{"title":"Na/Co 双掺杂橄榄石 LiMn0.6Fe0.4PO4 阴极在锂离子电池中具有优异的反应动力学性能","authors":"Pengxu Wang, Erdong Zhang, Yaoguo Fang, Yihong Chen, Haifeng Yu, Ya Zhang, Qian Cheng, Hao Jiang","doi":"10.1007/s10008-024-06043-w","DOIUrl":null,"url":null,"abstract":"<div><p>Olivine-type lithium manganese iron phosphate (LMFP) has been a promising cathode for Li-ion batteries (LIB) owing to its superior safety performance and low cost, yet the intrinsic low ionic/electronic conductivities result in large electrochemical polarization and inferior rate performance. Herein, we report a LMFP with high-power Li-storage capability through a Na/Co co-doped strategy. The Na<sup>+</sup> with a larger ionic radius (1.02 Å) locates at Li-sites, effectively widening the Li<sup>+</sup> diffusion channel to improve the Li-ion transfer dynamic. The Co<sup>2+</sup> located at transition metal sites (TM-sites) can lower the band gap to improve the electronic conductivity, while it can also alleviate the increase in the <i>b</i>-axis parameter to shorten the Li<sup>+</sup> transfer path. Accordingly, the concurrently improved ionic/electronic transfer rate endows the superior rate performance of LMFP, with a high reversible capacity of 113.5 mAh g<sup>−1</sup> at 5 C, much higher than the pristine sample (only 79.5 mAh g<sup>−1</sup>). The modified LMFP also displays excellent cycling stability, maintaining 97.1% of its initial capacity after 1000 cycles at 1 C.</p><h3>Graphical abstract</h3>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":665,"journal":{"name":"Journal of Solid State Electrochemistry","volume":"28 11","pages":"4303 - 4310"},"PeriodicalIF":2.6000,"publicationDate":"2024-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Na/Co dual-doped olivine LiMn0.6Fe0.4PO4 cathode with superior reaction kinetics for Li-ion batteries\",\"authors\":\"Pengxu Wang, Erdong Zhang, Yaoguo Fang, Yihong Chen, Haifeng Yu, Ya Zhang, Qian Cheng, Hao Jiang\",\"doi\":\"10.1007/s10008-024-06043-w\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Olivine-type lithium manganese iron phosphate (LMFP) has been a promising cathode for Li-ion batteries (LIB) owing to its superior safety performance and low cost, yet the intrinsic low ionic/electronic conductivities result in large electrochemical polarization and inferior rate performance. Herein, we report a LMFP with high-power Li-storage capability through a Na/Co co-doped strategy. The Na<sup>+</sup> with a larger ionic radius (1.02 Å) locates at Li-sites, effectively widening the Li<sup>+</sup> diffusion channel to improve the Li-ion transfer dynamic. The Co<sup>2+</sup> located at transition metal sites (TM-sites) can lower the band gap to improve the electronic conductivity, while it can also alleviate the increase in the <i>b</i>-axis parameter to shorten the Li<sup>+</sup> transfer path. Accordingly, the concurrently improved ionic/electronic transfer rate endows the superior rate performance of LMFP, with a high reversible capacity of 113.5 mAh g<sup>−1</sup> at 5 C, much higher than the pristine sample (only 79.5 mAh g<sup>−1</sup>). The modified LMFP also displays excellent cycling stability, maintaining 97.1% of its initial capacity after 1000 cycles at 1 C.</p><h3>Graphical abstract</h3>\\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>\",\"PeriodicalId\":665,\"journal\":{\"name\":\"Journal of Solid State Electrochemistry\",\"volume\":\"28 11\",\"pages\":\"4303 - 4310\"},\"PeriodicalIF\":2.6000,\"publicationDate\":\"2024-08-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Solid State Electrochemistry\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s10008-024-06043-w\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"ELECTROCHEMISTRY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Solid State Electrochemistry","FirstCategoryId":"5","ListUrlMain":"https://link.springer.com/article/10.1007/s10008-024-06043-w","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"ELECTROCHEMISTRY","Score":null,"Total":0}
引用次数: 0
摘要
橄榄石型磷酸锰铁锂（LMFP）因其优越的安全性能和低廉的成本而一直是锂离子电池（LIB）的理想正极，但其固有的低离子/电子电导率导致了较大的电化学极化和较差的速率性能。在此，我们报告了一种通过 Na/Co 共掺杂策略实现高功率锂离子存储能力的 LMFP。具有较大离子半径（1.02 Å）的 Na+ 位于锂基点，可有效拓宽 Li+ 扩散通道，从而改善锂离子传输动态。位于过渡金属位（TM-sites）的 Co2+ 可降低带隙，从而提高电子传导性，同时还能缓解 b 轴参数的增加，缩短 Li+ 传输路径。因此，同时提高的离子/电子转移率赋予了 LMFP 优异的速率性能，在 5 C 时可逆容量高达 113.5 mAh g-1，远高于原始样品（仅 79.5 mAh g-1）。改性 LMFP 还具有出色的循环稳定性，在 1 C 下循环 1000 次后，其初始容量仍能保持 97.1%。
Na/Co dual-doped olivine LiMn0.6Fe0.4PO4 cathode with superior reaction kinetics for Li-ion batteries
Olivine-type lithium manganese iron phosphate (LMFP) has been a promising cathode for Li-ion batteries (LIB) owing to its superior safety performance and low cost, yet the intrinsic low ionic/electronic conductivities result in large electrochemical polarization and inferior rate performance. Herein, we report a LMFP with high-power Li-storage capability through a Na/Co co-doped strategy. The Na+ with a larger ionic radius (1.02 Å) locates at Li-sites, effectively widening the Li+ diffusion channel to improve the Li-ion transfer dynamic. The Co2+ located at transition metal sites (TM-sites) can lower the band gap to improve the electronic conductivity, while it can also alleviate the increase in the b-axis parameter to shorten the Li+ transfer path. Accordingly, the concurrently improved ionic/electronic transfer rate endows the superior rate performance of LMFP, with a high reversible capacity of 113.5 mAh g−1 at 5 C, much higher than the pristine sample (only 79.5 mAh g−1). The modified LMFP also displays excellent cycling stability, maintaining 97.1% of its initial capacity after 1000 cycles at 1 C.
期刊介绍：
The Journal of Solid State Electrochemistry is devoted to all aspects of solid-state chemistry and solid-state physics in electrochemistry.
The Journal of Solid State Electrochemistry publishes papers on all aspects of electrochemistry of solid compounds, including experimental and theoretical, basic and applied work. It equally publishes papers on the thermodynamics and kinetics of electrochemical reactions if at least one actively participating phase is solid. Also of interest are articles on the transport of ions and electrons in solids whenever these processes are relevant to electrochemical reactions and on the use of solid-state electrochemical reactions in the analysis of solids and their surfaces.
The journal covers solid-state electrochemistry and focusses on the following fields: mechanisms of solid-state electrochemical reactions, semiconductor electrochemistry, electrochemical batteries, accumulators and fuel cells, electrochemical mineral leaching, galvanic metal plating, electrochemical potential memory devices, solid-state electrochemical sensors, ion and electron transport in solid materials and polymers, electrocatalysis, photoelectrochemistry, corrosion of solid materials, solid-state electroanalysis, electrochemical machining of materials, electrochromism and electrochromic devices, new electrochemical solid-state synthesis.
The Journal of Solid State Electrochemistry makes the professional in research and industry aware of this swift progress and its importance for future developments and success in the above-mentioned fields.
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