessment of hydrogen fuel production processes. Int
J Hydrogen Energy 2004;29:1443e50. https://doi.org/10.1016/j.
ijhydene.2004.01.016.
[78] Finnveden G, Hauschild MZ, Ekvall T, Guine
e J, Heijungs R,
Hellweg S, et al. Recent developments in life cycle
assessment. J Environ Manag 2009;91:1e21. https://doi.org/
10.1016/j.jenvman.2009.06.018.
[79] Balomenos E, Panias D, Paspaliaris I. Energy and exergy
analysis of the primary aluminum production processes: a
review on current and future sustainability. Miner Process
Extr Metall Rev 2011;32:69e89. https://doi.org/10.1080/
08827508.2010.530721.
[80] Das S. Achieving carbon neutrality in the global aluminum
industry. JOM 2012;64:285e90. https://doi.org/10.1007/
s11837-012-0237-0.
[81] Wang HZ, Leung DYC, Leung MKH. Energy analysis of
hydrogen and electricity production from aluminum-based
processes. Appl Energy 2012;90:100e5. https://doi.org/10.
1016/j.apenergy.2011.02.018.
[82] Tang JB. Investigation on the flow manipulation and motion
actuation of gallium-based liquid metal [dissertation].
Beijing: University of Chinese Academy of Sciences; 2016.