Uncommon Behavior of Li Doping Suppresses Oxygen Redox in P2-Type Manganese-Rich Sodium Cathodes

Xiao, Biwei; Liu, Xiang; Chen, Xi; Lee, Gi‐Hyeok; Song, Miao; Yang, Xin; Omenya, Fred; Reed, David M.; Sprenkle, Vincent; Ren, Yang; Sun, Cheng‐Jun; Yang, Wanli; Amine, Khalil; Li, Xin; Xu, Guiliang; Li, Xiaolin

doi:10.1002/adma.202107141

Uncommon Behavior of Li Doping Suppresses Oxygen Redox in P2-Type Manganese-Rich Sodium Cathodes

Journal Article · Mon Oct 11 00:00:00 EDT 2021 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202107141· OSTI ID:1878593

^[1]; Liu, Xiang ^[2]; Chen, Xi ^[3]; Lee, Gi‐Hyeok ^[4]; Song, Miao ^[1]; Yang, Xin ^[1]; Omenya, Fred ^[1]; Reed, David M. ^[1]; Sprenkle, Vincent ^[1]; Ren, Yang ^[2]; Sun, Cheng‐Jun ^[2]; Yang, Wanli ^[5]; Amine, Khalil ^[6]; Li, Xin ^[3]; Xu, Guiliang ^[2]; ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Harvard Univ., Cambridge, MA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Dongguk Univ., Seoul (Korea, Republic of)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Stanford Univ., CA (United States)

Utilizing both cationic and anionic oxygen redox reactions is regarded as an important approach to exploit high-capacity layered cathode materials with earth abundant elements. It has been popular strategies to effectively elevate the oxygen redox activities by Li-doping to introduce unhybridized O 2p orbitals in Na_xMnO₂-based chemistries or enabling high covalency transition metals in P2-Na_0.66Mn_xTM_1-xO₂ (TM = Fe, Cu, Ni) materials. Here, we investigated the effect of Li doping on regulating the oxygen redox activities P2-structured Na_0.66Ni_0.25Mn_0.75O₂ materials. Systematic X-ray characterizations and ab initio simulations have shown that the doped Li has uncommon behavior in modulating the density of states of the neighboring Ni, Mn and O, leading to the suppression of the existing oxygen and Mn redox reactivities and the promotion of the Ni redox. Furthermore, the findings provide a complementary scenario to current oxygen redox mechanisms and shed lights on developing new routes for high-performance cathodes.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Electricity (OE); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office, Battery Materials Research (BMR) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; AC05-76RL01830

OSTI ID:: 1878593

Alternate ID(s):: OSTI ID: 1829126
OSTI ID: 1962541

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 52 Vol. 33; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Uncommon Behavior of Li Doping Suppresses Oxygen Redox in P2-Type Manganese-Rich Sodium Cathodes

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