Cu Substitution Stabilizes Oxygen Redox in High Na Content P3-Type Na_0.75Li_0.2Cu_0.05Mn_0.75O₂ Cathode with Unexpected High Energy Density

Li, Yan1; Wu, Duojie2,3; Zheng, Jiening1; Gu, Meng4; Chang, Chengkang1

2024-09-01

10.1002/adfm.202411561

ADVANCED FUNCTIONAL MATERIALS   影响因子和分区

1616-301X

1616-3028

Oxygen redox enhances the specific energy of sodium cathodes, but the other performance remains unsatisfactory. By introducing Cu into P2 lattice to replace Li cations, P3-type Na0.75Li0.2Cu0.05Mn0.75O2 with high Na concentration is achieved. This modification induces notable alteration in the lattice structure, specifically increasing the interplanar spacing of NaO6 from 3.6 & Aring; to 3.8 & Aring;. The resultant P3-type cathode delivers a remarkable capacity of 253 +/- 1.3 mAh g(-1) with energy density of 680 mWh g(-1), setting a benchmark for P3-type sodium cathodes. The high capacity can be attributed to the activation of Mn3+/ Mn4+ redox pair following Cu substitution. Further investigations confirm that Mn3+/ Mn4+, Cu2+/ Cu3+ and O2-/On- redox pairs all contribute to the high performance. The absence of O vacancy and the reduction in phase transitions enhance the cyclic performance with capacity retention of 86.3% at 0.5C. Additionally, the small diffusion energy barrier (34.6 KJ mol(-1)) results in a high Na diffusion coefficient (1.332 x 10(-9) cm(2) s(-1)), thereby promoting superior rate behavior with a capacity of 200.8 +/- 2.1 mAh g(-1) at 5C. These results demonstrate the advantages of the P3-type Na0.75Li0.2Cu0.05Mn0.75O2 cathode over the other Na cathodes, suggesting high potential for application in high-energy storage fields.

capacity cathode EELS iDPC-STEM oxygen redox rate performance

SCI

英语

通讯

National Natural Science Foundation of China[52273225] ; Guangdong scientific program[2019QN01L057] ; Shanghai Institute of Technology[1021GK240006003] ; null[2022B1515120013]

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

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

WOS:001308552400001

WILEY-V C H VERLAG GMBH

Web of Science

1.Shanghai Inst Technol, Sch Mat Sci & Engn, 100 Haiquan Rd, Shanghai 201418, Peoples R China
2.Eastern Inst Technol, Eastern Inst Adv Study, Ningbo 315200, Zhejiang, Peoples R China
3.Shanghai Jiao Tong Univ, Sch Mat Sci & Engn, 120 Dongchuan Rd, Shanghai 200240, Peoples R China
4.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China

Li, Yan,Wu, Duojie,Zheng, Jiening,et al. Cu Substitution Stabilizes Oxygen Redox in High Na Content P3-Type Na_0.75Li_0.2Cu_0.05Mn_0.75O₂ Cathode with Unexpected High Energy Density[J]. ADVANCED FUNCTIONAL MATERIALS,2024.

Li, Yan,Wu, Duojie,Zheng, Jiening,Gu, Meng,&Chang, Chengkang.(2024).Cu Substitution Stabilizes Oxygen Redox in High Na Content P3-Type Na_0.75Li_0.2Cu_0.05Mn_0.75O₂ Cathode with Unexpected High Energy Density.ADVANCED FUNCTIONAL MATERIALS.

Li, Yan,et al."Cu Substitution Stabilizes Oxygen Redox in High Na Content P3-Type Na_0.75Li_0.2Cu_0.05Mn_0.75O₂ Cathode with Unexpected High Energy Density".ADVANCED FUNCTIONAL MATERIALS (2024).