Zhaolu Liu, Yongjie Cao, Ning Wang, Hui Yang, Hao Zhang, Xinyue Xu, Nan Wang, Jie Xu, Yao Liu, Junxi Zhang, Yongyao Xia
{"title":"通过非化学计量揭开钠离子电池铁基混合磷酸盐阴极的神秘面纱","authors":"Zhaolu Liu, Yongjie Cao, Ning Wang, Hui Yang, Hao Zhang, Xinyue Xu, Nan Wang, Jie Xu, Yao Liu, Junxi Zhang, Yongyao Xia","doi":"10.1007/s12274-024-6804-1","DOIUrl":null,"url":null,"abstract":"<div><p>The off-stoichiometric iron-based phosphate (Na<sub>3.12</sub>Fe<sub>2.44</sub>(P<sub>2</sub>O<sub>7</sub>)<sub>2</sub>, denoted as Na<sub>3.12</sub>) as a low cost and high structure stability cathode material has been widely studied for sodium-ion batteries (SIBs). However, the lower theoretical specific capacity (117 mAh·g<sup>−1</sup>) has seriously limited its practical application. In this work, we incorporate varying proportion of sodium-iron phosphate (NaFePO<sub>4</sub>) into the Na<sub>3.12</sub> to form a series of new high specific capacity mixed-phosphates Na<sub>3.12+<i>x</i></sub>Fe<sub>2.44+<i>x</i></sub>(P<sub>2</sub>O<sub>7</sub>)<sub>2</sub>(PO<sub>4</sub>)<sub><i>x</i></sub> cathode materials for SIBs. After optimizing the introduction amount of NaFePO<sub>4</sub> into Na<sub>3.12</sub>, the practical reversible of Na<sub>3.12+<i>x</i></sub>Fe<sub>2.44+<i>x</i></sub>(P<sub>2</sub>O<sub>7</sub>)<sub>2</sub>(PO<sub>4</sub>)<sub><i>x</i></sub> increased from 92 to 125.2 mAh·g<sup>−1</sup>. The nano-size Na<sub>5.12</sub>Fe<sub>4.44</sub>(P<sub>2</sub>O<sub>7</sub>)<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub> cathode material shows a reversible specific capacity of 125.2 mAh·g<sup>−1</sup> at 0.1 C in SIBs. Even at 60 C, it still exhibits a reversible specific capacity of 93.3 mAh·g<sup>−1</sup> and keeps a capacity retention ratio of 87% after 3000 cycles at 20 C. Thereby, we present a novel approach to design a series of off-stoichiometric mixed-phosphates cathode materials for SIBs.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":713,"journal":{"name":"Nano Research","volume":"17 9","pages":"8119 - 8125"},"PeriodicalIF":9.5000,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Unlocking iron-based mixed-phosphate cathode for sodium-ion batteries through off-stoichiometry\",\"authors\":\"Zhaolu Liu, Yongjie Cao, Ning Wang, Hui Yang, Hao Zhang, Xinyue Xu, Nan Wang, Jie Xu, Yao Liu, Junxi Zhang, Yongyao Xia\",\"doi\":\"10.1007/s12274-024-6804-1\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The off-stoichiometric iron-based phosphate (Na<sub>3.12</sub>Fe<sub>2.44</sub>(P<sub>2</sub>O<sub>7</sub>)<sub>2</sub>, denoted as Na<sub>3.12</sub>) as a low cost and high structure stability cathode material has been widely studied for sodium-ion batteries (SIBs). However, the lower theoretical specific capacity (117 mAh·g<sup>−1</sup>) has seriously limited its practical application. In this work, we incorporate varying proportion of sodium-iron phosphate (NaFePO<sub>4</sub>) into the Na<sub>3.12</sub> to form a series of new high specific capacity mixed-phosphates Na<sub>3.12+<i>x</i></sub>Fe<sub>2.44+<i>x</i></sub>(P<sub>2</sub>O<sub>7</sub>)<sub>2</sub>(PO<sub>4</sub>)<sub><i>x</i></sub> cathode materials for SIBs. After optimizing the introduction amount of NaFePO<sub>4</sub> into Na<sub>3.12</sub>, the practical reversible of Na<sub>3.12+<i>x</i></sub>Fe<sub>2.44+<i>x</i></sub>(P<sub>2</sub>O<sub>7</sub>)<sub>2</sub>(PO<sub>4</sub>)<sub><i>x</i></sub> increased from 92 to 125.2 mAh·g<sup>−1</sup>. The nano-size Na<sub>5.12</sub>Fe<sub>4.44</sub>(P<sub>2</sub>O<sub>7</sub>)<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub> cathode material shows a reversible specific capacity of 125.2 mAh·g<sup>−1</sup> at 0.1 C in SIBs. Even at 60 C, it still exhibits a reversible specific capacity of 93.3 mAh·g<sup>−1</sup> and keeps a capacity retention ratio of 87% after 3000 cycles at 20 C. 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Unlocking iron-based mixed-phosphate cathode for sodium-ion batteries through off-stoichiometry
The off-stoichiometric iron-based phosphate (Na3.12Fe2.44(P2O7)2, denoted as Na3.12) as a low cost and high structure stability cathode material has been widely studied for sodium-ion batteries (SIBs). However, the lower theoretical specific capacity (117 mAh·g−1) has seriously limited its practical application. In this work, we incorporate varying proportion of sodium-iron phosphate (NaFePO4) into the Na3.12 to form a series of new high specific capacity mixed-phosphates Na3.12+xFe2.44+x(P2O7)2(PO4)x cathode materials for SIBs. After optimizing the introduction amount of NaFePO4 into Na3.12, the practical reversible of Na3.12+xFe2.44+x(P2O7)2(PO4)x increased from 92 to 125.2 mAh·g−1. The nano-size Na5.12Fe4.44(P2O7)2(PO4)2 cathode material shows a reversible specific capacity of 125.2 mAh·g−1 at 0.1 C in SIBs. Even at 60 C, it still exhibits a reversible specific capacity of 93.3 mAh·g−1 and keeps a capacity retention ratio of 87% after 3000 cycles at 20 C. Thereby, we present a novel approach to design a series of off-stoichiometric mixed-phosphates cathode materials for SIBs.
期刊介绍：
Nano Research is a peer-reviewed, international and interdisciplinary research journal that focuses on all aspects of nanoscience and nanotechnology. It solicits submissions in various topical areas, from basic aspects of nanoscale materials to practical applications. The journal publishes articles on synthesis, characterization, and manipulation of nanomaterials; nanoscale physics, electrical transport, and quantum physics; scanning probe microscopy and spectroscopy; nanofluidics; nanosensors; nanoelectronics and molecular electronics; nano-optics, nano-optoelectronics, and nano-photonics; nanomagnetics; nanobiotechnology and nanomedicine; and nanoscale modeling and simulations. Nano Research offers readers a combination of authoritative and comprehensive Reviews, original cutting-edge research in Communication and Full Paper formats. The journal also prioritizes rapid review to ensure prompt publication.
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