当前位置:首页>南京>金属电池循环突破,南京邮电大学赖文勇教授通过无氟溶剂+无氟锂盐(LiBOB),实现电池500次循环几乎零衰减,容量保持率达99.7%

金属电池循环突破,南京邮电大学赖文勇教授通过无氟溶剂+无氟锂盐(LiBOB),实现电池500次循环几乎零衰减,容量保持率达99.7%

  • 2026-05-09 13:00:17
金属电池循环突破,南京邮电大学赖文勇教授通过无氟溶剂+无氟锂盐(LiBOB),实现电池500次循环几乎零衰减,容量保持率达99.7%
锂金属电池的高理论能量密度,被公认为下一代储能技术的核心方向。但搭配传统电解液含氟污染、易燃易泄漏、锂枝晶生长、离子传输效率低四大难题,始终卡在商业化的关键路口。
近期,南京邮电大学赖文勇教授及其团队发表国际材料领域顶级期刊《Advanced Materials》的一项成果。他们提出溶剂-聚合物弹性桥接策略,成功研发出无氟、高安全、单离子传导的新型凝胶聚合物电解质,为高性能、锂金属电池提供了从分子设计到器件应用的完整解决方案。

一、传统锂电池电解液、难题

目前商用锂电池电解液几乎离不开含氟锂盐(如 LiPF₆)与氟代稀释剂,这类体系虽能满足基本电化学需求,却暗藏多重隐患:

环境危害:氟化物难以降解,生产与回收过程会造成严重污染,不符合绿色储能趋势;安全风险:液态电解液易燃、易泄漏,在高温、穿刺等极端条件下易引发热失控;界面不稳定:易在锂负极表面形成不均匀固体电解质界面(SEI),诱发锂枝晶生长,导致电池短路、寿命骤减;离子传输短板:常规电解液锂离子迁移数仅约 0.5,阴离子自由迁移会加剧浓差极化,限制快充与长循环性能。

为解决这些问题,大家曾尝试局部高浓度电解液(LHCE)、凝胶聚合物电解质(GPE)等方向,但无氟 LHCE 研发极少、无氟体系锂盐溶解性差、溶剂与聚合物相互作用难以调控等问题,始终没有得到根本解决。

二、弹性桥接+无氟双体系设计

这项研究首创溶剂 - 聚合物弹性桥接架构,将无氟局部高浓电解液两性离子聚氨酯巧妙结合,实现 “机械性能 + 电化学性能” 双优。

1. 无氟局部高浓电解液

研究团队摒弃所有含氟组分,选用LiBOB(二草酸硼酸锂)作为唯一无氟锂盐,搭配双溶剂协同体系

四乙二醇二甲醚(T):强配位溶剂,负责高效结合 Li⁺,提升离子解离效率;γ- 戊内酯(V):弱配位稀释剂,优化溶剂化结构,降低体系粘度。

两种溶剂强弱配位互补,完美解决了无氟锂盐在有机溶剂中溶解性差的问题,构建出稳定透明的无氟局部高浓电解液,从源头实现绿色环保。

2. 弹性桥接载体

团队自主合成两性离子聚氨酯(TPU)作为聚合物基体,通过刚柔分子链设计+氢键 / 离子 - 偶极作用,实现三大核心功能:

弹性封装:将液态无氟电解液牢牢锁在聚合物网络中,彻底消除漏液、易燃风险;离子通道:形成两性离子纳米通道,定向快速传输 Li⁺,大幅提升离子迁移效率;动态自修复:依靠可逆氢键与离子作用,让电解质在室温下 5 小时即可自动修复损伤,提升电池耐用性。

3. 弹性桥接机制

“弹性桥接” 是在分子层面精准调控相互作用:

聚氨酯与溶剂分子形成氢键,弱化 Li⁺- 溶剂过度配位,促进 Li⁺脱溶剂化;离子 - 偶极作用引导阴离子主导的溶剂化结构形成,固定阴离子、释放自由 Li⁺;聚合物主链弱相互作用与刚柔协同,同步提升机械强度与离子传导能力。

这种设计从根源上实现了单离子传导,让锂离子迁移数达到惊人的 0.95,远超市面电解液与传统无氟体系。

三、性能全面突破

这款无氟弹性桥接电解质,在多项关键指标上实现领先,完美兼顾安全性、机械性与电化学性能。

1. 极致电化学性能

锂离子迁移数:0.95:接近理想单离子导体,远超商用电解液(≈0.5)与基础无氟体系(≈0.41);室温离子电导率:1.3 mS cm⁻¹:满足大功率、快充场景需求;电化学窗口:>4.8 V:适配 NCM622 等高压正极,拓展电池能量密度;活化能低至 1.33 kJ mol⁻¹:离子传输势垒极低,低温性能同样优异。

2. 超强机械与功能特性

力学性能:断裂强度 1.1 MPa,应变高达≈900%,兼具高强度与高弹性;自修复能力:室温下 5 小时完成断裂自愈,网络结构可逆重构;界面粘附:与 PET 基底粘附强度达 2.7 MPa,与金属电极结合力超 6 N,适配柔性器件。

3. 电池长循环稳定

研究团队将电解质组装成多种电池,验证实际应用潜力:

Li||Li 对称电池:稳定锂沉积 / 剥离 1000 小时,无锂枝晶生成,界面保持平整;Li||LFP 全电池:0.5C 循环 500 圈,容量保持率 99.7%,库仑效率 99.9%,倍率性能优于商用电解液;Li||NCM622 高载量电池(10 mg cm⁻²):200 圈平均面容量 1.6 mAh cm⁻²,库仑效率 99.4%;软包电池:容量达 1600 mAh,弯曲状态下仍可稳定供电,适配柔性电子。

更重要的是,电解质在负极表面诱导生成富硼化物无机 SEI 层,含 LiBₓOᵧ、Li₃N 等稳定组分,从界面层面彻底抑制枝晶,保障电池长期安全运行。

文献信息:

Title: Elastic Bridging Design of a Fluorine-Free Electrolyte Enables High-Performance Lithium Batteries
Author: Shi WangWenqing Sun,Wen-Yong Lai*, .et al.

DOI: 10.1002/adma.72977

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***声明***:本文基于公开学术成果及行业数据整理,实验数据和图片均引自文献,如有侵权,请联系公众号客服删除。

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  1. CONNECT:[ UseTime:0.000546s ] mysql:host=127.0.0.1;port=3306;dbname=b460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.000630s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000283s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.004001s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000661s ]
  6. SELECT * FROM `set` [ RunTime:0.000234s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000672s ]
  8. SELECT * FROM `article` WHERE `id` = 540155 LIMIT 1 [ RunTime:0.003253s ]
  9. UPDATE `article` SET `lasttime` = 1779473625 WHERE `id` = 540155 [ RunTime:0.010049s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 65 LIMIT 1 [ RunTime:0.000282s ]
  11. SELECT * FROM `article` WHERE `id` < 540155 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.002653s ]
  12. SELECT * FROM `article` WHERE `id` > 540155 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.006042s ]
  13. SELECT * FROM `article` WHERE `id` < 540155 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.012917s ]
  14. SELECT * FROM `article` WHERE `id` < 540155 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.006859s ]
  15. SELECT * FROM `article` WHERE `id` < 540155 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.003617s ]
0.122796s