RESEARCH ARTICLE

Zinc Batteries

Water-in-Polymer Salt Electrolyte for Long-Life

Rechargeable Aqueous Zinc-Lignin Battery
Divyaratan Kumar, Leandro R. Franco, Nicole Abdou, Rui Shu, Anna Martinelli,
C. Moyses Araujo, Johannes Gladisch, Viktor Gueskine, Reverant Crispin*, and
Ziyauddin Khan*

1. Introduction
Zinc metal batteries (ZnBs) are poised as the next-generation energy storage
solution, complementing lithium-ion batteries, thanks to their cost- The United Nations has identified 17 goals for
the 2030 Agenda for Sustainable Development.
effectiveness and safety advantages. These benefits originate from the
Among these, goal 7 aims to ensure access to
abundance of zinc and its compatibility with non-flammable aqueous affordable, reliable, sustainable, and modern
electrolytes. However, the inherent instability of zinc in aqueous energy for all human beings.[1] Energy is a cor-
environments, manifested through hydrogen evolution reactions (HER) and nerstone for both developed and low-income
dendritic growth, has hindered commercialization due to poor cycling countries that can lead to a positive impact on
stability. Enter potassium polyacrylate (PAAK)-based water-in-polymer salt the society, economy, and environment.[2]
Among all myriad energy technologies, energy
electrolyte (WiPSE), a novel variant of water-in-salt electrolytes (WiSE),
storage acting as a buffer of energy has been
designed to mitigate side reactions associated with water redox processes, identified as the bottleneck to further mass
thereby enhancing the cyclic stability of ZnBs. In this study, WiPSE was implement the renewable energy sources.
employed in ZnBs featuring lignin and carbon composites as cathode Rechargeable batteries are considered in the
materials. Our research highlights the crucial function of acrylate groups strategies to provide stored energy for short
time scale at demand.[3] Lithium-ion batteries
from WiPSE in stabilizing the ionic flux on the surface of the Zn electrode.
(LiBs) are today not only mass implemented in
This stabilization promotes the parallel deposition of Zn along the (002) portable electronics and electric vehicles, but
plane, resulting in a significant reduction in dendritic growth. Notably, our also considered for buildings as a backup
sustainable Zn-lignin battery showcases remarkable cyclic stability, retaining energy solution because of their versatile
80% of its initial capacity after 8000 cycles at a high current rate (1 A g
1) properties: high output voltage, high energy-
and maintaining over 75% capacity retention up to 2000 cycles at a low to-weight ratio, charge and discharge at high
currents, and low self-discharge.[4] Drawbacks
current rate (0.2 A g
1). This study showcases the practical application of
are related to the safety issues due to thermal
WiPSE for the development of low-cost, dendrite-free, and scalable ZnBs. runaway and flammable liquid electrolytes as
well as the fact that lithium and atomic ele-
D. Kumar, Dr. R. Shu, Dr. J. Gladisch, Dr. V. Gueskine, Prof. R. Crispin, Dr. Z. ments such as cobalt used in electrodes have limited natural abundance.
Khan Finally, the carbon footprint of making LIBs is high as there is an emis-
Laboratory of Organic Electronics, Department of Science and Technology, sion of 75 kg CO2 in making of 1 kWh LiBs.[5] These aspects have led
Linköping University, SE-60174, Norrköping, Sweden researchers to explore the potential of rechargeable batteries based on
E-mail: [email protected]
alternative monovalent (Na, K) or multivalent (Mg, Ca, Zn, Al) ele-
E-mail: [email protected]
D. Kumar, Dr. V. Gueskine, Prof. R. Crispin, Dr. Z. Khan ments of high abundance and low cost as next-generation battery tech-
Wallenberg Wood Science Center, Department of Science and Technology nology beyond LiB technology.
(ITN), Linköping University, SE-60174, Norrköping, Sweden Among multivalent ion batteries, rechargeable ZnBs normally called
Dr. L. R. Franco, Dr. C. Moyses Araujo Zn ion batteries have captivated attention owing to the abundance of
Department of Engineering and Physics, Karlstad University, 65188, Karlstad,
Sweden Zn, low cost, and low toxicity. Importantly, its redox potential is
Dr. N. Abdou, Prof. A. Martinelli
0.76 V versus the standard hydrogen electrode (SHE), which makes
Department of Chemistry and Chemical Engineering, Chalmers University of ZnBs operable in non-flammable aqueous electrolytes.[6] Moreover, the
Technology, SE-41296, Gothenburg, Sweden high theoretical specific capacity (820 mAh g
1), large volumetric
Dr. C. Moyses Araujo
capacity (5846 mAh mL
1), >99% recyclability of Zn metal from used
Department of Physics and Astronomy, Uppsala University, 75120, Uppsala,
Sweden batteries, and low CO2 emission (45.1 kg) for 1 kWh charge storage
The ORCID identification number(s) for the author(s) of this article can capacity makes the ZnB a frontrunner among the sustainable battery
be found under https://doi.org/10.1002/eem2.12752. technologies that could compete with LiBs in some applications.[7] For
instance, these properties enable large-scale manufacturing of ZnBs
DOI: 10.1002/eem2.12752

Energy Environ. Mater. 2024, 0, e12752 1 of 10 © 2024 The Authors. Energy & Environmental Materials published by
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This is an open access article under the terms of the Creative Commons
Attribution License, which permits use, distribution and reproduction
in any medium, provided the original work is properly cited.
which has been regarded as a safe, recyclable, cost-effective energy stor- resulting Zn-lignin battery in PAAK +0.2 m Zn(TFSI)2 displayed
age technology that can fulfill the sustainability goals set by the United 75 mAh g
1 of specific capacity, 80% retention in specific capacity, and
Nations. However, there are also concerns associated with ZnBs which >99% CE up to 8000 cycles.
require immediate attention. One of the major concerns is the thermo-
dynamic instability of unpolarized Zn metal in an aqueous electrolyte,
whether acidic or basic. The negatively polarized Zn metal electrode in 2. Results and Discussion
contact with aqueous electrolyte triggers the HER (2H+ → H2), which
raises the local pH around the electrode. As a result, a passivation layer 2.1. Electrolyte Characterization
of Zn(OH)2 is formed on top of Zn.[8] The interplay between dendritic
growth and HER leads to a degradation in the performance of ZnBs, 2.1.1. Electrochemical Stability Window, Ionic Conductivity, and Vis-
such as cyclic stability and coulombic efficiency (CE) of Zn plating/- cosity of WiPSE
stripping. To suppress HER and dendritic growth in ZnBs, mainly two
strategies have been employed: firstly, the surface modification of Zn In a precedent work, PAAK as WiPSE was synthesized and its transport
anode with Zn alloys, or a coating of an inorganic or organic properties were extensively characterized by our research group.[19,20]
material,[9] and, secondly, the modification of the electrolyte by using In this study, we prepared 0.1 and 0.2 m Zn2+-added PAAK as a WiPSE
additives or highly concentrated electrolytes.[10] Recently, one of the for ZnBs with the objective of reducing the concentration of fluorinated
mechanisms proposed to suppress dendritic growth is the promotion salt without compromising the advantages of WiSE. After the prepara-
of the Zn growth along its (002) plane.[11] Indeed, there seems to be a tion of the electrolyte, the electrochemical stability window (ESW) was
correlation between the (002) facets in a hexagonal close-packed Zn determined, a key parameter for assessing the electrochemical stability
crystal that has the least surface energy and prevention of dendrite of an electrolyte. On cathodic regions, Zn deposition and hydrogen
growth.[11] evolution reaction (HER) were observed beyond
1.0 V versus
In recent years, the strategy of super-concentrated electrolyte, also Ag/AgCl, whereas on the anodic side, it was observed that the oxygen
called WiSEs, was proposed to suppress HER by extending the electro- evolution reaction (OER) decreased significantly in PAAK-added
chemical stability windows of aqueous electrolytes beyond 1.2 V.[12] Zn(TFSI)2 electrolytes (Figure S1, Supporting Information).
This approach has also enabled the demonstration of aqueous electro- The ionic conductivity of PAAK added with Zn(TFSI)2, measured in
lytes for LiBs,[13] Na-ion batteries,[14] and ZnBs.[15] Additionally, a two-electrode cell by electrochemical impedance spectroscopy (EIS)
super-concentrated electrolytes also promote the reversibility of the (details can be found in experimental section), has been increased from
electrochemical plating/stripping for Zn electrode. For example, Wang 63.6 mS cm
1 (for PAAK only) to 91.6 mS cm
1 (for PAAK +0.05 m
et al. demonstrated 100% coulombic efficiency (CE) for Zn electro- Zn(TFSI)2) and then further it decreases to 73.8 mS cm
1 (for PAAK
plating/stripping using 1 m Zn(TFSI)2 + 20 m LiTFSI as WISE.[16] +0.2 m Zn(TFSI)2) (Figure S2a, Supporting Information). The
However, most of the ZnBs demonstrated using WiSE use high concen- improved ionic conductivity of Zn-based electrolyte in comparison to
tration of fluorinated salts such as those based on (TFSI)
or (OTf)
, PAAK could be attributed to the slightly reduced viscosity of the electro-
which are not only expensive but also have a negative environmental lyte [(Figure S2b, Supporting Information); detailed viscosity can be
impact. Also, for ZnBs to reach commercial application, it is essential to found in SI] and increased ionic concentrations.
develop WiSE with low or no fluorinated salts. Previously, our group
provided the first indication of a new strategy to decrease the fluori-
nated salt in the electrolyte which can transport cations.[17] Indeed, low 2.1.2. Investigation of Zn2+ Solvation Structure by Molecular Dynam-
concentration (0.2 m) Zn(TFSI)2 added to PAAK as a WiPSE could be ics Simulations
utilized for Zn deposition.[17] This means that the WiPSE’s ability to
increase the stability windows does not come from the Zn(TFSI)2 salt The introduction of different concentrations of Zn(TFSI)2 to PAAK is
but from the non-fluorinated PAAK salt, while only a small amount of expected to affect the solvation of ions as well as the dynamics of water
Zn(TFSI)2 is added for the charge storage.[17] It is worth underlining and the polymer chains. Figure 1 shows the Radial Distribution Func-
that in our first study, Zn plating/stripping was not investigated sys- tions (RDF) between selected atomic sites of the systems obtained by
tematically and no Zn-lignin battery was fabricated. This previous study molecular dynamics simulations. Table S1, Supporting Information,
investigated the electroactivity of lignin with various salts, including Li, gathers the specific distances of the RDFs and their respective coordina-
Ca, Mg, and Zn in half-cell configuration; however, Zn(TFSI)2-added tion numbers. Zinc ions interact with the oxygen atoms of the polymer
PAAK was selected strategically to fabricate Zn-lignin battery as Zn can (Op), which is related to two phenomena: electrostatic interaction
be electroplated contrary to other salts (Li, Ca and Mg) using PAAK. found in diluted solution, known as cation condensation along a polya-
In this work, we prepared PAAK + x m Zn(TFSI)2 (x = 0.1 and 0.2) nion, and the affinity of the oxygen electronic lone pairs to interact
as WiPSE and systematically studied the Zn plating/stripping phenom- with metallic cations. In our case, Op belongs to the solvation shell of
ena. The best performing electrolyte was found to be PAAK +0.2 m Zn2+ ions because polyanion behaves as a solvent to solvate the
Zn(TFSI)2 and has been integrated into a Zn-organic battery. This new ions which was evidenced by short distance between Zn and Op
strategy provides a stable Zn battery with significantly reduced electro- (Figure 1c). The solvation shell begins at 1.64 Å, reaches a peak at
lyte cost and a noteworthy cut in environmental impact by usage of 1.82 Å, and has a minimum at 2.79 Å (at 0.1 m Zn(TFSI)2) or 2.63 Å
low concentration of fluorinated salt. Moreover, it was observed that (at 0.2 m Zn(TFSI)2), comprising a number of 0.3 and 0.4 Zn ions at
WiPSE facilitates Zn deposition via (002) plane which enables the concentrations of 0.1 and 0.2 m Zn(TFSI)2, respectively. Such prox-
dendrite-free ZnB. The organic electrode chosen is the biopolymer lig- imity of Zn2+ cations to the polymer chains leads to local dehydration
nin, which can be electrochemically active when combined with con- of the polymer chains, resulting in the loss of approximately 0.6 water
ductive carbon as demonstrated previously by Ail et al.[18] The molecules per monomer at a concentration of 0.2 m Zn(TFSI)2. The

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John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.
Figure 1. Radial distribution functions (RDF) and coordination numbers (CN) of the PAAK simulations at 0.0, 0.1 m and 0.2 m Zn(TFSI)2 concentrations. a–c)
Polymer oxygen (Op) interacting with potassium ion (K+), water oxygen (Ow), and zinc ion (Zn2+). d–f) Zn2+ interacting with Op, oxygen of TFSI
(OTFSI
)
and Ow. g) K+ interacting with Ow. h, i) OTFSI
interacting with K+ and Ow. j, k) presents schematic illustration of solvation structure of hybrid electrolyte.

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Table 1. Self-diffusion coefficients (D) computed for the species included in diffusion coefficients (D) calculated from the slope of the atomic mean
the MD simulations of PAAK-based electrolytes with Zn(TFSI)2 concentra- squared displacements (MSD). For comparison, D values were also
tions equal to 0.0, 0.1, and 0.2 m.
computed for K+ (201.9  5.0), Zn2+ (76.5  2.5), TFSI
(79.6 
5.9), and water (258.3  0.9) in a water solution (at T = 298 K and
Probed species D (10
11 m2 s
1)
p = 1 bar), expressed in units of 10
11 m2 s
1. In the presence of
0.0 m Zn(TFSI)2 0.1 m Zn(TFSI)2 0.2 m Zn(TFSI)2
PAAK in the water and with 0.2 m of Zn(TFSI)2, water diffusion and
K+ 41.3  0.1 23.2  1.6 9.5  1.7 polymer diffusion exhibit values of 26.4  2.6 and 0.3  0.1
Zn2+
— 1.5  0.4 0.5  0.2 (10
11 m2 s
1), respectively, while K+, Zn2+, and TFSI
diffusion
TFSI
— 6.9  1.5 2.0  0.7
exhibit values of 9.5  1.7, 0.5  0.2, and 2.0  0.7 (10
11 m2 s
1).
Therefore, we observe that both Zn2+ ions and PAA
polyanions
PAA
2.3  1.2 1.0  0.3 0.3  0.1
exhibit similar diffusion rates, suggesting a robust mutual interaction
H2O 93.9  2.5 52.8  2.7 26.4  2.6 between them. Compared to the dynamics of PAAK electrolyte, the
introduction of Zn(TFSI)2 leads to a reduction in the diffusion coeffi-
The self-diffusion coefficients were obtained from the slope of the MSD calculated cient of all species but mostly for the PAA
. Indeed, D decreases by a
from the MD simulations.
factor of 7.7 for this polymer, 4.3 for K+, and 3.6 for water. As each
Zn2+ ion attracts 3 water molecules from the solution, we can consider
number of hydrogen bonds (NHB) per monomer, formed between the the existence of two very distinct micro-environments for water mole-
polymer chain and water molecules, is 5.8 for a PAAK 1:2 solution cules; one primarily consisting of free water molecules, and another
without Zn(TFSI)2, while it decreases to 4.6 at 0.1 m Zn(TFSI)2 and characterized by interactions with Zn2+ ions. In summary, our observa-
3.8 at 0.2 m Zn(TFSI)2. This represents a reduction by 2 hydrogen tions indicate a modification in the solvation structure of Zn2+, with its
bonds per monomer at the 0.2 m Zn(TFSI)2 concentration. Figure S5, solvation sheath now comprising PAA
, TFSI
, and water.
Supporting Information, shows the time evolution of key parameters
characterizing the hydrogen bonds, that is, NHB, donor-acceptor dis-
tance, and H-donor-acceptor angle distribution. 2.1.3. Raman Spectroscopy of Zn(TFSI)2-added PAAK
The local polymer chain dehydration by the addition of Zn salt is
due to the interaction between Zn2+ ions and the negatively charged The nature of the interactions between the different ionic species in
monomer. Now, we can observe the solvation shell around the Zn2+ both PAAK- and H2O-based solutions was investigated by Raman spec-
cations. When Zn2+ ions are diluted in water, they can coordinate to troscopy. The interactions established between cations (Zn2+, K+) and
six oxygen of water molecules[21] (Ow). In presence of PAAK and anion (TFSI
) are typically analyzed in the spectral range of the
water, Zn2+ cations possess multiple oxygen types in their solvation expansion-contraction mode of the TFSI
anion (νs S-N-S, νs CF3 of
shell either coming from acrylate or water. In a PAAK + x m Zn(TFSI)2 the TFSI
), which typically appears as an intense peak in the 741–
(where x = 0.1, 0.2) electrolytes system, such oxygen coordination 744 cm
1 frequency range in the case of weakly coordinated
number keeps equal to 6 but these oxygen atoms come from different TFSI-based complexes.[22–24] We therefore collected the Raman spectra
sources (Figure 1d–f). At a concentration of 0.2 m Zn(TFSI)2, Zn2+ of different PAAK- and H2O-based solutions containing various
ions coordinate on average with 3.2 [3.3] oxygens of water molecules amounts of the Zn(TFSI)2 salt (see Figure 2a for Raman spectra of the
(Ow), 0.6 [1.0] oxygens of TFSI
(OTFSI
), and 2.2 [1.7] polymer PAAK-Zn(TFSI)2 series). A thorough peak fitting analysis of the col-
oxygens (Op) (values in “[]” coordination number for 0.1 m lected Raman spectra reveals that the position of the main component
Zn(TFSI)2). In conclusion, Zn2+ ions preferentially interact with PAA
changes marginally keeping values close to 746.7 cm
1 upon adding
rather than with TFSI
. However, the interaction between Zn2+ and Zn(TFSI)2 to the PAAK electrolyte (Figure 2b). The trend shows a weak
TFSI
increases with the TFSI
concentration. Moreover, it was redshift of the frequency upon increased Zn(TFSI)2 content, which is
observed that an average of 1 OTFSI
in the first solvation shell of each in qualitative agreement with the observed decreased viscosity
Zn2+ ion indicates a tendency of Zn2+ and TFSI
to stabilize as a par- (Figure S2b, Supporting Information). We also observe a systematic
tially neutralized ion-pair in the PAAK electrolyte (Figure 1j,k). increase of this peak intensity with the concentration of Zn(TFSI)2,
The presence of Zn(TFSI)2 salt also modifies the solvation of the K+ which directly correlates to the increased amount of TFSI
anions in
ions, which suffer from a slight dehydration (see K+ RDFs in the detected sample volume (inset of Figure 2b).
Figure 1a,g). On average, the first solvation shell of K+ in PAAK For a better understanding of this finding, as well as for rationalizing
+0.2 m Zn(TFSI)2 electrolyte has 1.4 less water molecules than in the role of PAAK, Raman spectra were also recorded for neat (no PAAK)
PAAK without the Zn salt. The number of K+ ions coordinating to Op H2O-based solutions with different Zn(TFSI)2 salt concentrations (blue
is slightly reduced by around 0.1 within the first solvation shell of Op symbols in Figure 2b). We find that the Raman shift of the investigated
because some K+ ions interact instead with the TFSI
molecules vibrational mode increases slightly with composition but remains close
(Figure 1h). Around 0.3 K+ ions are found in the immediate vicinity to 746 cm
1, keeping values just below those of the PAAK-based elec-
of the OTFSI
and NTFSI
. Finally, we analyzed the interaction between trolytes (yellow symbols in Figure 2b). Based on the available literature
the oxygen and nitrogen atoms of TFSI
with water (Figure 1i). OTFSI
on the correlation between Raman shift and inter-ionic
exhibits a higher hydration level with a coordination number of 1.6 interactions[16,25] the latter indicates that the TFSI
anion experiences,
compared to NTFSI
with a coordination number of 0.9. on average, stronger interactions in the PAAK-based electrolytes than in
Regarding the dynamics of the cations, anions and polymer chains, the neat H2O-based electrolytes. This aspect corroborates with the result
a significant and monotonic decrease in mass mobility is observed for from MD simulations that TFSI
and Zn2+ are in closest proximity in
all ions upon addition of Zn(TFSI)2. In particular, K+ ions and water the PAAK-based electrolyte (see e.g., Figure 1e); their interaction is pos-
molecules are most strongly slowed down. Table 1 presents the self- sibly strengthened since water can screen less in the co-presence of K+

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 2.2. Zn Deposition and Morphological
Properties

Zn plating/stripping in PAAK +0.1 m

Zn(TFSI)2 and PAAK +0.2 m Zn(TFSI)2 electro-
lytes was investigated by cyclic voltammetry
(CV) in a coin cell configuration using a Zn||Zn
symmetric cell (Figure 3a). The voltammo-
gram displays a pair of redox peaks originating
from the reversible plating and stripping of Zn
in both electrolytes which reveals that Zn can
be plated and stripped using this hybrid WiPSE.
In the CV, recorded at different sweep rates
(Figure S12a, Supporting Information), the
cathodic peak current (associated with
Figure 2. a) Raman spectra collected at room temperature for the PAAK-based electrolytes at Zn2+ → Zn process) displays a linear relation-
different Zn(TFSI)2 salt concentration; b) Raman shifts of the interaction sensitive mode (associated to ship with the square root of scan rate (ν1/2).
the expansion/contraction of the TFSI
anion) as a function of the Zn(TFSI)2 salt concentration, here This indicates that the electroplating process
found at 746.6 cm
1; the inset of b) shows Raman intensities calculated as the integrated area under
the peak at 746.6 cm
1; dashed lines in b) are simple guides to the eye.
(nucleation, growth) is limited by a mass diffu-
sion mechanism (Figure S12b, Supporting
Information).[29,30] The long-term stability of


cations. Notably, the vibrational mode of TFSI in the 4 m Zn(TFSI)2 Zn plating/stripping process in both these electrolytes was estimated
aqueous solution is observed at 747 cm
1 (Figure S10, Supporting under galvanostatic conditions at 0.1 mA cm
2 current rate by uninter-
Information), a blue shifted value that can be associated with the for- rupted cycling. In both WiPSEs, the average voltage polarization was
mation of strong Zn2+-TFSI ion pairs, higher order complexes, or even about 150 mV, which is higher than other reported literature
Zn(TFSI)2 crystals dispersed in the solute on, in agreement with this (Figure 3b).[16,31] The rate performance of Zn||Zn cell was also investi-
solution being at the limit of saturation. In summary, these results indi- gated at different current rates ranging from 0.1 to 2 mA cm
2 where
cate that for intermediate concentrations (i.e., in the range 0.05–0.2 m increase in overpotentials with increase in current was observed
of Zn(TFSI)2 salt in solution), the interactions between TFSI
and its (Figure S13, Supporting Information). This high overpotential could be
surrounding change slightly with composition (both in the PAAK- and attributed to the high viscosity and low Zn2+ concentration in our
the H2O-based electrolytes) but are apparently stronger in the WiPSE. It is worth mentioning here that 0.2 m Zn(TFSI)2 is the maxi-
PAAK-based electrolytes. mum concentration soluble in PAAK. The early cell breakdown was
Typically, polyanions are known to form a strong cross-linking net- observed after continuous cycling up to 350 h for the cell using PAAK
work with multivalent cations such as Zn2+ ions.[26] However, despite +0.1 m Zn(TFSI)2 electrolyte, whereas the cell with 0.2 m Zn(TFSI)2 in
the high concentration of PAAK, the added Zn(TFSI)2 dissolved and PAAK can withstand up to 750 h with small increase in voltage polari-
formed a homogeneous clear solution without forming any precipitate zation upon cycling. Therefore, PAAK +0.2 m Zn(TFSI)2 has been
(Figure S11, Supporting Information; digital image showing precipita- selected for further studies even though PAAK +0.1 m Zn(TFSI)2 dis-
tion at lower concentration of PAAK). Furthermore, we observe that played superior ionic conductivity and self-diffusion coefficients. After
the viscosity of the prepared hybrid electrolyte decreases slightly with more than 750 cycles, a uniform, dense and dendrite free morphology
increasing the concentration of Zn2+ in PAAK (Figure S2b, Supporting was observed (Figure 3c) by SEM analysis of the cross section of Zn
Information), which disagrees with the hypothesis of the Zn2+ ions electrode. Further, the high magnification SEM images reveal formation
being strongly cross-linked with the PAA
polyanions. In general, at of Zn flakes (Figure 3d).
low concentrations the electrostatic attraction between polyanions and To understand the growth mechanism of Zn, plating/stripping pro-
cations is strong leading to the formation of a crosslinked network.[27] cesses were performed at different cycles (10 and 100 cycles) using
On the contrary, at high concentrations of the polymer, the electro- two different Zn||Zn cells, whereby deposited Zn was characterized by
static repulsion between the polyanionic chains becomes more pro- ex-situ methods. We fixed the electrolyte composition to PAAK +0.2 m
nounced and prevents the formation of crosslinked networks thereby Zn(TFSI)2. At low magnification (2 μm scale), the Zn deposit appears
decreasing the viscosity of the electrolyte. It would be worth mention- dense (Figure 4a,c) whereas in the magnified images (200 nm scale)
ing here that previous studies on the interaction between PAA
anions layered plate structures are visible (Figure 4d). The cell, which was
and Zn2+ showed that environment around the polyanion was largely cycled 100 times, displayed the formation of a hexagonal structure of
independent on the concentration of Zn2+ ions.[28] Nonetheless, the Zn (see the inset marked in yellow dotted line in Figure 4c). Those
MD simulations presented here reveal that the self-diffusion of PAA
hexagonal patterns are composed of several layers of hexagonal Zn
decreases by a factor of 8 with the addition of 0.2 m Zn(TFSI)2 in (002) plane aligned above each other and parallel to the Zn metal sur-
PAAK, suggesting a strong polyanion interaction with Zn2+ cations. face. Importantly, there is no dendrite formation on those surfaces
This information altogether indicates that even in the absence of pre- (Figure 4d). To examine the purity of deposited product, X-ray diffrac-
cipitation a strong interaction exists between Zn2+ and PAA
, both tion (XRD) was performed on both samples and compared it with pris-
exhibiting slow diffusion rates. Given such peculiar properties, the tine Zn. All the diffraction peaks were assigned to pure hexagonal Zn
question arises whether this type of WiPSE would enable reversible Zn (JCPDS card 04-0831) with no impurity peaks in the diffractogram
plating, or not. (Figure 4e). The XRD of Zn after 100 cycles displays an increase in the

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 intensity of the (002) peak in comparison to
the (100) peak as estimated by the ratio of
I(002)/I(100) for Zn plating, which increases
with cycles. For bare Zn, the I(002)/I(100) ratio
is 0.49, increasing to 0.69 after 10 cycles, and
further to 1.02 after 100 cycles. This implies
that Zn2+ ions deposit along (002) plane. The
growth of Zn deposit along (002) plane is
advantageous for the formation of dendrite-free
Zn structure compared to (101) plane.[32–34]
Contrary to the (002) plane, the (101) plane is
vertically aligned to the Zn surface, hence pro-
moting dendritic growth. Also, the (002) crys-
tal plane retains a high activation energy for Zn
dissolution, thus suppressing the side reactions
during cycling and hampering the growth of
dendrites.[35]
The Zn plating/stripping reversibility was
further investigated in PAAK +0.2 m Zn(TFSI)2
using an asymmetric Ti||Zn as half-cell. The
coulombic efficiency (CE) was calculated by
ratio of Zn stripped from Ti to the Zn deposited
Figure 3. a) CV in PAAK +0.1 m Zn(TFSI)2 and PAAK +0.2 m Zn(TFSI)2 in the potential range of
0.4 during the same cycle. It can be deduced
to 0.5 V at 2 mV s
1. b) Comparison of voltage profiles and cyclic stability of a Zn‖Zn symmetric cell from the results that the CE gradually increases
at 0.1 mA cm
2, in a coin cell configuration in PAAK +0.1 m Zn(TFSI)2 and PAAK +0.2 m Zn(TFSI)2 with cycles and reaches >95% up to 200 cycles
(color coding is same as in 2a). Cross-sectional SEM images of Zn electrodes after 750 cycles in PAAK+ (Figure 4f). Importantly, this result indicates
0.2 m Zn(TFSI)2 at c) 2 μm and d) 200 nm magnification scales.
that most of the deposited Zn on Ti substrate
could be retrieved during the successive strip-
ping processes. Ex-situ XRD was performed on
the Ti used to deposit Zn at different cycles (10
and 100 cycles). The peak intensity of the
(002) plane increased steadily after 10 cycles
and continued to increase even more after
100 cycles (Figure 4g). This was also con-
firmed by estimate the peak intensity ratio of
(002) plane to (101) plane which increases
from 0.49 to 0.98 with cycling. This is remi-
niscent of a uniform and parallel deposition of
Zn on the Ti surface. The other distinctive
peaks in the diffractogram at 43.2° and 54.3°
corroborate the pure Zn deposition (marked
with light yellow strip).
Electrochemical quartz crystal microbalance
(EQCM) is the technique we used to quantify
the amount of deposited Zn from PAAK
+0.2 m Zn(TFSI)2. The quartz crystal is coated
by a gold layer acting as the working electrode
and its resonance frequency is followed versus
the applied potential controlling the deposi-
tion/stripping. A CV comprising 15 cycles was
carried out, with the potential swept between

0.3 and
1.6 V at a scan rate of 1 mV s
1.
Figure 4. a) SEM images of Zn electrodes after a) and b) 10 cycles; c) top and d) cross-section after During the first sweep, as the potential reached
100 cycles in PAAK+ 0.2 m Zn(TFSI)2. The inset of c shows formation of hexagonal pattern Zn (scale approximately
1.2 V, a substantial amount of
bar is 200 nm). e) XRD of pristine Zn and Zn after 10 and 100 cycles of deposition/stripping using two Zn (50 μg cm
2) was deposited (Figure S15,
different symmetric Zn||Zn cells showing deposition of pure Zn as no impurity peaks were observed. f)
Coulombic efficiency related with Zn deposition on Ti in a Ti||Zn-based symmetric cell in PAAK+ 0.2 m
Supporting Information) which increases fur-
Zn(TFSI)2 to observe reversibility of Zn deposition. g) the XRD of Ti subjected to charge–discharge for ther on the reversal of potential before reduc-
10 and 100 cycles at 0.1 mA cm
2 current rate. Zn deposition via (002) plane can be clearly seen on Ti tion in mass starts. This kind of behavior is
surface without any impurity. similar to the previously reported WiSE

Energy Environ. Mater. 2024, 0, e12752 6 of 10 © 2024 The Authors. Energy & Environmental Materials published by
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systems.[36] In the potential range of
0.3 to
1.6 V, the initial Zn carbon.[18] The electrochemical analysis of Zn in the hybrid electrolyte
deposition was not completely stripped; however, in subsequent cycles, was presented comprehensively in the previous section, while the half-
a mass increase and decrease were observed above the initial deposition cell study of L-C electrode was performed in one of our previous
level, indicating reversible exchange of Zn in the electrolyte and Au on studies.[17] We now demonstrate a low-cost, sustainable Zn-lignin bat-
the surface. As the number of cycles increased, the overall deposited tery, where two abundant materials, Zn and L-C, are chosen as elec-
mass also increased. In contrast to the observations in the electrolyte trodes, by fabricating a 2032 type coin cell (Figure 5a). The specific
PAAK without Zn(TFSI)2, a loss of mass was noticed, suggesting that capacity, specific energy, and self-discharge of the cell were thereby
Au from the quartz surface was leaving the surface. estimated. In Zn-lignin battery, lignin undergoes oxidation–reduction
reaction, whereas Zn plates/strips at the Zn anode. Thus, the reversibil-
ity of Zn stripping/plating is coupled to the reversibility of redox reac-
2.3. Zn-Lignin Battery Characterization in PAAK +0.2 m tion at the lignin electrode. The CV of Zn and L-C shows that the
Zn(TFSI)2 position of redox peak potentials of Zn and L-C lies in from
0.4 to
1.7 V versus Zn, thus L-C and Zn can be used as positive and negative
In the Zn-lignin battery, the lignin electrode is a composite made of the electrode, respectively, in the assembled battery (Figure 5b). Based on
insulating lignin and the conducting carbon nanoparticles with a 1:1 the redox potential of those two electroactive materials a cell with 1.3 V
weight ratio. Those materials were mixed using ball milling method to potential can be achieved. The voltammogram at 5 mV s
1 of the Zn-
obtain electronically conductive and electrochemically active lignin cell (Figure 5c) shows one broad oxidation and one broad
lignin-carbon (L-C) nanocomposite. It is worth mentioning that ball reduction peak, where the former one is attributed to the oxidation of
milling helps to achieve an intimate interface between lignin and C═C–O
to C–C═CO in the L-C (shown in inset of Figure 5b). The
peak currents increase with scan rates (from 10
to 50 mV s
1), which suggests that the ionic
and electronic charge transport, along with the
interfacial redox processes, are fast.
To understand the charge storage better and
to assess whether it is diffusion controlled
(which is usually ascribed to faradaic processes)
or capacitive, the relationship between current
and scan rate was evaluated (i = aνb), where i
and ν are defined as peak current and scan rate
(1–5 mV s
1), respectively (Figure S16a, Sup-
porting Information). In this relation, a and b
are the constants which can be estimated by the
intercept and slope of log(i) vs log(ν) plot. If
the estimated value of b is close to 0.5, then the
charge storage process occurs via diffusion-
controlled process, whereas if it reaches close to
1, then mechanism is dictated by non-faradaic
process. Herein, the slope was found to be 0.84
(Figure S16b, Supporting Information) which
indicates that energy storage process is domi-
nated by diffusion-controlled process originating
from the Faradic redox processes of Zn and lig-
nin in hybrid electrolyte. Further, the diffusion
and capacitive contribution to total capacity was
estimated by CV using the following equation,

ⅈ ¼ k1 ν þ k2 ν05 (1)

where k1, k2 are constants. k1ν and k2ν0.5

are the contribution from capacitive con-
trolled process and the faradaic controlled
processes, respectively. Figure S16c, Sup-
porting Information, illustrates the typical
separations of capacitive and diffusive cur-
Figure 5. a) Schematic illustration of Zn-lignin battery with WiPSE b) CV of both Zn and L-C rents using Equation (1). We estimate that
electrode in WiPSE showing that the device exhibits 1.3 V of cell potential. c) CV at different sweeps
85% of the total stored charge in the Zn-
and d) GCD at different current rates of Zn-lignin battery in WiPSE. e) presents capacity retention and
coulombic efficiency estimation as cyclic stability analysis of Zn-lignin battery in WiPSE up to lignin cell is due to a faradaic process,
8000 cycles at 1 A g
1 current rate. f) Voltage vs time plot for 48 h to analyze the self-discharge of Zn- whereas the remaining 15% is due the sur-
lignin battery in WiPSE. face controlled capacitive process.

Energy Environ. Mater. 2024, 0, e12752 7 of 10 © 2024 The Authors. Energy & Environmental Materials published by
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 specific capacity supporting our claim of low
parasitic side reactions and no dissolution of
active material during the rest period.

3. Discussion about Dendrite-

Free Zn Deposition
It was observed that utilizing 0.2 m Zn(TFSI)2
in WiPSE exhibited dendrite-free Zn deposition.

Based on previous literatures, we propose a
Scheme 1. Schematic of mechanism of uniform Zn deposition in presence of PAA polymer on the
Zn substrate.
hypothesis for uniform, compact, and
dendrite-free Zn deposition. The reduction of
Zn2+ ions on Zn anode is proposed to occur
Galvanostatic charge discharge at different current rates were per- via a “diffusion-controlled” process in the electrolyte, initiated by the
formed to estimate the specific discharge capacity of Zn-lignin cell in migration of Zn2+ ions toward the anode under the influence of
hybrid electrolyte (Figure 5d). The discharge curve shows a quasi- applied electric field.[38] As these ions reach the anode, uncontrolled
plateau within the range from 1.3 to 0.6 V and then the potential drops 2D diffusion begins leading to lateral diffusion of Zn2+ ions to find
rapidly at 50 mA g
1 of current rate. The device shows a maximum favorable sites for charge transfer to reduce and plated to form crystal
specific capacity of 75 mAh g
1 which decreases to 50 mAh g
1 tips. These crystal tips can act as charge centers for further deposition
(33% loss in specific capacity) as the current increases about 10 times due to the tip effect, potentially forming zinc dendrites. In the presence
(500 mA g
1 current rate). The fabricated cell displays a maximum of of electrolytes with functional groups (polyacrylate in this case), it is
23 Wh kg
1 of specific energy and maximum specific power hypothesized that these electrolytes tend to adsorb onto the Zn electrode
of 610 W kg
1 (Figure S18, Supporting Information). The charge stor- surface. Zn2+ ions then transferred to the surface through interaction
2+
age process occurs via the migration of Zn from the electrolyte and with the functional groups, leading to a uniform electric field
its reduction followed by deposition on Zn during charging step of cell, distribution.[39–41] This increased nucleation sites may result in uni-
2+
whereas the deposited Zn is oxidized to Zn ions on discharge pro- form Zn deposition. Cross-sectional SEM images (Figure 3c,d) indicate
cess. Moreover, the cyclability of the assembled device was tested up to layer-by-layer Zn deposition on Zn anode, suggesting that the presence
8000 cycles at 1 A g
1 current rate, which retained 80% of its initial of PAA
anions modulates the electric filed, promoting uniform Zn2+
capacity with >99% of CE after 8000 cycles (Figure 5e). We also sum- diffusion without inducing any concentration difference polarization
marize in Table S2, Supporting Information, the performance of various between regions near the Zn anode and the electrolyte interior.[42] This
Zn-organic batteries reported in the literature, where except for a few mechanism explains the creation of densely packed hexagonal Zn crys-
works many suffer to achieve decent cyclic stability. Further, the assem- tals, exhibiting no dendritic growth over a 750-cycle duration within a
bled device underwent a cyclability test of 2000 cycles at low current Zn||Zn symmetric device. A schematic representation of Zn growth via
rates of 0.2 and 0.4 A g
1, demonstrating an impressive 75% capacity the (002) plane using the hybrid WiPSE is illustrated in Scheme 1. At
retention (Figure S19, Supporting Information). The 80% retention in the metal-electrolyte interface, polyacrylate anions from the electrolyte
initial capacity and >99% of CE suggest that this WiPSE electrolyte not may adhere to the metal surface, assisting Zn2+ ions to reach the inter-
only prevents the dissolution of the organic polymer into the electrolyte face through the electrostatic potential landscape generated by the nega-
but also suppresses the side reactions associated with HER, which are tively charged acrylate groups. However, an analysis of current (i)
both major bottlenecks in the development of organic as well as Zn versus the square root of the scan rate (ν1/2) (depicted in Figure S12b,
batteries. Supporting Information) during Zn deposition reveals a mass transfer-
Self-discharge is a challenging issue to avoid in aqueous batteries limited process. This limitation may originate from the orientation of
where one of the electrodes is organic.[37] Also, Zn batteries suffer from the hydrophobic backbone of polyanions toward the electrode surface,
self-corrosion and HER in aqueous electrolyte thereby initiating self- restricting the movement of Zn2+ ions and preventing dendritic
discharge in batteries. Therefore, self-discharge of Zn-lignin battery growth. Under these conditions, Zn growth parallel to the metal surface
should also be assessed. Herein, the parasitic reactions in Zn-lignin bat- along the (002) plane is promoted due to constrained diffusion of
tery were evaluated by monitoring the decay in voltage at open circuit Zn2+ ions. It is important to note that this proposed mechanism is
condition for different resting times, i.e., 1, 2, 5, 24, 48, and 72 h. Zn- based on previous literature and requires further experimentation to
lignin battery was charged and discharged for 5 cycles at 100 mA g
1 validate this hypothesis.
in the 1.7–0.4 V voltage range. After the last charging step to 1.7 V, the
cell was allowed to rest at OCV for 1 h, then the cell was discharged to
0.4 V. The same protocol was repeated for different OCV rest time 2, 5, 4. Conclusion
24, 48, and 72 h (Figure S20, Supporting Information). After a 48 h
period of rest, the battery exhibits a 71% and 68% retention of its In this work, our objective was to formulate and create a novel hybrid
voltage (indicating a low self-discharge rate of 0.01 V h
1) and specific electrolyte functioning as a WiPSE for ZnBs. The primary objective was
capacity, respectively, in proposed WiPSE (Figure 5f). Further, the fab- to leverage a lower concentration of fluorinated salt in creating a WiSE
ricated Zn-lignin battery was subjected to prolonged rest period of that not only encompasses all the benefits associated with WiSE but also
72 h; afterwards, the battery was discharged to 0.4 V at 100 mA g
1 significantly reduces the electrolyte’s overall cost. Comparatively, the
current. After 72 h of resting period, the battery retains 63% of its estimated cost of utilizing PAAK with 0.2 m Zn(TFSI)2 is notably lower

Energy Environ. Mater. 2024, 0, e12752 8 of 10 © 2024 The Authors. Energy & Environmental Materials published by
John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.
than that of employing higher concentrations of fluorinated salt, such 5.4. Electrode and Electrolyte Characterization
as 1 m Zn(TFSI)2 + 20 m LiTFSI (see Table S3, Supporting Informa-
tion). Additionally, this study yields compelling evidence that the inclu- Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR)
sion of just 0.2 m Zn(TFSI)2 into PAAK yields reversible Zn deposition (VERTEX FTIR spectrometer, MA, USA) spectra were recorded for PAAK, and
and dissolution along the (002) plane. After the successful Zn plating/- PAAK added different concentration of Zn(TFSI)2 from 400 to 4000 cm
1 at
4 cm
1 resolution. Rheological studies of the electrolytes were measured using
stripping study in half-cell and solvation structure study, a sustainable
Anton-Paar Rheometer (model MCR 102) at room temperature with a cone
Zn-lignin battery was constructed, demonstrating remarkable perfor- plate CP-50-1 using rotational method. Thermogravimetric analysis (TGA) was
mance with an outstanding 80% capacity retention after 8000 cycles at measured using TA instruments TGA-5500, for the materials thermal stability
a high current rate of 1 A g
1. It achieved a maximum energy output and plotted rate of weight change as a function of temperature, time. Elec-
of 23 Wh kg
1 and a peak power delivery of 610 W kg
1. This trochemical QCM experiments were performed with Au quartz sensors
achievement is particularly noteworthy as both lignin and Zn stand as (QSense QSX301) in a QSense Analyzer instrument. In the QCM chamber,
among the most economical, reversible electroactive materials globally. the Au quartz sensor served as a working electrode in a 3-electrode setup
with a Pt counter and a reference electrode of type WPI Dri-Ref (Ag/AgCl).
Moreover, they possess the advantages of being non-toxic and readily The electrochemistry was controlled with a Metrohm μAutolab Type III and
recyclable. The Zn-lignin battery’s appeal lies in the fact that both zinc NOVA 2 software. The frequency changes were transformed into mass
(at a cost of 0.4 USD Ah
1) and lignin (ranging from 0.1 to 0.4 changes with the Sauerbrey equation for the third overtone (QSense Dfind
USD Ah
1) exhibit a favorable low-cost to capacity ratio. This economic software toolbox). Impedance measurements were carried out using an imped-
advantage positions Zn-lignin batteries as an appealing option in the ance spectrometer (an Alpha high resolution dielectric analyzer, Novocontrol
emerging market of sustainable, large-scale stationary batteries. Technologies GmbH) using a two-point probe method. An AC voltage of
5 mV is applied while sweeping the frequency from 105 to 10 Hz, and the
measurements were carried out at room temperature. Electrolyte was filled in
the Teflon cylindrical cavity of 11.2 mm diameter and length 3.05, and Pt was
5. Experimental Section used as the electrode on either side of the cavity. The final value of the resis-
tance used for the calculation of the ionic conductivity was considered from
the linear fitted data. The bulk ionic conductivity was calculated as
σ = d/(R × A), where d, A, and R are the distance between the electrodes, area
of cross section, and resistance, respectively. Scanning Electron Microscope
5.1. Materials and Chemicals (SEM) (Zeiss Sigma 500 Gemini) along with the energy dispersive X-ray spec-
troscopic analysis (EDX) was used to analyze microstructure or morphology of
Softwood kraft lignin was obtained from Bäckhammar. Potassium hydroxide deposited Zn. X-ray diffraction (XRD) measurements were performed for these
(>85% purity) was purchased from Merck. Zinc bis(trifluoromethanesulfonyl) samples before and after 10 and 100 cycles using a diffractometer (PANalyti-
imide (Zn(TFSI)2) with a purity of 99.5%, potassium acetate (CH3COOK), and cal X’Pert) with a Cu Kα radiation and a nickel filter in a Bragg–Brentano
polyacrylic acid (average Mw ≈ 250 000, 35 wt% in H2O) were all purchased from geometry.
Sigma Aldrich and used as received. The purchased materials for the project also
include conductive carbon (ENSACO 360 G from IMERYS Graphite and Carbon,
with a BET surface area of 780 m2 g
1), carboxymethyl cellulose (CMC), and 5.5. Cell Fabrication and Electrochemical Characterization
styrene-butadiene rubber (SBR) from TOB New Energy Technology, Xiamen,
China, as well as graphite foil (SIGRAFLEX® from SGL Carbon). Electrochemical measurements of the full cells were performed by assembling
CR2032- type coin cells at ambient condition. The L-C electrodes were used as
cathode and had a mass loading of 3.5 mg cm
2 whereas Zn was used as anode.
5.2. Electrolyte Preparation A glass fiber type A soaked with PAAK added Zn(TFSI)2 was used as separator.
For the device measurement, the cell was charged at different current 0.1–1 A g
1
Potassium polyacrylate (PAAK) as “water-in-polymer salt electrolyte” was pre- in the potential range of 0.4 and 1.7 V. Galvanostatic Cycling with Potential Limi-
pared by deprotonating 25 mL polyacrylic acid using aqueous solution of potas- tation (GCPL) technique was used as a testing method for galvanostatic charge
sium hydroxide until pH become neutral. Thereafter, the obtained solution discharge (GCD) and sate of charge (SOC) determination. Specific energy (E ) and
stirred for 24 h followed by the removal of water by heating this solution at specific power (P ) were calculated using the equations below where m is total
80 °C. The obtained dry product was dissolved in water in 1:2 wt-ratio (PAAK: mass, t is discharging time, i is discharge current, and V is the potential.
water) thereby resulting in the WiPSE.[19] PAAK-Zn(TFSI)2 with 0.1 and 0.2 m con- Z t
centration was prepared by adding subsequent amount of 0.1 and 0.2 m of 1
E¼ iVdt (2)
Zn(TFSI)2 salt in PAAK (in estimated water content) and stirred at room m 0
temperature.[17]

E
5.3. Lignin-Carbon (L-C) Electrode Preparation P¼ (3)
t

The lignin/carbon (L-C) electrode material was fabricated through solvent-free

mechanical milling (ball milling) of conductive carbon and kraft lignin in a plane-
tary ball mill (TOB-XQM-4) using titanium balls. The dry ratio of lignin to carbon Acknowledgment
was 1:1. Mechanical milling was carried out like the procedure reported
previously.[18] The milled powder was then combined with 6 wt% of CMC/SBR This work was primarily supported by the Proof-of-Concept project “high-voltage
(carboxymethyl cellulose/styrene butadiene rubber; 2:4) binder system with water aqueous electrolytes (KAW 2020.0174)” and the “Wood Wallenberg Science
as solvent. The water-based slurry was coated on graphite foil and dried at 60 °C Center” funded by Knut and Alice Wallenberg (KAW) foundation. This work is
for 1–2 h. The wet thickness was varied between 100 and 400 μm. It was then cut also supported by the Swedish Research Council (2016-05990), the Swedish
into 16 mm diameter, disk-shaped electrodes for coin cell measurements. The dry Government Strategic Research Area in Materials Science on Functional Materials
weight of the electrodes was between 2 and 4 mg cm
2. at Linköping University (Faculty Grant SFO-Mat-LiU No. 2009-00971), and the

Energy Environ. Mater. 2024, 0, e12752 9 of 10 © 2024 The Authors. Energy & Environmental Materials published by
John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.
competence center FunMat-II funded by the Swedish Agency for Innovation [15] Y. Zhao, Y. Wang, Z. Zhao, J. Zhao, T. Xin, N. Wang, J. Liu, Energy Sto-
Systems (Vinnova, grant no 2016-05156). ZK and RC acknowledge Åforsk founda- rage Mater. 2020, 28, 64.
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(22-134).” RC, AM, CMA DK, and ZK acknowledge Swedish Electricity Storage Dura, K. Xu, C. Wang, Nat. Mater. 2018, 17, 543.
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