Enhanced cycling stability of high-voltage lithium metal batteries with a trifunctional electrolyte additive

Chen, Huiyang; Chen, Jiawei; Zhang, Wenguang; Xie, Qiming; Che, Yanxia; Wang, Huirong; Xing, Lidan; Xu, Kang; Li, Weishan

doi:10.1039/d0ta07438a

Cited by 73 publications

(49 citation statements)

References 34 publications

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“…Since the commercialization of the lithium-ion battery, its energy density and cycle life have been significantly improved and become an indispensable part of modern life. − Compared with the rapid evolution of electrode materials, especially the cathode chemistries, the electrolyte composition has remained largely static, with lithium hexafluorophosphate (LiPF 6 ) dissolved in mixture of carbonates as the skeletal composition . This relative lack of activity has been mainly due to the success of the current electrolyte composition with well-balanced properties. − However, there are still bottlenecks imposed by such traditional electrolyte, especially with the increase of working voltage of the battery .…”

Section: Does High Voltage Accelerate the Hydrolysis Of Lipf6?mentioning

confidence: 99%

Hydrolysis of LiPF₆-Containing Electrolyte at High Voltage

Liu

Vatamanu

Chen³

et al. 2021

ACS Energy Lett.

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155

128

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While lithium hexafluorophosphate (LiPF6) still prevails as the main conducting salt in commercial lithium-ion batteries, its prominent disadvantage is high sensitivity toward water, which produces highly corrosive HF that degrades battery performance. The hydrolysis mechanism and its correlation with high voltage in the battery environment remain poorly understood, despite the wide application of high voltage cathode. In this work, combining theoretical and experimental approaches, we identified the direct reaction between H2O and PF6 – as main source of HF based on the preferential solvation of PF6 – anion by water and the low energy barrier for the decomposition of PF6 ––H2O complex. Such a hydrolysis process would be accelerated by high voltage the electrolytes face at the cathode side. This important clarification of electrolyte failure mechanism points us to design more effective mitigation strategies with the purpose of stabilizing LiPF6-based electrolytes for high voltage LIBs.

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Section: Does High Voltage Accelerate the Hydrolysis Of Lipf6?mentioning

confidence: 99%

Hydrolysis of LiPF₆-Containing Electrolyte at High Voltage

Liu

Vatamanu

Chen³

et al. 2021

ACS Energy Lett.

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155

128

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“…[28][29][30] At cathode/electrolyte interface, the introduction of artificially inorganic/polymeric layers is a general and effective strategy to improve the stability. [17,31] For example, Choudhury et al reported lithium's semi-crystalline anionic polymer electrolyte to coat the cathode to improve cyclic stability of high-voltage oxide materials. [2] Although the aforementioned strategies show their advantages for improving the cyclic stability of anode/ cathode, they still cannot concurrently meet the high requirements of stable interfaces for both high oxidation cathode and reduction anode.…”

mentioning

confidence: 99%

A Multifunctional Silicon‐Doped Polyether Network for Double Stable Interfaces in Quasi‐Solid‐State Lithium Metal Batteries

Zhang

Liu

et al. 2022

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are difficult to be simultaneously compatible with Li metal anode with a strong reducibility and metal-oxide cathode with high oxidizability. [9][10][11] The most effective strategy to solve the above-mentioned problems is the formation of stable solidelectrolyte-interface (SEI) layer between electrolyte and anode/cathode. [12][13][14] Therefore, the development of polymer-based QSE that can form the stable SEI layers on anode and cathode have great potential to improve the cyclic stability and safety of Li-metal batteries. [15][16][17] Great efforts have been done on the structure in regulation of polymer-based electrolyte to construct the stable SEI layer on anode, such as co-polymerization, [18,19] cross-linking, [20,21] blending, [8,22] plasticizing, [23] and adding inorganic materials. [24] For example, Wu et al. reported a quasi-solid-state polymer-brush electrolytes with robust strength and single lithium-ion conduction to realize the dendrite-free Li-metal batteries. [25] Compared with general polymer-based electrolyte, [26,27] the above strategies can effectively improve the mechanical strength to inhibit the growth of lithium dendrite for the increased stability of anode. [28][29][30] At cathode/electrolyte interface, the introduction of artificially inorganic/polymeric layers is a general and effective strategy to improve the stability. [17,31] For example, Choudhury et al. reported lithium's semi-crystalline anionic polymer electrolyte to coat the cathode to improve cyclic stability of high-voltage oxide materials. [2] Although the aforementioned strategies show their advantages for improving the cyclic stability of anode/ cathode, they still cannot concurrently meet the high requirements of stable interfaces for both high oxidation cathode and reduction anode. [33,34] Additionally, the mobility of present gel polymer electrolyte (GPE) has improved as the temperature increases, which limits the safety performance of batteries. [35,36] Therefore, the development of new strategy that simultaneously meets the requirements of QSE with high safety, the formation of SEI layers with resistance to high oxidation and reduction potentials, and is the key to the construction of highperformance lithium-metal batteries. [37][38][39] In this study, we first demonstrate that a silicon-doped polyether (Silicon, ≈10 wt%) can act as a multifunctional unit Polymer-based quasi-solid-state electrolyte (QSE) is an effective means to solve the safety problem of lithium (Li) metal batteries, and stable solidelectrolyte-interface (SEI) layers between electrolyte and anode/cathode are highly required for their long-term stability. Herein, it is demonstrated that a silicon-doped polyether functions as a multifunctional unit, which can induce the formation of stable and robust SEI layers with rich Li x SiO y on both the surfaces of cathode and anode. It simultaneously solves the compatibility of electrolyte and electrodes in the quasi-solid-state Li-metal battery. Moreover, the robust polymer skeleton with a cross-linked network...

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“…The discharge capacity of LNMO in the baseline electrolyte drops dramatically after around 300 cycles, which is similar to our previous works showing the poor cycle stability of LNMO in an additive-free electrolyte. [16][17][18]21,35,37 Application of a 2 wt % 4TP additive prominently enhances the longterm cycle stability of the LNMO/Li cell, which achieves a capacity retention of 89% after 480 cycles at the current rate of 1C in comparison with that of only 26% achieved by without additive. It can be also found that the capacity retention of LNMO with 1 wt % 4TP additive is not as high as that of LNMO with 2 wt % 4TP, which might be due to the insufficient content of additive to form an integral CEI film.…”

Section: Resultsmentioning

confidence: 99%

“…In our recent work, a film-forming additive TTS has been demonstrated to effectively improve the capacity retention of LNMO/Li cell up to 92% from 48% after 500 cycles by generating a stable cathode/electrolyte interphase (CEI) film on the surface of LNMO. 16 However, in addition to the effect of additive, its price is also a concern. Therefore, it is of great significance to develop an efficient and economical electrolyte additive to achieve the industrial application of a high-voltage LNMO.…”

Section: Introductionmentioning

confidence: 99%

“…The traditional organic electrolyte (carbonate-based) oxidative decomposition occurring on the surface of LNMO not only increases the interphasial impedance but also induces transition-metal ions in the electrode material dissolving into an electrolyte, which leads to the rapid capacity decay of LNMO . Such electrolyte oxidation can be effectively inhibited by coating the high-voltage electrode surface with inert oxides, − or using film-forming electrolyte additives, − which isolate the transmission of electrons between electrodes and electrolytes while allowing ion transport. So far, various film-forming electrolyte additives, including tris(trimethylsilyl) phosphate (TMSP), trimethoxy(3,3,3-trifluoropropyl)silane (TTS), pentafluorophenyltriethoxysilane (TPS), boric acid tris(trimethylsilyl) ester (TMSB), tris(pentafluorophenyl)silane (TPFPS), 1,10-sulfonyldiimidazole (SDM), and (pentafluorophenyl)diphenylphosphine (PFPDPP), ,,− have been put forward to enhance the high-voltage LNMO cycling performances.…”

Section: Introductionmentioning

confidence: 99%

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Cost-Efficient Film-Forming Additive for High-Voltage Lithium–Nickel–Manganese Oxide Cathodes

Chen

Zhou

et al. 2021

ACS Omega

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The operating voltage of lithium–nickel–manganese oxide (LiNi0.5Mn1.5O4, LNMO) cathodes far exceeds the oxidation stability of the commercial electrolytes. The electrolytes undergo oxidation and decomposition during the charge/discharge process, resulting in the capacity fading of a high-voltage LNMO. Therefore, enhancing the interphasial stability of the high-voltage LNMO cathode is critical to promoting its commercial application. Applying a film-forming additive is one of the valid methods to solve the interphasial instability. However, most of the proposed additives are expensive, which increases the cost of the battery. In this work, a new cost-efficient film-forming electrolyte additive, 4-trifluoromethylphenylboronic acid (4TP), is adopted to enhance the long-term cycle stability of LNMO/Li cell at 4.9 V. With only 2 wt % 4TP, the capacity retention of LNMO/Li cell reaches up to 89% from 26% after 480 cycles. Moreover, 4TP is effective in increasing the rate performance of graphite anode. These results show that the 4TP additive can be applied in high-voltage LIBs, which significantly increases the manufacturing cost while improving the battery performance.

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Enhanced cycling stability of high-voltage lithium metal batteries with a trifunctional electrolyte additive

Abstract: Carbonate-based electrolytes have been extensively employed in commercial Li-ion batteries, but they faces numerous interphasial stability challenges while supporting the high-voltage cathode chemistries and lithium metal anode, which result in...

Cited by 73 publications

References 34 publications

Hydrolysis of LiPF₆-Containing Electrolyte at High Voltage

Hydrolysis of LiPF₆-Containing Electrolyte at High Voltage

A Multifunctional Silicon‐Doped Polyether Network for Double Stable Interfaces in Quasi‐Solid‐State Lithium Metal Batteries

Cost-Efficient Film-Forming Additive for High-Voltage Lithium–Nickel–Manganese Oxide Cathodes

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Enhanced cycling stability of high-voltage lithium metal batteries with a trifunctional electrolyte additive

Abstract: Carbonate-based electrolytes have been extensively employed in commercial Li-ion batteries, but they faces numerous interphasial stability challenges while supporting the high-voltage cathode chemistries and lithium metal anode, which result in...

Cited by 73 publications

References 34 publications

Hydrolysis of LiPF6-Containing Electrolyte at High Voltage

Hydrolysis of LiPF6-Containing Electrolyte at High Voltage

A Multifunctional Silicon‐Doped Polyether Network for Double Stable Interfaces in Quasi‐Solid‐State Lithium Metal Batteries

Cost-Efficient Film-Forming Additive for High-Voltage Lithium–Nickel–Manganese Oxide Cathodes

Contact Info

Product

Resources

About

Hydrolysis of LiPF₆-Containing Electrolyte at High Voltage

Hydrolysis of LiPF₆-Containing Electrolyte at High Voltage