高容量锂离子电池正极补锂材料Li5FeO4@C的性能研究

doi:10.19799/j.cnki.2095-4239.2024.1092

摘要/Abstract

摘要：

正极补锂添加剂Li₅FeO₄(LFO)具有理论比容量高、成本低且无毒等优点，是发展前景广大的补锂技术之一，但其残碱值高、导电性低等问题导致其在实际使用中脱锂容量大大降低，限制了其进一步应用。针对此问题，本工作采用高温固相法制备出纯相的LFO材料，并使用等离子增强型化学气相沉积法(PECVD)对LFO材料进行碳包覆处理得到LFO@C材料，分析了不同包覆时间、温度下LFO@C材料的理化性能和电化学性能。扫描电子显微镜(SEM)、透射电子显微镜(TEM)和能量分析谱(EDS)显示不同的PECVD碳包覆工艺会在LFO@C材料表面沉积不同的碳层结构，包覆温度为500℃、包覆时间为2h时会在材料表面沉积了一层均匀且致密的碳层。X射线衍射分析(XRD)结果表明包覆温度为500℃、包覆时间≤2h时LFO@C材料不会发生不可逆相变。碳含量和导电性分析结果表明LFO@C材料的碳含量和电导率随包覆时间的延长呈现增大后减小的趋势、随包覆温度的增加呈上升趋势。残碱值分析结果显示LFO材料的残碱值经过PECVD碳包覆改性后发生了明显的下降，且LFO@C材料的残碱值大小与其表面碳层结构相关。碳包覆改性后的LFO@C材料的电化学性能得到了极大改善，其中容量最高的LFO-5002材料在2.0~4.2V下首次充电克比容量为756.4mAh/g，不可逆容量达到623.51mAh/g，超过纯相LFO材料200mAh/g以上。分析结果表明使用PECVD可以在 LFO材料颗粒表面包裹一层均匀致密的碳层，碳包覆后材料的残碱值大大降低，导电性、容量大大提升，补锂效果得到了极大改善。本工作通过碳包覆改性显著提升了正极补锂材料LFO的不可逆容量，为高容量的正极补锂材料设计提供了技术指导。

关键词: 锂离子电池, 正极补锂添加剂, Li₅FeO₄, 等离子增强型化学气相沉积法, 碳包覆改性

Abstract:

Li₅FeO₄(LFO) prelithium cathode additive has the advantages of high theoretical specific capacity, low cost and non-toxicity, and is one of the most promising prelithiation technologies. However, its high residual alkali and low electrical conductivity lead to its greatly reduced delithium capacity in practical use, which limits its further application. To solve this problem, this study employed a high temperature solid phase method to prepare pure LFO material, and used plasma enhanced chemical vapor deposition (PECVD) to obtain LFO@C material and investigated the physicochemical and electrochemical properties of LFO@C material at different carbon-coating time and temperature. Scanning electron microscopy (SEM), transmission electron microscope (TEM) and energy analysis spectroscopy (EDS) showed that different PECVD carbon-coating paramaters deposited different carbon layer structures on the surface of LFO@C. A uniform and dense carbon layer was deposited on the surface of the LFO@C material when the carbon-coating was perfoermed at 500℃ for 2h. X-ray diffraction (XRD) analysis showed that there was no irreversible phase transition of LFO@C when the carbon-coating temperature was 500℃ and the carbon-coating time was less than 2h.The carbon content and electrical conductivity of LFO@C increased and then decreased with the increase of carbon-coating time, and increased with the increase of carbon-coating temperature. The residual alkali analysis showed that the residual alkali value of LFO material decreased obviously after PECVD carbon-coating, and the residual alkali value of LFO@C material was related to the surface carbon layer structure. The electrochemical properties of the carbon-coated LFO@C materials have been greatly improved. Among the carbon-coated materials, the LFO-5002 material exhibited the highest initial charge specific capacity of 756.4mAh/g at 2.0~4.2V, and an irreversible capacity reaches 623.51mAh/g, which exceeded that of the uncoated LFO material by more than 200mAh/g. The results showed that PECVD could be used to coat the surface of LFO particles with a uniform and dense carbon layer, and the residual alkali of the carbon-coated materials was greatly reduced, the electrical conductivity and capacity were greatly improved, and the prelithium effect was greatly improved. In this work, the irreversible capacity of cathode prelithium material LFO was significantly improved by carbon-coating modification, which provided technical guidance for the design of high capacity cathode prelithium materials.

Key words: lithium-ion battery, cathode prelithium additive, Li₅FeO₄, plasma enhanced chemical vapor deposition(PECVD), carbon-coating modification

中图分类号:

TM 911

曾州岚, 尚雷, 胡志金, 王宗凡, 辛小超, 刘瑛. 高容量锂离子电池正极补锂材料Li₅FeO₄@C的性能研究[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2024.1092.

Zhoulan Zeng, Lei Shang, Zhijin Hu, Zongfan Wang, Xiaochao Xin, Ying Liu. Li₅FeO₄@C high capacity prelithium cathode materials for lithium-ion batteries[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2024.1092.

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高容量锂离子电池正极补锂材料Li₅FeO₄@C的性能研究

Li₅FeO₄@C high capacity prelithium cathode materials for lithium-ion batteries

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