Sunkyu Park, Ziliang Wang, Kriti Choudhary, Jean-Noël Chotard, Dany Carlier, François Fauth, Pieremanuele Canepa, Laurence Croguennec, Christian Masquelier
{"title":"从单相 NaxV2(PO4)3 (1 < x < 3) 正极材料中通过钠萃取获得 V2(PO4)3","authors":"Sunkyu Park, Ziliang Wang, Kriti Choudhary, Jean-Noël Chotard, Dany Carlier, François Fauth, Pieremanuele Canepa, Laurence Croguennec, Christian Masquelier","doi":"10.1038/s41563-024-02023-7","DOIUrl":null,"url":null,"abstract":"<p>We report on single-phase Na<sub><i>x</i></sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> compositions (1.5 ≤ <i>x</i> ≤ 2.5) of the Na super ionic conductor type, obtained from a straightforward synthesis route. Typically, chemically prepared c-Na<sub>2</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, obtained by annealing an equimolar mixture of Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> and NaV<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, exhibits a specific sodium-ion distribution (occupancy of the Na(1) site of only 0.66(4)), whereas that of the electrochemically obtained e-Na<sub>2</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (from Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>) is close to 1. Unlike conventional Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, when used as positive electrode materials in Na-ion batteries, the Na<sub><i>x</i></sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> compositions lead to unusual single-phase Na<sup>+</sup> extraction/insertion mechanisms with continuous voltage changes upon Na<sup>+</sup> extraction/insertion. We demonstrate that the average equilibrium operating voltage observed upon Na<sup>+</sup> deintercalation from single-phase Na<sub>2</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> is increased up to an average value of ~3.70 V versus Na<sup>+</sup>/Na (thanks to the activation of the V<sup>4+</sup>/V<sup>5+</sup> redox couple) compared to 3.37 V versus Na<sup>+</sup>/Na in conventional Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, thus leading to an increase in the theoretical energy density from 396.3 Wh kg<sup>–1</sup> to 458.1 Wh kg<sup>–1</sup>. Electrochemical and chemical Na<sup>+</sup> deintercalation from c-Na<sub>2</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> enables complete Na-ion extraction, increasing energy density.</p>","PeriodicalId":19058,"journal":{"name":"Nature Materials","volume":null,"pages":null},"PeriodicalIF":37.2000,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Obtaining V2(PO4)3 by sodium extraction from single-phase NaxV2(PO4)3 (1 < x < 3) positive electrode materials\",\"authors\":\"Sunkyu Park, Ziliang Wang, Kriti Choudhary, Jean-Noël Chotard, Dany Carlier, François Fauth, Pieremanuele Canepa, Laurence Croguennec, Christian Masquelier\",\"doi\":\"10.1038/s41563-024-02023-7\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>We report on single-phase Na<sub><i>x</i></sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> compositions (1.5 ≤ <i>x</i> ≤ 2.5) of the Na super ionic conductor type, obtained from a straightforward synthesis route. Typically, chemically prepared c-Na<sub>2</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, obtained by annealing an equimolar mixture of Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> and NaV<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, exhibits a specific sodium-ion distribution (occupancy of the Na(1) site of only 0.66(4)), whereas that of the electrochemically obtained e-Na<sub>2</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (from Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>) is close to 1. Unlike conventional Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, when used as positive electrode materials in Na-ion batteries, the Na<sub><i>x</i></sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> compositions lead to unusual single-phase Na<sup>+</sup> extraction/insertion mechanisms with continuous voltage changes upon Na<sup>+</sup> extraction/insertion. We demonstrate that the average equilibrium operating voltage observed upon Na<sup>+</sup> deintercalation from single-phase Na<sub>2</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> is increased up to an average value of ~3.70 V versus Na<sup>+</sup>/Na (thanks to the activation of the V<sup>4+</sup>/V<sup>5+</sup> redox couple) compared to 3.37 V versus Na<sup>+</sup>/Na in conventional Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, thus leading to an increase in the theoretical energy density from 396.3 Wh kg<sup>–1</sup> to 458.1 Wh kg<sup>–1</sup>. Electrochemical and chemical Na<sup>+</sup> deintercalation from c-Na<sub>2</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> enables complete Na-ion extraction, increasing energy density.</p>\",\"PeriodicalId\":19058,\"journal\":{\"name\":\"Nature Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":37.2000,\"publicationDate\":\"2024-10-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Nature Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1038/s41563-024-02023-7\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Nature Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1038/s41563-024-02023-7","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Obtaining V2(PO4)3 by sodium extraction from single-phase NaxV2(PO4)3 (1 < x < 3) positive electrode materials
We report on single-phase NaxV2(PO4)3 compositions (1.5 ≤ x ≤ 2.5) of the Na super ionic conductor type, obtained from a straightforward synthesis route. Typically, chemically prepared c-Na2V2(PO4)3, obtained by annealing an equimolar mixture of Na3V2(PO4)3 and NaV2(PO4)3, exhibits a specific sodium-ion distribution (occupancy of the Na(1) site of only 0.66(4)), whereas that of the electrochemically obtained e-Na2V2(PO4)3 (from Na3V2(PO4)3) is close to 1. Unlike conventional Na3V2(PO4)3, when used as positive electrode materials in Na-ion batteries, the NaxV2(PO4)3 compositions lead to unusual single-phase Na+ extraction/insertion mechanisms with continuous voltage changes upon Na+ extraction/insertion. We demonstrate that the average equilibrium operating voltage observed upon Na+ deintercalation from single-phase Na2V2(PO4)3 is increased up to an average value of ~3.70 V versus Na+/Na (thanks to the activation of the V4+/V5+ redox couple) compared to 3.37 V versus Na+/Na in conventional Na3V2(PO4)3, thus leading to an increase in the theoretical energy density from 396.3 Wh kg–1 to 458.1 Wh kg–1. Electrochemical and chemical Na+ deintercalation from c-Na2V2(PO4)3 enables complete Na-ion extraction, increasing energy density.
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Nature Materials is a monthly multi-disciplinary journal aimed at bringing together cutting-edge research across the entire spectrum of materials science and engineering. It covers all applied and fundamental aspects of the synthesis/processing, structure/composition, properties, and performance of materials. The journal recognizes that materials research has an increasing impact on classical disciplines such as physics, chemistry, and biology.
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