Manganese Local Environment Modulation via SiO4 Substitution to Boost Sodium Storage Performance of Na4MnCr(PO4)(3)

Hou, Yan1; Liu, Qiong2,3; Yang, Lin1; Hu, Jing2; Wang, Zhenyu2; Zhang, Xinmiao1; Pan, Jialiang1; Bai, Zhengyu1; Wang, Haijiang4; Lu, Zhouguang2

2023-02-01

10.1002/smll.202207466

Small   Impact Factor & Quartile

1613-6810

1613-6829

Manganese-based Na superionic conductors (NASICONs) Na4MnCr(PO4)(3) with three-electron reaction are attractive cathode materials for sodium-ion batteries. However, the irreversible distortion of Mn local structure leads to sluggish electrode kinetics, voltage hysteresis, and poor cycling stability. Here, SiO4 is introduced to substitute PO4 to modulate the local environment of Mn to activate the redox activity and stabilize the reversibility of Na4MnCr(PO4)(2.9)(SiO4)(0.1) (NMCP-Si). A combined experimental and theoretical investigation have been undertaken to reveal the evolution of electronic structures and Na storage properties associated with SiO4 substitution. The NMCP-Si exhibits much-enhanced rate capability and cycling stability, being attributed to the unique Jahn-Teller distortion (Mn3+) that facilitates sodium de/insertion kinetics by optimizing the Na ion diffusion channels. This work addresses the challenge of stabilizing the structure of Mn-based NASICONs and represents a breakthrough in understanding how to improve the Na+ conductivity by regulating local structure.

cathode materials Jahn-Teller distortion Na superionic conductors SiO4 substitution sodium-ion batteries

SCI

English

Corresponding

National Natural Science Foundation of China["51922008","52072114","52271176"] ; 111 Project[D17007] ; Henan Center for Outstanding Overseas Scientists[GZS2022017] ; Xinxiang Major Science and Technology Projects[21ZD001] ; Basic Research Project of the Science and Technology Innovation Commission of Shenzhen[JCYJ20200109141640095] ; Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials[ZDSYS20200421111401738] ; Guangdong-Hong Kong-Macao Joint Laboratory[2019B121205001]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Multidisciplinary ; Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Applied ; Physics, Condensed Matter

WOS:000922755000001

WILEY-V C H VERLAG GMBH

Web of Science

1.Henan Normal Univ, Collaborat Innovat Ctr Henan Prov Green Mfg Fine C, Sch Chem & Chem Engn, Key Lab Green Chem Media & React,Minist Educ, Xinxiang 453007, Henan, Peoples R China
2.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen Key Lab Interfacial Sci & Engn Mat, Guangdong Hong Kong Macao Joint Lab Photon Thermal, Shenzhen 518055, Guangdong, Peoples R China
3.Katholieke Univ Leuven, Dept Mat Engn, B-3001 Leuven, Belgium
4.Southern Univ Sci & Technol, Dept Mech & Energy Engn, Key Lab Energy Convers & Storage Technol, Shenzhen 518055, Guangdong, Peoples R China

Hou, Yan,Liu, Qiong,Yang, Lin,et al. Manganese Local Environment Modulation via SiO4 Substitution to Boost Sodium Storage Performance of Na4MnCr(PO4)(3)[J]. Small,2023.

Hou, Yan.,Liu, Qiong.,Yang, Lin.,Hu, Jing.,Wang, Zhenyu.,...&Lu, Zhouguang.(2023).Manganese Local Environment Modulation via SiO4 Substitution to Boost Sodium Storage Performance of Na4MnCr(PO4)(3).Small.

Hou, Yan,et al."Manganese Local Environment Modulation via SiO4 Substitution to Boost Sodium Storage Performance of Na4MnCr(PO4)(3)".Small (2023).