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Nat. Commun. | 郑州大学 | 醚类溶剂“分子抱团”,钠电池耐寒又耐热

  • 2026-07-02 08:46:02
Nat. Commun. | 郑州大学 | 醚类溶剂“分子抱团”,钠电池耐寒又耐热

醚类溶剂“分子抱团”,钠电池耐寒又耐热

在极寒的北极科考站、酷热的沙漠无人区,甚至未来的深空探测器上,电池常常“罢工”——低温下充不进电,高温下又怕起火爆炸。如何让电池在宽温域(比如从零下40℃到70℃)都能稳定工作,一直是能源领域的难题。

最近,郑州大学付永柱教授与唐帅副教授团队在《自然·通讯》(Nature Communications)发表了一项突破性研究:他们通过巧妙设计醚类电解液溶剂的分子结构,不仅保留了其“弱溶剂化”优势以提升低温性能,还显著增强了分子间的“抱团力”,大幅提高沸点,从而实现了钠金属电池在−40℃至70℃宽温范围内的稳定循环。

这项工作颠覆了一个长期被忽视的认知:低温脱溶剂化能垒不仅取决于离子与溶剂的相互作用,还受溶剂分子之间相互作用的显著影响


为什么钠电池适合极端温度?

相比广泛应用的锂离子电池,钠金属电池天生更适合低温环境。这是因为钠离子半径更大、电离能更低,与溶剂分子的结合更“松散”——专业术语叫弱溶剂化作用。这种特性使得钠离子在低温下更容易“甩掉”包裹它的溶剂分子(即“脱溶剂化”),从而顺利嵌入电极,维持电池反应。

然而,传统用于钠电池的弱溶剂化醚类溶剂(如1,3-二氧戊环DOL、四氢呋喃THF)虽然低温性能好,却有一个致命缺点:沸点低、易挥发。例如,DOL沸点仅75℃,THF更是只有66℃。一旦电池在高温环境(如夏季户外或密闭舱体)中运行,溶剂极易气化,引发胀气、泄漏甚至燃烧。

这就形成了一个两难困境:要低温性能,就得用弱溶剂化溶剂;但这类溶剂往往不耐高温。


巧妙“升级”分子结构:让溶剂既“松”又“稳”

研究团队没有另起炉灶,而是对经典弱溶剂化醚DOL进行了分子层面的精巧改造

他们将DOL五元环中的一个亚甲基(–CH₂–)替换为氧原子,得到六元环的1,3-二氧六环(DX);再进一步在环上引入一个甲基,得到4-甲基-1,3-二氧六环(MDX)。

这一改动看似微小,效果却显著:

  • 保留弱溶剂化能力
    计算显示,DX和MDX与Na⁺的结合能仅为约−1.35 eV,远低于强溶剂化溶剂如DME(−2.33 eV),说明它们仍能让钠离子轻松脱溶。
  • 大幅提升沸点
    DX和MDX的蒸发热高于DOL,甚至超过商用碳酸酯溶剂DMC;预测饱和蒸气压也显著更低,实验证实其热稳定性更好。
  • 增强分子间作用
    通过结合能计算、扩散核磁(DOSY)和分子动力学模拟,团队证实DX和MDX分子之间存在更强的范德华力等分子间相互作用,就像分子“抱团”更紧,不易逃逸。

宽温域性能实测:−40℃照样稳定充放电

研究人员将DX与MDX按比例混合,并加入少量高沸点醚G2(提升离子电导率),配制成新型电解液(记为NaPF₆–GDX)。

结果令人振奋:

  • −40℃的极寒环境下,钠金属对称电池仍能在0.5 mA cm⁻²电流密度下稳定循环超过500小时;
  • 70℃高温下,电池无明显胀气或分解,循环稳定性优异;
  • 全电池(搭配Na₃V₂(PO₄)₃正极)在−20℃下容量保持率达90%以上,远超传统电解液体系。

更重要的是,动力学分析揭示了一个新机制:在低温下,溶剂分子之间的强相互作用会“拖住”整个溶剂化鞘层,反而增加脱溶剂化能垒。而DX/MDX恰到好处的中等分子间作用力,在保证低挥发的同时,并未显著阻碍脱溶过程——找到了性能与安全的“黄金平衡点”。


未来可期:为极端环境储能提供新思路

这项研究不仅解决了钠金属电池的宽温域难题,更提出了一个普适性策略:通过调控溶剂分子间相互作用来优化电解液性能。过去的研究多聚焦于“离子-溶剂”作用,而忽略了“溶剂-溶剂”这一隐藏变量。

该策略有望推广至锂、钾等其他金属电池体系,为电动汽车高寒地区使用、航空航天电源、深海探测设备等场景提供更安全、更可靠的储能解决方案。

如果你的手机在南极也能满电刷视频,或许就靠这样的“聪明溶剂”。你认为下一代电池最需要突破的极限是什么?欢迎留言讨论!

📚 参考文献

Mengjie He, Yunsen Liu, Zhiling Wang, Yongzhu Fu, Shuai Tang. Intermolecular interactions optimization in weakly solvating ether solvents for wide-temperature Na metal batteries. Nat. Commun., 2026. DOI: https://doi.org/10.1038/s41467-026-74051-7.

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#钠金属电池 #宽温域电池 #电解液设计 #弱溶剂化 #分子间作用力

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  1. CONNECT:[ UseTime:0.000605s ] mysql:host=127.0.0.1;port=3306;dbname=i460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.000843s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000321s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000254s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000474s ]
  6. SELECT * FROM `set` [ RunTime:0.000201s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000499s ]
  8. SELECT * FROM `article` WHERE `id` = 554342 LIMIT 1 [ RunTime:0.000777s ]
  9. UPDATE `article` SET `lasttime` = 1783888749 WHERE `id` = 554342 [ RunTime:0.016587s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 64 LIMIT 1 [ RunTime:0.000261s ]
  11. SELECT * FROM `article` WHERE `id` < 554342 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.003830s ]
  12. SELECT * FROM `article` WHERE `id` > 554342 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.002586s ]
  13. SELECT * FROM `article` WHERE `id` < 554342 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.000855s ]
  14. SELECT * FROM `article` WHERE `id` < 554342 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.005333s ]
  15. SELECT * FROM `article` WHERE `id` < 554342 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.006291s ]
0.110026s