Chelating Ligands as Electrolyte Solvent for Rechargeable Zinc-Ion Batteries

Verma, Vivek; Chan, Raymond; Yang, Li; Kumar, Sonal; Sattayaporn, Suchinda; Chua, Rodney; Cai, Yi; Kidkhunthod, Pinit; Manalastas, William; Srinivasan, Madhavi

doi:10.1021/acs.chemmater.0c04358

Cited by 63 publications

(47 citation statements)

References 74 publications

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“…[36][37][38][39][40][41] Among all of them, electrolytes act as the medium for the transport of zinc ions between the electrodes during the cycle processes, playing an important role in determining the operating environment of the electrodes and the energy storage mechanism of the battery. [42][43][44] In recent years, aqueous electrolytes have received widespread attention due to their low cost, safety, and environmental friendliness. However, the aqueous electrolyte also meets a series of problems (Figure 3), which have been highlighted below.…”

Section: Problems Of Aqueous Electrolytes In Zinc-ion Batteriesmentioning

confidence: 99%

“…[ 36–41 ] Among all of them, electrolytes act as the medium for the transport of zinc ions between the electrodes during the cycle processes, playing an important role in determining the operating environment of the electrodes and the energy storage mechanism of the battery. [ 42–44 ] In recent years, aqueous electrolytes have received widespread attention due to their low cost, safety, and environmental friendliness. However, the aqueous electrolyte also meets a series of problems ( Figure ), which have been highlighted below. 1)Narrow electrochemical stability window—The operating voltage of the ZIBs depends on the redox potential of the cathodes and anodes, which must be within the electrochemical stability window of the aqueous electrolytes, otherwise, the water splitting reaction will occur accompany by the evolution of H 2 and O 2 .…”

Section: Problems Of Aqueous Electrolytes In Zinc‐ion Batteriesmentioning

confidence: 99%

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Recent Advances in Electrolytes for “Beyond Aqueous” Zinc‐Ion Batteries

et al. 2021

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Designing high performance electrolyte is an efficient strategy to circumvent these problems. As one of the most important components, electrolytes provide the basic operating environment to guarantee the transmission of the Zn 2+ between the two electrodes during the charge-discharge processes, affect the Zn 2+ /Zn plating/ stripping on the anode and deciding the electrochemically stable potential windows. [12] Since the utilization of alkaline electrolytes in batteries in earlier studies, Zn|KOH|MnO 2 batteries became a hot topic. [13] However, the using of an alkaline electrolyte always leads to the growth of Zn dendrites and the corrosion of the anode, resulting in rapid capacity fading. [14][15][16] Until 1986, the replacement of corrosive alkaline electrolyte systems by neutral aqueous electrolytes greatly improved the performance and safety of ZIBs. [17] Although the aqueous electrolytes alleviated the corrosion of the Zn electrode in some extent, the problems related to the growth of dendrites and the dissolution of the cathode, especially the limited electrochemical stability window (≈1.23 V) still are the challenge in the application of ZIBs. [18][19][20] The aqueous electrolytes of ZIBs often suffer from the water splitting process, including hydrogen evolution reaction and oxygen evolution reaction. [21][22][23] Therefore, in order to overcome the problems mentioned above, "beyond aqueous" electrolytes for ZIBs have attracted extensive attention in recent years. [24][25][26] At present, the "beyond aqueous" electrolytes for ZIBs have been reported mainly include liquid organic electrolytes and solid electrolytes. Zn anode in the organic electrolytes have high thermodynamic stability, avoiding the appearance of passivation products inevitably generated in traditional aqueous solution, i.e., ZnO and Zn(OH) 4 −2. [27] Solid-state electrolytes have sufficient mechanical strength to inhibit the growth of dendrites. [28] Moreover, the "beyond aqueous" electrolytes without water fundamentally avoid the decomposition of water and the formation of side products related to water. Compared with aqueous electrolytes, the "beyond aqueous" electrolytes exhibit a wide electrochemical stability window (Figure 1) and excellent thermodynamic stability of Zn anode leading to Zn plating/ stripping high reversibility with higher Coulombic efficiencies (CEs). [29] Although significant advances have been made in improving the electrochemical performance of the "beyond aqueous" electrolytes for ZIBs, several severe issues still exist, which largely prevent the development of "beyond aqueous" ZIBs. [30][31][32][33][34][35] The main issues of "beyond aqueous" electrolytes With the growing demands for large-scale energy storage, Zn-ion batteries (ZIBs) with distinct advantages, including resource abundance, low-cost, high-safety, and acceptable energy density, are considered as potential substitutes for Li-ion batteries. Although numerous efforts are devoted to design and develop high performance cathodes and aqueous electrolyt...

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Section: Problems Of Aqueous Electrolytes In Zinc-ion Batteriesmentioning

confidence: 99%

Section: Problems Of Aqueous Electrolytes In Zinc‐ion Batteriesmentioning

confidence: 99%

Recent Advances in Electrolytes for “Beyond Aqueous” Zinc‐Ion Batteries

et al. 2021

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“…As shown in Supplementary Figure 9 and Figure 3b, the Zn||Zn cell in ZnSO4-H2O-DMF (4:2) electrolyte achieved a stable operating status of over 1400 h at 2 mA cm -2 and 1000 h at 4 mA cm -2 , respectively, with the specific capacity of 1 mA h cm -2 . As compared to the cycling performances of symmetrical cells plotting the cumulative capacities of Zn||Zn cells as shown in Figure 3c (based on the data summarized in Supplementary Table 4), ZnSO4-H2O-DMF (4:2) electrolyte surpasses the values of most of the previous works at different current densities using the electrolyte optimization strategies 12,13,[16][17][18][19][20][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] . Figure 3d and Supplementary Figure 10 exhibit the rate capability of the symmetric cells in hybrid and ZnSO4-H2O electrolytes at an area capacity of 1 mA h cm -2 .…”

Section: High Zn/zn 2+ Reversibility and Uniform Zn Depositsmentioning

confidence: 99%

Solvation Structure and Interfacial Regulation for Extremely Stable Zinc Metal Anodes Operating in a Wide Range of Temperatures

Kang

Yao

Chen

et al. 2021

Preprint

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Aqueous zinc-metal batteries are promising for large-scale energy storage owing to their reasonable energy density, safety and low cost. However, their practical applications are limited by hydrogen evolution, corrosion, and dendrite formation of Zn anode and there is trade-off between efficiency and stability at high and low temperatures. Herein, we propose a solvation chemistry regulation strategy that can adjust the Zn2+-solvation structure and in situ form a robust and Zn2+-conducting Zn5(CO3)2(OH)6 SEI on the Zn surface, using hybrid electrolytes of water and a polar aprotic N, N-dimethylformamide. As verified by experimental characterizations and computational analyses, the unique solvation structure and the newly formed solid electrolyte interface are created by hybrid electrolytes, resulting in highly reversible and dendrite-free Zn plating/stripping process as well as thermal stability and high ionic conductivity from −30 to 70 °C. The Zn||Zn symmetric cells in hybrid electrolytes are very stable over 2500 h at 25 ℃ and 2000 h even at –20 ℃. Thus, the stability and reversibility of the hybrid zinc-ion capacitors with Zn metal anode in hybrid electrolytes are firstly achieved in a wide and extreme temperature range, demonstrating high capacity retentions and Coulombic efficiencies over 14000, 10000, and 600 cycles at 25, −20, and 70 ℃, respectively.

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“…Besides, as for the zinc metal anode, hydrogen evolution reaction (HER), zinc corrosion and inhomogeneous zinc deposition severely affect its stability. [ 13,14 ]…”

Section: Introductionmentioning

confidence: 99%

Achieving Highly Reversible Zinc Anodes via N, N‐Dimethylacetamide Enabled Zn‐Ion Solvation Regulation

Chen

et al. 2022

Small

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Although rapid progress on designing and exploring proper cathode materials with high specific capacities and long cycling life, such as manganese oxides, [5,6] vanadium oxides, [7,8] metal chalcogenides, [9,10] and organic materials, [11,12] has been already achieved, the practical application of ZIBs is still hindered by the utilization of aqueous electrolyte. In comparison to the well-studied organic electrolytes, the nature of aqueous electrolyte results in a limited potential window. Besides, as for the zinc metal anode, hydrogen evolution reaction (HER), zinc corrosion and inhomogeneous zinc deposition severely affect its stability. [13,14] Recently, various efforts have been devoted to improve Zn anode reversibility. The modification of metallic Zn anode, e.g., preparation of protective layer and construction of 3D structured anode, is one of the most typical and widely adopted approaches to achieve a boosting Zn reversibility. [15,16] Comparatively, the optimization of electrolyte composition is a relatively practical and facile way to improve Coulombic efficiency (CE) and Zn plating/stripping reversibility. [17][18][19] The aqueous electrolytes with different zinc salts, e.g., ZnCl 2 , Zn(CF 3 SO 3 ) 2 , and Zn(TFSI) 2 , have been investigated in order to realize an optimal Zn 2+ -anion coordination. [20][21][22] Moreover, the "water-in-salt" types of electrolytes were developed that inhibit the occurrence of side reactions through the decrease of H 2 O content. [23,24] Compared with those aforementioned electrolytes, ZnSO 4 aqueous solution still remains the most widely used electrolyte for ZIBs due to the stability of SO 4 2and low cost of ZnSO 4 . Fortunately, it has been demonstrated that a proper electrolyte additive can adjust the solvation structure of Zn 2+ , thereby it is helpful for minimizing the side reactions, controlling the nucleation-deposition process, and improving the electrochemical performance of ZIBs. [25,26] For example, it is revealed that dimethyl sulfoxide (DMSO) is capable to substitute for the H 2 O molecules in the Zn 2+ solvation sheath, and forms a new solid electrolyte interphase (SEI) protection layers, in which HER and Zn dendrite growth are both suppressed. [27] In principle, an ideal electrolyte additive should possess a large Gutmann donor number (DN), a high absorption energy with Zn, a strong Hbond with H 2 O, low-cost and nontoxicity. [13,27,28] Organic molecules with functional groups, such as O, CO, SO, N, have been proved to regulate Although aqueous zinc-ion batteries (ZIBs) are promising for scalable energy storage application, the actual performance of ZIBs is hampered by the irreversibility. Optimization of electrolyte composition is a relatively practical and facile way to improve coulombic efficiency (CE) and Zn plating/ stripping reversibility of ZIBs. N,N-Dimethylacetamide (DMA) has a higher Gutmann donor number (DN) than that of H 2 O, abundant polar groups, and economic price. Herein, a mixture electrolyte containing 10 vol% DMA and ZnSO 4 , whi...

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Chelating Ligands as Electrolyte Solvent for Rechargeable Zinc-Ion Batteries

Cited by 63 publications

References 74 publications

Recent Advances in Electrolytes for “Beyond Aqueous” Zinc‐Ion Batteries

Recent Advances in Electrolytes for “Beyond Aqueous” Zinc‐Ion Batteries

Solvation Structure and Interfacial Regulation for Extremely Stable Zinc Metal Anodes Operating in a Wide Range of Temperatures

Achieving Highly Reversible Zinc Anodes via N, N‐Dimethylacetamide Enabled Zn‐Ion Solvation Regulation

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