Proton Insertion Chemistry of a Zinc–Organic Battery

Article abstract of DOI:10.1002/anie.201916529

Proton storage in rechargeable aqueous zinc-ion batteries (ZIBs) is attracting extensive attention owing to the fast kinetics of H⁺ insertion/extraction. However, it has not been achieved in organic materials-based ZIBs with a mild electrolyte. Now, aqueous ZIBs based on diquinoxalino [2,3-a:2′,3′-c] phenazine (HATN) in a mild electrolyte are developed. Electrochemical and structural analysis confirm for the first time that such Zn–HATN batteries experience a H⁺ uptake/removal behavior with highly reversible structural evolution of HATN. The H⁺ uptake/removal endows the Zn–HATN batteries with enhanced electrochemical performance. Proton insertion chemistry will broaden the horizons of aqueous Zn–organic batteries and open up new opportunities to construct high-performance ZIBs.

Full text of DOI:10.1002/anie.201916529

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Accepted Article
Title: Proton Insertion Chemistry of Zn/Organic Battery
Authors: Zhiwei Tie, Luojia Liu, Shenzhen Deng, Dongbing Zhao, and
Zhiqiang Niu
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201916529
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Proton Insertion Chemistry of Zn/Organic Battery
Zhiwei Tie, Luojia Liu, Shenzhen Deng, Dongbing Zhao, and Zhiqiang Niu*
Dedicated to 100th anniversary of Nankai University
Abstract: The proton storage in rechargeable aqueous zinc-ion
batteries (ZIBs) are attracting extensive attention due to the fast
kinetics of H+ insertion/extraction. However, up to now, it is not
achieved in organic materials-based ZIBs with a mild electrolyte.
Herein, we developed aqueous ZIBs based on diquinoxalino
[2,3-a:2',3'-c] phenazine (HATN) in
a
mild electrolyte.
Electrochemical and structural analysis confirm for the first time that
such Zn/HATN batteries experience a H+ uptake/removal behavior
with highly reversible structural evolution of HATN. The H+
uptake/removal endows the Zn/HATN batteries with enhanced
electrochemical performance. Proton insertion chemistry will broaden
the horizons of aqueous Zn/organic batteries and open up new
opportunities to construct high-performance ZIBs.
Rechargeable aqueous zinc-ion batteries (ZIBs) are
attracting more attention since the Zn anode possesses low
redox potential (-0.76 V vs. standard hydrogen electrode (SHE)),
high specific capacity (820 mAh g-1), excellent stability in water
and low cost.[1] The electrochemical performance of ZIBs mainly
depends on the design of cathode materials.[2] Recently, various
active materials such as transition metal oxides or sulfides
(based on vanadium[3] and manganese[4]), Prussian blue
analogues[5] and organic compounds[6] were developed to serve
as the cathode materials of aqueous ZIBs. Among them, organic
materials are considered as a promising candidate because of
their renewability, environmental friendliness, low cost and
structural diversity.[7]
Figure 1. a) The mechanism of proton insertion chemistry in the aqueous
Zn/HATN battery system. b) SEM image of HATN. c) STEM-HAADF image and
STEM-EDS mapping of C, N distributions in HATN. d) HRTEM of HATN (Inset
shows the SAED pattern).
reaction in a three-electrode cell with 1M H2SO4 electrolyte.[11]
However, it could not be used in two-electrode Zn/organic
batteries because of the violent chemical reaction between Zn
anode and acidic electrolyte. As a result, until now, H+ energy
storage has not been observed in organic materials-based
aqueous ZIBs with mild electrolytes. If H+ uptake/removal could
be realized in aqueous Zn/organic batteries, their energy density
would be enhanced significantly and the horizons of aqueous
ZIBs chemistry could be also broadened.
The π-conjugated aromatic compounds with imino moiety =N
is a kind of neutral organic base, where the imino moiety =N will
have an ability to chelate proton by a coordination reaction.[12]
Furthermore, a lone pair of electrons in imino moiety =N ensure
these π-conjugated aromatic compounds with high redox
activity.[13] Inspired by this, we developed an aqueous Zn/organic
battery system based on diquinoxalino [2,3-a:2',3'-c] phenazine
(HATN) in mild electrolyte. The Zn/HATN systems display H+
uptake/removal by coordination/incoordination reaction rather
than conventional Zn2+ insertion/extraction (Figure 1a). As a
result, they achieve enhanced specific capacity and rate
performance due to the fast kinetics of H+ uptake/removal.
Furthermore, reversible structural evolution of HATN guarantees
long-term cycle life of Zn/HATN batteries.
Generally, the energy storage/release mechanism of
Zn/organic battery is the coordination/incoordination reaction
between Zn2+ and active group carbonyl.[6b]. However, the
electronic conductivity of organic active materials is intrinsically
inferior and their corresponding discharge products often
dissolve in H2O. As a result, they usually suffer from poor rate
performance and limited cycle life.[8] Apart from Zn2+, H+ is also
considered as an attractive charge carrier due to its small ionic
radius and low relative atomic mass.[9] Recently, the
energy-storage based on H+ has been achieved in inorganic
materials-based ZIBs.[10]
insertion/extraction display
.
Furthermore, these ZIBs with H+
excellent electrochemical
performance due to the fast kinetics of the H+ insertion/extraction.
In some cases of organic materials, their redox-active groups
such as carbonyl (C=O) could incorporate H+ by a coordination
The HATN compound was synthesized by
dehydration condensation reaction
a
simple
between
Z. Tie, L. Liu, S. Deng, Prof. Z. Niu
hexaketocyclohexane octahydrate and o-phenylenediamine.
HATN exhibits a nano-belt morphology with about 100 μm in
length and 400-600 nm in width (Figure 1b; Figures S1 and S2,
Supporting Information). Impressively, the HATN possesses
good polycrystalline nature with the homogeneous distributions
of C and N, which is different from conventional organic
compounds with poor crystallinity (Figure 1c, d).[6b] Its chemical
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of
Education), Renewable Energy Conversion and Storage Center, College of
Chemistry, Nankai University
Tianjin, 300071, P. R. China
E-mail: zqniu@nankai.edu.cn
Prof. D. Zhao
State Key Laboratory and Institute of Elemento-Organic Chemistry, College
of Chemistry, Nankai University
Tianjin, 300071, P. R. China
1
structure is confirmed by H NMR, 13C NMR, ESI-MS and FTIR
Supporting information for this article is given via a link at the end of the
document
spectra (Figures S3-S6, Supporting Information). Furthermore,
there is only one peak at 385.1 in the ESI-MS spectrum, which
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10.1002/anie.201916529
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protonated HATN structures will be achieved during the
discharge processes, corresponding to three voltage platforms in
the discharge curves. According to the discharge capacities at
different voltage platforms of the second cycle, the calculated
electron-transfer number is about 2 at each voltage platform
(Supplementary Methods), which is ascribed to the uptake of 2
H+. Therefore, the discharged products at the end of three
voltage platforms are defined as HATN-xH (x = 2, 4, 6),
respectively. This is to say, all six electroactive pyrazine N atoms
in a HATN molecule will react with H+. The gradual formation of
-NH- groups in the discharged HATN can be also reflected by ex
situ XPS (Figure 2d). The peak corresponding to -NH- group is
obviously observed in N 1s XPS,[6d, 17] suggesting the structural
evolution from HATN to HATN-6H. Reversibly, in the following
charging processes, three voltage platforms are also found,
corresponding to the removal of H+ from three pairs of
electroactive pyrazine N atoms in the HATN molecule, as
suggested by FTIR spectra. The FTIR spectra show that the
peaks of C=N and C-C groups gradually recover to the initial
state, while the peaks of C-N and -NH- groups become weaker
and disappear. At the same time, the corresponding peak of -NH-
group also disappears in N 1s XPS spectrum. These suggest
that H+ ions remove from -NH- groups successively and
structural evolution from HATN-6H to HATN is gradually
achieved during the charging process.
Figure 2. a) Charge-discharge curves in first two cycles under a current density
of 100 mA g-1. Various ex situ tests of HATN-based electrodes at the marked
points in the charge-discharge curves: b) and c) Ex situ FTIR spectra. d) Ex situ
XPS spectra of N 1s. e) Ex situ 1H solid-state NMR spectra. f) and g) Ex situ
XRD profile. h)-l) SEM images at the marked points of 1, 4, 7, 10 and 13,
respectively.
suggests the high purity of HATN.
Above reversible H+ uptake/removal can also be confirmed
by ex situ 1H solid-state NMR (Figure 2e). The 1H solid-state
NMR shows that the pristine HATN exhibits a wide peak from
10.0 to 5.0 ppm, which represents the H of benzene ring with two
different chemical environments. During the discharging
processes, a new peak at about 3.0 ppm emerged and gradually
enhanced. This peak is ascribed to H resonances in -NH- groups
of the discharged HATN-2H, HATN-4H and HATN-6H,
confirming that the H+ ions participate in the coordination reaction
with the C=N groups of HATN. Furthermore, it is noted that the
gradual widening of the wide peak from 10.0 to 5.0 ppm indicates
that the chemical environments of H in discharge products are
different from the pristine HATN since the H+ ions participate in
coordination reaction. Reversibly, in the subsequent charging
process, this peak recovers to initial state and the peak at about
3.0 ppm is gradually invisible, indicating the H+ removal from
HATN-6H.
As discussed above, the H+ ions take part in the energy
storage of the Zn/HATN systems by the structural evolution from
HATN to HATN-6H. These H+ ions come from the decomposition
of water in the aqueous ZnSO4 electrolyte. Accompanying with
the consumption of H+, a large amount of OH- will yield
synchronously. To reach a neutral charge system, these OH-
could not exist in the electrolyte. They would move to the surface
of HATN-based electrodes and react with ZnSO4 to form
Zn4SO4(OH)6·5H2O (JCPDS:39-0688) successively during the
discharge process, which is detected by the ex situ XRD analysis
(Figure 2f, g). Furthermore, SEM images display that
Zn4SO4(OH)6·5H2O possesses a flake-like morphology and the
corresponding SEM-EDS mapping images display the uniform
distribution of the elements C, N, Zn, O, S, further confirming the
formation of Zn4SO4(OH)6·5H2O (Figures 2h, i and k; Figure S8,
Supporting Information). More impressively, in the subsequent
charging process, Zn4SO4(OH)6•5H2O can be gradually
decomposed after charging from 0.3 to 1.1 V, as revealed by the
XRD and SEM images (Figure 2j, l). These results indicate the
reversible formation/decomposition of Zn4SO4(OH)6·5H2O on the
The favorable morphological features of HATN would be
beneficial for the fast kinetics of coordination/incoordination
reaction. Based on HATN, the cathodes were prepared by a
conventional method (Figure S7, Supporting Information). Then
the typical coin-type cells were assembled. Figure 2a shows the
charge/discharge curves of Zn/HATN battery at 100 mA g-1 in the
initial two cycles. Owing to the activation of electrode, the initial
discharging curve is different from subsequent case.[14] After that,
Zn/HATN battery shows normal charge-discharge behavior with
three voltage platforms, which indicates that there are
three-steps coordination/incoordination reactions during the
charging-discharging process. In general, the energy
storage/release mechanism of Zn/organic battery is the
coordination/incoordination reaction between Zn2+ and active
groups. However, in our case, Zn element is not observed in the
STEM-EDS and SEM mapping images of the HATN electrode at
the discharged states (Figures S8 and S9, Supporting
Information). It confirms that Zn2+ would not insert into the HATN
nanobelt by a coordination reaction to realize the energy storage.
To further understand the energy storage mechanism of
Zn/HATN battery, various ex situ tests including FTIR, Raman,
1
XPS, solid state H nuclear magnetic resonance (1H NMR) and
X-ray diffraction (XRD) were employed to analyze the HATN
electrodes at the selected states of initial two charge/discharge
cycles, as marked in Figure 2a. In the FTIR spectra, the peaks of
C=N (1520 cm-1) and C-C (1127 cm-1) groups gradually
disappeared in the discharge processes,[15] indicating that the
redox active centers of HATN are C=N groups (Figure 2c).
Simultaneously, the FTIR spectra show that the peaks of C-N
(1160 cm-1) and N-H (3307, 3232, 3166 and 1642 cm-1) groups
are enhanced (Figure 2b).[16] It suggests that C=N groups of
HATN are reduced to C-N step by step and H+ ions were stored
to form -NH- by three-steps coordination reactions in the
discharge processes. It can be also reflected by the ex situ
Raman spectra (Figure S10, Supporting Information). In HATN
molecules, there are three pairs of electroactive pyrazine N
atoms, which can strongly coordinate with H+. As a result, three
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10.1002/anie.201916529
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Figure 4. a) The CV curves of aqueous Zn/HATN batteries (0.01 mV s-1). b)
Rate capabilities of Zn/HATN batteries at various current rates. c) Cycle
performance of Zn/HATN batteries under a current density of 5 A g-1 for 5000
cycles. d) Comparison of electrochemical performance of aqueous Zn/organic
batteries.
ascribed to the reversible structural evolution from HATN to
HATN-2H, HATN-4H and HATN-6H, respectively, which agree
well with their galvanostatic charge/discharge curves (Figure 2a).
More importantly, these CV curves show similar shapes,
indicating that Zn/HATN battery possesses excellent capacity
retention. Owing to the uptake of six H+ ions, the Zn/HATN
battery exhibits an initial discharge capacity of 405 mAh g-1 at a
current density of 100 mA g-1 (Figure S15 and S16, Supporting
Information), which is close to its theoretical capacity of 419 mAh
g-1 (Supplementary Methods for details) and higher than the
cases of previously reported organic electrode materials of
ZIBs.[6-7] Apart from the high capacity, the Zn/HATN batteries
also exhibit outstanding rate performance due to the
π-conjugated aromatic structure and fast kinetics of H+
coordination/incoordination reaction (Figure 4b). They can
display a high capacity of 123 mAh g-1 even at a high current
density of 20 A g-1 (the charge/discharge process was completed
in 44 s), maintaining 33.2% of that at 0.1 A g-1. Furthermore,
when the current density goes back to 0.1 A g-1 after 150 cycles,
the corresponding specific capacity can be recovered to 320
mAh g-1.
The morphology and structural evolution of HATN and Zn
anode during the charge/discharge processes play an important
role in the stable electrochemical properties of Zn/HATN
batteries (Figure S17 and S18, Supporting Information). Even
after 5000 cycles, the HATN nanobelts in the cathodes still
display a similar morphology without obvious change. It is
ascribed to the π-conjugated aromatic structure of HATN, which
strengthens π-π intermolecular interactions and suppresses the
dissolution of HATN in aqueous electrolyte (Figure S19,
Supporting Information). Such reversible structural evolution will
endow the Zn/HATN batteries with stable long-term cycling
performance. After 10 cycles at the current density of 0.1 A g-1,
the Zn/HATN battery delivers a specific capacity of about 150
mAh g-1 and remains around 140 mAh g-1 after 5000 cycles
under a current density of 5 A g-1 (Figure 4c), corresponding to a
high capacity retention of 93.3%. As a result, the H+ uptake in
HATN nanobelts results in enhanced electrochemcial
performance than other previously reported Zn/organic system in
common aqueous electrolytes (ZnSO4 or Zn(CF3SO3)2) (Figure
4d; Table S1, Supporting Information).
Figure 3. a) Calculated MESP distribution on the van der Waals surface of
HATN molecule. b) Optimized structure and calculated frontier molecular
orbital energy of HATN molecule. c) Calculated structural evolution and
protonation pathway at discharging process.
HATN electrode along with the uptake and removal of H+ during
the charge/discharge processes, which was also proved by the
FTIR spectra (Figure 2c; Figure S11 and S12, Supporting
Information).
To further understand the H+ uptake in HATN molecule in the
discharging process, we conducted theoretical calculations with
density functional theory (DFT). The molecular electrostatic
potential (MESP) method was employed to speculate the
electrophilic and nucleophilic reaction-active sites to get further
insight into the active-sites of H+ uptake.[18] On the van der Waals
surface of a HATN molecule (Figure 3a), the red region
represents the positive MESP value (nucleophilic center) and
blue region stands for the negative MESP value (electrophilic
center). Obviously, the sites with more negative MESP are
attractive for the uptake of carriers.[6b] As a result, the pyrazine
nitrogen atoms with negative MESP are the highly active sites for
H+ ions uptake. It suggests that the acceptance of H+ is prior to
Zn2+ in the Zn/HATN systems (Figure S13, Supporting
Information). In addition, on the basis of the minimum energy
principle, the protonation pathway of HATN was calculated and
shown in Figures 3c and S14 (Supporting Information). Such
calculated structural evolutions of HATN along with the
protonation pathway are in accordance with the experimental
results. Besides, we also conducted the frontier molecular
orbitals of HATN, including the lowest unoccupied molecular
orbital (LUMO) and the highest occupied molecular orbital
(HOMO) (Figure 3b). The energies of LUMO and HOMO in the
system were calculated to be -2.78 and -6.46 eV, respectively.
Therefore, the energy gap (ΔE) between HOMO and LUMO is
3.68 eV, which is lower than most of the organic electrodes,
indicating the intrinsic electronic conductivity of HATN is higher
than those organic materials.[19] It will be beneficial to enhancing
the electrochemical properties of HATN.
The unique H+ energy storage mechanism would endow
Zn/HATN batteries with enhanced electrochemical performance.
Their typical cyclic voltammetry (CV) curves are presented in
Figure 4a. They display three pairs of redox peaks, which are
In summary, aqueous Zn/HATN batteries with H+ insertion
chemistry were developped in mild electrolyte. The H+
uptake/removal behavior of HATN is deeply discussed by
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[11] X. Wang, C. Bommier, Z. Jian, Z. Li, R. S. Chandrabose, I. A.
Rodriguez-Perez, P. A. Greaney, X. Ji, Angew. Chem. Int. Ed. 2017, 56,
2909-2913.
[12] a) V. Raab, E. Gauchenova, A. Merkoulov, K. Harms, J. Sundermeyer, B.
Kovaꢀević, Z. B. Maksić, J. Am. Chem. Soc. 2005, 127, 15738-15743; b) M. A.
Zirnstein, H. A. Staab, Angew. Chem. Int. Ed. 1987, 26, 460-461.
[13] C. Peng, G.-H. Ning, J. Su, G. Zhong, W. Tang, B. Tian, C. Su, D. Yu, L. Zu, J.
Yang, M.-F. Ng, Y.-S. Hu, Y. Yang, M. Armand, K. P. Loh, Nat. Energy 2017,
2, 17074.
[14] M. H. Alfaruqi, V. Mathew, J. Gim, S. Kim, J. Song, J. P. Baboo, S. H. Choi, J.
Kim, Chem. Mater. 2015, 27, 3609-3620.
[15] a) B. Tian, Z. Ding, G.-H. Ning, W. Tang, C. Peng, B. Liu, J. Su, C. Su, K. P.
Loh, Chem. Commun. 2017, 53, 2914-2917; b) M. Takahashi, Y. Ishikawa, J.-i.
Nishizawa, H. Ito, Chem. Phys. Lett. 2005, 401, 475-482.
combining various ex situ characterization techniques and DFT
calculations. The pyrazine nitrogen atoms with negative MESP
are the active sites of H+ ions uptake in HATN and six H+ ions will
react with these pyrazine nitrogen atoms by reversible structural
evolution from HATN to HATN-2H, HATN-4H and HATN-6H,
respectively. Owing to the fast kinetics of H+ uptake/removal
behavior, the Zn/HATN batteries not only exhibit an initial
discharge capacity of 405 mAh g-1 at 100 mA g-1, but also display
excellent rate performance, and long cycle stability with a high
capacity retention of 93.3% after 5000 cycles at 5 A g-1. Proton
insertion chemistry will broaden the horizons of aqueous
Zn/organic batteries and provide a strategy to enhance the
electrochemical performance of aqueous ZIBs.
[16] V. Krishnakumar, N. Prabavathi, Spectrochim. Acta. A. 2010, 77, 238-247.
[17] J. Hong, M. Lee, B. Lee, D. H. Seo, C. B. Park, K. Kang, Nat. Commun. 2014,
5, 5335.
[18] L. Liu, L. Miao, L. Li, F. Li, Y. Lu, Z. Shang, J. Chen, J. Phys. Chem. Lett.
2018, 9, 3573-3579.
[19] J. Lee, H. Kim, M. J. Park, Chem. Mater. 2016, 28, 2408-2416.
Acknowledgements
This work was supported by National Key R&D Program of China
(2017YFA0206701), National Natural Science Foundation of
China (51822205 and 21875121), China Postdoctoral Science
Foundation (2019M650045), Ministry of Education of China
(B12015) and Natural Science Foundation of Tianjin
(18JCJQJC46300).
Keywords: Zn ion battery • organic electrode • proton •
high-capacity • long-cycle
[1]
[2]
a) J. Zheng, Q. Zhao, T. Tang, J. Yin, C. D. Quilty, G. D. Renderos, X. Liu, Y.
Deng, L. Wang, D. C. Bock, C. Jaye, D. Zhang, E. S. Takeuchi, K. J. Takeuchi,
A. C. Marschilok, L. A. Archer, Science 2019, 366, 645-648; b) H. Qiu, X. Du,
J. Zhao, Y. Wang, J. Ju, Z. Chen, Z. Hu, D. Yan, X. Zhou, G. Cui, Nat.
Commun. 2019, 10, 5374; c) M. Song, H. Tan, D. Chao, H. J. Fan, Adv. Funct.
Mater. 2018, 28, 1802564; d) H. Zhang, Q. Liu, Y. Fang, C. Teng, X. Liu, P.
Fang, Y. Tong, X. Lu, Adv. Mater. 2019, 31, 1904948.
a) J. Ding, Z. Du, L. Gu, B. Li, L. Wang, S. Wang, Y. Gong, S. Yang, Adv.
Mater. 2018, 30, 1800762; b) F. Wan, L. Zhang, X. Dai, X. Wang, Z. Niu, J.
Chen, Nat. Commun. 2018, 9, 1656; c) C. Xia, J. Guo, P. Li, X. Zhang, H. N.
Alshareef, Angew. Chem. Int. Ed. 2018, 57, 3943-3948; d) M. H. Alfaruqi, V.
Mathew, J. Song, S. Kim, S. Islam, D. T. Pham, J. Jo, S. Kim, J. P. Baboo, Z.
Xiu, K.-S. Lee, Y.-K. Sun, J. Kim, Chem. Mater. 2017, 29, 1684-1694; e) F.
Wan, Z. Niu, Angew. Chem. Int. Ed. 2019, 58, 16358-16367.
[3]
[4]
a) T. Wei, Q. Li, G. Yang, C. Wang, Adv. Energy Mater. 2019, 9, 1901480; b)
J. Ding, Z. Du, B. Li, L. Wang, S. Wang, Y. Gong, S. Yang, Adv. Mater. 2019,
31, 1904369; c) F. Wan, Y. Zhang, L. Zhang, D. Liu, C. Wang, L. Song, Z.
Niu, J. Chen, Angew. Chem. Int. Ed. 2019, 58, 7062-7067.
a) D. Chao, W. Zhou, C. Ye, Q. Zhang, Y. Chen, L. Gu, K. Davey, S.-Z. Qiao,
Angew. Chem. Int. Ed. 2019, 58, 7823-7828; b) M. Li, Q. He, Z. Li, Q. Li, Y.
Zhang, J. Meng, X. Liu, S. Li, B. Wu, L. Chen, Z. Liu, W. Luo, C. Han, L. Mai,
Adv. Energy Mater. 2019, 9, 1901469; c) C. Xu, B. Li, H. Du, F. Kang, Angew.
Chem. Int. Ed. 2012, 51, 933-935.
[5]
[6]
a) Q. Yang, F. Mo, Z. Liu, L. Ma, X. Li, D. Fang, S. Chen, S. Zhang, C. Zhi,
Adv. Mater. 2019, 31, 1901521; b) L. Zhang, L. Chen, X. Zhou, Z. Liu, Adv.
Energy Mater. 2015, 5, 1400930.
a) Z. Guo, Y. Ma, X. Dong, J. Huang, Y. Wang, Y. Xia, Angew. Chem. Int. Ed.
2018, 57, 11737-11741; b) Q. Zhao, W. Huang, Z. Luo, L. Liu, Y. Lu, Y. Li, L.
Li, J. Hu, H. Ma, J. Chen, Sci. Adv. 2018, 4, eaao1761; c) D. Kundu, P.
Oberholzer, C. Glaros, A. Bouzid, E. Tervoort, A. Pasquarello, M.
Niederberger, Chem. Mater. 2018, 30, 3874-3881; d) H. Y. Shi, Y. J. Ye, K.
Liu, Y. Song, X. Sun, Angew. Chem. Int. Ed. 2018, 57, 16359-16363.
a) H. Glatz, E. Lizundia, F. Pacifico, D. Kundu, ACS Appl. Energy Mater.
2019, 2, 1288-1294; b) F. Wan, L. Zhang, X. Wang, S. Bi, Z. Niu, J. Chen,
Adv. Funct. Mater. 2018, 28, 1804975; c) A. Khayum, M. Ghosh, V.
Vijayakumar, A. Halder, M. Nurhuda, S. Kumar, M. Addicoat, S. Kurungot, R.
Banerjee, Chem. Sci. 2019, 10, 8889-8894; d) S. Huang, F. Wan, S. Bi, J. Zhu,
Z. Niu, J. Chen, Angew. Chem. Int. Ed. 2019, 58, 4313-4317.
[7]
[8]
[9]
Y. Lu, Q. Zhang, L. Li, Z. Niu, J. Chen, Chem 2018, 4, 2786-2813.
X. Wu, J. J. Hong, W. Shin, L. Ma, T. Liu, X. Bi, Y. Yuan, Y. Qi, T. W. Surta,
W. Huang, J. Neuefeind, T. Wu, P. A. Greaney, J. Lu, X. Ji, Nat. Energy 2019,
4, 123-130.
[10] a) H. Pan, Y. Shao, P. Yan, Y. Cheng, K. S. Han, Z. Nie, C. Wang, J. Yang, X.
Li, P. Bhattacharya, K. T. Mueller, J. Liu, Nat. Energy 2016, 1, 16039; b) W.
Sun, F. Wang, S. Hou, C. Yang, X. Fan, Z. Ma, T. Gao, F. Han, R. Hu, M. Zhu,
C. Wang, J. Am. Chem. Soc. 2017, 139, 9775-9778; c) J. Huang, Z. Wang, M.
Hou, X. Dong, Y. Liu, Y. Wang, Y. Xia, Nat Commun 2018, 9, 2906; d) Y. Jin,
L. Zou, L. Liu, M. H. Engelhard, R. L. Patel, Z. Nie, K. S. Han, Y. Shao, C.
Wang, J. Zhu, H. Pan, J. Liu, Adv. Mater. 2019, 31, 1900567.
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10.1002/anie.201916529
Angewandte Chemie International Edition
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Proton insertion chemistry: The proton insertion chemistry based on organic aqueous ZIBs was developped in mild electrolyte. The
H+ insertion/extraction endows the battery system enhanced electrochemical performance. Moreover, the proton insertion chemistry
will broaden horizons of aqueous ZIBs.
Zhiwei Tie, Luojia Liu, Shenzhen Deng, Dongbing Zhao, and Zhiqiang Niu*
Proton Insertion Chemistry of Zn/Organic Battery
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