Hierarchical Doping Engineering with Active/Inert Dual Elements Stabilizes LiCoO2 to 4.6 V

Qin, Ning1,2; Gan, Qingmeng1; Zhuang, Zhaofeng1; Wang, Yanfang1; Li, Yingzhi1; Li, Zhiqiang1; Iftikhar, Hussain2; Zeng, Chun1; Liu, Guiyu1; Bai, Yunfei1; Zhang, Kaili2; Lu, Zhouguang1

2022-07-01

10.1002/aenm.202201549

Advanced Energy Materials   Impact Factor & Quartile

1614-6832

1614-6840

It is highly desirable to raise the charge cutoff voltage to realize the potential of LiCoO2 (LCO) with its ultra-high theoretical capacity of 275 mAh g(-1). However, rapid fading due to structure collapse caused by the formation of the H1-3 metastable phase and the release of surface lattice oxygen has largely hindered the operation of LCO under voltages of higher than 4.55 V. Here, stable cycling of LCO at 4.6 V through hierarchical doping engineering with inert P-outside and active Ni-inside dual doping is achieved. This ingenious outside-in structure design enables Ni2+ occupation in the Li layer in the bulk layered phase and P gradient doping at the superficial lattice. Compared with the conventional inert element substitution strategy, the doped active Ni2+ can not only serve as a "pillar" to restrain the formation of the metastable H1-3 phase, but also regulate the electronic structure of LCO and trigger the superexchange interaction of Ni2+-O-Co4+, together with strong P-O coordination to substantially suppress the lattice oxygen escape from the surface. Therefore, it considerably reduces the risk of layer structure collapse and consequently achieves stable and high-capacity operation over 4.6 V. This hierarchical outside-in doping strategy may serve as inspiration for stabilizing high energy electrode materials working under high voltages.

hierarchical doping high voltage cathodes lithium cobalt oxide lithium-ion batteries metastable structure stabilization

SCI ; EI

English

First ; Corresponding

Basic Research Project of the Science and Technology Innovation Commission of Shenzhen["JCYJ20200109141640095","JCYJ20200925154236004"] ; Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials[ZDSYS20200421111401738] ; National Natural Science Foundation of China[21875097] ; Donations for Research Projects_RMGS[9229006]

Chemistry ; Energy & Fuels ; Materials Science ; Physics

Chemistry, Physical ; Energy & Fuels ; Materials Science, Multidisciplinary ; Physics, Applied ; Physics, Condensed Matter

WOS:000820805500001

WILEY-V C H VERLAG GMBH

20222712325589

Cathodes ; Cobalt compounds ; Electronic structure ; Lithium compounds ; Metastable phases ; Oxygen

Physical Chemistry:801.4 ; Chemical Products Generally:804 ; Physical Properties of Gases, Liquids and Solids:931.2

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Key Lab Interfacial Sci & Engn Mat, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China
2.City Univ Hong Kong, Dept Mech Engn, 83 Tat Chee Ave, Hong Kong 999077, Peoples R China

Qin, Ning,Gan, Qingmeng,Zhuang, Zhaofeng,et al. Hierarchical Doping Engineering with Active/Inert Dual Elements Stabilizes LiCoO2 to 4.6 V[J]. Advanced Energy Materials,2022,12.

Qin, Ning.,Gan, Qingmeng.,Zhuang, Zhaofeng.,Wang, Yanfang.,Li, Yingzhi.,...&Lu, Zhouguang.(2022).Hierarchical Doping Engineering with Active/Inert Dual Elements Stabilizes LiCoO2 to 4.6 V.Advanced Energy Materials,12.

Qin, Ning,et al."Hierarchical Doping Engineering with Active/Inert Dual Elements Stabilizes LiCoO2 to 4.6 V".Advanced Energy Materials 12(2022).