Unveiling Nickel Chemistry in Stabilizing High‐Voltage Cobalt‐Rich Cathodes for Lithium‐Ion Batteries. (29th November 2019)

• Record Type: Journal Article
• Authors: Yoon, Moonsu; Dong, Yanhao; Yoo, Youngbin; Myeong, Seungjun; Hwang, Jaeseong; Kim, Junhyeok; Choi, Seong‐Hyeon; Sung, Jaekyung; Kang, Seok Ju; Li, Ju; Cho, Jaephil
• Is Part Of: Advanced functional materials. Volume 30:Number 6(2020)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2019-11-29
• Subjects: cathode degradation -- cathode–electrolyte interphase -- Co‐rich cathode -- lithium‐ion batteries -- surface reactivity management; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adfm.201907903
• Languages: English
• ISSNs: 1616-301X

Abstract

Abstract: A practical solution is presented to increase the stability of 4.45 V LiCoO2 via high‐temperature Ni doping, without adding any extra synthesis step or cost. How a putative uniform bulk doping with highly soluble elements can profoundly modify the surface chemistry and structural stability is identified from systematic chemical and microstructural analyses. This modification has an electronic origin, where surface‐oxygen‐loss induced Co reduction that favors the tetrahedral site and causes damaging spinel phase formation is replaced by Ni reduction that favors octahedral site and creates a better cation‐mixed structure. The findings of this study point to previously unspecified surface effects on the electrochemical performance of battery electrode materials hidden behind an extensively practiced bulk doping strategy. The new understanding of complex surface chemistry is expected to help develop higher‐energy‐density cathode materials for rechargeable batteries. Abstract : 5% Ni doping of LiCoO2 profoundly modifies its surface chemistry, thereby stabilizing the cathode–electrolyte interface at high voltage, with a partially cation‐mixed surface structure (not rock‐salt NiO‐like structure as is the case for Ni‐rich cathodes) even after prolonged cycling. In contrast, undoped LiCoO2 suffers from severe surface oxygen loss, triggering surface phase transition to an unstable Co3 O4 ‐like outcome that further exacerbates O‐loss in a chain‐reaction fashion.