ARTICLES

PUBLISHED: 26 AUGUST 2016 | ARTICLE NUMBER: 16129 | DOI: 10.1038/NENERGY.2016.129

Hydrate-melt electrolytes for high-energy-density

aqueous batteries
Yuki Yamada1,2, Kenji Usui1, Keitaro Sodeyama2,3,4, Seongjae Ko1, Yoshitaka Tateyama2,4
and Atsuo Yamada1,2*

Aqueous Li-ion batteries are attracting increasing attention because they are potentially low in cost, safe and environmentally
friendly. However, their low energy density (<100 Wh kg−1 based on total electrode weight), which results from the narrow
operating potential window of water and the limited selection of suitable negative electrodes, is problematic for their future
widespread application. Here, we explore optimized eutectic systems of several organic Li salts and show that a room-
temperature hydrate melt of Li salts can be used as a stable aqueous electrolyte in which all water molecules participate
in Li+ hydration shells while retaining fluidity. This hydrate-melt electrolyte enables a reversible reaction at a commercial
Li4 Ti5 O12 negative electrode with a low reaction potential (1.55 V versus Li+ /Li) and a high capacity (175 mAh g−1 ). The resultant
aqueous Li-ion batteries with high energy density (>130 Wh kg−1 ) and high voltage (∼2.3–3.1 V) represent significant progress
towards performance comparable to that of commercial non-aqueous batteries (with energy densities of ∼150–400 Wh kg−1
and voltages of ∼2.4–3.8 V).

T
here is a growing demand for rechargeable batteries that
are high energy density and retain a high level of safety1–3 .
Lithium-ion batteries have relied to date on non-aqueous
electrolytes (with wide potential windows)4,5 in combination
with low-potential and high-capacity negative electrodes, for
example, graphite (0.15 V versus Li+ /Li, 372 mAh g−1 ) and spinel
Li4 Ti5 O12 (1.55 V versus Li+ /Li, 175 mAh g−1 ), to store the high
energies per weight (∼150–400 Wh kg−1 based on total electrode
weight) found in commercially available batteries1–3,6 . However,
the use of highly volatile, flammable, and toxic non-aqueous
electrolytes compromises battery safety4,5 . Although various
measures have been taken to minimize the safety risk7 , accidental
fires due to non-aqueous Li-ion batteries in notebook computers,
automobiles, and aeroplanes have still occurred8,9 . In most cases,
these accidents have been aggravated by leakage of the highly
flammable electrolyte induced by thermal runaway (that is,
out-of-control exothermic reactions)7,9 .
Aqueous Li-ion batteries, first reported by Li et al. in 199410 , are
receiving considerable attention as a safer battery technology based
on non-flammable and low-toxicity aqueous electrolytes11–14 . Aque-
ous Li-ion batteries also have an advantage in terms of production
cost because there is no need to build an ultradry manufacturing
facility, as is required for current non-aqueous batteries. However, a
critical issue that limits their application is their low energy density
resulting from their inherently narrow potential window (1.23 V for
pure water)10,13 . The limited selection of suitable negative electrodes
(with low reaction potential and high capacity) also makes it more
difficult to achieve a higher energy density13 . As a result, even with a
highly stable aqueous electrolyte14,15 , the energy density of aqueous
Li-ion batteries has remained limited to <100 Wh kg−1 , which is
much smaller than those of current commercial non-aqueous Li-ion
batteries (∼150–400 Wh kg−1 ).
Herein, we report the use of a Li salt hydrate melt as an
electrolyte to bridge the energy-density gap between aqueous and
non-aqueous Li-ion batteries. A hydrate melt is a metal salt mixed
with an extremely small amount of water, in which all water
molecules are coordinated with the metal cations while retaining
their fluidity16 . Multivalent cation salts (for example, Mg(NO3 )2
and Mn(NO3 )2 ) are known to form hydrate melts at ambient
temperatures, and have been studied with a focus on their peculiar
physicochemical properties, which are analogous to those of molten
salts16,17 . By contrast, Li salt hydrate melts are usually obtainable
only at high temperatures (for example, >100 ◦ C; ref. 18) or in
the form of an unstable supercooled droplet19 and have never
previously been obtained at ambient temperatures. We discovered
a room-temperature hydrate melt of Li salts by carefully selecting
Li salt anions and then exploring their optimized eutectic systems
with the aim of expanding the liquidus range. Using this hydrate
melt as an electrolyte, we demonstrated the reversible reaction of
a commercial Li4 Ti5 O12 negative electrode in an aqueous system,
thereby significantly increasing the energy density of aqueous
batteries into the energy-density range of commercial non-aqueous
Li-ion batteries.
Room-temperature hydrate melts
Our strategy for seeking a room-temperature hydrate melt of Li
salts consisted of the careful selection of Li salt anions and the
utilization of a eutectic system thereof. We selected two organic
imide anions, N(SO2 CF3 )−2 (TFSI) and N(SO2 C2 F5 )−2 (BETI). These
bulky anions occupy a large volume in solution, thereby reducing
the water concentration. Moreover, these anions are weakly Lewis
basic and thus interact only weakly with Li+20,21 , thereby promoting
the solvation of the Li+ ions by water molecules rather than the
abundant formation of ion pairs. Finally, these anions exert a

1 Department of Chemical System Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan. 2 Elements Strategy Initiative for
Catalysts & Batteries (ESICB), Kyoto University, 1-30, Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245, Japan. 3 PRESTO, Japan Science and Technology Agency
(JST), 4-1-8, Honcho, Kawaguchi, Saitama 333-0012, Japan. 4 Center for Green Research on Energy and Environmental Materials and Center for Materials
Research by Information Integration, National Institute for Materials Science (NIMS), 1-1, Namiki, Tsukuba, Ibaraki 305-0044, Japan.
*e-mail: yamada@chemsys.t.u-tokyo.ac.jp

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ARTICLES NATURE ENERGY DOI: 10.1038/NENERGY.2016.129

a 4 b
Li(TFSI)x(BETI)1−x /(H2O)n

Liquid

Water content, n
LiTFSI LiBETI H2O
3
Eutectic
Salt
deposition x = 0.7
n = 2.0

0.0 0.2 0.4 0.6 0.8 1.0 Molar

ratio 0.7 0.3 2.0 Hydrate melt
Salt mixing ratio, x

Figure 1 | Preparation of a room-temperature hydrate melt. a, Liquidus line of Li(TFSI)x (BETI)1−x salt–water mixtures. The liquidus line was drawn by
connecting saturation points (filled circles) that were experimentally obtained through the gradual addition of water to Li(TFSI)x (BETI)1−x salts with the
given values of x. The light blue region above the liquidus line represents a stable liquid phase of fully miscible salts and water, whereas the shaded blue
region represents a partially miscible phase of salts and water containing deposited crystalline salt or hydrate. The Li(TFSI)0.7 (BETI)0.3 salt (x = 0.7)
corresponds to a eutectic mixture that enables the formation of a hydrate melt state, Li(TFSI)0.7 (BETI)0.3 · 2H2 O, with the lowest water content (n = 2.0).
b, Stoichiometric amounts of LiTFSI, LiBETI and water used to prepare a Li(TFSI)0.7 (BETI)0.3 · 2H2 O hydrate melt. The red arrows indicate the liquid levels.

‘plasticizing’ effect22,23 , inhibiting the crystallization of both the
Li salts and the Li salt solvates (hydrates). These characteristics
of TFSI and BETI anions result in an amorphous liquid state
at a minimal water concentration. In addition, these anions are
known to be highly resistant to hydrolysis24 . Next, to further
expand the liquidus range, we explored a eutectic composition of
LiTFSI and LiBETI salts. Figure 1a shows the miscibility limits of
mixed LiTFSI–LiBETI salts in pure water at room temperature. We
found that a eutectic composition of Li(TFSI)0.7 (BETI)0.3 showed
the highest miscibility with water, forming a stable, transparent,
colourless liquid with an extremely low water content (molar ratio:
n = H2 O/Li+ = 2.0), corresponding to a water molar concentration
of 10.1 mol dm−3 (Fig. 1b). Because of this low water concentration,
the water molecules can be isolated from each other by the bulky
anions, thereby decreasing the opportunity for the formation of
clusters of free water molecules (without coordination with Li+ ).
Indeed, the discovered liquid material is regarded as a Li salt
hydrate melt, Li(TFSI)0.7 (BETI)0.3 · 2H2 O (dihydrate), with all water
molecules participating in Li+ hydration shells, as is evidenced both
experimentally and theoretically (shown later). Very recently, we
have found published works on water-in-salt electrolytes14,15 , but
these other electrolytes are not hydrate melts and contain non-
negligible amounts of remaining free water molecules (more than
10% of all water molecules) because of the use of much smaller and
off-eutectic anions.
Information on the physicochemical properties of the hydrate
melt is presented in Table 1. The hydrate melt has a vapour pressure
of 0.50 kPa at 30 ◦ C, which is quite low for an aqueous system
(for example, 4.25 kPa for pure water25 at 30 ◦ C), suggesting that
the water activity is significantly decreased to 0.12 (=0.50/4.25)
because of a hydration effect in the hydrate melt. The viscosity
is high (203 mPa s at 30 ◦ C), but the ionic conductivity is
3 mS cm−1 , which is comparable to that of Li-salt-based non-
aqueous solutions26 . Interestingly, on the basis of the Walden plot
(Supplementary Fig. 1), the hydrate-melt electrolyte can be classified
as a ‘superionic solution’ because it lies above the ideal KCl line
(full dissociation)27,28 , which indicates that the ionic conductivity
is decoupled from the viscosity (fluidity); in other words, the ions
move faster than would be expected based on the viscosity29 . The
‘superionicity’ of the hydrate melt is an interesting feature for its
use as a battery electrolyte and is worth scrutinizing in the future,
although it is not the main focus of the present work.
Liquid structure
The hydrate melt state was characterized using both experimental
and theoretical approaches. Figure 2a,b shows the O–H stretching
vibration modes of water molecules30–32 in various aqueous solutions
studied via Raman spectroscopy. In pure water, the O–H stretching
vibration gave rise to a broad Raman band consisting of several
components, which are attributed to various water molecules with
different hydrogen-bonding environments in water clusters31,32 . This
broad band remained pronounced in saturated aqueous solutions
of two conventional inorganic Li salts, LiNO3 and Li2 SO4 (Fig. 2a),
suggesting the presence of water clusters that were not participating
in the Li+ hydration shells because of the high water content.
However, increasing the concentration of the organic LiTFSI salt led
to a completely different situation (Fig. 2b); a new peak appeared at
3,565 cm−1 at the expense of the broad water-cluster band. Finally,
Li(TFSI)0.7 (BETI)0.3 · 2H2 O, with the lowest water content, showed
only a sharp peak at 3,565 cm−1 without the broad band, indicating
that the abundance of water clusters was significantly diminished
in this extreme-state aqueous liquid. A sharp O–H vibration peak
is characteristic of crystalline hydrates19,33 and has rarely been
observed in aqueous solutions; thus, these findings suggest that the
state of the water molecules in Li(TFSI)0.7 (BETI)0.3 · 2H2 O is rather
close to that in crystalline hydrates.
To achieve theoretical insight into the liquid structure, we
conducted first-principles density-functional-theory-based
molecular dynamics (DFT-MD) simulations. In a typical aqueous
solution of 0.93 mol kg−1 LiTFSI/H2 O (n = 60), Li+ is solvated by
four (or five) water molecules, and many free water molecules form
a network with each other through hydrogen bonding (Fig. 2c).
For Li(TFSI)0.7 (BETI)0.3 · 2H2 O, after considering various initial
structures at various temperatures, we found a stable state in which
all water molecules were coordinated with Li+ by the Lewis-basic
oxygen atoms and exhibited negligible hydrogen bonding with
other water molecules (Fig. 2d). The disappearance of free water
molecules was further confirmed by tracking all water molecules’
coordination states over 100,000 DFT-MD steps (Supplementary
Fig. 2). This simulation result indicates the incorporation of all
water molecules into Li+ hydration shells and is fully consistent
with the absence of the broad Raman band originating from water
clusters, suggesting that Li(TFSI)0.7 (BETI)0.3 · 2H2 O can indeed be
classified as a hydrate melt.
Li+ intercalation electrode reactions
Spinel Li4 Ti5 O12 (1.55 V versus Li+ /Li) is used for negative
electrodes in commercial non-aqueous Li-ion batteries but has
never previously functioned reversibly in an aqueous electrolyte
because of the intensive hydrogen evolution that occurs instead
of Li+ intercalation during charging13 . Figure 3 presents cyclic
voltammograms of a Li4 Ti5 O12 electrode (on an Al current collector)

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Table 1 | Physicochemical properties of the Li(TFSI)0.7 (BETI)0.3 · 2H2 O hydrate melt.

Material Salt molality Salt molar Density∗ Viscosity† Conductivity† Vapour pressure† Water activity‡
(mol kg−1 ) fraction (%) (g cm−3 ) (mPa s) (mS cm−1 ) (kPa) (-)
LiTFSI/H2 O solution 1.2 2.05 1.145 1.51 42.1 4.1 0.96
Hydrate melt 27.8 33.3 1.783 203 3.0 0.5 0.12
Data of a typical aqueous solution of 1.2 mol kg−1 LiTFSI/H2 O are listed for comparison. ∗ Density was measured at 25 ◦ C. † Viscosity, ionic conductivity and vapour pressure were measured at 30 ◦ C.
‡
Water activity was evaluated from the vapour pressure divided by that of pure water (4.25 kPa) at 30 ◦ C. The vapour pressure of pure water was calculated from an equation presented in ref. 25.

a Hydration to Li+ b Hydration to Li+ d Li(TFSI)0.7(BETI)0.3 ⋅ 2H2O

Li(TFSI)0.7(BETI)0.3 ⋅ 2H2O Li(TFSI)0.7(BETI)0.3 ⋅ 2H2O

Sat. 9.5 mol kg−1

LiNO3/H2O LiTFSI/H2O
Intensity (a.u.)

Intensity (a.u.)

Sat. 1.2 mol kg−1 c Dilute LiTFSI/H2O

Li2SO4/H2O LiTFSI/H2O

Water clusters Water clusters

Pure Pure
water water

2,500 3,000 3,500 4,000 2,500 3,000 3,500 4,000

Raman shift (cm−1) Raman shift (cm−1)

Figure 2 | Structural characterization of the hydrate melt. a,b, Raman spectra of Li(TFSI)0.7 (BETI)0.3 · 2H2 O compared with those of inorganic Li salt
aqueous solutions, namely, saturated 12 mol kg−1 LiNO3 /H2 O and saturated 2.9 mol kg−1 Li2 SO4 /H2 O (a), and organic Li salt aqueous solutions, namely,
dilute 1.2 mol kg−1 LiTFSI/H2 O and concentrated 9.5 mol kg−1 LiTFSI/H2 O (b). The Raman bands observed in the range of 2,500–4,000 cm−1 correspond
to the O–H stretching modes of water molecules. The broad bands in the range of 2,900–3,700 cm−1 (between the blue dashed lines) are attributed to
clusters of water molecules with various hydrogen-bonding environments. The sharp peak at 3,565 cm−1 (orange dashed line) is attributed to Li+ -solvated
water molecules that are not clustered through hydrogen bonding. c,d, Snapshots of equilibrium trajectories obtained from first-principles DFT-MD
simulations of 1-LiTFSI/60-H2 O (corresponding to 0.93 mol kg−1 ) (c) and 7-LiTFSI/3-LiBETI/20-H2 O (corresponding to Li(TFSI)0.7 (BETI)0.3 · 2H2 O
hydrate melt, 28 mol kg−1 ) (d). Atom colours: Li, purple (presented with a larger size for emphasis); C, dark grey; H, light grey; O, red; N, blue; S, yellow;
F, light green. The cubic boxes represent the periodic boundaries of the supercells used in the DFT-MD simulations.

together with the linear sweep voltammograms of the Al current
collector. In a typical aqueous electrolyte of 1.2 mol kg−1 LiTFSI
(1.0 mol dm−3 ), no reversible redox pair was observed; instead, a
cathodic current was observed below 2.0 V versus Li+ /Li for both the
Li4 Ti5 O12 and Al electrodes (Fig. 3a), which was simply attributed
to hydrogen evolution by means of the reduction of water. The
same behaviour was observed when using a Zn current collector
with a large overpotential for hydrogen evolution (Supplementary
Fig. 3) or aqueous electrolytes of conventional inorganic Li salts
(for example, LiNO3 or Li2 SO4 ) even at saturation (Supplementary
Fig. 4). However, a reversible redox pair emerged on increasing the
concentration of organic Li salts, that is, LiTFSI and/or LiBETI,
at the expense of the hydrogen evolution (Supplementary Figs 5
and 6). In the extreme state of the Li(TFSI)0.7 (BETI)0.3 · 2H2 O
hydrate melt, hydrogen evolution was suppressed on both Li4 Ti5 O12
and Al (and Zn), and a fully reversible redox pair appeared at
1.85 V (Fig. 3b and Supplementary Fig. 3), which corresponds to the
Li+ intercalation/de-intercalation reaction of Li4+x Ti5 O12 . Notably,
the reaction potential in the Li(TFSI)0.7 (BETI)0.3 · 2H2 O hydrate
melt was found to be approximately 0.3 V higher than that in a
conventional organic electrolyte. This upward shift in the reaction
potential combined with the suppression of hydrogen evolution is
the key to achieving a reversible Li+ intercalation reaction, as shown
in the Discussion section.
For the positive electrode side, layered LiCoO2 and spinel
LiNi0.5 Mn1.5 O4 are established materials with high reaction
potentials of approximately 4.0 V and 4.7 V versus Li+ /Li,
respectively3,13 . Figure 3 shows cyclic voltammograms of these
active electrodes (on a Ti current collector) together with the
linear sweep voltammograms of the Ti current collector. The Ti
current collector was found to be inactive up to high potentials
of above 5.5 V in the investigated aqueous systems by virtue of
a stable native oxide layer on the surface. In a typical aqueous
electrolyte of 1.2 mol kg−1 LiTFSI, a reversible redox pair of Li+
de-intercalation/intercalation was observed for LiCoO2 , with
its reaction potential of 4.0 V, but not for LiNi0.5 Mn1.5 O4 , with its
higher reaction potential of 4.7 V, because of the high level of oxygen
evolution from the oxidation of water on the active LiNi0.5 Mn1.5 O4 .
By contrast, the Li(TFSI)0.7 (BETI)0.3 · 2H2 O hydrate-melt electrolyte
enabled the reversible Li+ de-intercalation/intercalation of both
LiCoO2 and LiNi0.5 Mn1.5 O4 at 4.25 V and 5.00 V versus Li+ /Li,
respectively. The reaction potentials were again approximately
0.3 V higher than those in the conventional dilute organic
electrolyte, as was the case for the Li4 Ti5 O12 electrode.
High-energy-density aqueous Li-ion batteries
Having confirmed the occurrence of reversible reactions on both
the negative and positive electrodes, we fabricated full Li-ion cells to

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ARTICLES
a 0.4
1.2 mol kg−1 LiTFSI/H2O
0.2
Current (mA)
0.0
Al
Li4Ti5O12 LiCoO2
−0.2
1 2 3 4
Potential (V) versus Li+/Li
b Supplementary Fig. 11, a LiNi0.5 Mn1.5 O4 /Li4 Ti5 O12 cell showed a
0.2 Li(TFSI)0.7(BETI)0.3 ⋅ 2H2O
0.1
Current (mA)
0.0
−0.1
2.4 V
−0.2 3.1 V
1 2 3 4
Potential (V) versus Li+/Li
Figure 3 | Reversibility of Li+ intercalation/de-intercalation reactions.
a,b, Cyclic voltammograms (scan rate: 0.1 mV s−1 , electrode area:
0.50 cm2 ) of Li4 Ti5 O12 , LiCoO2 and LiNi0.5 Mn1.5 O4 electrodes in a typical
aqueous solution of 1.2 mol kg−1 LiTFSI/H2 O (a) and in a hydrate-melt
electrolyte of Li(TFSI)0.7 (BETI)0.3 · 2H2 O (b). The three vertical lines
indicate the redox potentials of the electrodes. The LiCoO2 and
LiNi0.5 Mn1.5 O4 electrodes exhibited reaction potentials of 2.4 V and 3.1 V,
respectively, relative to that of the Li4 Ti5 O12 electrode. The current
collectors were Al for the negative electrode (Li4 Ti5 O12 ) and Ti for the
positive electrodes (LiCoO2 and LiNi0.5 Mn1.5 O4 ). The dashed lines
represent the linear sweep voltammograms (scan rate: 0.1 mV s−1 ,
electrode area: 0.50 cm2 ) of the current collectors.
study their charge–discharge cyclability (Fig. 4 and Supplementary
Fig. 7). As shown in Fig. 4a, the fabricated LiCoO2 /Li4 Ti5 O12
cell with the hydrate-melt electrolyte showed a voltage plateau
at ∼2.3–2.5 V during both charging and discharging, suggesting
the reversible operation of the battery. Under high-rate cycling
at 10C, the capacity retention after 200 cycles was 75%, with the
retention of approximately 100% Coulombic efficiency. It should
be noted that irreversible capacity was observed in the initial
cycle (Supplementary Fig. 7) but was markedly decreased in the
following cycles (Fig. 4a), suggesting that a passivation reaction
occurred to suppress further electrolyte decomposition (as shown
in the Discussion section). It is well known that H+ -Li+ exchange
reactions cause the gradual capacity decay of a LiCoO2 electrode
on cycling34 . To circumvent this inessential electrode degradation
by means of pH control11 , we used an alkaline hydrate melt,
Li1+x (TFSI)0.7 (BETI)0.3 (OH)x · (2 − x)H2 O (x = 0.035), for further
prolonged cycling tests at low and high rates (Supplementary Fig. 8).
Under low-rate cycling at 0.2C and 0.5C, the levels of capacity
retention after 100 cycles were 67% and 79%, respectively, with the
Coulombic efficiency approaching 100% and with limited voltage
fading during cycling (Supplementary Fig. 9). High-rate cycling
at 10C resulted in a capacity retention of 84% after 500 cycles
with the retention of approximately 100% Coulombic efficiency.
Notably, despite the high viscosity of the electrolyte, the voltage
polarization was small even at this high rate, presumably because of
the decoupling of the ionic conductivity from the viscosity due to the
‘superionicity’ of the electrolyte (Supplementary Fig. 1) and/or the
small interfacial activation energy in aqueous systems35 that enables
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fast interfacial reactions. More importantly, such stable cycling was
observed exclusively for the hydrate-melt electrolyte. For the typical
aqueous electrolyte of 1.2 mol kg−1 LiTFSI, the Li4 Ti5 O12 negative
electrode did not function at all, as is clear from Fig. 3a. Even a water-
in-salt electrolyte with high electrochemical stability (but also free
Ti water molecules)14 suffered severe capacity decay on cycling (only
LiNi0.5Mn1.5O4 12% capacity retention after 30 cycles at 0.2C with <90% Coulombic
efficiency), as shown in Supplementary Fig. 10, suggesting that the
hydrate melt state is important to achieve stable cycling.
Additionally, as an extreme example, the hydrate-melt electrolyte
5 enabled the partial use (that is, <0.5 Li+ extraction) of a high-
potential LiNi0.5 Mn1.5 O4 positive electrode. As shown in Fig. 4b and
voltage plateau at ∼3.0–3.3 V during both charging and discharging,
although the cell capacity was lower than that of the 2.4 V
LiCoO2 /Li4 Ti5 O12 cell because of the partial use of the positive
electrode. Under high-rate cycling at 6.8C, the capacity retention
over 100 cycles was 63%, with the retention of nearly 100%
Coulombic efficiency (Fig. 4b). The reversible charge–discharge
reaction was also confirmed under low-rate cycling at 0.5C and
1.0C, although the capacity faded and the Coulombic efficiency
declined during cycling (Supplementary Fig. 11), suggesting that
5 oxygen evolution occurred in parallel with the Li+ de-intercalation
at the LiNi0.5 Mn1.5 O4 during slow charging. These findings indicate
that the reaction potential of LiNi0.5 Mn1.5 O4 is positioned at
the edge of the anodic stability window of the hydrate melt,
thereby hampering the full utilization of the high-potential positive
electrode. This is the voltage limitation of the present hydrate melt
technology, although it implies the possibility of 3 V-class aqueous
batteries with further optimization of the hydrate-melt electrolyte.
By virtue of the utilization of the low-potential and high-capacity
Li4 Ti5 O12 negative electrode, the energy density of the aqueous cells
was considerably increased. Figure 4c shows the theoretical and
actual energy densities of various battery chemistries, including
those investigated in this work, with respect to the total weight of the
positive and negative active materials. Importantly, the actual energy
density (as experimentally obtained) of the LiCoO2 /Li4 Ti5 O12 cell
was 130 Wh kg−1 (55.3 Ah kg−1 and 2.35 V on average), based on the
first discharge curve shown in Supplementary Fig. 12. This value can
be made to approach the theoretical value of 184 Wh kg−1 (Fig. 4c)
by applying an engineering approach to optimize the cell design
to more effectively utilize the active materials, decrease the initial
irreversible capacity (Supplementary Fig. 7), and reduce the internal
resistance of the cell. This energy density is comparable to that
of a commercial non-aqueous LiMn2 O4 /Li4 Ti5 O12 Li-ion battery
(theoretical energy density: 160 Wh kg−1 ).
Discussion
The hydrate melt state, in which all water molecules participate
in Li+ hydration shells, gives rise to a widening of the potential
window in both a thermodynamic and a kinetic manner (Fig. 5a)
and an upward shift in the Li+ intercalation potential (Fig. 5b),
which synergistically contribute to enabling the reversible operation
of high-energy-density aqueous batteries.
Figure 5a shows the potential windows evaluated for various
metal electrodes by means of linear sweep voltammetry using
a low scan rate (0.1 mV s−1 ). For the most catalytically active
Pt electrode, for which the kinetic factor (that is, overpotential)
can be minimized, the Li(TFSI)0.7 (BETI)0.3 · 2H2 O hydrate melt
exhibited a wide potential window of 2.7 V (∼2.35–5.05 V versus
Li+ /Li), whereas that of the typical 1.2 mol kg−1 LiTFSI aqueous
electrolyte was only 2.1 V (∼2.35–4.45 V versus Li+ /Li). Notably,
this widening of the potential window primarily resulted from the
extension of the anodic limit up to 5.05 V, suggesting that the
oxidation potential of the water molecules (or dissociated OH− ) was
increased in the hydrate melt state, in which all water molecules
NATURE ENERGY DOI: 10.1038/NENERGY.2016.129 ARTICLES
a 4.0 b 4.0
LiCoO2 /Li4Ti5O12 (10C) LiNi0.5Mn1.5O4/Li4Ti5O12 (6.8C)
3rd 2nd

3.0 5th−2nd 3.0

Voltage (V)

Voltage (V)
2.0 75 100 2.0 40 100
Capacity (Ah kg−1)

Capacity (Ah kg−1)

Efficiency (%)

Efficiency (%)
30
50 80 80
20
1.0 25 60 1.0 60
10
0 40 0 40
0 50 100 150 200 0 25 50 75 100
Cycle number Cycle number
0.0 0.0
0 20 40 60 0 10 20 30
Cell capacity (Ah kg−1) Cell capacity (Ah kg−1)

c 100 150 200 250 300 350 Wh kg−1

4.0
Non-aqueous LiMn2O4/C LiCoO2/C
LiNi0.5Mn1.5O4 /Li4Ti5O12

3.0 0.5 Li+

LiMn2O4/Li4Ti5O12
Cell voltage (V)

Hydrate melt
LiCoO2/Li4Ti5O12

2.0
LiMn2O4/Mo6S8 (ref. 14)

LiMn2O4/VO2 (ref. 10)

1.0
Aqueous LiFePO4 /LiTi2(PO4)3 (ref. 11)

20 40 60 80 100
Cell capacity (Ah kg−1)

Figure 4 | High-energy-density aqueous Li-ion batteries with Li4 Ti5 O12 negative electrodes. a,b, Charge–discharge voltage profiles of two Li-ion full cells,
2.4 V LiCoO2 /Li4 Ti5 O12 (a) and 3.1 V LiNi0.5 Mn1.5 O4 /Li4 Ti5 O12 (b), with Li(TFSI)0.7 (BETI)0.3 · 2H2 O hydrate-melt electrolytes. Charging and discharging
were performed at 10C (1.37 A g−1 for LiCoO2 ) (a) and 6.8C (1.00 A g−1 for LiNi0.5 Mn1.5 O4 ) (b) at 25 ◦ C. The LiCoO2 /Li4 Ti5 O12 cell was composed of
1.4 mg cm−2 LiCoO2 , 1.4 mg cm−2 Li4 Ti5 O12 and a glass fibre separator. The LiNi0.5 Mn1.5 O4 /Li4 Ti5 O12 cell was composed of 3.0 mg cm−2 LiNi0.5 Mn1.5 O4 ,
1.0 mg cm−2 Li4 Ti5 O12 and a quartz crystal separator. The current collectors were Al and Ti for the negative and positive electrodes, respectively. The cell
capacity was calculated on the basis of the total weight of the positive and negative active materials. The insets show the discharge capacity (open red
circles) and Coulombic efficiency (open blue circles) of the cells on cycling. c, Theoretical (filled circles and stars) and actual (open circles and stars)
energy densities of various aqueous and non-aqueous Li-ion chemistries with respect to the total weight of the positive and negative electrodes (the
weights of the electrolyte and cell are not considered). The electrode capacities and voltages used to calculate the theoretical energy densities are shown
in Supplementary Table 1. The actual energy densities of the LiCoO2 /Li4 Ti5 O12 and LiNi0.5 Mn1.5 O4 /Li4 Ti5 O12 cells were experimentally obtained from the
first discharge curves shown in Supplementary Fig. 12. The hydrate-melt electrolyte, as represented by the red area, enables the fabrication of
high-energy-density and high-voltage Li-ion batteries that bridge the traditional gap between aqueous and non-aqueous Li-ion batteries, which are
represented by the blue and orange areas, respectively.

were coordinated with Li+ . When coordinated with Li+ (a Lewis that anions are predominantly reduced to create a peculiar anion-
acid), a water molecule (or dissociated OH− ) donates its electron based passivation film on a negative electrode because of the
from the lone pair of the oxygen atom to the Li+ , which lowers its downward shift of the anions’ lowest unoccupied molecular orbital
highest occupied molecular orbital (HOMO) level and thus raises its level37,38 . Subsequently, it was reported that a similar anion-based
oxidation potential36 . This thermodynamic extension of the anodic passivation film can also form in superconcentrated aqueous
limit enables not only the fully reversible reaction of LiCoO2 but also electrolytes14 . Motivated by these previous reports, we analysed
the partial use of the higher-potential LiNi0.5 Mn1.5 O4 (although with the surface of a cycled Li4 Ti5 O12 electrode via X-ray photoelectron
parasitic oxygen evolution at low rates). spectroscopy (XPS; Supplementary Fig. 13) and identified a sulfur-
By contrast, no remarkable extension of the cathodic limit based passivation film on the electrode. According to the S2p
was observed for a Pt electrode in the hydrate-melt electrolyte. spectra recorded following Ar+ etching, an SOx moiety (167 eV)
Interestingly, however, the reversible redox pair of Li4 Ti5 O12 existed on the electrolyte side and sulfide species (160–162 eV)
appeared outside the cathodic limit in the hydrate-melt electrolyte. existed on the electrode side (Supplementary Fig. 13). Neither
To understand this seemingly paradoxical phenomenon, one should of these is a post-mortem decomposition product of residual
also consider a kinetic factor (that is, passivation) suppressing salts due to X-ray radiation or Ar+ etching in the XPS chamber
hydrogen evolution, thus further extending the cathodic limit. In (Supplementary Fig. 13), and thus, they should instead have formed
our previous work on superconcentrated non-aqueous electrolytes electrochemically on the Li4 Ti5 O12 during charging as reductive
(that is, a non-aqueous analogue of hydrate melts), we reported decomposition products of the TFSI and/or BETI anions; this

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a b 0.3
0.2 1.2 mol kg−1 LiTFSI/H2O V
Current (mA) Ag/AgCl Li(TFSI)0.7(BETI)0.3 ⋅ 2H2O
0.1 in sat. KCl
Pt
SUS SUS Ti
0.0
Al Zn LiTFSI
Pt LixFePO4

Potential shift (V)

−0.1 0.2
Liquid
Passivation Lower HOMO

High γ Li
−0.2 junction
22 mol kg−1 (sat.)
Li(TFSI)0.7(BETI)0.3 ⋅ 2H2O SUS
0.2
Li4Ti5O12/Al
Current (mA)

0.1 0.1 Sat. LiNO3

γ Li = 1
Pt Ti
0.0
Al Zn SUS Pt

High mLi
−0.1 Sat. Li2SO4
LiNi0.5Mn1.5O4/Ti
−0.2 1.25 V 2.35 V 5.05 V
0.0
1.0 1.5 2.0 2.5 4.0 4.5 5.0 5.5 0 5 10 15 20 25 30
Potential (V) versus Li+/Li mLi (mol kg−1)

c
Pure water

Li4Ti5O12 LiCoO2 LiNi0.5Mn1.5O4

LiTFSI/H2O solution
with free H2O

Nernst shift

Hydrate melt

Passivation Lower HOMO

1.25 2.35 4.45 5.05

Potential (V) versus Li+/Li (std.)

Figure 5 | Thermodynamic and kinetic factors accounting for the battery operating mechanism. a, Potential window of Li(TFSI)0.7 (BETI)0.3 · 2H2 O
hydrate melt compared with that of a typical 1.2 mol kg−1 LiTFSI/H2 O solution, evaluated via linear sweep voltammetry (scan rate: 0.1 mV s−1 ) on various
electrodes (Pt, Al, Ti, Zn, and stainless steel (SUS)). The dashed curves represent the cyclic voltammograms (scan rate: 0.1 mV s−1 ) of Li4 Ti5 O12 (on an Al
current collector) and LiNi0.5 Mn1.5 O4 (on a Ti current collector). The reduction potential of the hydrate melt at Pt (red dashed line at 2.35 V) is the same as
that of the typical aqueous solution, but it is markedly extended at Al (red dashed line at 1.25 V) as a result of passivation. The oxidation potential of the
hydrate melt at Pt (red dashed line at 5.05 V) is extended compared with that of the conventional aqueous solution because of the lowered HOMO level of
the water (and OH− ) molecules due to Li+ hydration. b, Equilibrium potential shift of the Li+ intercalation reaction as a function of the Li+ molality (mLi ) in
the electrolyte. The potential of Lix FePO4 (x ∼ 0.5) was measured versus Ag/AgCl in the cell configuration shown in the inset and was compared with that
in a 1.2 mol kg−1 LiTFSI aqueous solution. The electrolyte solutions used were the Li(TFSI)0.7 (BETI)0.3 · 2H2 O hydrate melt (red star), 1.2–22 mol kg−1
LiTFSI/H2 O (blue circles), saturated 12 mol kg−1 LiNO3 /H2 O (orange circle), and saturated 2.9 mol kg−1 Li2 SO4 /H2 O (brown circle). The dashed violet
line represents the potential shift in an ideal solution based on the Nernst equation, in which the Li+ activity coefficient (γ Li ) is supposed to be 1. The
hydrate melt shows the highest potential shift of 0.25 V by virtue of its high γ Li and high mLi . c, Relation between the potential windows (light blue bands)
of pure water, the conventional LiTFSI/H2 O solution, and the hydrate melt and redox reaction potentials (vertical red bars) of Li4 Ti5 O12 , LiCoO2 and
LiNi0.5 Mn1.5 O4 . The LiTFSI/H2 O solution has a wider potential window (∼2.35–4.45 V at Pt) than that of pure water, but the reaction potentials of
Li4 Ti5 O12 and LiNi0.5 Mn1.5 O4 still lie outside this potential window. For the hydrate melt, the anodic limit is extended up to 5.05 V (at Pt) because of the
lowered HOMO level of the water molecules (violet arrow), and the cathodic limit is extended down to 1.25 V (at Al) as a result of passivation (blue arrow).
Furthermore, the redox reaction potentials of all electrodes are shifted upwards by approximately 0.25 V according to the Nernst equation (orange arrows).

mechanism is consistent with the irreversible capacity observed
in the initial cycle (Supplementary Fig. 7). Lithium fluoride (LiF)
was also found on the cycled electrode; importantly, however,
this material can form as a post-mortem decomposition product
of LiTFSI and LiBETI salts due to X-ray radiation and/or Ar+
etching (Supplementary Fig. 13), as reported previously39,40 . Hence,
we cannot conclude that this LiF forms in an electrochemical
manner and is a major component of the passivation film.
The sulfur-based passivation film, which predominantly forms
through anion reduction, should play a key role in effectively
suppressing parasitic hydrogen evolution, thus kinetically extending
the cathodic limit.
Interestingly, the effectiveness of the passivation strongly
depends on the electrodes to be passivated, as well as the
electrolytes that participate in the passivation reaction (Fig. 5a).
For a Pt electrode, the cathodic limit was found to remain nearly
unchanged regardless of the electrolyte, suggesting that passivation
failed to occur because of its strong catalytic activity towards
hydrogen evolution. By contrast, other electrodes (Al, Zn, stainless
steel (SUS), and Li4 Ti5 O12 ) in combination with the hydrate-melt
electrolyte resulted in markedly widened cathodic limits, and thus,
anion-based passivation was successfully achieved. Notably, the
passivation effect was maximal on the Al electrode, yielding a
wide cathodic limit extending down to 1.25 V versus Li+ /Li in the
hydrate-melt electrolyte, whereas for the SUS current collector,
such as those previously used in aqueous systems14 , massive
hydrogen evolution was observed at a higher potential than the
redox pair of Li4 Ti5 O12 (1.85 V versus Li+ /Li). Hence, the use of
an Al current collector in combination with the hydrate-melt
electrolyte is a key factor in enabling the reversible reaction of

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NATURE ENERGY DOI: 10.1038/NENERGY.2016.129
Li4 Ti5 O12 with remarkably suppressed hydrogen evolution through
kinetic hindrance.
In addition to the extension of the potential window in
both a thermodynamic and a kinetic manner, the equilibrium
potential shift of the Li+ intercalation reaction greatly contributes
to enabling the reversible operation of the investigated aqueous
cells. Figure 5b shows the equilibrium potential shift as evaluated
on the basis of electromotive force measurements on Lix FePO4
(x ∼ 0.5) in various electrolyte solutions. With an increase in the
Li+ molality, the equilibrium potential shifted upwards compared
with the 1.2 mol kg−1 LiTFSI/H2 O standard. In the extreme state
of the Li(TFSI)0.7 (BETI)0.3 · 2H2 O hydrate melt the equilibrium
potential shift reached 0.25 V. Such a large upward potential shift
was an exclusive characteristic of the Li(TFSI)0.7 (BETI)0.3 · 2H2 O
hydrate-melt electrolyte with the highest Li+ molality and without
free solvent molecules. These observations reasonably explain
the approximately 0.3 V higher reaction potentials of Li4 Ti5 O12 ,
LiCoO2 and LiNi0.5 Mn1.5 O4 observed in the cyclic voltammograms
compared with those in conventional dilute organic (and aqueous)
electrolytes. The observed upward shift in potential by 0.25 V was
considerably larger than that expected in an ideal solution (that is,
with a Li+ activity coefficient of 1), which is shown as a dashed
line in Fig. 5b, suggesting a large contribution from a high Li+
activity coefficient as well as the high Li+ molality. This effect can
be attributed to the maximization of the hydration effect41–44 in
the hydrate-melt electrolyte in the absence of free water molecules
(Supplementary Note 1). The large upward potential shift was also
independently verified on the basis of the water activities (Table 1)
using the Gibbs–Duhem equation (Supplementary Note 2).
On the basis of the above discussion, the high-energy-density
battery operating mechanism that is exclusively enabled by the
hydrate-melt electrolyte is summarized in Fig. 5c. In a conventional
aqueous electrolyte, the reaction potentials of Li4 Ti5 O12 and
LiNi0.5 Mn1.5 O4 are both completely outside the electrolyte’s
potential window. By contrast, in the hydrate-melt electrolyte,
the anodic and cathodic potential limits are extended through a
thermodynamic mechanism (lowered HOMO level) and a kinetic
mechanism (anion-based passivation), respectively, which results in
an extremely wide potential window with a maximum width of 3.8 V
(∼1.25–5.05 V versus Li+ /Li). In addition, the Li+ intercalation
potential shifts upwards by approximately 0.3 V, allowing the
reaction potential of Li4 Ti5 O12 to lie fully inside the potential
window. On the positive electrode side, the reaction potential of
LiCoO2 , although shifted upwards by approximately 0.3 V, is also
fully encompassed by the remarkably widened potential window.
Even for the higher-potential LiNi0.5 Mn1.5 O4 , the upward-shifted
reaction potential remains at the edge of the potential window.
The synergetic contributions of the thermodynamic and kinetic
effects, both maximized in the hydrate melt without free water
molecules, enable the stable cycling of aqueous Li-ion batteries of
high energy density.
In conclusion, we discovered a room-temperature Li salt
hydrate melt by carefully selecting Li salt anions and exploring
their eutectics. The reversible Li+ intercalation reaction of the
commercially used Li4 Ti5 O12 electrode material was demonstrated
in an aqueous system with the Li salt hydrate melt as the electrolyte.
The use of a low-potential and high-capacity Li4 Ti5 O12 negative
electrode significantly increases the energy density of an aqueous
battery, bridging the traditional energy-density gap between
aqueous (<100 Wh kg−1 ) and non-aqueous (>150 Wh kg−1 ) Li-ion
batteries. As a proof of concept, charge–discharge cycling was
demonstrated in LiCoO2 /Li4 Ti5 O12 and LiNi0.5 Mn1.5 O4 /Li4 Ti5 O12
batteries with the hydrate-melt electrolyte, and the results pave the
way towards high-voltage (∼2.3–3.1 V) and high-energy-density
(>130 Wh kg−1 ) aqueous Li-ion batteries. Reversible charge–
discharge cycling was achieved by means of the synergetic effect of
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ARTICLES
the thermodynamic and kinetic extension of the potential window
and the upward shift of the electrode potentials, both of which
are consequences of the unusual aqueous liquid state unique to
hydrate melts, in which all water molecules are coordinated with
Li+ and free (un-coordinated) water molecules therefore disappear.
This work will open up a new field of hydrate melt electrochemistry
and expand the potential avenues of research in the search for safe
aqueous batteries of high energy density.
Methods
Materials. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, LiN(SO2 CF3 )2 )
and lithium bis(pentafluoroethanesulfonyl)imide (LiBETI, LiN(SO2 C2 F5 )2 ) were
purchased from Kishida Chemical. Inorganic Li salts—LiNO3 , Li2 SO4 · H2 O and
LiOH · H2 O—were purchased from Wako Pure Chemical Industries. The
electrolyte solutions were prepared by mixing the Li salts with ultrapure water
(Kanto Chemical). In particular, the hydrate-melt electrolyte,
Li(TFSI)0.7 (BETI)0.3 · 2H2 O, was prepared by dissolving LiTFSI and LiBETI salts
in ultrapure water at a molar ratio of LiTFSI:LiBETI:H2 O = 7:3:20. To prepare an
alkaline hydrate melt, a LiOH/H2 O solution (LiOH:H2 O = 1:57.6 by mol) was
prepared by first dissolving LiOH · H2 O in ultrapure water and then dissolving
LiTFSI and LiBETI salts in the LiOH/H2 O solution at a molar ratio of
LiTFSI:LiBETI:(LiOH/H2 O) = 7:3:20. The composition of the resultant alkaline
hydrate melt was Li1+x (TFSI)0.7 (BETI)0.3 (OH)x · (2 − x)H2 O (x = 0.035). To serve
as active electrode materials, Li4 Ti5 O12 and LiCoO2 were provided by Ishihara
Sangyo and Nippon Chemical Industrial, respectively, and LiNi0.5 Mn1.5 O4 and
LiMn2 O4 were purchased from Hosen. LiFePO4 powder was synthesized via a
solid-state reaction from stoichiometric amounts of Li2 CO3 (Wako, 99.0%),
FeC2 O4 · 2H2 O (JUNSEI, 99%) and (NH4 )2 HPO4 (Wako, 99.0%) as starting
materials. During the synthesis, Ketjen black (ECP, Lion) was mixed with LiFePO4
powder in a weight ratio of 90:10. The detailed synthesis conditions are reported
elsewhere45 . To prepare electrode films (of Li4 Ti5 O12 , LiCoO2 , LiNi0.5 Mn1.5 O4 and
LiMn2 O4 ), the active material powder was well mixed with acetylene black (AB,
HS-100, Denki Kagaku Kogyo) and polyvinylidene difluoride (PVdF, Kureha) in
N -methylpyrrolidone (NMP, Wako) solvent, with weight ratios of active
material:AB:PVdF of 85:5:10, 85:9:6, 85:9:6 and 85:10:5, for Li4 Ti5 O12 , LiCoO2 ,
LiNi0.5 Mn1.5 O4 and LiMn2 O4 , respectively. For the preparation of a LiFePO4
electrode film, the LiFePO4 /Ketjen black powder was well mixed with PVdF in a
weight ratio of 95:5 in NMP solvent. The obtained slurry was uniformly spread
onto a current collector using a doctor blade and dried at 60 ◦ C under vacuum
for 12 h. The current collectors were Al foil for the negative electrodes (Li4 Ti5 O12 )
and Ti foil for the positive electrodes (LiCoO2 , LiNi0.5 Mn1.5 O4 and LiMn2 O4 ),
unless otherwise noted. The dried LiFePO4 electrode was then electrochemically
oxidized in 1.1 mol kg−1 Li(TFSI)0.7 (LiBETI)0.3 aqueous electrolyte to obtain a
Lix FePO4 (x ∼ 0.5) electrode. The loading of the active material was controlled
by the doctor blade depending on the usage, as described later.
Physicochemical properties. The density and viscosity of the electrolyte solutions
were evaluated using a DMA 35 density meter (Anton Paar) and a Lovis 2000 M
viscometer (Anton Paar), respectively. The ionic conductivity was measured via
the a.c. impedance method using a Solartron 147055BEC measuring system
(Solartron Analytical). A cell with a pair of platinum-plate electrodes was used,
and the cell constant was defined with respect to a standard KCl aqueous
solution. The vapour pressures of the electrolyte solutions were evaluated via a
static method using a Baratron high-accuracy pressure manometer (MKS
Instruments) and a stainless-steel pressure vessel (Taiatsu Techno) in a circulation
bath (PolyScience).
Liquid structures. The coordination states in the electrolyte solutions were
studied via Raman spectroscopy using an NRS-5100 spectrometer (JASCO). A
laser was excited at 532 nm. Each electrolyte solution was placed in a quartz cell,
and the laser was directed through the quartz crystal window.
Electrochemical measurements. All electrochemical measurements except the
charge–discharge tests were performed using a VMP3 potentiostat (BioLogic).
The reaction reversibility of the Li4 Ti5 O12 , LiCoO2 and LiNi0.5 Mn1.5 O4 electrodes
was studied via cyclic voltammetry at a scan rate of 0.1 mV s−1 . The cyclic
voltammetry measurements were performed in a three-electrode cell with a
LiMn2 O4 counter electrode (an excess amount compared with the working
electrode) and a Ag/AgCl (in saturated KCl aqueous solution) reference electrode
(3.239 V versus standard Li+ /Li, in which both the Li+ and H2 O activities are 1
and the temperature is 298.15 K). The surface area of the working electrode was
defined to be 0.50 cm2 using an O-ring. The active material loading was
approximately 2 mg cm−2 . The electrochemical stability windows of the electrolyte
solutions were evaluated via linear sweep voltammetry at a scan rate of
0.1 mV s−1 using a three-electrode cell. The cathodic and anodic limits were
7
ARTICLES
measured using Al, Zn, stainless steel (SUS), Pt and Ti as working electrodes. The
counter electrode was platinum mesh, and the reference electrode was Ag/AgCl
(in saturated KCl aqueous solution). To study the Li+ intercalation potential shift
as a function of the Li+ molality, the equilibrium potentials of the Lix FePO4
(x ∼ 0.5) electrode in various electrolyte solutions were measured using a
two-electrode cell with a Ag/AgCl (in saturated KCl aqueous solution) reference
electrode. The potentials versus Ag/AgCl were converted into potentials versus
standard Li+ /Li, under the assumption that the potential of the Ag/AgCl electrode
was 3.239 V versus Li+ /Li. Charge–discharge tests were performed using a
TOSCAT-3100 charge–discharge unit (Toyo System), using a 2032-type coin cell
with a Li4 Ti5 O12 negative electrode, a LiCoO2 or LiNi0.5 Mn1.5 O4 positive
electrode, and a quartz fibre separator of 380 µm in thickness (Advantec, QR100)
or a glass fibre separator of 420 µm in thickness (Whatman GF/F). The electrode
sheets were punched out to form disc electrodes. The active material loadings of
the positive and negative electrodes are described in the corresponding figure
legends. For the LiNi0.5 Mn1.5 O4 /Li4 Ti5 O12 cells, the negative/positive capacity
ratio was set to a small value (Li4 Ti5 O12 /LiNi0.5 Mn1.5 O4 = 0.4) with the intent of
partial use of the LiNi0.5 Mn1.5 O4 capacity (that is, <0.5 Li extraction). To
minimize side reactions between the electrolyte and the coin cell components, an
18 mmφ Ti foil was placed between the positive electrode sheet and the positive
casing bottom, another 18 mmφ Al foil was placed between the negative electrode
sheet and the spacer, and the spacer was wrapped with Al foil. Here, a rate of xC
corresponded to an applied current density of 137 × x mAh g−1 or
147 × x mAh g−1 for the LiCoO2 /Li4 Ti5 O12 or LiNi0.5 Mn1.5 O4 /Li4 Ti5 O12 cell,
respectively, based on the active mass of the positive electrode. All
electrochemical measurements were performed at 25 ◦ C.
Electrode surface characterization. The surface chemistry of the Li4 Ti5 O12
electrode was analysed using an X-ray photoelectron spectrometer (PHI5000
VersaProbe II, ULVAC-PHI) with a monochromatic Al Kα X-ray source. A
LiCoO2 /Li4 Ti5 O12 cell was subjected to a one-cycle charge–discharge
measurement at 10C and was then disassembled in an Ar-filled glove box;
subsequently, the cycled Li4 Ti5 O12 electrode was washed thrice with
1,2-dimethoxyethane (DME) solvent to minimize the amount of residual Li salts.
The washed electrode was dried and transferred into the XPS chamber without
being exposed to air. For XPS measurements of the Li salts, LiTFSI and LiBETI
powders were deposited on a carbon tape in an Ar-filled glove box and then
transferred into the XPS chamber without being exposed to air. The depth profile
was obtained via Ar+ sputtering at 1 kV.
Computational details. The liquid structure was theoretically studied on the
basis of first-principles DFT-MD simulations. Car–Parrinello-type DFT-MD
simulations were conducted using CPMD code46,47 . Cubic supercells with linear
dimensions of 1.2337 nm and 1.4874 nm were used for the DFT-MD simulations
of 1-LiTFSI/60-H2 O and 7-LiTFSI/3-LiBETI/20-H2 O, respectively. A fictitious
electronic mass of 500 a.u. and a time step of 4 a.u. (0.10 fs) were chosen. The
temperature was controlled using a Nosé thermostat48 with a target temperature
of 298 K. To obtain the equilibrated liquid structure, we considered six, four and
four initial structures at 298 K, 350 K and 400 K, respectively. After 5 ps
equilibration steps, statistical averages were computed from trajectories of
at least 10 ps in length. The electronic wavefunction was quenched to the
Born–Oppenheimer surface approximately every 1 ps to maintain
adiabaticity. The energy cutoff of the plane wave basis was set to 90 Ry.
Goedecker–Teter–Hutter-type norm-conserving pseudopotentials49,50 for C,
H, O, N, S, F and Li were used. The detailed methods are presented in our
previous publication38 .
Received 10 February 2016; accepted 29 July 2016;
published 26 August 2016
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Acknowledgements
This work was supported by a JSPS Grant-in-Aid for Specially Promoted Research
(No. 15H05701). The calculations in this work were performed on the K computer at the
RIKEN AICS and on the Oakleaf-FX at the University of Tokyo with the support of the
HPCI Systems Research Projects (Proposal Numbers hp150275 and hp150068) and on
the supercomputers at NIMS, ISSP and ITC at the University of Tokyo and
Kyushu University.
Author contributions
Y.Y. and A.Y. proposed the concept. Y.Y., K.U. and S.K. designed the experiments.
K.U. developed the hydrate melt system and analysed the structures and basic
physicochemical/electrochemical properties. S.K. designed the electrochemical cell and
performed the cycling tests and the post-mortem electrode analyses. K.S. and Y.T.
designed and performed the theoretical calculations. All authors contributed to the
discussion. Y.Y. and A.Y. wrote the manuscript. A.Y. supervised the overall project.
Additional information
Supplementary information is available online. Reprints and permissions information is
available online at www.nature.com/reprints. Correspondence and requests for materials
should be addressed to A.Y.
Competing interests
The authors declare no competing financial interests.
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