Suppressing dendrite growth by a functional electrolyte additive for robust Li metal anodes

Wang, Gang; Xiong, Xunhui; Xie, Dong; Fu, Xiangxiang; Ma, Xiangdong; Li, Youpeng; Liu, Yanzhen; Zhang, Lin; Yang, Chenghao; Liu, Meilin

doi:10.1016/j.ensm.2019.02.026

Cited by 137 publications

(77 citation statements)

References 30 publications

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“…The uniform lithium deposition morphology renders improved interfacial stability and enhanced electrochemical cycling performance of Li metal anodes (Figure 16e,f). Apart from these, several other additives such as organic molecules (N-methyl-N-butylpiperidinium, thiourea) [141,142] and metal halide (LiCl, LiI, and AlCl 3 ) [143][144][145] have been utilized to stabilize the anode/electrolyte interface by affecting Li ion diffusion and plating behavior.…”

Section: Dft Calculationmentioning

confidence: 99%

Interface Engineering for Lithium Metal Anodes in Liquid Electrolyte

Zhai

Liu

et al. 2020

Advanced Energy Materials

290

194

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Interfacial chemistry between lithium metal anodes and electrolytes plays a vital role in regulating the Li plating/stripping behavior and improving the cycling performance of Li metal batteries. Constructing a stable solid electrolyte interphase (SEI) on Li metal anodes is now understood to be a requirement for progress in achieving feasible Li‐metal batteries. Recently, the application of novel analytical tools has led to a clearer understanding of composition and the fine structure of the SEI. This further promoted the development of interface engineering for stable Li metal anodes. In this review, the SEI formation mechanism, conceptual models, and the nature of the SEI are briefly summarized. Recent progress in probing the atomic structure of the SEI and elucidating the fundamental effect of interfacial stability on battery performance are emphasized. Multiple factors including current density, mechanical strength, operating temperature, and structure/composition homogeneity that affect the interfacial properties are comprehensively discussed. Moreover, strategies for designing stable Li‐metal/electrolyte interfaces are also reviewed. Finally, new insights and future directions associated with Li‐metal anode interfaces are proposed to inspire more revolutionary solutions toward commercialization of Li metal batteries.

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Section: Dft Calculationmentioning

confidence: 99%

Interface Engineering for Lithium Metal Anodes in Liquid Electrolyte

Zhai

Liu

et al. 2020

Advanced Energy Materials

290

194

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“…Lithium (Li)‐metal anode is the most likely used for batteries with energy densities higher than 300 Wh kg −1 due to having the highest theoretical capacity of 3840 mAh g −1 . [ 4–6 ] However, commonly used organic liquid electrolytes (LEs) cannot perfectly match with Li metal anodes due to an overgrowth of Li dendrites and their hyperreactivity. [ 7–10 ] Additionally, the volatility and leakage of LEs present a safety risk of fire or explosion, which may cause great damage, especially with batteries that have a high energy density [11 . ]…”

Section: Figurementioning

confidence: 99%

Investigation on the Copolymer Electrolyte of Poly(1,3‐dioxolane‐co‐formaldehyde)

Liu

Yang

et al. 2020

Macromol. Rapid Commun.

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have been found in preventing the pen etration of Li dendrites. [15][16][17] However, the excessive interfacial resistance and the complex processing art of inorganic SSEs limit their practical application. [18][19][20] Solid polymer electrolytes (SPEs), on the other hand, can offer good flexibility and stable contact between the electrodes and electrolytes. [20][21][22][23] Several types of polymer matrices have been developed, such as poly(ethyleneoxide) (PEO), [24][25][26] poly carbonate, [27][28][29] and polysiloxane. [30][31][32] SPEs are prepared by mixing polymer matrices with Li salts. PEO is the most popular and deeply studied polymer matrix, [33] and the ethylene oxide chain segments in PEO can dissolve Li salts as well as form complexes with Li + and dis sociated Li salts. [34] Li + is conducted by repeatedly carrying out a "decomplexa tion-recomplexation" process through the movement of chain segments in an amorphous polymer region. [35] The movement of chain segments in an amorphous polymer region is affected by the glass transition temperature (T g ) and crystallinity. Low T g and crystallinity are beneficial for the move ment of chain segments as well as the ionic conductivity. Due to the high crystallinity of PEO, PEObased SPEs have a low ionic conductivity (10 −8 -10 −7 S cm −1 ) at room temperature, which does not meet the requirement for ionic conductivity (>10 −4 S cm −1 at room temperature) of electrolytes with prom ising applications. [33,36,37] Many strategies, such as adding inorganic nanoparticles, [38][39][40] blending, [41] copolymerization, [42] and crosslinking [43][44][45] have been adopted to effectively sup press the crystallization of PEO and improve the ionic conduc tivity of PEObased SPEs. Coat et al. [46] reported the synthesis of poly(diethylene oxidealtoxymethylene) (P(2EOMO)) as a polymer matrix for SPE, which has higher T g than that of PEO in the electrolyte. They found the P(2EOMO)/LiTFSI electro lyte exhibits a slightly lower ionic conductivity due to higher T g , but much higher Li ion transference number can be obtained in P(2EOMO)/LiTFSI electrolyte (0.36) than that in PEO/ LiTFSI (0.19). So tailoring the main chain structure is the most feasible way to optimize the performance of SPEs.Recently, the strategy of in situ polymerizing SPEs in the batteries has attracted extensive attention due to the ability to construct stable ionic conduction networks inside the electrodes to reduce the interfacial resistance, the biggest challenge faced by most SSEs. Cui et al. [13] in situ prepared A series of copolymers are prepared via cationic ring-opening polymerization with 1,3-dioxolane (DOL) and trioxymethylene (TOM) as monomers. The crystallization behaviors of the copolymers can be suppressed by adjusting the ratio of DOL/TOM. With LiBF 4 as a source for a BF 3 initiator, copolymer electrolytes (CPEs) can be prepared in situ inside cells without needing nonelectrolyte catalysts or initiators. The ionic conductivities and Li + diffusion coefficients (D Li + ) of the CPEs inc...

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“…One way is to make electrolyte additives form a stable SEI film on the cathode, which inhibits LNMO electrode interface erosion and electrolyte decomposition, scavenging type to capture HF (Haregewoin et al, 2016; Wang et al, in press). As the strong acid produced from LiPF 6 is considered the initiator which induces the cleavage and polymerization of cyclic carbonate under high voltage conditions, many researchers are trying to add some oxidation-resistant solvents, for example, sulfones (Hilbig et al, 2017; Su et al, 2017), nitriles (Abu-Lebdeh and Davidson, 2009) and fluoro solvents (Kim et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Analysis for Enhancing Interface Layer of Spinel LiNi0.5Mn1.5O4 Using p-Toluenesulfonyl Isocyanate as Electrolyte Additive

Xiao

Wang

et al. 2019

Front. Chem.

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LiNi 0. 5Mn 1.5 O 4 (LNMO) is a potential cathode material for lithium-ion batteries with outstanding energy density and high voltage plateau (>4.7 V). However, the interfacial side reaction between LNMO and the liquid electrolyte seriously causes capacity fading during cycling at the high voltage. Here, p-toluenesulfonyl isocyanate (PTSI) is used as the electrolyte additive to overcome the above problem of LNMO. The results show that the specific capacity of LNMO/Li cell with 0.5 wt.% PTSI at the first cycle is effectively enhanced by 36.0 mAh/g and has better cycling performance than that without PTSI at 4.98 V. Also, a stable solid electrolyte interface (SEI) film derived from PTSI is generated on the electrode surface, which could alleviate the strike of hydrofluoric acid (HF) caused by electrolyte decomposition. These results are explained by the molecular structure of PTSI, which contains SO 3 . The S=O groups can delocalize the nitrogen nucleus to block the reactivity of PF 5 .

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Suppressing dendrite growth by a functional electrolyte additive for robust Li metal anodes

Cited by 137 publications

References 30 publications

Interface Engineering for Lithium Metal Anodes in Liquid Electrolyte

Interface Engineering for Lithium Metal Anodes in Liquid Electrolyte

Investigation on the Copolymer Electrolyte of Poly(1,3‐dioxolane‐co‐formaldehyde)

Electrochemical Analysis for Enhancing Interface Layer of Spinel LiNi0.5Mn1.5O4 Using p-Toluenesulfonyl Isocyanate as Electrolyte Additive

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