High‐ionicity fluorophosphate lattice via aliovalent substitution as advanced cathode materials in sodium‐ion batteries
Abstract As a cathode for sodium‐ion batteries (SIBs), Na3V2(PO4)2F3 (NVPF) with 3D open framework is a promising candidate due to its high working voltage and large theoretical capacity. However, the severe capacity degradation and poor rate capability hinder its practical applications. The present...
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| Format: | Article |
| Language: | English |
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Wiley
2021-06-01
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| Series: | InfoMat |
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| Online Access: | https://doi.org/10.1002/inf2.12184 |
| _version_ | 1818623074875998208 |
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| author | Zhen‐Yi Gu Jin‐Zhi Guo Xin‐Xin Zhao Xiao‐Tong Wang Dan Xie Zhong‐Hui Sun Chen‐De Zhao Hao‐Jie Liang Wen‐Hao Li Xing‐Long Wu |
| author_facet | Zhen‐Yi Gu Jin‐Zhi Guo Xin‐Xin Zhao Xiao‐Tong Wang Dan Xie Zhong‐Hui Sun Chen‐De Zhao Hao‐Jie Liang Wen‐Hao Li Xing‐Long Wu |
| author_sort | Zhen‐Yi Gu |
| collection | DOAJ |
| description | Abstract As a cathode for sodium‐ion batteries (SIBs), Na3V2(PO4)2F3 (NVPF) with 3D open framework is a promising candidate due to its high working voltage and large theoretical capacity. However, the severe capacity degradation and poor rate capability hinder its practical applications. The present study demonstrated the optimization of Na‐storage performance of NVPF via delicate lattice modulation. Aliovalent substitution of V3+ at Na+ in NVPF induces the generation of electronic defects and expansion of Na+‐migration channels, resulting in the enhancement in electronic conductivity and acceleration of Na+‐migration kinetics. It is disclosed that the formed stronger NaO bonds with high ionicity than VO bonds lead to the significant increase in structural stability and ionicity in the Na+‐substituted NVPF (NVPF‐Nax). The aforementioned effects of Na+ substitution achieve the unprecedented electrochemical performance in the optimized Na3.14V1.93Na0.07(PO4)2F3 (NVPF‐Na0.07). As a result, NVPF‐Na0.07 delivers a high‐rate capability (77.5 mAh g−1 at 20 C) and ultralong cycle life (only 0.027% capacity decay per cycle over 1000 cycles at 10 C). Sodium‐ion full cells are designed using NVPF‐Na0.07 as cathode and Se@reduced graphene oxide as anode. The full cells exhibit excellent wide‐temperature electrochemical performance from −25 to 25°C with an outstanding rate capability (96.3 mAh g−1 at 20 C). Furthermore, it delivered an excellent cycling performance over 300 cycles with a capacity retention exceeding 90% at 0.5 C under different temperatures. This study demonstrates a feasible strategy for the development of advanced cathode materials with excellent electrochemical properties to achieve high‐efficiency energy storage. |
| first_indexed | 2024-12-16T18:35:17Z |
| format | Article |
| id | doaj.art-73d2a1a5a9e7402996f2bf45c158da09 |
| institution | Directory Open Access Journal |
| issn | 2567-3165 |
| language | English |
| last_indexed | 2024-12-16T18:35:17Z |
| publishDate | 2021-06-01 |
| publisher | Wiley |
| record_format | Article |
| series | InfoMat |
| spelling | doaj.art-73d2a1a5a9e7402996f2bf45c158da092022-12-21T22:21:11ZengWileyInfoMat2567-31652021-06-013669470410.1002/inf2.12184High‐ionicity fluorophosphate lattice via aliovalent substitution as advanced cathode materials in sodium‐ion batteriesZhen‐Yi Gu0Jin‐Zhi Guo1Xin‐Xin Zhao2Xiao‐Tong Wang3Dan Xie4Zhong‐Hui Sun5Chen‐De Zhao6Hao‐Jie Liang7Wen‐Hao Li8Xing‐Long Wu9MOE Key Laboratory for UV Light‐Emitting Materials and Technology Northeast Normal University Changchun Jilin ChinaMOE Key Laboratory for UV Light‐Emitting Materials and Technology Northeast Normal University Changchun Jilin ChinaDepartment of Chemistry Northeast Normal University Changchun Jilin ChinaMOE Key Laboratory for UV Light‐Emitting Materials and Technology Northeast Normal University Changchun Jilin ChinaDepartment of Chemistry Northeast Normal University Changchun Jilin ChinaCenter for Advanced Analytical Science, School of Chemistry and Chemical Engineering Guangzhou University Guangzhou Guangdong ChinaDepartment of Chemistry Northeast Normal University Changchun Jilin ChinaMOE Key Laboratory for UV Light‐Emitting Materials and Technology Northeast Normal University Changchun Jilin ChinaMOE Key Laboratory for UV Light‐Emitting Materials and Technology Northeast Normal University Changchun Jilin ChinaMOE Key Laboratory for UV Light‐Emitting Materials and Technology Northeast Normal University Changchun Jilin ChinaAbstract As a cathode for sodium‐ion batteries (SIBs), Na3V2(PO4)2F3 (NVPF) with 3D open framework is a promising candidate due to its high working voltage and large theoretical capacity. However, the severe capacity degradation and poor rate capability hinder its practical applications. The present study demonstrated the optimization of Na‐storage performance of NVPF via delicate lattice modulation. Aliovalent substitution of V3+ at Na+ in NVPF induces the generation of electronic defects and expansion of Na+‐migration channels, resulting in the enhancement in electronic conductivity and acceleration of Na+‐migration kinetics. It is disclosed that the formed stronger NaO bonds with high ionicity than VO bonds lead to the significant increase in structural stability and ionicity in the Na+‐substituted NVPF (NVPF‐Nax). The aforementioned effects of Na+ substitution achieve the unprecedented electrochemical performance in the optimized Na3.14V1.93Na0.07(PO4)2F3 (NVPF‐Na0.07). As a result, NVPF‐Na0.07 delivers a high‐rate capability (77.5 mAh g−1 at 20 C) and ultralong cycle life (only 0.027% capacity decay per cycle over 1000 cycles at 10 C). Sodium‐ion full cells are designed using NVPF‐Na0.07 as cathode and Se@reduced graphene oxide as anode. The full cells exhibit excellent wide‐temperature electrochemical performance from −25 to 25°C with an outstanding rate capability (96.3 mAh g−1 at 20 C). Furthermore, it delivered an excellent cycling performance over 300 cycles with a capacity retention exceeding 90% at 0.5 C under different temperatures. This study demonstrates a feasible strategy for the development of advanced cathode materials with excellent electrochemical properties to achieve high‐efficiency energy storage.https://doi.org/10.1002/inf2.12184cathodefull cellionicityNa3V2(PO4)2F3sodium‐ion batteries |
| spellingShingle | Zhen‐Yi Gu Jin‐Zhi Guo Xin‐Xin Zhao Xiao‐Tong Wang Dan Xie Zhong‐Hui Sun Chen‐De Zhao Hao‐Jie Liang Wen‐Hao Li Xing‐Long Wu High‐ionicity fluorophosphate lattice via aliovalent substitution as advanced cathode materials in sodium‐ion batteries InfoMat cathode full cell ionicity Na3V2(PO4)2F3 sodium‐ion batteries |
| title | High‐ionicity fluorophosphate lattice via aliovalent substitution as advanced cathode materials in sodium‐ion batteries |
| title_full | High‐ionicity fluorophosphate lattice via aliovalent substitution as advanced cathode materials in sodium‐ion batteries |
| title_fullStr | High‐ionicity fluorophosphate lattice via aliovalent substitution as advanced cathode materials in sodium‐ion batteries |
| title_full_unstemmed | High‐ionicity fluorophosphate lattice via aliovalent substitution as advanced cathode materials in sodium‐ion batteries |
| title_short | High‐ionicity fluorophosphate lattice via aliovalent substitution as advanced cathode materials in sodium‐ion batteries |
| title_sort | high ionicity fluorophosphate lattice via aliovalent substitution as advanced cathode materials in sodium ion batteries |
| topic | cathode full cell ionicity Na3V2(PO4)2F3 sodium‐ion batteries |
| url | https://doi.org/10.1002/inf2.12184 |
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