Review

Aqueous Metal-Ion Batteries www.small-methods.com

Recent Progress of Rechargeable Batteries Using Mild

Aqueous Electrolytes
Jianhang Huang, Zhaowei Guo, Yuanyuan Ma, Duan Bin, Yonggang Wang,*
and Yongyao Xia

high ion conductivity of aqueous elec-

Given the low cost, ease of fabrication, high safety, and environmental- trolyte, aqueous rechargeable batteries
friendly characteristics, aqueous rechargeable batteries using mild aqueous have been considered as the promising
solutions as electrolytes (pH is close to 7) and a monovalent/multivalent candidate for large-scale energy storage.
metal ion as charge carrier, are attracting extensive attention for energy However, some disadvantages of electro-
lyte for traditional aqueous battery limit
storage. However, accompanied by advantages of mild aqueous electrolyte
their application, for example, corrosivity
mentioned above, there are some challenges that stand in the way of the of strong acid electrolyte and toxic issue
development of these aqueous rechargeable batteries, such as the narrow for lead-acid battery, significant causticity
stable electrochemical window of water, instability of electrode materials, of strong alkali electrolyte for nickel-
undesired side reactions, etc. In recent years, a massive effort is devoted to metal hydride battery, and toxic issue for
all-vanadium redox flow battery. In such
overcoming the drawbacks, and some encouraging works have arisen. In this
circumstance, aqueous rechargeable bat-
review, the latest advances of electrolyte and electrode materials in aqueous teries using mild electrolyte (containing
batteries based on monovalent ion (Li+, Na+, K+) and multivalent ion (Zn2+, metal salt as solute, mainly including
Mg2+, Ca2+, Al3+) are briefly reviewed. aqueous metal-ion batteries with inter-
calation electrodes) have been attracting
increasing attention during recent decade
1. Introduction not only in the field of grid-scale energy storage, but also for the
wearable and biocompatible application.[3,4] Up to now, most
With the increasing consumption of fossil energy, it becomes of intercalation-electrode materials for aqueous battery can be
an inevitable choice of restructuring the current energy mix tracked back to a corresponding version for nonaqueous elec-
to put the emphasis on the renewable energy sources, such trolyte. However, unlike the nonaqueous systems, the choice
as solar, wind, and tidal energy. However, the instinct inter- of electrode materials in aqueous electrolyte is seriously lim-
mittency and instability of renewable energy sources eagerly ited due to the following problems: the narrow stable electro-
require effective large-scale energy storage/conversion system chemical window of water (≈1.23 V), side reaction with water or
that has ability to integrate energy sources with electrical grid with oxygen, proton coinsertion along with insertion of metal
smoothly.[1] The commercial lithium-ion batteries (LIBs) pos- ion, dissolution of electrode materials in aqueous electrolyte,
sess high energy density, cycle stability, and energy efficiency, etc.[2] Aqueous Li-ion batteries (ALIBs) are the most investi-
but its enlargement for electrical grid is hindered by the safety gated system because of the solid research basis in nonaqueous
and cost mainly derived from organic electrolyte and electrode electrolyte. However, due to the limited Li resource, other metal
material.[2] Benefiting from the high safety, easy-to-fabrication, ions with abundant reserves including Na, K, Zn, Mg, Ca, and
Al-ion battery with mild aqueous electrolyte were proposed in
Dr. J. Huang, Dr. Z. Guo, Dr. Y. Ma, Dr. D. Bin, Prof. Y. Wang, Prof. Y. Xia
recent years. In particular, aqueous rechargeable zinc batteries
Department of Chemistry received much attention recently in light of the high theoretical
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials capacity of 820 mAh g−1, which is much higher than that of
Institute of New Energy anode materials for any others metal-ion batteries.
iChEM (Collaborative Innovation Center of Chemistry for Energy In this review, the batteries with mild aqueous electrolyte are
Materials)
Fudan University categorized according to the different charge carrier (monovalent
Shanghai 200433, China charge carrier Li+, Na+, K+ and multivalent charge carrier Zn2+,
E-mail: [email protected] Mg2+, Ca2+, Al3+). The ion radii are given in Table 1 because the
Dr. J. Huang electrochemical performance of battery is tightly associated with
School of Materials Science and Engineering ion radius of charge carrier. First, as to the most investigated
Nanchang Hangkong University
Nanchang 330063, China
aqueous Li and Na-ion batteries (ASIBs), there are good reviews
summarizing the anode/cathode materials, battery systems,
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smtd.201800272. challenges and solutions in past several years.[2,5,6] Therefore,
we here focus only on the advances in the latest several years:
DOI: 10.1002/smtd.201800272 “water-in-salt” electrolyte and organic anode materials. Second,

Small Methods 2019, 3, 1800272 1800272 (1 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Table 1. The radius of metal ions.

Jianhang Huang received his
Ion Radius [nm] Ph.D. degree from Central
Li+ 0.076 South University, China, in
June 2015, and B.S. degree
Na+ 0.102
in chemistry from Southwest
K+ 0.138 University of Science and
Zn2+ 0.074 Technology, China, in 2009.
Mg2+ 0.072 He has been working as
Ca2+ 0.100
a teacher at Nanchang
Hangkong University, China,
Al3+ 0.054
from 2015. He then moved to
Fudan University to complete
Zn batteries with mild aqueous electrolyte attract tremendous his postdoctoral training in the Department of Chemistry
attention recently, so we systematically reviewed the aqueous Zn under the supervision of Prof. Yongyao Xia and Yonggang
batteries in the following aspects: cathode materials (including Wang. His research is focused on energy storage materials
manganese oxides, vanadium oxide, Prussian blue analogs, and and aqueous rechargeable batteries.
other materials, and the mechanism of Zn2+ storage); anode
materials (from development of zinc anode in alkaline electro- Yonggang Wang received his
lyte to the latest advances in the mild electrolyte); electrolyte Ph.D. in physical chemistry
(including the selection of solute salt, additives in electrolyte and from Fudan University in
high concentration electrolyte). Third, the development of K, 2007. From 2007 to 2011,
Mg, Ca, Al-ion aqueous batteries is still in the incipient stage. he worked as a postdoc-
The history and the latest development of these batteries are toral research associate at
briefly summarized to give readers an easy understanding of the National Institute of
these batteries. Advanced Industrial Science
and Technology (AIST), Japan.
He is currently a full professor
2. Aqueous Rechargeable Batteries Using at the Department of
Monovalent Ions (Li+, Na+, K+) as Charge Carriers Chemistry at Fudan University,
China. His research interests include electrochemical
2.1. Aqueous Li-Ion Batteries functional materials and their application in lithium-ion bat-
teries, metal–air batteries, supercapacitors, and fuel cells.
Aqueous Li-ion battery was first proposed in 1994 by Dahn
and co-workers,[7] in which VO2 and LiMn2O4 were employed
Yongyao Xia is a professor in
as anode and cathode material, respectively, in 5 m LiNO3
the Department of Chemistry
aqueous electrolyte. Henceforth, various aqueous lithium-ion
of Fudan University. He
batteries have been developed. Generally, the stable voltage
received a Ph.D. degree in
window of aqueous electrolytes (≈1.23 V) is much narrower
energy-related materials sci-
than that of organic electrolytes (>3.0 V) used in the commer-
ence from Saga University,
cialized Li-ion batteries. In 2015, Wang and co-workers[8] pro-
Japan in 1997. His research
posed a “water-in-salt” electrolyte to expanded electrochemical
interests involve advanced
stability window to ≈3.0 V (1.9–4.9 V vs Li+/Li), which makes a
materials and technologies
revolutionary step in the development of ALIBs. The “water-
for energy storage and con-
in-salt” definition was applied when the salt outnumbers the
version devices, for example,
solvent in the binary system by both weight and volume. Lithium
lithium-ion batteries,
bis(trifluoromethane sulfonyl)imide (LiTFSI) was chosen as the salt
electrochemical supercapacitors, lithium–air, lithium–sulfur
in the work due to its high solubility in water (molality>20 m) and
batteries, etc.
high stability against hydrolysis. In such concentrated electrolyte,
the average number of water molecules available to solvate each
cation is very small. The H2O molecules/Li+ ratios is only 2.6 at
21 m, such minute quantities of H2O can no longer effectively of solid-electrolyte interphase (SEI) just like organic electrolyte
neutralize the electrostatic field created by the formal charge does, which can be proved by high-resolution transmission elec-
on Li+ (Figure 1a). That is to say, the H2O solvation sheath is tron microscopy (HRTEM) images (Figure 1c). When coupled
partially replaced by anion-containing Li+ solvation sheath, and with LiMn2O4 cathode in such “water-in-slat” electrolyte, the
the electrochemical activity of water is reduced substantially. assembled LiMn2O4/Mo6S8 cell shows an open-circuit voltage
Fascinatingly, density functional theory calculations indicate (OCV) of 2.3 V (Figure 1d) and stable cycle performance with
that TFSI− in “water-in-salt” will reduce before H2O during high capacity retention of 78% after 100 cycles at 0.15 C. The
cathodic polarization (Figure 1b). This results in the formation “water-in-salt” electrolyte opens new avenues for an interphase

Small Methods 2019, 3, 1800272 1800272 (2 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Figure 1. a) Illustration of the difference between Li+ solvation sheath in diluted and “water-in-salt” solutions. b) Predicted reduction potentials based
on the density functional theory calculations, the reduction potential ≈2.9 V versus Li of the aggregates [such as Li2(TFSI)(H2O)x] in “water-in-salt”
electrolyte is substantially higher than that of the isolated TFSI anion at 1.4 V and hydrogen evolution at 2.63 V versus Li+/Li. c) TEM images of cycled
Mo6S8 anode, indicating the formation of imperfect crystalline LiF. d) Charge/discharge profiles of LiMn2O4 and Mo6S8 electrodes in 21 m LiTFSI solu-
tion at 0.2 C. Reproduced with permission.[8] Copyright 2015, American Association for the Advancement of Science.

in aqueous electrolytes, which makes energy density of aqueous full ALIBs with low potential anode and high potential cathode,
Li-ion batteries comparable to commercial nonaqueous Li-ion such as Li4Ti5O12/LiNi0.5Mn1.5O4 (≈3.1 V with energy density
batteries. Apparently, the efficiency of SEI formation highly ≈90.6 Wh kg−1) and LiCoO2/Li4Ti5O12 (≈2.4 V with energy den-
depends on the salt concentration, more concentrated electro- sity ≈130 Wh kg−1). However, there is still a significant gap com-
lytes are needed to further elevate the energy density of ALIBs. pared to the state-of-the-art LIB with nonaqueous electrolyte
The same group[9] reported a “water-in-bisalt” electrolyte con- (400 Wh kg−1). Wang et al.[11] indicated that the key factor limiting
taining 21 m LiTFSI and 7 m LiOTf, providing 28 m Li+ with the further improvement of energy density of ALIBs is the awk-
H2O/Li+ ratio of ≈2. The more concentrated electrolyte shows ward reduction potential of aqueous electrolyte. The developed
a wider electrochemical stability window (1.83–4.9 V vs Li+/Li) “water-in-salt” and hydrate-melt electrolytes mentioned above
and lower water activity. As a result, it promotes the formation of are stable only >1.2 V versus Li+/Li. So there is no expectation to
more compact and protective SEI, which allows a 2.5 V (average use most anode materials with low redox potential (e.g., metallic
discharge voltage ≈2.1 V) ALIB with 100 Wh kg−1 based on the Li, 0.0 V; graphite, 0.10 V; silicon, 0.30 V vs Li+/Li).[11] Molecular
total electrode mass of LiMn2O4 cathode and TiO2 anode. In dynamics simulations reveal the reason why they are unstable
the same year, Yamada et al.[10] explored an optimized eutectic under 1.2 V versus Li+/Li: the repulsion between anions (TFSI−
composition of TFSI and N(SO2C2F5)2 (BETI) to form a hydrate- and OTf−) and anode surface will dramatically increase with the
melt electrolyte (Li(TFSI)0.7(BETI)0.3·2H2O) with extremely low gradual decrease of applied potential (polarized to 0.50 V vs Li+/
water content (molar ratio: H2O/Li+ = 2.0, all water molecules Li or below), leading to desorption of anions away from anode
participating in Li+ hydration shells). And the potential window surface. Instead, water molecules start to adsorb with hydro-
of this hydrate-melt electrolyte can be expanded to a maximum gens pointing toward the anode surface.[11] In order to overcome
width of 3.8 V (1.25−5.05 V vs Li+/Li), it enables to assemble this challenge, an “inhomogeneous SEI additive” (ISA) strategy

Small Methods 2019, 3, 1800272 1800272 (3 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

was proposed.[11] By coating a selected thin film ISA (which In fact, organic compounds have been widely investigated as
is in the form of gel, immiscible with electrolyte and strongly electrode materials in organic electrolytes.[15] Polypyrrole (PPy)
hydrophobic) on the anode surface (metallic Li and graphite), with doping/dedoping mechanism was the first anode material
a conformal and dense SEI containing both inorganic LiF/ reported for ALIBs. But it suffers from low practical capacity
organic CF species will form upon lithiation of anode. Com- (<80 mAh g−1) and a sloping discharge profile.[16] A few years
bining the improved version of previous “water-in-bisalt” elec- later, polyimide was proposed as the anode material for alkali-
trolyte, “gel-water-in-bisalt,” a series of 4.0 V full ALIBs were ion battery (including Li+ and Na+) by Zhou and co-workers
assembled, including Li/LiVPO4F (discharge plateau voltage with fast charge storage kinetics,[17] which is based on enoliza-
≈ 4.1 V), graphite/LiVPO4F (≈4.0 V), and Li/LiMn2O4 (≈4.0 V), tion process involving charge redistribution within the conju-
whose energy densities approach those state-of-the-art LIBs gated aromatic molecule. In contrast to the sloping discharge
with nonaqueous electrolyte. But note that the cycling stability plateau of PPy, polyimide presents a high reversible capacity of
of these ≈4.0 VALIBs needs further improvement. Based on the 160 mAh g−1 with a flat plateau at (−0.5 V vs saturated calomel
advantages of high salt concentration electrolyte, various battery electrode (SCE)) in 5 m LiNO3 aqueous electrolyte. Nevertheless,
systems have been developed to enhance the energy density of most of the developed organic electrodes were coupled with
ALIBs.[4,12,13] And a recent review[14] discussed the application of traditional electrodes with insertion/extraction mechanism,
“solvent-in-salt” electrolyte in rechargeable batteries. Note that limiting the rate performance of full battery. In order to take
“water-in-salt” electrolyte is not a classic aqueous electrolyte. full advantage of organic electrodes, I−/I3− liquid cathode with
The superior properties of “water-in-salt” electrolyte are mainly fast kinetics was coupled with polyimide anode by our group.[18]
derived from the anion-containing solvation sheath, which is The battery exerts a supercapacitor-like high power density and
sharply different with typical H2O solvation sheath in conven- 50 000 cycles long life span when operated between 0 and 1.6 V.
tional dilute solution. The application of organic electrodes in aqueous electrolytes is
Besides the high salt concentration electrolyte, another also restricted by the narrow electrochemical stability window
notable progress recently in ALIBs is the development of organic of water. Recently, by introducing the “water-in-salt” electrolyte,
electrode. Different from the redox reactions of metal ions for a full aqueous battery with all-organic electrodes (polyimide as
traditional electrode materials, organic-based electrode with anode, p-dopable polytriphenylamine (PTPAn) as cathode) was
electroactive group (which can store metal ions and electrons proposed.[13] The full battery can exert a maximum 52.8 Wh kg−1
using conjugated chemical bonds) have attracted increasing energy density that is comparable to the aqueous batteries for
interest not only because the energy storage pattern of organic large-scale energy storage. Meanwhile, it has a high power of
anode can minimize damages and volume expansion of the pri- 32 000 W kg−1 and a long cycle life (700 cycles with 86% capacity
mary structures, but also because the structure of organic mole­ retention). Yao and co-workers[19] reported universal quinones-
cules can be functionalized to make them robust and stable based electrode materials as stable anode materials from acid to
during repetitive reduction/oxidation in aqueous electrolytes. alkaline electrolyte (Figure 2). Specially, polymerized version of

Figure 2. Schematics of aqueous rechargeable batteries based on quinone anodes operating at various pH values (from acid to alkaline electrolyte)
with the indicated corresponding redox chemistries. The anode side (left panel) shows the redox/ion-coordination reaction of 1,2-benzoquinone and
1,4-benzoquinone structures. The middle panel shows the various electrolytes (including acid, neutral, and alkaline electrolytes) that are compatible
to the universal quinone anodes. The cathode side (right panel) shows the redox reaction of different cathode materials based on the choice of the
different pH electrolyte, including the industrially mature PbO2 in acid electrolyte, LiMn2O4 in neutral electrolyte, and Ni(OH)2 in alkaline electrolyte.
Reproduced with permission.[19] Copyright 2017, Macmillan Publishers Ltd.

Small Methods 2019, 3, 1800272 1800272 (4 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

pyrene-4,5,9,10-tetraone (PPTO) was prepared as anode mate- discharge voltage makes it possible to apply Ti-substituted
rials in mild electrolyte with high discharge capacity. When samples as anode material for ASIBs. When evaluated at rate
coupled with LiMn2O4 cathode in Li2SO4 electrolyte (pH = 7), of 2 C (100 mA g−1) from 0 to 0.6 V versus SCE in Na2SO4
the full cell exerts an average voltage of 1.13 V with specific/ aqueous electrolytes, a stable discharge capacity of 37 mAh g−1
volumetric energy density of 92 Wh kg−1/208 Wh L−1, high sta- can be exerted, which is higher than that of activated carbon.
bility (80% capacity retention after 3000 deep cycles at 1 C, i.e., Moreover, an impressive long-span cycle life for 400 cycles
280 mAg−1), excellent rate performance (60% of the maximum can be achieved without eliminating oxygen in electrolyte
capacity delivered at 20 C, i.e., 5.6 Ag−1), and low polarization (Figure 3b).[25] Recently, an electrode material that can serve
during rate test.[19] What’s more, not only as the anode material simultaneously as anode and cathode (symmetric battery)
for ALIBs, the developed quinone-based electrodes show great has been attracting increasing attention recently. The utiliza-
universal to other metal-ion batteries, including sodium-ion tion of the same material for both anode and cathode not only
battery and magnesium-ion battery.[19] lowers the manufacturing costs, but also buffers the volume
In addition, similar to the versatile quinone-based materials, change of material (one electrode shrinking accompanied by
δ-Bi2O3 was evaluated as a versatile inorganic anode material the expansion of another electrode). Goodenough and Gao[26]
with reversible redox reaction in various aqueous metal-ion synthesized NASICON-type compound of Na3MnTi(PO4)3 to
electrolytes (including Li+, Na+, K+, Mg2+, Ca2+, Sr2+, Ba2+, and construct aqueous symmetric battery, and the redox potential of
Al3+) by Liu and co-workers.[20] The reversible charge storage Mn2+/Mn3+ and Ti4+/Ti3+ is within the water stable window in
process of Bi2O3 involves the intermediate state of Bi2+, which 1 m Na2SO4 (Figure 3c,d). The extraction of one Na+ from one
can be ascribed as B2O3 ↔ Bi2+ (Bi2O2) ↔ Bi0. And as-prepared Na3MnTi(PO4)3 results in the formation of one Na2MnTi(PO4)3
δ-Bi2O3 will completely transform to α-Bi2O3 after the first cycle accompanied with oxidation of Mn2+ to Mn3+. On the other
due to the fact that the latter is more stable than former under hand, the insertion of one Na+ into one Na3MnTi(PO4)3 results
ambient conditions. in the formation of one Na4MnTi(PO4)3 accompanied with
reduction of Ti4+ to Ti3+. With the Mn2+/Mn3+ and Ti4+/Ti3+
redox couples, an operating voltage of 1.4 V without obvious
2.2. Aqueous Na-Ion Batteries polarization can be obtained (Figure 3e), as well as 57.9 mAh g−1
discharge capacity at 0.5 C (1 C = 58.7 mA g−1), and ≈98%
The development of ASIBs is based on the fact that the capacity retention after 100 cycles at 1 C (Figure 3f). Another
resource of sodium in the earth’s crust is much more abun- NASICON-structured compound of Na2VTi(PO4)3 was prepared
dant than lithium. Similar to the ALIBs, “water-in-salt” electro- by Liang and co-workers for symmetric battery.[27] V4+/V3+
lyte can also be applied to ASIBs to broaden electrochemical and Ti4+/Ti3+ redox couples are responsible for the reaction of
window.[21–23] Interestingly, Wang and co-workers[21] found cathode and anode, respectively. The assembled symmetric bat-
that the ion aggregation between Na+ and trifluoromethane tery shows 1.14 V operating voltage, 50.4 mAh g−1 capacity at
sulfonate anion (CF3SO3−) is much more intense than that 1 C (1 C = 62 mA g−1), 40.6 mAh g−1 at 10 C with ≈70% capacity
between Li+ and TFSI−, which means a lower salt concentra- retention after 1000 cycles. In addition, organic anodes such as
tion of 9.26 m NaCF3SO3 aqueous solution is enough to form polyimide and PPTO are also feasible to ASIBs.[17–19]
a Na+-conducting SEI (in a sharp contrast with 21 m LiTFSI).
And a 2.5 V electrochemical window can be achieved. Com-
bining with NaTi2(PO4)3 anode and Na0.66[Mn0.66Ti0.34]O2 2.3. Aqueous K-Ion Batteries (AKIBs)
cathode, the assembled full battery exerts an energy density
of 31 Wh kg−1 with >99.2% coulombic efficiency at 0.2 C for As to AKIBs, the development of high-performance electrode
>350 cycles. And more than 1500 cycles can be achieved with materials is limited by the high ionization potential and large
a high capacity retention of 92.7% at high rate of 1 C.[21] Batt- ionic radius of K+ (0.138 nm). Up to now, the most prom-
aglia and co-workers[23] found that the solubility of sodium ising cathode material for AKIBs is Prussian blue analogues
bis(fluorosulfonyl)imide (NaFSI) in water is ultrahigh (Figure 4a),[28,29] which have been comprehensively studied
(up to 37 m). And the 35 m NaFSI “water-in-salt” electrolyte by Cui and co-workers, including copper hexacyanoferrate,
shows 2.6 V stability electrochemical window. The preliminary nickel hexacyanoferrate, and copper-nickel alloy hexacyano-
studies show that an aqueous sodium-ion battery (more than ferrate with tunable reaction potential. Among them, copper
2 V) based on 35 m NaFSI electrolyte, NaTi2(PO4)3 anode, and hexacyanoferrate (CuHCF) shows the most impressive perfor-
Na3(VOPO4)2F cathode is feasible.[23] mance, including pH-independent reaction potential of 0.946 V
In the case of the electrode materials for ASIBs, the choice versus SHE, good rate performance (59.14 mAh g−1 at 0.83 C,
of electrode materials is limited due to the larger radius of 1 C = 60 mAg−1, and 40.1 mAh g−1 at 83 C) (Figure 4b), excel-
Na+ (0.102 nm).[6,24] Especially the anode materials, only few lent cycle performance (83% after 40 000 cycles at current rate
materials (activated carbon (AC), NaTi2(PO4)3, polyaniline, of 17 C), and high coulombic efficiency of 99.7%.[28] Generally,
and PPy) have been developed in recent years.[6] Huang and the discharge capacity of Prussian blue analogues is relatively
co-workers[25] prepared a series of Ti-substituted tunnel-type low (<60 mAh g−1). Recently, Wang and co-workers[30] prepared
Na0.44MnO2 oxide (Na0.44[Mn1−xTix]O2, x = 0.11–0.56) for the potassium iron (II) hexacyanoferrate dehydrate nanocubes
Na+ insertion. The discharge voltage of Ti-substituted samples (K2FeII[FeII(CN)6]·2H2O) with high K+ content as cathode mate-
during 2.8–1.5 V is about 0.2 V in average lower than that of rial for AKIBs. Benefiting from the high K+ content and the
the unsubstituted sample (Figure 3a). The interesting lower two one-electron redox processes, this compound can exert as

Small Methods 2019, 3, 1800272 1800272 (5 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Figure 3. a) Comparison of the charge/discharge curve for Na0.44[Mn1−xTix]O2 and b) the cycle performance of Na0.44[Mn0.44Ti0.56]O2. Reproduced
with permission.[25] Copyright 2015, Macmillan Publishers Ltd. c) The cyclic voltammogram of Na3MnTi(PO4)3 (solid line) for the Mn3+/Mn2+ redox
couple (Ag/AgCl as the reference electrode) and the linear sweep voltammogram of the activated carbon electrode (dotted line) at 1.0 mV s−1 scan
rate. d) The cyclic voltammogram of Na3MnTi(PO4)3 (solid line) for the Ti4+/Ti3+ redox couple and the linear sweep voltammogram of the activated
carbon electrode (dot line) at 1.0 mV s−1 scan rate. e) Charge/discharge profiles of the symmetric sodium-ion battery between 0.4 and 1.8 V at 0.5 C
rate. f) The cycle performance and coulombic efficiency of the symmetric sodium-ion battery at 1 C rate. Reproduced with permission.[26] Copyright
2016, Wiley-VCH.

high as 120 mAh g−1 capacities. Whereas, there are two respec- Recently, a “water-in-salt” electrolyte of concentrated potassium
tive discharge plateaus at ≈0.9 and ≈0.3 V corresponding to K+ acetate (KAc) solution was utilized by Ji and co-workers to extend
insertion into two respective coordination sites (Figure 4c,d). electrochemical window for AKIBs.[32] In virtue of the wide elec-
The resulting average operating potential is ≈0.6 V versus Ag/ trochemical window (from −1.7 to 1.5 V vs Ag/AgCl), KTi2(PO4)3
AgCl. In addition, Baioun et al.[31] prepared Prussian yellow (KTP, only feasible in nonaqueous electrolyte previously) can be
film (FeIII[FeIII(CN)6]) as potassium-ion storage cathode mate- evaluated as anode in 30 m KAc, and it can deliver 53 mAh g−1
rial. When coupled with Zn anode, the battery shows impressive specific capacity.[32] Interestingly, the ion conductivity of KAc is
1.9 V open-circuit voltage, and 142 mAh g−1 at 3 C (416 mA g−1). much better than LiTFSI under the same salt concentration.

Small Methods 2019, 3, 1800272 1800272 (6 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Figure 4. a) The Prussian blue crystal structure of CuHCF. b) Galvanostatic discharge profiles of CuHCF at various current densities between 0.6
and 1.4 V versus SHE showed a maximum specific capacity of 59.14 mAh g−1 centered at 0.946 V. Reproduced with permission.[28] Copyright 2011,
Macmillan Publishers Ltd. c) Unit formula of potassium iron(II) hexacyanoferrate dehydrate. d) The first cycle profiles at current densities of 200, 500,
1000, 2000, and 3000 mA g−1 with two respective discharge plateaus at ≈0.9 and ≈0.3 V versus Ag/AgCl. Reproduced with permission.[30] Copyright
2017, Wiley-VCH.

3. Aqueous Batteries Using Multivalent Ions oxide is the most widely investigated cathode material for
(Zn2+, Mg2+, Ca2+, Al3+) as Charge Carriers zinc-ion storage.[33–37] As early as 1988, Zn/ZnSO4/MnO2
rechargeable battery system was exploited by Yamamoto and
3.1. Aqueous Zinc Batteries (AZBs) co-workers,[38] but the mechanism of battery was unclear.
Until 2009, Kang and co-workers[39] found that alpha manga-
Besides the above mentioned aqueous metal-ion battery sys- nese dioxide (α-MnO2) can store and release zinc ion fast and
tems, AZBs have been attracting keen interests from global reversibly, which is suitable to be the cathode materials storing
researchers in the very recent years because of their high spe- zinc ion. And combining with the metal zinc anode and mild
cific capacity. Generally, aqueous zinc batteries are composed aqueous electrolyte containing zinc salt, the concept of “zinc
of zinc-ion storage materials as cathode, zinc metal anode, and ion battery” was proposed, although where the anode is metal
neutral (or mild acid) electrolyte. Each of the three components zinc rather than the ion storage materials. Up to now, α-MnO2,
of AZBs will be discussed below. β-MnO2, γ-MnO2, δ-MnO2, spinel-type MnO2, todorokite-type
MnO2, and α-Mn2O3 have been reported as host materials for
zinc-ion storage.[34–37,40–45] Due to the various crystallographic
3.1.1. Cathode Materials for AZBs polymorphs of manganese oxides, the electrochemical reaction
mechanism of manganese oxides in neutral (or mild acid) elec-
Generally, most ion storage materials used in aqueous Li, Na, trolyte still remains controversial.
K-ion battery can be employed as cathode materials in zinc-ion Basically, zinc-ion insertion/extraction and proton insertion/
batteries, such as manganese oxides, vanadium oxides, Prus- extraction during redox of manganese oxides are the two main-
sian blue analogs, etc. Because of the high theoretical capacity stream views. Oh and co-workers[42,43] reported the zinc-ion
(308 mAh g−1 based on single electron transfer between Mn4+ insertion mechanism accompanied with a series of single and
and Mn3+), nontoxicity, and abundance reserve, manganese two-phase electrochemical reaction, which involves reversible

Small Methods 2019, 3, 1800272 1800272 (7 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Figure 5. Schematic of the zinc intercalation into a) α-MnO2, b) β-MnO2, and c) γ-MnO2, respectively. (a) Reproduced with permission.[43] Copyright
2015, The Royal Society of Chemistry. (b) Reproduced with permission.[36] Copyright 2017, Nature Publishing Group. (c) Reproduced with permis-
sion.[44] Copyright 2015, American Chemical Society.

phase transition between 2 × 2 tunneled α-MnO2 and layered impedance spectroscopy (EIS), Wang et al.[34] demonstrated
Zn-buserite MnO2. In detail, during the zinc-ion insertion pro- that akhtenskite nano-MnO2 experienced the successive H+ and
cess, Mn2+-dissolution from the channel wall of α-MnO2 results Zn2+ insertion processes with a distinct difference in reaction
in the formation of layered birnessite. Then hydrated Zn2+ kinetics, which is responsible to the two respective discharge
rather than naked Zn2+ will insert into birnessite to form Zn- platform. Due to the much faster reaction kinetics of H+ than
buserite MnO2, which is proved by the large lattice spacing of Zn2+, H+ insertion is in charge of the first (high) discharge plat-
≈1 nm (Figure 5a).[43] The preferential hydrated Zn2+ insertion form, and Zn2+ is responsible to the second (low) discharge
can be explained by the fact that the high ionic charge of zinc platform (Figure 6c).[34] Very recently, our group prepared poly-
ion is distributed by polarized intimate water molecules, and aniline (PANI)-intercalated MnO2 nanolayers as cathode mate-
mitigate the repulsive interaction between Zn2+ and host mate- rial for aqueous zinc battery.[37] And the mechanism studies
rial.[43] Chen and co-workers[36] reported that β-MnO2 also con- support the subsequent insertion of H+ and Zn2+ into layered
vert to a layer-type phase in the beginning of discharging, and nano-MnO2 (Figure 6d).[37] Moreover, due to the typical nano-
subsequent reversible Zn2+ insertion/extraction could happen size, expanded interlayer space, uniform mesostructure, and
in such layered structure (Figure 5b). Alfaruqi et al.[44] reported polymer-reinforced layered structure, the polyaniline-interca-
that tunnel-type γ-MnO2 suffers from a structural transforma- lated MnO2 nanolayers show superior cycle stability at deep
tion to spinel-type ZnMn2O4 phase and some new intermediary charge/discharge than conventional MnO2.[37]
phases (involves spinel-type, tunnel-type, and layered-type man- Vanadium oxide is another attractive zinc-ion storage mate-
ganese oxides) during insertion of zinc ion. And a majority of rial because of its large capacity (>300 mAh g−1), fast dynamics,
these phases can revert back to the parent γ-MnO2 phase after and low cost.[46–49] These advantages are mainly ascribed to
extraction of zinc ion (Figure 5c). Besides the zinc-ion inser- the multiple oxidation states of vanadium and the large open-
tion/extraction, Liu and co-workers[35] presented a chemical framework crystal structure. Especially, the charge-shield
conversion reaction mechanism (i.e., proton insertion) of α- effect of the crystal H2O during interspace could reduce the
MnO2 nanofiber evidenced by the observation of MnOOH in effective charges of intercalated Zn2+ ions, and thus enhance
the discharging products (Figure 6a,b) and very limited capacity the capacity and rate performance.[46,49–52] Much of vanadium
in organic electrolyte (i.e., there is no H+ ions in organic elec- oxides (or hydroxides) have been exploded for cathode mate-
trolytes). Generally, the discharge profile of zinc-ion battery is rials of AZBs, such as Ca0.25V2O5·nH2O,[48] NaV3O8·1.5H2O,[53]
usually characterized by two respective discharge platforms. Zn3V2O7(OH)2·2H2O,[52] H2V3O8,[47] LiV3O8,[50] VO1.52(OH)0.77,[51]
With the detailed kinetic studies by galvanostatic intermittent Na2V6O16·1.63H2O nanowire,[54] Na1.1V3O7.9 nanoribbons/
titration technique (GITT) (Figure 6c) and electrochemical graphene,[55] Na0.33V2O5 nanowire,[56] layered zinc orthovanadate,[57]

Small Methods 2019, 3, 1800272 1800272 (8 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Figure 6. a) HRTEM images of α-MnO2 nanofiber after being discharged to 1 V. The lattice fringes of 0.33 nm are corresponding to d spaces from the
(210) planes in monoclinic MnOOH, and b) 0.26 nm is corresponding to (020) planes. Reproduced with permission.[35] Copyright 2016, Macmillan
Publishers Ltd. c) Discharge galvanostatic intermittent titration technique profiles of the Zn/akhtenskite MnO2@CFP cell, the overvoltage in region I
(the first discharge platform) is 80 mV, which is much less than 600 mV in region II (the second discharge platform). Reproduced with permission.[34]
Copyright 2017, American Chemical Society. d) Diagram showing the sequential insertion of H+ and Zn2+ into PANI intercalated MnO2 nanolayer.
Reproduced with permission.[37] Copyright 2018, Nature Publishing Group.

etc. Nazar and co-workers[46] reported a vanadium oxide bronze V2O5·nH2O is effectively improved by the largely reduced effec-
pillared by interlayer Zn2+ ions and water (Zn0.25V2O5·nH2O) tive charge of Zn2+. Mai and co-workers[56] prepared Na0.33V2O5
as the positive electrode for zinc-ion battery. The capacity can nanowire as cathode for AZBs. The intercalating Na+ between
achieve 300 mAh g−1 at a moderate current density of 50 mA g−1, the [V4O12]n layers can serve as “pillars” to increase the stability
which yields intercalation of 1.2 Zn2+ (i.e., Zn1.45V2O5·nH2O). of the tunnel structure during ions insertion/extraction. Very
The co-intercalated water molecules along with Zn2+ buffer the recently, the “pillars”-induced stability was also reported by Chen
relative high charge density of Zn2+ and lower the activation and co-workers for NaV3O8·1.5H2O cathode materials.[53] From
energy for charge transfer at the electrode interface, leading above works, it can be concluded that vanadium oxides usually
to fast kinetics and corresponding high rate performance. In possess large capacity (>300 mAh g−1, the discharge capacity of
addition, the indigenous Zn ions in Zn0.25V2O5 stabilize the manganese oxides usually <300 mAh g−1) and good high-rate
layered structure, thereby ensuring long-term cycling stability performance. However, the average operating voltage is always
(Figure 7).[46] The critical role of structural H2O on Zn2+ inser- under 1 V along with a slopy discharge platform, which is lower
tion into bilayer V2O5·nH2O is also demonstrated by Yang than ≈1.3 V versus Zn2+/Zn of manganese oxides. And the
and co-workers.[49] The diffusion of H2O-solvated Zn2+ in toxicity of vanadium oxides is also a concern for enlargement.

Small Methods 2019, 3, 1800272 1800272 (9 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Figure 7. Illustration showing the structure of pristine Zn0.25V2O5·nH2O, reversible water insertion into Zn0.25V2O5·nH2O when immersed in electrolyte/
H2O, and the water deinsertion accompanying Zn2+ insertion during discharge process. The H2O molecules interact with the oxygen layers through
hydrogen bonding. And a fraction of insertion H2O remains in the discharged material. The red and blue spheres represent O and H, respectively;
double-sheet V2O5 layers are indicated in dark red, and the interlayer ZnO6 polyhedra are indicated in gray. Here, y > z > n. Reproduced with permis-
sion.[46] Copyright 2016, Macmillan Publishers Ltd.

Prussian blue analogs (metal hexacyanoferrates (MeHCFs)), Organic electrodes materials are also feasible for aqueous
as one kind of metal–organic framework materials, possess an AZBs. Very recently, Chen and co-workers[67] reported the
open and tunable crystal structure. The stable and open frame- application of quinone electrodes in aqueous zinc battery. The
work containing large interstitial sites allows the kinetically easy results indicated that the quinone compounds with carbonyls
and fast insertion/removal of guest ions. Liu and co-workers[58] in ortho-position (1,2-naphthoquinone (1,2-NQ) and 9,10-phen-
proposed zinc hexacyanoferrate (ZnHCFs) as intercalation anthrenequinone (9,10-PQ)) generally show lower capacity and
hosts for Zn2+. And yielding an average operation voltage of larger polarization than those with carbonyls in para-position
≈1.7 V versus Zn2+/Zn, which is the highest recorded operation (1,4-naphthoquinone (1,4-NQ), 9,10-anthraquinone (9,10-AQ),
voltage for aqueous Zn batteries. Furthermore, this group syn- and calix[4]quinone (C4Q)) due to the larger steric hindrance.
thesized three rhombohedral phase ZnHCF particles (cubooc- And the carbonyls with more negative electrostatic potential
tahedral, truncated octahedral, and octahedral shapes),[59] and (ESP) prefer to be active sites for Zn-ion storage (Figure 8).[67]
pointed out that the sample with cubooctahedral shape exerts
the best rate capability and cyclic stability. Besides the zinc hex-
acyanoferrate, copper hexacyanoferrate,[60,61] nickel hexacyano- 3.1.2. Anode Materials for AZBs
ferrate,[62] and iron hexacyanoferrate[63] can also be employed as
cathode materials for aqueous zinc battery. Unfortunately, the As we know, zinc metal anode is the most widely used anode
capacity of Prussian blue analogs is relative low (<100 mAh g−1 material, for example, AA, AAA primary alkaline batteries,
at 1 C, i.e., 60 mA g−1, lower than both vanadium oxides and Zn-Air battery, Zn-Ni battery, and Zn-Ag battery. The biggest
manganese oxides). Although some of Prussian blue analogs advantage of metallic Zn over Li, Na, K is that metallic Zn is rela-
exert high and flat discharge voltage > 1.5 V versus Zn2+/Zn, tively stable and redox reversible in aqueous medium (although
the energy density is still uncompetitive. Mg, Al are stable in water, their electrodeposition is not thermo-
Besides the above cathode materials, there are some other dynamically feasible in aqueous electrolytes),[68,69] so it can be
zinc insertion materials reported in recent years. Huang and directly used as anode in aqueous electrolyte.[70] And the theoret-
co-workers[64] demonstrated the mechanism of Zn insertion/ ical capacity is 820 mAh g−1,[71,72] which is much larger than any
extraction into/from the NASICON structured Na3V2(PO4)3 other ion storage anode materials (either insertion/extraction or
host: Na+ first extracted out of Na3V2(PO4)3 to form NaV2(PO4)3 organic electrodes). On the other hand, due to a high overpoten-
during charging, and Zn2+ insertion leads to the formation tial for hydrogen evolution, metallic Zn possesses the low redox
ZnxNaV2(PO4)3 over subsequent discharging. Liu and co- potential (−0.76 V vs SHE)[46] in aqueous electrolyte without
workers[65] reported chevrel phase Mo6S8 nanocubes exert low obvious hydrogen evolution. Combining the high capacity, low
redox potential (during 0.3–0.4 V vs Zn2+/Zn), which can be used redox potential, nontoxicity, and abundant reserves in the Earth’s
as anode for zinc insertion. Kang and co-workers[66] made a com- crust, metallic Zn has been considered as promising anode
prehensive evaluation on oxides (MoO3, TiO2, and Fe3O4), sulfides material for large-scale energy storage. Not only used in the zinc-
(MoS2,WS2, and MnS), and borides (TiB2 and ZrB2) in order to ion battery, it is also widely used in “hybrid aqueous battery sys-
develop new electrode materials for aqueous zinc batteries. And tems,” which are usually composed of Zn anode, Li/Na ion (or
they found only MnS could be a promising alternative cathode other metal ions) storage cathode materials, and aqueous electro-
material due to its high reversibility and good cycle stability. lyte containing Zn ion and Li/Na ion (or other metal ions).[71,73]

Small Methods 2019, 3, 1800272 1800272 (10 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Figure 8. Illustration showing the theoretical calculations results of the active sites and structure evolution of quinone electrodes using density func-
tional theory. The ESP-mapped molecular van der Waals surface of a) 1,2-NQ, b) 1,4-NQ, c) 9,10-AQ, d) 9,10-PQ, and e) C4Q. Surface local minima
of ESP are represented as blue spheres, and the corresponding ESP values are indicated with numbers. f) Optimized configurations of C4Q before
and after Zn2+ capture. Bottom: Corresponding configurations at different viewpoints. The distance between OO and ZnO has been indicated in
angstroms. Reproduced with permission.[67] Copyright 2018, American Association for the Advancement of Science.

However, the commercial application of metallic Zn anode in or hydroxides)[76–78] in zinc electrode, alloying zinc with other
secondary battery has been hindered by the zinc dendrite and metals[78,79] and optimizing structure/morphology of zinc elec-
low plating/stripping efficiency.[33,71,72] Zinc dendrite is serious trode[80,81] were found to be effective to suppress the hydrogen
especially in alkaline electrolyte, such as alkaline Zn/Mn, Zn/ evolution. Recently, Rolison and co-workers[80] demonstrated
Ni, and Zn/air secondary battery. Take Zn/Ni alkaline battery that the 3D zinc sponge electrode with predoped In and Bi
as an example, Zn↔Zn(OH)42− and NiOOH↔Ni(OH)2 redox could suppress hydrogen evolution in alkaline Zn/Ni secondary
couples are responsible for anode and cathode reaction, respec- battery (Figure 9a). Although these methods are developed in
tively. Generally, the Zn↔Zn(OH)42−redox reaction prefers the alkaline electrolyte, most of them are also helpful in mild elec-
formation of zinc dendrite, whose mechanism has been studied trolyte. Kang and co-workers[82] presented a composite anode
widely.[33,74] But for the neutral (or mild acid) electrolyte of zinc- prepared by mixing metallic zinc particles with AC for zinc bat-
ion battery, the issue of zinc dendrite is not as serious as that in tery with mild electrolyte. The activated carbon induce the pref-
the alkaline electrolyte because of the redox couple of Zn↔Zn2+ erential deposition of anodic products in the pores of activated
in mild electrolyte is different from that in alkaline electrolyte. carbon rather than on the surface of Zn particles (Figure 9b),
There are only slight or no obvious zinc dendrite in neutral or which greatly improved the electrochemical reaction kinetics
mild acid,[35,40,60,75,76] so the zinc dendrite issue will not be dis- and reversibility of zinc anode. Mantia and co-workers[83] devel-
cussed in detail in this review, and we will focus on the plating/ oped Zn-Al-layered double hydroxide (Zn-Al-LDH) as a suit-
stripping efficiency of zinc anode. Generally, the plating/strip- able substrate to improve the plating/stripping efficiency of Zn
ping efficiency (Coulombic efficiency) is closely relative with the anode for neutral pH electrolyte. The achieved 98% coulombic
side reaction during charge/discharge process, mainly including efficiency for Zn-Al-LDH electrode is much higher than that
hydrogen evolution and passivation. Hydrogen evolution for bare metallic Zn (≈85%). Chen and co-workers[84] prepared
derived from charging process and corrosion (self-discharge) plating zinc electrode possessing less hydrogen gas evolution
is the most important side reaction, not only decreases cou- and dendrite formation by an optimized neutral electrolyte
lombic efficiency, but also leads to the irreversible consumption (0.6 m zinc sulfate and 0.1 m ammonium sulfate) containing
of water in electrolyte. Passivation, which is related to the for- selected inorganic additives (indium sulfate, tin oxide, and boric
mation of secondary species (such as ZnO and Zn(OH)2), can acid). The advantages can be ascribed to the special crystallog-
reduce the reversibility and enhance polarization of zinc anode. raphy and surface texture of the plating zinc materials.[84] Very
Over the past decades, tremendous efforts have been made to recently, Fan and co-workers[57] reported the dendrite-free zinc
improve coulombic efficiency in alkaline electrolyte. Tradition- battery, in which a Zn nanoflakes array anode and an optimized
ally, introducing additives (such as Ca, In, Bi, Ti, Nd, Ag oxides quasi-solid-state electrolyte are explored.

Small Methods 2019, 3, 1800272 1800272 (11 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Figure 9. a) Illustration showing the configuration evolution of conventional powder zinc anode versus 3D Zn anode for the alkaline rechargeable Ni/
Zn battery during repeated cycling. The 3D Zn anode is redesigned as a monolithic aperiodic sponge ensuring persistent 3D wiring of the metallic
Zn core. Dendrites that form at conventional powder-composite Zn anodes can reach hundreds of micrometers in length while the 3D Zn anode is
dendrite-free. Reproduced with permission.[80] Copyright 2017, American Association for the Advancement of Science. b) Schematic illustration of the
electrochemical deposition of anodic products in the pores of activated carbon during charge process. Reproduced with permission.[82] Copyright 2015,
the Electrochemical Society.

3.1.3. Electrolytes for AZBs electrolyte. Especially, pre-addition of Mn2+ above or below the
equilibrium amount does not address the capacity fading issue
As mentioned in the start of this section, the electrolyte for well. Recently, our group demonstrated that Mn2+ in electro-
aqueous zinc battery is neutral (or mild acid) aqueous solution. lyte not only avoids dissolution of MnO2, but also can effec-
And most of them contain one or more kinds of soluble zinc tively improve coulombic efficiency of zinc electrode.[37] Wang
salts, such as zinc sulfate, zinc nitrate, zinc acetate, or other et al.[71] presented a highly concentrated aqueous electrolyte,
salts of organic acid. Actually, compared to alkaline electrolyte, 1 m Zn(TFSI)2 + 20 m LiTFSI, which shows dendrite-free plating/
the mild electrolyte is already “optimized”[35] because zinc anode stripping of Zn at nearly 100% coulombic efficiency. And
possesses much better reversibility, slighter dendrite and pas- unprecedented reversibility of aqueous Zn batteries containing
sivation than in alkaline electrolyte. However, the decrease of either LiMn2O4 or O2 cathodes is obtained. At LiTFSI concentra-
pH value will induce hydrogen evolution during charge process, tions ≥ 20 m, a tremendous number of anions surround the Zn2+
brings challenge to the improvement of coulombic efficiency. to form close ion pairs (Zn-TFSI)+, which significantly suppress
Generally, mild electrolyte, such as the most used ZnSO4 solu- the formation of (Zn-(H2O)6)2+ (Figure 10). And H2 evolution is
tion, suffers from intrinsically limited solubility and low Zn effectively prevented, which leads to a dendrite-free and highly
stripping/plating coulombic efficiency. Chen and co-workers[45] reversible Zn plating/stripping (CE ≈ 100%).
reported that 3 m Zn(CF3SO3)2 electrolyte presents smaller
polarization and higher coulombic efficiency of Zn stripping/
plating compared to ZnSO4 electrolyte. The superior properties 3.2. Aqueous Mg-Ion Batteries (AMIBs)
could be ascribed to the bulky CF3SO3− anions. It decreases the
number of water molecules surrounding Zn2+ cations and effec- In addition to Zn2+, other multivalent metal ions, such as Mg2+,
tively reduce solvation effect, which facilitates Zn2+ transporta- Ca2+, Al3+, are also exploited as charge carrier for the large-
tion and charge transfer. Liu and co-workers[35] investigated the scale energy storage systems. Multivalent ions have the ability
rapid capacity failure process of manganese oxides cathode in to transport more electrons per ion relative to monovalent ion.
electrolyte containing only ZnSO4. And the dissolution of Mn2+ That means there is less ion storage per formula of a host lattice
from Mn3+ disproportionation during discharge process is con- to exert a given energy density, leading to less lattice distortion
sidered as the main reason for the capacity fading. Therefore, of host materials. However, the high charge density of multiva-
Mn2+ ions were pre-added into the electrolyte to adjust the dis- lent ions induces strong coulombic interactions with both the
solution equilibrium of Mn3+ disproportionation reaction. And lattice of electrode materials and electrolyte solvent, which is an
the result is encouraging, the electrode stability and the utiliza- adverse factor for improving electrochemical performance.
tion of MnO2 is much improved. The pre-added Mn2+ provides Rechargeable nonaqueous Mg batteries have been long
an appropriate equilibrium between Mn2+ dissolution from the considered as a highly promising battery system for energy
electrode to the electrolyte and the reoxidation of Mn2+ in the storage/conversion system due to the dendrite-free property,

Small Methods 2019, 3, 1800272 1800272 (12 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Figure 10. Molecular dynamics (MD) studies of the Zn2+-solvation structure. a) Snapshot of the MD simulation cell for electrolyte of
1 m Zn(TFSI)2 + 20 m LiTFSI at 363 K. b) Typical Zn2+-solvation structures in the electrolytes containing 1 m Zn(TFSI)2 and three concentrations of
LiTFSI (5, 10, and 20 m). c) Zn2+-O(TFSI) and d) Zn2+-O(H2O) coordination numbers for aqueous electrolytes containing 1 m Zn(TFSI)2 and three
concentrations of LiTFSI (5, 10, and 20 m). e) The cycling stability and columbic efficiency of the Zn/LiMn2O4 full cell in 1 m Zn(TFSI)2 + 20 m LiTFSI
at 4 C rates. Reproduced with permission.[71] Copyright 2018, Macmillan Publishers Ltd.

low reduction potential (−2.37 V vs SHE), and high volumetric that the slow solid-state diffusion of polyvalent metal ion might
capacity (specific volumetric capacity of Mg is 3833 mAh cm−3, not be the sole penalizing factor on reversible insertion/extrac-
higher than Li metal 2046 mAh cm−3).[69,85,86] However, the tion, the efficient disruption of the ion pairing in the electrolyte
development of nonaqueous Mg-ion batteries was plagued with is also of importance,[87] which is consistent with the results
scarcity of electrolyte (moisture-sensitive property, confined reported by Choi’ group.[93]
electrochemical stability, and strong corrosivity) and cathode Recently, researchers turn their attention to AMIBs due to
materials (slow diffusion of Mg2+ ion in host materials due to the faster insertion/extraction kinetics of Mg2+. Our group pro-
strong electrostatic interaction).[86–88] As early as 1993, Novak posed a full aqueous Mg-ion battery based on Prussian blue
et al.[89] suggested that water molecules preferentially solvating type nickel hexacyanoferrate (PBN, Na1.4Ni1.3Fe(CN)6·5H2O)
Mg2+ ion appear to facilitate the insertion into V2O5. But Mg-ion cathode, polyimide anode (synthesized from 1,4,5,8-naphtha-
batteries with aqueous electrolyte had not received enough lenetetracarboxylic dianhydride and ethylene diamine), and
attention until recently. Cao and co-workers[90] found that Mg2+ 1 m MgSO4 aqueous solution as electrolyte.[94] Na+ is extracted
and Zn2+ could intercalate/deintercalate into/out of γ-MnO2 from PBN cathode during the first charge process, followed by
structure in aqueous electrolyte. Lee and co-workers[91] reported subsequent cycles involving insertion/extraction of Mg2+ into
the water-containing electrolyte of Mg(ClO4)2·XH2O/propylene PBN open framework without structure destruction. The as-
carbonate can effectively improve insertion/extraction capa- assembled full aqueous Mg-ion battery shows sloping voltage
bility of Mg2+ into MnO2 nanowire. And the best performance profile with an average voltage of 1 V, and delivers 33 mAh g−1
can be achieved at a ratio of 6H2O/Mg2+. Interestingly, with a capacity based on the total weight of anode and cathode at
precycling process of MnO2 in water-containing electrolyte, it 1 A g−1, corresponding to 33 Wh kg−1 (Figure 11a,b). Moreover,
becomes feasible for MnO2 to work smoothly in nonaqueous 15 mAh g−1 capacity is maintained at a rather high 10 A g−1,
electrolyte.[91] Besides adding water to electrolyte, the benefi- and 60% capacity retention after 5000 cycles with almost
cial effect of interfoliar water molecular in layered host frame- 100% coulombic efficiency (Figure 11c). Wang et al.[95] dem-
work was also reported.[92,93] Choi and co-workers[93] revealed onstrated an aqueous Mg-ion battery in a concentrated 4 m
that the water in electrolyte dramatically decrease desolvation Mg(TFSI)2 electrolyte with a stable electrochemical window
energy penalty at cathode/electrolyte interface, endowing the to 2.0 V (Figure 11d), using Li3V2(PO4)3 (LVP) cathode and
birnessite MnO2 with high reversible capacity of 231.1 mAh g−1 polypyromellitic dianhydride anode (PPMDA, one kind of
at a high operating voltage (2.8 V vs Mg2+/Mg) with excellent polyimide). During the first charge process, nearly two Li+ are
cyclic stability (62.5% retention after 10 000 cycles). Mean- extracted from LVP framework. And Mg2+ rather than Li+ is
while, Nazar and co-workers[87] investigated the mechanism of intercalated/deintercalated in LVP framework in the following
Mg2+ insertion in nanometric birnessite Mg0.15MnO2·0.9H2O discharge/charge cycles. The full battery exerts a high voltage
with nonaqueous (0.25 m Mg(TFSI)2 in diglyme) and aqueous of 1.9 V, 52 mAh g−1 discharge capacity, and 62.4 Wh kg−1
electrolyte (0.5 m Mg(ClO4)2 in water), respectively. It shows a energy density based on total weight of both electrode mate-
conversion reaction in nonaqueous electrolyte. In contrast, the rials at 1 C rate (100 mA g−1). Moreover, a rather high power
interlaminar water can effectively screen interlayer electrostatic density of 6400 W kg−1 is achieved, which is 30 times higher
repulsions in the beginning of discharge, and the Mg2+ inser- than the highest record obtained by the organic Mg batteries,
tion is feasible in aqueous electrolyte. Finally, authors indicated along with a superior cycling stability of 6000 cycles with high

Small Methods 2019, 3, 1800272 1800272 (13 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Figure 11. a) Cyclic voltammetry curves for PBN and polyimide at 1 mV s−1. b) Representative charge/discharge curves of aqueous Mg-ion battery with
PBN cathode and polyimide anode at 1 A g−1. c) Cycle performance and coulombic efficiency of the aqueous Mg-ion battery at 2 A g−1 with the voltage
range from 0 to 1.55 V. The current density (A g−1) is calculated based on the weight of anode material only. The capacity (mAh g−1) is calculated based
on the total weight of cathode and anode material. Reproduced with permission.[94] Copyright 2017, American Chemical Society. d) The broadened elec-
trochemical stable window by 4 m Mg(TFSI)2 aqueous electrolytes measured with cyclic voltammetry on stainless steel working electrodes at 10 mV s−1.
The potential has also been converted to Mg/Mg2+ reference (upper X-axis) for convenience. The O2/H2 evolution potential and Mg2+-intercalation
potentials of various reported electrode materials are presented. e) The cycling performance and coulombic efficiency of the battery at 20 C rate and
2 C rate (inset), respectively. Reproduced with permission.[95] Copyright 2017, American Chemical Society.

capacity retention of 92% (Figure 11e).[95] Recently, Chen and and ethylene carbonate. Cheng and co-workers[98] reported a
co-workers[67] briefly demonstrated the Mg2+ storage of C4Q, reversible electrochemistry of Ca-ion battery at room tempera-
which shows a capacity of 247.4 mAh g−1 with a flat discharge ture, which is composed of hexafluorophosphate intercala-
platform of 1.54 V versus Mg2+/Mg. tion/deintercalation for graphite cathode, and a Ca-involved
alloying/dealloying reaction for tin anode in the electrolyte
containing Ca(PF6)2 and carbonate solvents. Although these
3.3. Aqueous Ca-Ion Batteries good achievement offers some hope for Ca electrode in non-
aqueous, the performance of Ca electrode is still far from satis-
Ca2+ is another divalent ion that has potential for energy storage faction. Replacing metal Ca anode with intercalation electrodes
application due to its chemical similarity with Mg2+. Although is feasible method to bypass the incompatibility between metal
Ca2+ ion radius (0.100 nm) is larger than that of Li+ ion Ca and electrolyte. In such a case, some intercalation elec-
(0.076 nm) and Mg2+ (0.072 nm), the relative low redox potential trodes including layered vanadium oxides,[99] Prussian blue
(−2.87 V vs NHE), abundant resource, and low charge density analogs,[100] and CaCo2O4[101] have been investigated as host
(i.e., low polarization strength, approximately equal to that of Li+ materials for Ca2+ insertion.[102] However, most of them suffer
ion)[96,97] make it an alternative candidate for post-Li-ion battery. from sluggish diffusion of Ca2+. Recently, some works[103] dem-
However, the previous studies have indicated that due to the onstrated that the existence of water can effectively facilitate
huge resistance of SEI to Ca2+ migration, Ca electroplating/ the Ca2+ ion diffusion because of the weakened charge den-
stripping is virtually impossible in nonaqueous electrolyte. sity derived from the shielding effect of water, which is similar
Palacin and co-workers[97] reported the feasibility of calcium to Mg-ion battery mentioned above. Jeong and Lee[104] inves-
plating at more than 75 °C using the electrolyte composed of tigated the effect of electrolyte concentration on the storage
a calcium bis(trifluoromethanesulphonimide (Ca(TFSI)2) dis- performance of Ca2+ ion in CuHCF host. They found that the
solved in a mixture 50/50 wt% mixture of propylene carbonate superconcentrated aqueous electrolyte, 8.37 mol L−1 Ca(NO3)2,

Small Methods 2019, 3, 1800272 1800272 (14 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Figure 12. a) Schematic illustration of the polyimide-CaxCuHCF aqueous rechargeable Ca2+ ion battery. b) CV curves of PNDIE anode and Ca0.3CuHCF
cathode in 2.5 m Ca(NO3)2 at 1 mV s−1. The dashed line represents the electrochemical stability of the electrolyte. Reproduced with permission.[105]
Copyright 2017, Wiley-VCH. c) CV curves of anatase TiO2 nanotube arrays in 1 m AlCl3, MgCl2, and LiCl aqueous solutions at 20 mV s−1. d) The typical
charge/discharge profile in the 13th cycle and electrochemical cycle performance of the TiO2 nanotube arrays at a current density of 4 mA cm−2 in 1 m
aqueous AlCl3 solution. Reproduced with permission.[109] Copyright 2012, The Royal Society of Chemistry.

is beneficial to the improvement of discharge capacity and 3.4. Aqueous Al-Ion Batteries
cycle life compared to dilute electrolyte (1 mol L−1 Ca(NO3)2).
The small hydration radius of calcium ion and the suppres- Aluminum is the third abundant element in crust, which has
sion of structural collapse of CuHCF in concentrated electro- been investigated widely as the anode material for Al-air batteries
lyte are considered as the possible reason for the improved because of the high theoretical capacity and specific energy.[106]
performance. Recently, Yao and co-workers[105] reported a However, there is great trouble in Al–air battery due to the
aqueous calcium-ion full battery based on polyimide (poly incompatibility of metal Al in water, for example, hydrogen evo-
[N,N′-(ethane-1,2-diyl)-1,4,5,8-naphthalenetetracarboxiimide], lution, corrosion and passivation of Al metal anode.[107] One of
PNDIE) anode and Prussian blue analogue copper hexacyano- the feasible solutions is replacing the aqueous electrolyte with
ferrate (CuHCF, K0.02Cu[Fe(Cu)6]0.66·3.7H2O) cathode using nonaqueous electrolyte, and another is to develop Al-ion bat-
Ca(NO3)2 aqueous solution electrolyte (Figure 12a,b). PNDIE teries based on reversible insertion/extraction of Al3+ in elec-
anode stores Ca2+ at −0.45 V (vs Ag/AgCl) with a reversible trode materials. There are some nonaqueous Al-ion batteries
capacity of 160 mAh g−1 through a two-step two-electron enoli- with excellent performance reported in recent years.[108] But it
zation reaction. And CuHCF cathode using Fe2+/Fe3+ couple will not be discussed here because our focus in this review is
accommodates Ca2+ at a potential of 0.72 V (vs Ag/AgCl) with aqueous battery system. Although trivalent ion Al3+ (0.054 nm)
a capacity of 58 mAh g−1 at a 0.2 C rate, corresponding to ion possesses a smaller radius than Li+ (0.076 nm) and Mg2+
0.3 Ca2+ transfer per formula of CuHCF to form Ca0.3CuHCF. cation (0.072 nm), the high charge density of Al3+ is the major
Comparison of Ca2+ and Mg2+ kinetics in electrolyte and problem for the reversible insertion of Al3+. So the key for devel-
electrodes reveals the superiority of Ca chemistry, including oping aqueous Al-ion battery is to exploit high-performance
faster ion diffusion and higher electrolytic conductivity, electrodes which can accommodate/release Al3+ ions smoothly.
mainly results from smaller size of hydrated Ca2+ and more Anatase TiO2, a widely used lithium storage material with good
facile dehydration. The full aqueous battery exhibits a spe- chemical stability and nontoxicity, is adopted as electrode mate-
cific capacity of 40 mAh g−1 at 1 C (1 C = 40 mA g−1) with rial for aqueous Al-ion battery in AlCl3 aqueous solution elec-
an average operating voltage of 1.24 V, corresponding to the trolyte by Gao and co-workers.[109] The reversible insertion/
energy density of 54 Wh kg−1. And 88% capacity retention with extraction of Al3+ in anatase TiO2 nanotube arrays occurs at
almost 100% coulombic efficiency is obtained when cycled at −1.26 V and −0.84 V (vs SCE). Note that as a dominantly diffu-
10 C after 1000 cycles.[105] sion-controlled reaction, Al3+ insertion/extraction presents much

Small Methods 2019, 3, 1800272 1800272 (15 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

stronger redox peak than that of Li+ and Mg2+ under the same
conditions (Figure 12c,d). This may be due to the small radius
of Al3+ and the charge-shield effect of water. The maximum dis-
charge capacity of 75 mAh g−1 at 4 mA cm−2 is obtained with a
flat discharge plateau voltage centered at −0.98 V versus SCE,
where Ti4+/Ti3+ redox pair is responsible for the capacity con-
tribution. After this work, the modification on morphology and
structure of titanium dioxide was investigated to improve elec-
trochemical performance of TiO2. Black mesoporous anatase
TiO2 nanoleaves with high electroactive have been developed
as a high-rate electrode material for aqueous Al-ion battery.[110]
Combining the large surface area, the introduction of conduc-
tive Ti3+ into TiO2 nanoleaves, the well-crystallized nanoparticles,
and the structural robustness, black mesoporous anatase TiO2
nanoleaves exhibit a high specific capacity of 278.1 mAh g−1 at
a current density of 50 mA g−1 with a small capacity fading of
8.4% after 300 cycles in Al(NO3)3 aqueous solution. And a spe-
cific capacity of 141.3 mAh g−1 at 2 A g−1, indicating good rate Figure 13. Comparison of the energy/power density in mild aqueous
capability and cycle stability. Furthermore, high surface area TiO2 electrolyte systems with different charge carrier (Li+, Na+, Zn2+, Mg2+,
and Ca2+).
nanospheres with mesoporous structure were synthesized,[111]
which can exert 183 mAh g−1 at 0.15 C (1 C = 335 mA g−1), and
108 mAh g−1 even at 6.0 C in 1.0 m AlCl3 electrolyte. Graphene- with different charge carrier is given in Figure 13, including
wrapped TiO2 nanoparticles were prepared to enhance high Al3+ Li+, Na+, Zn2+, Mg2+, and Ca2+, the absence of K+ and Al3+ is
ion diffusion coefficient,[112] and an initial discharge capacity of ascribed to the fact that there are no full cell reported about K
52 mAh g−1 at a very high 6.25 A g−1 can be achieved in 0.5 m and Al-ion battery. Furthermore, the summary of the configura-
AlCl3 electrolyte. Liu et al.[113] synthesized TiO2 nanotube arrays tion and electrochemical properties of typical batteries is given
and investigated the electrochemical properties in different in Table 2.
aqueous electrolyte. An assistant effect of Cl− to Al3+ insertion As shown in Figure 13, the recently reported aqueous Li-ion
was demonstrated. Besides TiO2, the widely used Prussian blue batteries show the highest energy density, which is mainly
analogues is also feasible for aqueous Al-ion batteries, Gao and attributable to the expanded electrochemical window of “water-
co-workers[114] introduced copper hexacyanoferrate (CuHCF, in-salt” electrolyte. From the first report of “water-in-salt” elec-
KCu[Fe(CN)6]·8H2O) as cathode material using Al2(SO4)3 trolyte in 2015 to today, the energy density of aqueous Li-ion
aqueous solution. A two-step reaction occurs during Al3+ inser- battery exhibits encouraging increase from ≈100 to >200 Wh kg−1,
tion/extraction in CuHCF with a pair of redox peaks centered which is even comparable to the commercial Li-ion battery with
at 0.48 V/0.73 V and 0.76 V/0.80 V versus Ag/AgCl, which con- organic electrolyte. Furthermore, it can also be found that the
tributes to 62.9 mAh g−1 specific capacity at 50 mA g−1, and concept of “water-in-salt” is being applied in other aqueous
46.9 mAh g−1 at 400 mA g−1 with a capacity retention of 54.9% batteries, such as Na, K, and Mg-ion batteries. However, it
after 1000 cycles. Huang and co-workers[115] prepared ultrathin should be noted that the scale-up of such batteries is confined
graphite nanosheet through an electrochemically expanded by the high cost of “water-in-salt” electrolyte. Accordingly, the
method. When evaluated as cathode for hybrid zinc/aluminum- exploitation of low-cost Li salt for “water-in-salt” electrolyte
ion battery in an Al2(SO4)3/Zn(CH3COO)2 (0.25/0.5 m) electro- should be the next logic step.
lyte, it shows a high average working voltage of 1 V and over Besides the energy densities, it can also be observed from
200 stable cycles at 0.5 A g−1. The large specific surface area Figure 13 that the achieved power densities of aqueous Li-ion
of ultrathin graphite nanosheet is convenient for Al-ion inter- batteries are much higher than other batteries because of the
calation into the outer graphene layers of graphite. Up to now, fast electrode kinetics. As shown in Table 1, Li+ combines
although some electrode materials have been reported for Al-ion the advantages of both the small size and low charge density,
batteries, there are scarcely any full cell reported. which thus facilitates the charge storage. Furthermore, the
development of aqueous Li-ion batteries experiences a very
long history (from 1994 to present). Some mature aqueous
4. Conclusion and Outlook Li-ion batteries with conventional aqueous electrolytes (not
the recently reported “water-in-salt” electrolyte) are being com-
In summary, aqueous rechargeable batteries using safe, low- mercialized for grid-scale storage. That is to say, up to now, the
cost mild electrolyte have been reviewed in this paper. The investigations of aqueous Li-ion batteries still dominate the
development of these batteries can be briefly summarized as: aqueous metal-ion batteries systems. In recent years, in view
(1) the charge carriers from monovalent metal ion to multiva- of the limited lithium resources, other monovalent ions as
lent metal ion, (2) the electrolyte composition from “salts-in- charge carrier (Na and K-ion battery) were proposed. However,
water” to “water-in-salts,” and (3) the electrodes materials from due to the much larger ion radius of Na+ and K+, the signifi-
inorganic materials to organic materials. The rough comparison cant interaction between guest ions and host skeleton plagues
of the energy/power density in mild electrolyte battery systems the reversible insertion/extraction. Therefore, the electrode

Small Methods 2019, 3, 1800272 1800272 (16 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Table 2. Summary of the configuration and electrochemical properties of typical batteries using aqueous mild electrolyte.

Cathode Anode Electrolyte Current rate Voltage [V] Capacity [mAh g−1] Retention % [cycles] Ref.
LiMn2O4 Mo6S8 21 m LiTFSI 0.15 C 2.0/1.5 50 (for full cell) 78% (100) [8]
4.5 C – 40 (for full cell) 68% (1000)
LiMn2O4 Carbon-coated TiO2 21 m LiTFSI + 7 m LiOTf 0.5 C (75 mA g−1) 2.1 48 (for full cell) 78% (100) [9]
(WIBS)
LiNi0.5Mn1.5O4 Li4Ti5O12 Li(TFSI)0.7(BETI)0.3•2H2O 6.8 C (1 A g−1 for 3.1 30 (for full cell) 63% (100) [10]
cathode)
LiCoO2 Li4Ti5O12 Li(TFSI)0.7(BETI)0.3•2H2O 10 C (1.35 A g−1 for 2.4 55 (for full cell) 75% (200) [10]
cathode)
LiVPO4F Li with ISA Gel-WIBS 0.3 C 4.1 130 (for cathode) ≈94% (50) [11]
LiVPO4F Graphite with ISA Gel-WIBS 0.3 C 4.0 290 (for anode) ≈83% (50) [11]
LiMn2O4 Li with ISA Gel-WIBS 0.3 C 4.0 120 (for cathode) ≈94% (50) [11]
PTPAn Polyimide 21 m LiTFSI 500 mA g−1 ≈1.1 105 (for cathode) ≈86% (700) [13]
LiMn2O4 PPTO 2.5 m Li2SO4 1 C (280 mA g−1 for 1.13 210 (for anode) 80% (3000) [19]
anode)
Na0.66[Mn0.66Ti0.34]O2 NaTi2(PO4)3 9.26 m NaOTF 1C 1 25 (for full cell) ≈72% (>1500) [21]
– Na0.44[Mn0.44Ti0.56]O2 Na2SO4 2 C (100 mA g−1) −0.3 versus SCE 37 ≈95% (400) [25]
Na3MnTi(PO4)3 Na3MnTi(PO4)3 1 m Na2SO4 1 C (58.7 mA g−1) 1.4 56.5 (for anode) ≈98% (100) [26]
Na2VTi(PO4)3 Na2VTi(PO4)3 1 m Na2SO4 10 C (620 mA g−1) 1.1 40.6 (for anode) 70% (1000) [27]
CuHCF – 1 m KNO3 per 0.01 m HNO3 17 C (≈1 A g−1) 0.9 versus SHE 52.2 83% (40 000) [28]
II II
K2Fe [Fe (CN)6]•2H2O – 0.5 m K2SO4 3.6 C (500 mA g−1) 0.9/0.3 versus Ag/AgCl 111 ≈96% (500) [30]
α-MnO2 nanofiber Zn 2 m ZnSO4 + 0.1 m MnSO4 5 C (1.5 A g−1) ≈1.3 161 (for cathode) ≈92% (5000) [35]
β-MnO2 Zn 3 m Zn(CF3SO3)2 + 0.1 m 6.5 C (2 A g−1) ≈1.3 151 (for cathode) 94% (2000) [36]
Mn(CF3SO3)2
Akhtenskite MnO2 Zn 2 m ZnSO4 + 0.2 m MnSO4 6.5 C (2 A g−1) ≈1.3 50 (for cathode) No capacity loss [34]
(10 000)
PANI-intercalated MnO2 Zn 2 m ZnSO4 + 0.1 m 200 mA g−1 1.4/1.3 280 (for cathode) ≈93% (200) 37]
nanolayer
MnSO4 2 A g−1 ≈1.3 145 (for cathode) ≈83% (5000)
Zn0.25V2O5•nH2O Zn 1 m ZnSO4 8 C (2.4 A g−1) ≈0.8 260 (for cathode) 80% (1000) [46]
nanobelts
V2O5·nH2O/graphene Zn 3 m Zn(CF3SO3)2 6 A g−1 ≈0.8 300 (for cathode) 71% (900) [49]
Na0.33V2O5 Zn 3 m Zn(CH3F3SO3)2 1 A g−1 ≈0.8 235 (for cathode) 93% (1000) [56]
NaV3O8·1.5H2O Zn 1 m ZnSO4 + 1 m NaSO4 4A g−1 ≈0.8 150 (for cathode) 82% (1000) [53]
ZnHCF Zn 1 m ZnSO4 5 C (300 mA g−1) 1.7 52.5 (for cathode) 81% (100) [58]
CuHCF Zn 20 × 10−3 m ZnSO4 1 C (60 mA g−1) 1.73 ≈55 (for cathode) 96.3% (100) [60]
Na3V2(PO4)3 Zn 0.5 m Zn(CH3COO)2 0.5 C (50 mA g−1) 1.1 97 (for cathode) 74% (100) [64]
C4Q Zn 3 m Zn(CF3SO3)2 500 mA g−1 1 ≈160 (for cathode) 87% (1000) [67]
LiMn2O4 Zn 1 m Zn(TFSI)2 + 20 m LiTFSI 0.2 C 1.7 66 (for full cell) 83.8% (500) [71]
4C – 32 (for full cell) 85% (4000)
PBN Polyimide 1 m MgSO4 2 A g−1 for anode ≈1 30 (for full cell) 60% (5000) [94]
Li3V2(PO4)3 PPMDA 4 m Mg(TFSI)2 20 C (2 A g−1) ≈1.2 42 (for full cell) 92% (6000) [95]
Ca0.3CuHCF PNDIE 2.5 m Ca(NO3)2 10 C (400 mA g−1) ≈1.24 27 (for full cell) 88% (1000) [105]
– Black mesoporous 1.0 m Al(NO3)3 50 mA g−1 −0.95 versus SCE 254.6 91.6% (300) [110]
anatase TiO2
CuHCF – 0.5 m Al(NO3)3 400 mA g−1 0.54 versus SCE 41 54.9% (1000) [114]

materials for Na, K-ion storage suffer from low selectivity rela- Among the multivalent metal-ion batteries, aqueous Zn
tive to Li-ion battery, especially the anode materials for Na, batteries show the highest energy density, which is ascribed
K-ion battery. to the high capacity of metallic zinc electrode. In fact, the

Small Methods 2019, 3, 1800272 1800272 (17 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

aqueous rechargeable Zn batteries with alkaline electro- Keywords

lyte were once considered as ideal battery system for energy
aqueous metal-ion batteries, aqueous zinc batteries, organic electrodes,
storage during the 1970s energy crisis, but the dendrite-
“water-in-salt” electrolytes
induced poor cycle life in alkaline electrolyte make it uncom-
petitive. The development of mild electrolyte takes aqueous Received: July 30, 2018
Zn batteries back to researchers’ horizons. Note that the rela- Revised: August 22, 2018
tive high energy density of aqueous Zn batteries is achieved Published online: September 19, 2018
without “water-in-salt” electrolyte. Based on the low cost of
electrodes and mild electrolyte, it possesses tremendous
potential for large-scale energy storage. However, the lim-
[1] a) B. Dunn, H. Kamath, J. M. Tarascon, Science 2011, 334,
ited cycle stability in the depth charging/discharging brings
928; b) Z. Yang, J. Zhang, M. C. Kintner-Meyer, X. Lu,
a challenge in the practical application. So more efforts
D. Choi, J. P. Lemmon, J. Liu, Chem. Rev. 2011, 111, 3577;
should be devoted on the investigation of the Zn2+ storage c) J. B. Goodenough, Energy Environ. Sci. 2014, 7, 14.
mechanism and the compatibility between electrodes and [2] a) H. Kim, J. Hong, K. Y. Park, H. Kim, S. W. Kim, K. Kang,
electrolyte. Besides, in light of the high capacity and relative Chem. Rev. 2014, 114, 11788; b) Y. Wang, J. Yi, Y. Xia, Adv. Energy
reversibility of Zn electrode in aqueous electrolyte, coupling Mater. 2012, 2, 830.
Zn anode with other ion-storage materials (such as Li+ and [3] a) Z. Guo, Y. Zhao, Y. Ding, X. Dong, L. Chen, J. Cao, C. Wang,
Na+) to compose high-performance hybrid battery systems is Y. Xia, H. Peng, Y. Wang, Chem 2017, 3, 348; b) Y. Zhang, W. Bai,
an attractive development direct. The rest aqueous Mg, Ca, X. Cheng, J. Ren, W. Weng, P. Chen, X. Fang, Z. Zhang, H. Peng,
and Al-ion batteries are at the primary stage of development. Angew. Chem., Int. Ed. Engl. 2014, 53, 14564; c) X. Dong, L. Chen,
X. Su, Y. Wang, Y. Xia, Angew. Chem., Int. Ed. Engl. 2016, 55, 7474;
And the explored electrode materials for these batteries are
d) H. Li, C. Han, Y. Huang, Y. Huang, M. Zhu, Z. Pei, Q. Xue,
still very limited. Z. Wang, Z. Liu, Z. Tang, Y. Wang, F. Kang, B. Li, C. Zhi, Energy
In addition of the charge carriers and electrolyte, electrode Environ. Sci. 2018, 11, 941; e) J. W. Zhao, K. K. Sonigara, J. J. Li,
materials are also a significant component for aqueous bat- J. Zhang, B. B. Chen, J. J. Zhang, S. S. Soni, X. H. Zhou, G. L. Cui,
teries. Most of intercalation electrodes in aqueous batteries L. Q. Chen, Angew. Chem., Int. Ed. 2017, 56, 7871; f) M. Han,
can be derived from Li-ion batteries with organic electrolyte. X. Wang, C. Chen, M. Zou, Z. Niu, Q.-H. Yang, A. Cao, L. Song,
And their development is slowly recent years. Different from J. Chen, S. Xie, Energy Storage Mater. 2018, 13, 119.
the intercalation mechanism of inorganic materials, the charge [4] C. Yang, X. Ji, X. Fan, T. Gao, L. Suo, F. Wang, W. Sun, J. Chen,
storage mechanism of conjugated bonds reactions for organic L. Chen, F. Han, Adv. Mater. 2017, 29, 1701972.
electrodes brings high capacity and fast kinetics. More impor- [5] a) W. Tang, Y. Zhu, Y. Hou, L. Liu, Y. Wu, K. P. Loh, H. Zhang,
K. Zhu, Energy Environ. Sci. 2013, 6, 2093; b) Q. Zhao, Y. Lu,
tantly, the conjugated bonds reactions are feasible to various
J. Chen, Adv. Energy Mater. 2017, 7, 1601792; c) Y. Li, Y. Lu,
metal ions (no matter the ion radius and charge density) from
C. Zhao, Y.-S. Hu, M.-M. Titirici, H. Li, X. Huang, L. Chen, Energy
monovalent ions to multivalent ions. However, some instinct Storage Mater. 2017, 7, 130.
disadvantages, for example, insulativity and solubility, plague [6] D. Bin, F. Wang, A. G. Tamirat, L. Suo, Y. Wang, C. Wang, Y. Xia,
the electrode performance. Fortunately, these problems could Adv. Energy Mater. 2018, 1703008.
be conquered by the reasonable functionalization of organic [7] W. Li, J. R. Dahn, D. S. Wainwright, Science 1994, 264, 1115.
materials. In our opinion, an ideal organic electrode material [8] L. M. Suo, O. Borodin, T. Gao, M. Olguin, J. Ho, X. L. Fan, C. Luo,
should simultaneously be composed of the branched chain C. S. Wang, K. Xu, Science 2015, 350, 938.
for charge storage and the backbone for electron conductivity. [9] L. Suo, O. Borodin, W. Sun, X. Fan, C. Yang, F. Wang, T. Gao,
Besides, another limit on organic electrode is that most of Z. Ma, M. Schroeder, A. von Cresce, S. M. Russell, M. Armand,
A. Angell, K. Xu, C. Wang, Angew. Chem., Int. Ed. Engl. 2016, 55,
them are available only to be anode materials. Because they
7136.
tend to be oxidized when used as cathode materials. And the
[10] Y. Yamada, K. Usui, K. Sodeyama, S. Ko, Y. Tateyama, A. Yamada,
structure evolution of organic electrodes during cycling is still Nat. Energy 2016, 1, 16129.
unclear. So deeper investigation is urgently needed to illumi- [11] C. Yang, J. Chen, T. Qing, X. Fan, W. Sun, A. von Cresce,
nate the structure–performance relationship, and finally guide M. S. Ding, O. Borodin, J. Vatamanu, M. A. Schroeder, N. Eidson,
better design and synthesis of organic materials to obtain high- C. Wang, K. Xu, Joule 2017, 1, 122.
performance materials. [12] a) F. Wang, L. Suo, Y. Liang, C. Yang, F. Han, T. Gao,
W. Sun, C. Wang, Adv. Energy Mater. 2017, 7, 1600922;
b) A. Ramanujapuram, D. Gordon, A. Magasinski, B. Ward,
Acknowledgements N. Nitta, C. Huang, G. Yushin, Energy Environ. Sci. 2016, 9, 1841;
c) M. S. Ding, A. von Cresce, K. Xu, J. Phys. Chem. C 2017, 121,
The authors acknowledge funding support from the National Natural 2149; d) W. Sun, L. Suo, F. Wang, N. Eidson, C. Yang, F. Han,
Science Foundation of China (21622303, 21333002, 21805126) and Z. Ma, T. Gao, M. Zhu, C. Wang, Electrochem. Commun. 2017,
National Key Research and Development Plan (2016YFB0901500, 82, 71; e) F. Wang, Y. Lin, L. Suo, X. Fan, T. Gao, C. Yang, F. Han,
2016YFA0203302). Y. Qi, K. Xu, C. Wang, Energy Environ. Sci. 2016, 9, 3666; f) L. Suo,
F. Han, X. Fan, H. Liu, K. Xu, C. Wang, J. Mater. Chem. A 2016,
4, 6639; g) M. Zhao, B. Zhang, G. Huang, H. Zhang, X. Song,
J. Power Sources 2013, 232, 181.
Conflict of Interest [13] X. Dong, H. Yu, Y. Ma, J. L. Bao, D. G. Truhlar, Y. Wang, Y. Xia,
The authors declare no conflict of interest. Chemistry 2017, 23, 2560.

Small Methods 2019, 3, 1800272 1800272 (18 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

[14] V. A. Azov, K. S. Egorova, M. M. Seitkalieva, A. S. Kashin, F. Kang, J. Phys. Chem. Solids 2012, 73, 1487; f) J. Lee, J. B. Ju,
V. P. Ananikov, Chem. Soc. Rev. 2018, 47, 1250. W. I. Cho, B. W. Cho, S. H. Oh, Electrochim. Acta 2013, 112, 138;
[15] a) S. Lee, G. Kwon, K. Ku, K. Yoon, S. K. Jung, H. D. Lim, K. Kang, g) B. Jiang, C. Xu, C. Wu, L. Dong, J. Li, F. Kang, Electrochim. Acta
Adv. Mater. 2018, e1704682; b) S. Muench, A. Wild, C. Friebe, 2017, 229, 422; h) B. Wu, G. Zhang, M. Yan, T. Xiong, P. He, L. He,
B. Häupler, T. Janoschka, U. S. Schubert, Chem. Rev. 2016, 116, X. Xu, L. Mai, Small 2018, 14, e1703850.
9438; c) Y. Liang, P. Zhang, J. Chen, Chem. Sci. 2013, 4, 1330. [42] B. Lee, C. S. Yoon, H. R. Lee, K. Y. Chung, B. W. Cho, S. H. Oh,
[16] G. Wang, Q. Qu, B. Wang, Y. Shi, S. Tian, Y. Wu, Chem. Phys. Chem. Sci. Rep. 2014, 4, 6066.
2008, 9, 2299. [43] B. Lee, H. R. Lee, H. Kim, K. Y. Chung, B. W. Cho, S. H. Oh,
[17] H. Qin, Z. P. Song, H. Zhan, Y. H. Zhou, J. Power Sources 2014, Chem. Commun. 2015, 51, 9265.
249, 367. [44] M. H. Alfaruqi, V. Mathew, J. Gim, S. Kim, J. Song, J. P. Baboo,
[18] X. Dong, L. Chen, J. Liu, S. Haller, Y. Wang, Y. Xia, Sci. Adv. 2016, S. H. Choi, J. Kim, Chem. Mater. 2015, 27, 3609.
2, e1501038. [45] N. Zhang, F. Cheng, Y. Liu, Q. Zhao, K. Lei, C. Chen, X. Liu,
[19] Y. L. Liang, Y. Jing, S. Gheytani, K. Y. Lee, P. Liu, A. Facchetti, J. Chen, J. Am. Chem. Soc. 2016, 138, 12894.
Y. Yao, Nat. Mater. 2017, 16, 841. [46] D. Kundu, B. D. Adams, V. Duffort, S. H. Vajargah, L. F. Nazar,
[20] W. H. Zuo, W. H. Zhu, D. F. Zhao, Y. F. Sun, Y. Y. Li, J. P. Liu, Nat. Energy 2016, 1, 16119.
X. W. Lou, Energy Environ. Sci. 2016, 9, 2881. [47] P. He, Y. Quan, X. Xu, M. Yan, W. Yang, Q. An, L. He, L. Mai, Small
[21] L. Suo, O. Borodin, Y. Wang, X. Rong, W. Sun, X. Fan, S. Xu, 2017, 13, 1702551.
M. A. Schroeder, A. V. Cresce, F. Wang, C. Yang, Y.-S. Hu, K. Xu, [48] C. Xia, J. Guo, P. Li, X. Zhang, H. N. Alshareef, Angew. Chem.,
C. Wang, Adv. Energy Mater. 2017, 7, 1701189. Int. Ed. Engl. 2018, 57, 3943.
[22] H. Zhang, S. Jeong, B. Qin, D. Carvalho, D. Buchholz, S. Passerini, [49] M. Yan, P. He, Y. Chen, S. Wang, Q. Wei, K. Zhao, X. Xu, Q. An,
ChemSusChem 2018, 11, 1382. Y. Shuang, Y. Shao, K. T. Mueller, L. Mai, J. Liu, J. Yang, Adv. Mater.
[23] R.-S. Kühnel, D. Reber, C. Battaglia, ACS Energy Lett. 2017, 2, 2005. 2017, 1703725.
[24] Y. Wang, L. Mu, J. Liu, Z. Yang, X. Yu, L. Gu, Y.-S. Hu, H. Li, [50] M. H. Alfaruqi, V. Mathew, J. Song, S. Kim, S. Islam, D. T. Pham,
X.-Q. Yang, L. Chen, X. Huang, Adv. Energy Mater. 2015, 5, 1501005. J. Jo, S. Kim, J. P. Baboo, Z. Xiu, K.-S. Lee, Y.-K. Sun, J. Kim,
[25] Y. Wang, J. Liu, B. Lee, R. Qiao, Z. Yang, S. Xu, X. Yu, L. Gu, Chem. Mater. 2017, 29, 1684.
Y. S. Hu, W. Yang, K. Kang, H. Li, X. Q. Yang, L. Chen, X. Huang, [51] J. H. Jo, Y. K. Sun, S. T. Myung, J. Mater. Chem. A 2017, 5, 8367.
Nat. Commun. 2015, 6, 6401. [52] C. Xia, J. Guo, Y. Lei, H. Liang, C. Zhao, H. N. Alshareef,
[26] H. Gao, J. B. Goodenough, Angew. Chem., Int. Ed. Engl. 2016, 55, Adv. Mater. 2018, 30, 1705580.
12768. [53] F. Wan, L. Zhang, X. Dai, X. Wang, Z. Niu, J. Chen, Nat. Commun.
[27] H. Wang, T. Zhang, C. Chen, M. Ling, Z. Lin, S. Zhang, F. Pan, 2018, 9, 1656.
C. Liang, Nano Res. 2017, 11, 490. [54] P. Hu, T. Zhu, X. Wang, X. Wei, M. Yan, J. Li, W. Luo, W. Yang,
[28] C. D. Wessells, R. A. Huggins, Y. Cui, Nat. Commun. 2011, 2, 550. W. Zhang, L. Zhou, Z. Zhou, L. Mai, Nano Lett. 2018, 18, 1758.
[29] a) C. D. Wessells, S. V. Peddada, M. T. McDowell, R. A. Huggins, [55] Y. Cai, F. Liu, Z. Luo, G. Fang, J. Zhou, A. Pan, S. Liang, Energy
Y. Cui, J. Electrochem. Soc. 2012, 159, A98; b) C. D. Wessells, Storage Mater. 2018, 13, 168.
M. T. Mcdowell, S. V. Peddada, M. Pasta, R. A. Huggins, Y. Cui, [56] P. He, G. Zhang, X. Liao, M. Yan, X. Xu, Q. An, J. Liu, L. Mai,
ACS Nano 2012, 6, 1688; c) C. D. Wessells, S. V. Peddada, Adv. Energy Mater. 2018, 8, 1702463.
R. A. Huggins, Y. Cui, Nano Lett. 2011, 11, 5421. [57] D. Chao, C. R. Zhu, M. Song, P. Liang, X. Zhang, N. H. Tiep,
[30] D. Su, A. McDonagh, S. Z. Qiao, G. Wang, Adv. Mater. 2017, 29, H. Zhao, J. Wang, R. Wang, H. Zhang, H. J. Fan, Adv. Mater. 2018,
1604007. e1803181.
[31] A. Baioun, H. Kellawi, A. Falah, Curr. Nanosci. 2018, 14, 227. [58] L. Zhang, L. Chen, X. Zhou, Z. Liu, Adv. Energy Mater. 2015, 5,
[32] D. P. Leonard, Z. Wei, G. Chen, F. Du, X. Ji, ACS Energy Lett. 2018, 1400930.
3, 373. [59] L. Zhang, L. Chen, X. Zhou, Z. Liu, Sci. Rep. 2015, 5, 18263.
[33] Y. Li, H. Dai, Chem. Soc. Rev. 2014, 43, 5257. [60] R. Trocoli, F. La Mantia, ChemSusChem 2015, 8, 481.
[34] W. Sun, F. Wang, S. Hou, C. Yang, X. Fan, Z. Ma, T. Gao, F. Han, [61] Z. Jia, B. Wang, Y. Wang, Mater. Chem. Phys. 2015, 149, 601.
R. Hu, M. Zhu, C. Wang, J. Am. Chem. Soc. 2017, 139, 9775. [62] M. S. Chae, J. W. Heo, H. H. Kwak, H. Lee, S.-T. Hong, J. Power
[35] H. L. Pan, Y. Y. Shao, P. F. Yan, Y. W. Cheng, K. S. Han, Z. M. Nie, Sources 2017, 337, 204.
C. M. Wang, J. H. Yang, X. L. Li, P. Bhattacharya, K. T. Mueller, [63] Z. Liu, P. Bertram, F. Endres, J. Solid State Electrochem. 2017, 21, 2021.
J. Liu, Nat. Energy 2016, 1, 16039. [64] G. Li, Z. Yang, Y. Jiang, C. Jin, W. Huang, X. Ding, Y. Huang, Nano
[36] N. Zhang, F. Cheng, J. Liu, L. Wang, X. Long, X. Liu, F. Li, J. Chen, Energy 2016, 25, 211.
Nat. Commun. 2017, 8, 405. [65] Y. Cheng, L. Luo, L. Zhong, J. Chen, B. Li, W. Wang, S. X. Mao,
[37] J. Huang, Z. Wang, M. Hou, X. Dong, Y. Liu, Y. Wang, Y. Xia, C. Wang, V. L. Sprenkle, G. Li, J. Liu, ACS Appl. Mater. Interfaces
Nat. Commun. 2018, 9, 2906. 2016, 8, 13673.
[38] T. Shoji, M. Hishinuma, T. Yamamoto, J. Appl. Electrochem. 1988, [66] W. Liu, J. Hao, C. Xu, J. Mou, L. Dong, F. Jiang, Z. Kang, J. Wu,
18, 521. B. Jiang, F. Kang, Chem. Commun. 2017, 53, 6872.
[39] C. Xu, H. Du, B. Li, F. Kang, Y. Zeng, Electrochem. Solid-State Lett. [67] Q. Zhao, W. Huang, Z. Luo, L. Liu, Y. Lu, Y. Li, L. Li, J. Hu, H. Ma,
2009, 12, A61. J. Chen, Sci. Adv. 2018, 4, eaao1761.
[40] C. Xu, B. Li, H. Du, F. Kang, Angew. Chem., Int. Ed. 2012, 51, 933. [68] R. Chen, R. Luo, Y. Huang, F. Wu, L. Li, Adv. Sci. 2016, 3, 1600051.
[41] a) M. H. Alfaruqi, J. Gim, S. Kim, J. Song, J. Jo, S. Kim, V. Mathew, [69] D. Aurbach, Z. Lu, A. Schechter, Y. Gofer, H. Gizbar, R. Turgeman,
J. Kim, J. Power Sources 2015, 288, 320; b) M. H. Alfaruqi, S. Islam, Y. Cohen, M. Moshkovich, E. Levi, Nature 2000, 407, 724.
J. Gim, J. Song, S. Kim, D. T. Pham, J. Jo, Z. Xiu, V. Mathew, [70] X. G. Zhang, Corrosion and Electrochemistry of Zinc, Springer, Berlin
J. Kim, Chem. Phys. Lett. 2016, 650, 64; c) M. H. Alfaruqi, 1996.
J. Gim, S. Kim, J. Song, D. T. Pham, J. Jo, Z. Xiu, V. Mathew, [71] F. Wang, O. Borodin, T. Gao, X. Fan, W. Sun, F. Han, A. Faraone,
J. Kim, Electrochem. Commun. 2015, 60, 121; d) X. Wu, Y. Xiang, J. A. Dura, K. Xu, C. Wang, Nat. Mater. 2018, 17, 543.
Q. Peng, X. Wu, Y. Li, F. Tang, R. Song, Z. Liu, Z. He, X. M. Wu, [72] a) T. K. A. Hoang, M. Acton, H. T. H. Chen, Y. Huang, T. N. L. Doan,
J. Mater. Chem. A 2017, 5, 17990; e) C. Wei, C. Xu, B. Li, H. Du, P. Chen, Mater. Today Energy 2017, 4, 34; b) H. Kim, G. Jeong,

Small Methods 2019, 3, 1800272 1800272 (19 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.small-methods.com

Y. U. Kim, J. H. Kim, C. M. Park, H. J. Sohn, Chem. Soc. Rev. 2013, [89] a) P. Novak, J. Desilvestro, J. Electrochem. Soc. 1993, 140, 140;
42, 9011. b) P. Novak, W. Scheifele, F. Joho, O. Haas, J. Electrochem. Soc.
[73] a) K. E. K. Sun, T. K. A. Hoang, T. N. L. Doan, Y. Yu, P. Chen, 1995, 142, 2544; c) P. Novák, W. Scheifele, O. Haas, J. Power
Chem. - Eur. J. 2018, 24, 1667; b) J. Yan, J. Wang, H. Liu, Z. Bakenov, Sources 1995, 54, 479.
D. Gosselink, P. Chen, J. Power Sources 2012, 216, 222; c) G. Li, [90] C. Yuan, Y. Zhang, Y. Pan, X. Liu, G. Wang, D. Cao, Electro-
Z. Yang, Y. Jiang, W. Zhang, Y. Huang, J. Power Sources 2016, 308, 52; chim. Acta 2014, 116, 404.
d) P. Hu, M. Yan, T. Zhu, X. Wang, X. Wei, J. Li, L. Zhou, Z. Li, L. Chen, [91] J. Song, M. Noked, E. Gillette, J. Duay, G. Rubloff, S. B. Lee,
L. Mai, ACS Appl. Mater. Interfaces 2017, 9, 42717; e) T. Gupta, Phys. Chem. Chem. Phys. 2015, 17, 5256.
A. Kim, S. Phadke, S. Biswas, T. Luong, B. J. Hertzberg, M. Chamoun, [92] S. H. Lee, R. A. DiLeo, A. C. Marschilok, K. J. Takeuchi, E. S. Takeuchi,
K. Evans-Lutterodt, D. A. Steingart, J. Power Sources 2016, 305, 22; ECS Electrochem. Lett. 2014, 3, A87.
f) M. M. Gross, A. Manthiram, ACS Appl. Mater. Interfaces 2018, 10, [93] K. W. Nam, S. Kim, S. Lee, M. Salama, I. Shterenberg, Y. Gofer,
10612; g) J. Zhao, Y. Li, X. Peng, S. Dong, J. Ma, G. Cui, L. Chen, Elec- J. S. Kim, E. Yang, C. S. Park, J. S. Kim, S. S. Lee, W. S. Chang, S. G. Doo,
trochem. Commun. 2016, 69, 6; h) K. Lu, B. Song, J. Zhang, H. Ma, Y. N. Jo, Y. Jung, D. Aurbach, J. W. Choi, Nano Lett. 2015, 15, 4071.
J. Power Sources 2016, 321, 257. [94] L. Chen, J. L. Bao, X. Dong, D. G. Truhlar, Y. Wang, C. Wang, Y. Xia,
[74] a) A. Despic, J. Diggle, J. M. Bockris, J. Electrochem. Soc. 1968, 115, ACS Energy Lett. 2017, 2, 1115.
507; b) J. Diggle, A. Despic, J. M. Bockris, J. Electrochem. Soc. 1969, [95] F. Wang, X. Fan, T. Gao, W. Sun, Z. Ma, C. Yang, F. Han, K. Xu,
116, 1503; c) R. Powers, M. Breiter, J. Electrochem. Soc. 1969, 116, C. Wang, ACS Cent. Sci. 2017, 3, 1121.
719; d) J. McBreen, J. Electrochem. Soc. 1972, 119, 1620; e) K. Bass, [96] A. Ponrouch, M. R. Palacin, Curr. Opin. Electrochem. 2018, 9, 1.
P. Mitchell, G. Wilcox, J. Smith, J. Power Sources 1991, 35, 333. [97] A. Ponrouch, C. Frontera, F. Barde, M. R. Palacin, Nat. Mater.
[75] C. Iwakura, H. Murakami, S. Nohara, N. Furukawa, H. Inoue, 2016, 15, 169.
J. Power Sources 2005, 152, 291. [98] M. Wang, C. Jiang, S. Zhang, X. Song, Y. Tang, H. M. Cheng,
[76] S.-H. Lee, C.-W. Yi, K. Kim, J. Phys. Chem. C 2011, 115, 2572. Nat. Chem. 2018, 10, 667.
[77] a) J. McBreen, E. Gannon, J. Electrochem. Soc. 1983, 130, 1980; [99] a) M. Hayashi, H. Arai, H. Ohtsuka, Y. Sakurai, J. Power Sources
b) J. McBreen, E. Gannon, J. Power Sources 1985, 15, 169; 2003, 119, 617; b) M. Hayashi, H. Arai, H. Ohtsuka, Y. Sakurai,
c) J. Jiri, J. Power Sources 2000, 88, 202; d) J. H. Huang, Z. H. Yang, Nucl. Phys. A 2004, 7, 76; c) G. G. Amatucci, F. Badway, A. Singhal,
Z. B. Feng, X. E. Xie, X. Wen, Sci. Rep. 2016, 6, 24471; e) J. Yu, B. Beaudoin, G. Skandan, T. Bowmer, I. Plitza, N. Pereira,
H. Yang, X. Ai, X. Zhu, J. Power Sources 2001, 103, 93; f) J.-I. Zhu, T. Chapman, R. Jaworski, J. Electrochem. Soc. 2001, 148, A940.
Y.-H. Zhou, H. Yang, J. Power Sources 1997, 69, 169; g) J. Jiri, [100] a) P. Padigi, G. Goncher, D. Evans, R. Solanki, J. Power Sources
J. Power Sources 1997, 66, 15; h) J. Shin, J. M. You, J. Z. Lee, 2015, 273, 460; b) A. L. Lipson, B. Pan, S. H. Lapidus, C. Liao,
R. Kumar, L. Yin, J. Wang, Y. S. Meng, Phys. Chem. Chem. Phys. J. T. Vaughey, B. J. Ingram, Chem. Mater. 2015, 27, 8442; c) T. Tojo,
2016, 18, 26376. Y. Sugiura, R. Inada, Y. Sakurai, Electrochim. Acta 2016, 207, 22.
[78] Y. Sato, M. Takahashi, H. Asakura, T. Yoshida, K. Tada, [101] M. Cabello, F. Nacimiento, J. R. González, G. Ortiz, R. Alcántara,
K. Kobayakawa, N. Chiba, K. Yoshida, J. Power Sources 1992, 38, 317. P. Lavela, C. Pérez-Vicente, J. L. Tirado, Electrochem. Commun.
[79] a) D. Bhatt, R. Udhayan, J. Power Sources 1994, 47, 2016, 67, 59.
177; b) A. S. Kannan, S. Muralidharan, K. Sarangapani, [102] R. K. Guduru, J. C. Icaza, Nanomaterials 2016, 6, 41.
V. Balaramachandran, V. Kapali, J. Power Sources 1995, 57, 93; [103] a) R. Y. Wang, B. Shyam, K. H. Stone, J. N. Weker, M. Pasta,
c) C. W. Lee, K. Sathiyanarayanan, S. W. Eom, M. S. Yun, J. Power H.-W. Lee, M. F. Toney, Y. Cui, Adv. Energy Mater. 2015, 5,
Sources 2006, 160, 1436. 1401869; b) C. Lee, S.-K. Jeong, Electrochim. Acta 2018, 265, 430;
[80] J. F. Parker, C. N. Chervin, I. R. Pala, M. Machler, M. F. Burz, c) R. Y. Wang, C. D. Wessells, R. A. Huggins, Y. Cui, Nano Lett.
J. W. Long, D. R. Rolison, Science 2017, 356, 415. 2013, 13, 5748.
[81] a) J. F. Parker, E. S. Nelson, M. D. Wattendorf, C. N. Chervin, [104] C. Lee, S.-K. Jeong, Chem. Lett. 2016, 45, 1447.
J. W. Long, D. R. Rolison, ACS Appl. Mater. Interfaces 2014, 6, [105] S. Gheytani, Y. Liang, F. Wu, Y. Jing, H. Dong, K. K. Rao, X. Chi,
19471; b) M. Chamoun, B. J. Hertzberg, T. Gupta, D. Davies, F. Fang, Y. Yao, Adv. Sci. 2017, 4, 1700465.
S. Bhadra, B. Van Tassell, C. Erdonmez, D. A. Steingart, NPG Asia [106] a) E. J. Rudd, D. W. Gibbons, J. Power Sources 1994, 47, 329;
Mater. 2015, 7, e178; c) M. Li, J. Meng, Q. Li, M. Huang, X. Liu, b) C. S. Li, W. Q. Ji, J. Chen, Z. L. Tao, Chem. Mater. 2007, 19, 5812.
K. A. Owusu, Z. Liu, L. Mai, Adv. Funct. Mater. 2018, 28, 1802016. [107] N. Jayaprakash, S. K. Das, L. A. Archer, Chem. Commun. 2011, 47,
[82] H. Li, C. Xu, C. Han, Y. Chen, C. Wei, B. Li, F. Kang, J. Electro- 12610.
chem. Soc. 2015, 162, A1439. [108] a) M. C. Lin, M. Gong, B. Lu, Y. Wu, D. Y. Wang, M. Guan,
[83] M. A. González, R. Trócoli, I. Pavlovic, C. Barriga, F. La Mantia, M. Angell, C. Chen, J. Yang, B. J. Hwang, H. Dai, Nature 2015,
Electrochem. Commun. 2016, 68, 1. 520, 325; b) J. Jiang, H. Li, T. Fu, B. J. Hwang, X. Li, J. Zhao, ACS
[84] K. Sun, H. Tka, D. Tnl, Y. Yu, P. Chen, Chemistry 2018, 24, 1667. Appl. Mater. Interfaces 2018, 10, 17942; c) S. Wang, S. Q. Jiao,
[85] a) H. D. Yoo, I. Shterenberg, Y. Gofer, G. Gershinsky, N. Pour, J. X. Wang, H. S. Chen, D. H. Tian, H. P. Lei, D. N. Fang, ACS
D. Aurbach, Energy Environ. Sci. 2013, 6, 2265; b) M. M. Huie, Nano 2017, 11, 469.
D. C. Bock, E. S. Takeuchi, A. C. Marschilok, K. J. Takeuchi, [109] S. Liu, J. J. Hu, N. F. Yan, G. L. Pan, G. R. Li, X. P. Gao, Energy
Coord. Chem. Rev. 2015, 287, 15; c) Z. Zhang, Z. Cui, L. Qiao, Environ. Sci. 2012, 5, 9743.
J. Guan, H. Xu, X. Wang, P. Hu, H. Du, S. Li, X. Zhou, S. Dong, [110] Y. J. He, J. F. Peng, W. Chu, Y. Z. Li, D. G. Tong, J. Mater. Chem. A
Z. Liu, G. Cui, L. Chen, Adv. Energy Mater. 2017, 7, 1602055. 2014, 2, 1721.
[86] C. B. Bucur, T. Gregory, A. G. Oliver, J. Muldoon, [111] M. Kazazi, P. Abdollahi, M. Mirzaei-Moghadam, Solid State Ionics
J. Phys. Chem. Lett. 2015, 6, 3578. 2017, 300, 32.
[87] X. Sun, V. Duffort, B. L. Mehdi, N. D. Browning, L. F. Nazar, [112] H. Lahan, S. K. Das, Ionics 2018, 24, 1855.
Chem. Mater. 2016, 28, 534. [113] Y. Liu, S. Sang, Q. Wu, Z. Lu, K. Liu, H. Liu, Electrochim. Acta 2014,
[88] a) K. Xu, Chem. Rev. 2014, 114, 11503; b) A. B. Du, Z. H. Zhang, 143, 340.
H. T. Qu, Z. L. Cui, L. X. Qiao, L. L. Wang, J. C. Chai, T. Lu, [114] S. Liu, G. L. Pan, G. R. Li, X. P. Gao, J. Mater. Chem. A 2014, 3, 959.
S. M. Dong, T. T. Dong, H. M. Xu, X. H. Zhou, G. L. Cui, Energy [115] F. Wang, F. Yu, X. Wang, Z. Chang, L. Fu, Y. Zhu, Z. Wen, Y. Wu,
Environ. Sci. 2017, 10, 2616. W. Huang, ACS Appl. Mater. Interfaces 2016, 8, 9022.

Small Methods 2019, 3, 1800272 1800272 (20 of 20) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim