Manipulation of Na3V2(PO4)2F3 via aluminum doping to alter local electron states toward an advanced cathode for sodium-ion batteries
With its unique 3D skeleton structure and exceptional cyclic stability, the Na + superionic conductor (NASICON)-type Na 3 V 2 (PO 4 ) 2 F 3 (NVPF) has been considered as a competitive cathode material for advanced Na-ion batteries. However, the release of fluorine during the heat treatment leads to...
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| Published in: | Rare metals Vol. 43; no. 9; pp. 4253 - 4262 |
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| Main Authors: | , , , , , , , , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
Beijing
Nonferrous Metals Society of China
01.09.2024
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| Subjects: | |
| ISSN: | 1001-0521, 1867-7185 |
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| Abstract | With its unique 3D skeleton structure and exceptional cyclic stability, the Na
+
superionic conductor (NASICON)-type Na
3
V
2
(PO
4
)
2
F
3
(NVPF) has been considered as a competitive cathode material for advanced Na-ion batteries. However, the release of fluorine during the heat treatment leads to the formation of an additional phase Na
3
V
2
(PO
4
)
3
(NVP), which results in a low-voltage plateau and compromises the energy density. Herein, we modulate the local electronic states of the V site by aluminum substitution to strengthen the stability of F. The results confirm that the aluminum introduction not only changes the local electron states of V sites, significantly reducing the formation of NVP by-product from 6.71 wt% to 1.01 wt%, but also effectively reduces the band gap, improving the electronic conductivity of NVPF. The optimized Na
3
V
1.9
Al
0.1
(PO
4
)
2
F
3
exhibits higher energy density of 340 Wh·kg
−1
and excellent rate performance of 106.7 mAh·g
−1
at 10C compared with the pristine cathode.
Graphical abstract |
|---|---|
| AbstractList | With its unique 3D skeleton structure and exceptional cyclic stability, the Na+ superionic conductor (NASICON)‐type Na3V2(PO4)2F3 (NVPF) has been considered as a competitive cathode material for advanced Na‐ion batteries. However, the release of fluorine during the heat treatment leads to the formation of an additional phase Na3V2(PO4)3 (NVP), which results in a low‐voltage plateau and compromises the energy density. Herein, we modulate the local electronic states of the V site by aluminum substitution to strengthen the stability of F. The results confirm that the aluminum introduction not only changes the local electron states of V sites, significantly reducing the formation of NVP by‐product from 6.71 wt% to 1.01 wt%, but also effectively reduces the band gap, improving the electronic conductivity of NVPF. The optimized Na3V1.9Al0.1(PO4)2F3 exhibits higher energy density of 340 Wh·kg−1 and excellent rate performance of 106.7 mAh·g−1 at 10C compared with the pristine cathode.
Graphical
摘要凭借其独特的3D骨架结构和卓越的循环稳定性，NASICON型Na3V2(PO4)2F3（NVPF）被认为是先进钠离子电池极具竞争力的正极材料。然而，在热处理过程中氟的释放导致形成额外的Na3V2(PO4)3（NVP）相，从而引发了低电压平台并损害其能量密度。本文通过Al取代V来调制V位的局部电子，从而增强F的稳定性。结果证实，Al的引入不仅改变了V位的局部电子态，使NVP副产物的形成从6.71 wt%显著降低到1.01 wt%，而且有效地减小了带隙，提高了NVPF材料的电子导电性。与原始正极材料相比，优化后的Na3V1.9Al0.1(PO4)2F3具有更高的能量密度（340 Wh·kg‒1）和更好的倍率性能（10C 下放电106.7 mAh·g‒1）。 With its unique 3D skeleton structure and exceptional cyclic stability, the Na + superionic conductor (NASICON)-type Na 3 V 2 (PO 4 ) 2 F 3 (NVPF) has been considered as a competitive cathode material for advanced Na-ion batteries. However, the release of fluorine during the heat treatment leads to the formation of an additional phase Na 3 V 2 (PO 4 ) 3 (NVP), which results in a low-voltage plateau and compromises the energy density. Herein, we modulate the local electronic states of the V site by aluminum substitution to strengthen the stability of F. The results confirm that the aluminum introduction not only changes the local electron states of V sites, significantly reducing the formation of NVP by-product from 6.71 wt% to 1.01 wt%, but also effectively reduces the band gap, improving the electronic conductivity of NVPF. The optimized Na 3 V 1.9 Al 0.1 (PO 4 ) 2 F 3 exhibits higher energy density of 340 Wh·kg −1 and excellent rate performance of 106.7 mAh·g −1 at 10C compared with the pristine cathode. Graphical abstract |
| Author | Xu, Li Huang, Wen-Jin Ren, Fu-Tong Guo, Hong Wang, Shi-Min Liu, Qing Duan, Ling-Yan Ma, Hang Li, Jin-Qi Sun, Yong-Jiang Sun, Meng-Jiao |
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| DOI | 10.1007/s12598-024-02777-8 |
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| Keywords | Electrochemistry Sodium-ion energy storage batteries Cathode NASICON Doping |
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batteries: combustion synthesis and combined analysis of structural, electrical, and dielectric properties publication-title: Ceram Int – volume: 37 start-page: 325 year: 2021 article-title: Unraveling the mechanism of optimal concentration for Fe substitution in Na V (PO4) F /C for Sodium‐Ion batteries publication-title: Energy Stor Mater – volume: 2 start-page: 8668 issue: 23 year: 2014 article-title: Na V (PO ) @C core–shell nanocomposites for rechargeable sodium‐ion batteries publication-title: J Mater Chem A – volume: 26 start-page: 4238 issue: 14 year: 2014 article-title: Na V (PO ) F revisited: a high‐resolution diffraction study publication-title: Chem Mater – volume: 8 start-page: 1801064 issue: 24 year: 2018 article-title: Fluorophosphates from solid‐state synthesis and electrochemical ion exchange: NaVPO F or Na V (PO ) F ? publication-title: Adv Energy Mater – volume: 148 start-page: 260 issue: 2 year: 1999 article-title: Phase transitions in the Na M (PO ) F Family (M=Al , V , Cr , Fe , Ga ): synthesis, thermal, structural, and magnetic studies publication-title: J Solid State Chem – volume: 25 start-page: 724 year: 2020 article-title: High performance cathode material based on Na V (PO ) F and Na V (PO ) for sodium‐ion batteries publication-title: Energy Stor Mater – volume: 47 start-page: 1756 issue: 12 year: 2023 article-title: Performance of cathode material of high‐power lithium‐ion battery publication-title: Chin J Rare Metals – volume: 790 start-page: 203 year: 2019 end-page: 211 article-title: Improved electrochemical performance of high voltage cathode Na V (PO ) F for Na‐ion batteries through potassium doping publication-title: J Alloys Compd – volume: 41 start-page: 115 issue: 1 year: 2022 article-title: Ultra‐stable carbon‐coated sodium vanadium phosphate as cathode material for sodium‐ion battery publication-title: Rare Met |
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| Snippet | With its unique 3D skeleton structure and exceptional cyclic stability, the Na
+
superionic conductor (NASICON)-type Na
3
V
2
(PO
4
)
2
F
3
(NVPF) has been... With its unique 3D skeleton structure and exceptional cyclic stability, the Na+ superionic conductor (NASICON)‐type Na3V2(PO4)2F3 (NVPF) has been considered as... |
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| SubjectTerms | Biomaterials Cathode Chemistry and Materials Science Doping Electrochemistry Energy Materials Engineering Materials Science Metallic Materials Nanoscale Science and Technology NASICON Original Article Physical Chemistry Sodium‐ion energy storage batteries |
| Title | Manipulation of Na3V2(PO4)2F3 via aluminum doping to alter local electron states toward an advanced cathode for sodium-ion batteries |
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