Organic skin layer with carboxyl and electron-withdrawing nitro groups to chemically bind with residual Li and Ni cations on single-crystal LiNi0.8Co0.1Mn0.1O2

•4-Nitrobenzoic acid (4-NBA) is grafted onto the surface of singe-crystal NCM811.•The carboxyl groups of 4-NBA neutralize the residual lithium compounds of NCM811.•A cathode/electrolyte interphase with low impedance is obtained.•The electron-withdrawing nitro groups of 4-NBA inhibit Ni dissolution.•...

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Veröffentlicht in:Electrochimica acta 2022-02, Vol.404, p.139743, Article 139743
Hauptverfasser: Long, Fu, Cao, Zhang, Liu, Yuyang, Liang, Rui, Qu, Qunting, Lv, Linze, Jin, Chengchang, Zheng, Honghe
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Sprache:eng
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Zusammenfassung:•4-Nitrobenzoic acid (4-NBA) is grafted onto the surface of singe-crystal NCM811.•The carboxyl groups of 4-NBA neutralize the residual lithium compounds of NCM811.•A cathode/electrolyte interphase with low impedance is obtained.•The electron-withdrawing nitro groups of 4-NBA inhibit Ni dissolution.•This surface grafting technique improves the electrochemical performance of NCM811. Interfacial issue is very critical to the electrochemical properties of LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode, and it also poses a great challenge for successful commercialization of NCM811 via construction of a desirable surface layer. This work constructs a novel metal-organic interface by grafting organic 4-NBA (4-nitrobenzoic acid) layer onto singe-crystal NCM811 surface. The electron transfer from the interfacial Ni2+ to the electron-withdrawing nitro group of 4-NBA promotes the formation of metal-organic interface, which inhibits Ni dissolution into the organic electrolyte. The neutralization reaction between the carboxyl groups of 4-NBA and residual lithium compounds of NCM811 constructs an interfacial layer with improved Li+ conductivity. The 4-NBA organic layer also helps constructing a thin and stable cathode/electrolyte interphase by alleviating the side reactions of electrolyte. The electrochemical properties of single-crystal NCM811 cathode are remarkably enhanced. At a high discharge rate of 20C, a capacity of 141 mAh g−1 can be delivered, significantly higher than that of 101 mAh g−1 of the pristine cathode. After 200 cycles at 1C, the modified sample exhibits excellent capacity retention of 84.5%. [Display omitted]
ISSN:0013-4686
1873-3859
DOI:10.1016/j.electacta.2021.139743