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深圳大学、湘潭大学、中国科学院深圳先进技术研究院联合Nature Sustainability:新型石墨负极!

  • 2026-07-31 00:48:04
深圳大学、湘潭大学、中国科学院深圳先进技术研究院联合Nature Sustainability:新型石墨负极!

石墨作为锂离子电池负极的核心材料,凭借储量丰富、成本低廉、安全性高的优势占据主导地位三十余年,但其在高倍率充电与低温等极端条件下,因电解液 - 石墨界面处锂离子传输动力学迟缓,难以满足现代储能需求,相关界面电子结构与固体电解质界面形成的耦合作用是性能受限的关键,现有界面改性策略多存在合成工艺复杂、通量低、与大规模工业生产不兼容等问题,亟需开发可规模化制备且能精准调控石墨界面的碳材料与合成路径。

近日,深圳大学刘剑洪、 张黔玲、叶盛华、胡江涛、湘潭大学欧阳晓平、中国科学院深圳先进技术研究院彭超团队开发了线性 - 梯形 - 平面化的可规模化合成方法,以液态可加工聚丙烯腈为前驱体,经低温预氧化与高温碳化制备出兼具短程石墨有序与长程结构无序的石墨聚集体,该前驱体可在商用石墨颗粒表面形成均匀包覆层,得到改性石墨负极 GHT,通过调控界面锂 - 碳相互作用与固体电解质界面形成,显著提升锂离子传输动力学,材料可批量生产且适配现有工业流程,在扣式电池与 18650 型圆柱电池中展现出优异的高倍率循环稳定性与低温性能,结合密度泛函理论计算揭示了石墨聚集体包覆弱化石墨边缘效应、加速锂离子扩散的内在机制。

该成果以 “Scalable synthesis of graphitic aggregates for high-rate battery anode” 为题发表在 “Nature Sustainability” 期刊,第一作者是 Hu Jiangtao、Liu Pei、Ye Shenghua。

(电化学能源整理,未经申请,不得转载)

本文pdf请扫描底部二维码直接下载。

【工作要点】

研究以液态聚丙烯腈为前驱体,通过线性-梯形-平面化策略制备石墨聚集体,先在220℃下完成环化与脱氢形成梯形中间体,再经惰性气氛下高温碳化实现石墨化,单批次产能约20千克,适配工业化批量生产,多种表征证实产物具备高石墨化程度、弱层间相互作用与扩大的层间距。  
将前驱体与商用石墨共混后经预氧化与1250℃烧结,得到表面均匀包覆石墨聚集体的改性负极GHT,其保持石墨原有形貌并具备良好电子导电性,在扣式电池中展现出更高首次充电容量、库仑效率与更小极化,循环与倍率性能显著优于纯石墨,且能抑制析锂与形成稳定固体电解质界面。  
在18650型圆柱电池中,GHT匹配LiNi₀.₅Mn₀.₃Co₀.₂O₂正极,1C下循环1000次容量保持率87.9%,3C下循环500次保持率83.9%,−10℃低温下2C与3C倍率容量保持率分别达93.2%与92.2%,兼具长循环、高倍率与优异低温特性。  
密度泛函理论与分子动力学计算表明,石墨聚集体包覆可弱化石墨边缘强吸附作用,降低锂离子结合能并提升扩散速率,锂离子扩散速度提升约三倍,从机制上阐明改性负极动力学提升的原因,该方法为高性能、可持续的高倍率储能器件提供工业化可行路径。

图 1 分析了石墨聚集体的可规模化制备路线与材料、电极的表征结果,呈现了从液态聚丙烯腈前驱体经低温预氧化形成固体中间体、再经高温碳化得到石墨聚集体的过程,通过红外图谱、热重 - 质谱、拉曼图谱、透射电镜等手段,证实了材料的结构演变、高石墨化程度、层间距特征以及改性石墨负极的均匀包覆结构,还分析了规模化生产设备与大批量制备的石墨聚集体实物。

图 2 为密度泛函理论计算相关结果,揭示了纯石墨与石墨聚集体包覆石墨的边缘结构、锂离子吸附能、成键特征及锂离子扩散动力学,阐明石墨聚集体包覆能够弱化石墨边缘效应、降低锂离子结合能、提升锂离子迁移速率,从理论层面解释了改性负极电化学性能提升的内在机制。

【结论】

研究证实采用液态聚丙烯腈前驱体可实现石墨聚集体的可规模化、工业兼容合成,该方法能形成均匀的界面包覆层,从根本上改变石墨负极的表面拓扑结构,该成果为下一代高倍率、长寿命储能系统提供了可工业化制造的策略。

链接:https://doi.org/10.1038/s41893-026-01813-y

文章来源:电化学能源

《固态电池行业技术发展与市场投资前景分析》

《钠离子电池技术发展与产业前景研究报告》

《富锂锰基动力电池产业研究及其市场前景分析》

《中国全固态薄膜电池和全固态超级电容器技术与市场调研报告》

《中国高能量高功率锂离子电池负极材料技术发展与市场投资规划报告》

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  1. CONNECT:[ UseTime:0.000833s ] mysql:host=127.0.0.1;port=3306;dbname=c460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.001352s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.003150s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.001412s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.001118s ]
  6. SELECT * FROM `set` [ RunTime:0.005607s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.001130s ]
  8. SELECT * FROM `article` WHERE `id` = 560395 LIMIT 1 [ RunTime:0.000891s ]
  9. UPDATE `article` SET `lasttime` = 1785741539 WHERE `id` = 560395 [ RunTime:0.019055s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 64 LIMIT 1 [ RunTime:0.000633s ]
  11. SELECT * FROM `article` WHERE `id` < 560395 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.011417s ]
  12. SELECT * FROM `article` WHERE `id` > 560395 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.003121s ]
  13. SELECT * FROM `article` WHERE `id` < 560395 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.001312s ]
  14. SELECT * FROM `article` WHERE `id` < 560395 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.018708s ]
  15. SELECT * FROM `article` WHERE `id` < 560395 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.012395s ]
0.212401s