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南京大学金钟Nature子刊:比纸还薄锌碘电池!

  • 2026-04-16 03:08:03
南京大学金钟Nature子刊:比纸还薄锌碘电池!

比纸还薄!-40℃80℃通吃:纳米相分离深共晶水凝胶电解质让锌碘电池循环36000

6μm超薄、4.1 MPa高强度、28.2 mS/cm高电导——三合一设计破解柔性电池世纪难题

柔性可穿戴电子设备的蓬勃发展,对电池提出了严苛要求:既要薄如纸片,又要安全柔韧,还要在极寒酷暑下稳定工作。传统水凝胶电解质虽然安全,但长期受困于不可能三角:机械强度、离子电导率和宽温域适应性难以兼得。厚了能量密度低,薄了又容易破损;自由水多了低温会冻结,少了离子又跑不动。

今天,南京大学金钟、李承辉团队在《Nature Communications》上发表的一项研究《Thinner-than-paper and broad-temperature-adaptive zinc-iodine batteries enabled by nanophase separated deep-eutectic hydrogel electrolytes》,用纳米相分离+深共晶溶剂+氢键网络三重协同策略,打造了一款比纸还薄的深共晶水凝胶电解质deep-eutectic-HE),一举突破了所有瓶颈:

  • 厚度仅6 μm(比A4纸薄55%),却能吊起2.2 kg重物
  • 断裂强度4.1 MPa,韧性13.66 MJ/m³
  • 离子电导率28.2 mS/cm20℃),-40℃仍达1.7 mS/cm
  • Zn²⁺迁移数0.65(远超液态对照组的0.36-0.38
  • Zn||I₂电池:室温36000圈容量保持75.28%-40℃保持92.31%80℃保持81.00%
  • 软包电池能量密度108.99 Wh/kg,可弯折、剪裁、折叠后仍正常供电

01 设计思路:三根支柱撑起一片天

研究团队的设计理念是三管齐下

支柱一:纳米相分离结构

通过溶剂交换法,将亲水的聚乙烯醇(PVA)和疏水的聚丙烯腈(PAN)在纳米尺度上自发形成双相分离结构(图1d-e)。亲水相贡献吸水保水能力,疏水相提供力学骨架。两相尺寸仅10-30 nm,远低于可见光波长,因此电解质透明且光学透过率>90%。这种纳米限域结构还大幅提升了力学性能:断裂应变752%、弹性模量1.84 MPa、韧性13.66 MJ/m³(图2a-b)。最薄可制成6 μm膜,却能吊起2.2 kg重物(图2c-d)。

1 | 设计、制备与表征a)通过溶剂交换过程制备深共晶水凝胶电解质的流程图。(b-c)(bATR-FTIR和(c)不同电解质及对照样品的拉曼光谱。(d-g)深共晶水凝胶电解质的(dSEM图像、(eAFM图像、(fXRD图谱和(gSAXS图谱。(g)中的插图为深共晶水凝胶电解质的2D SAXS图案。

2 | 力学性能与温度耐受性a-b)(a)拉伸应变曲线,(b)弹性模量和韧性。(b)中误差棒表示标准差。(c-d)厚度为6 μm的深共晶水凝胶电解质提起重物的照片。(e-f)不同电解质在(e)低温和(f)高温范围内的DSC曲线。(g)深共晶水凝胶电解质和非共晶水凝胶电解质的G'G''随温度的变化。(h-i)(hMD模拟快照和(i)对应的Zn²⁺溶剂化结构。(j-l)通过MD模拟计算的各种电解质中(j)水分子之间的氢键数量、(kRDF和配位数以及(lZn²⁺扩散系数。

支柱二:深共晶溶剂化

在电解质中加入氨基甲酸酯(UR),与Zn(ClO₄)₂和水形成深共晶体系。UR-NH-C=O基团与水、ClO₄⁻形成密集氢键网络,大幅降低自由水含量(图2j)。MD模拟显示,深共晶体系使Zn²⁺第一溶剂化壳层的水配位数从6降至3以下(图2k),离子扩散系数提升9倍(图2l)。同时,PAN链上的氰基(-C≡N)为Zn²⁺提供快速迁移通道,协同作用实现高离子电导率和高迁移数。

支柱三:氢键网络锁定水分子

URH₂OClO₄⁻之间的氢键网络将水分子锚定在聚合物网络中,抑制冰晶成核和高温蒸发。DSC显示,deep-eutectic-HE-40℃以下无结晶峰,80℃以上无吸热峰(图2e-f)。水保持率在25℃/15% RH48小时仍达88.4%

02 性能:全方位碾压

离子电导率与迁移数(图3a-b):

  • 20℃28.2 mS/cmdeep-eutectic-LE11.0,非共晶HE8.0
  • -40℃:仍保持1.7 mS/cm
  • Zn²⁺迁移数:0.62-0.68(深共晶LE0.36-0.38

界面阻抗(图3c):Zn|deep-eutectic-HE|Zn电池界面阻抗仅238 Ω,远低于其他对照组(466-664 Ω)。

锌沉积调控(图4):

  • 成核过电位42.6 mV vs 深共晶LE66.5 mV(降低35.9%
  • 传质过电位22.0 mV vs 46.4 mV(降低52.6%
  • 库仑效率(Aurbach法):98.47% vs 96.99%
  • XRD显示Zn(002)晶面强度提升40.97%Zn沿水平方向择优生长,无枝晶(图4e-g

宽温域对称电池循环(图3f-h):

  • 20℃:稳定循环超3600小时
  • -40℃:仍能稳定循环
  • 80℃:同样稳定

3 | 电化学性能a-c)不同温度下深共晶水凝胶电解质、深共晶液体电解质、非共晶水凝胶电解质和非共晶液体电解质的(a)离子电导率、(bZn²⁺迁移数和(c)界面阻抗。(c)中的点、线和插图为实验数据、拟合结果和等效电路。(d-h)(d)倍率性能、(eTafel曲线以及(f20℃、(g-40℃和(h80℃Zn||Zn对称电池的恒流循环稳定性。(i)深共晶水凝胶电解质与近期报道的其他水凝胶电解质在断裂强度、离子电导率、电化学窗口和低/高温耐受性方面的性能比较。

4 | 锌电镀/剥离行为a-b)分别使用深共晶水凝胶电解质和深共晶液体电解质组装的Zn||Cu半电池的(a)电位-时间曲线和(b)放大视图。(c-d)分别使用深共晶水凝胶电解质和深共晶液体电解质组装的Zn||Cu半电池的(c)初始锌沉积过程中的电压曲线和(dCV曲线。(e-g)从Zn||Zn对称电池中回收的锌电极在锌电镀/剥离后的(eXRD图谱以及使用(f)深共晶水凝胶电解质和(g)非共晶液体电解质的SEM图像。

03 全电池:36000圈奇迹

Zn||I₂电池(图5b-e):

  • 倍率性能:10 A/g下容量保持率99.80%(回到0.5 A/g时)
  • 室温5 A/g36,000,容量保持75.28%,平均衰减仅0.0007%/
  • -40℃ 5 A/g36,000圈,容量保持92.31%
  • 80℃ 5 A/g36,000圈,容量保持81.00%
  • I₂载量(4-5 mg/cm²):初始144.32 mAh/g88.35%保持率
  • 自放电(静置24h):容量保持93.50%(深共晶LE80.37%

软包电池(图5f):

  • 多层堆叠(11层负极,10层正极)
  • 能量密度:108.99 Wh/kg(基于整个软包总质量),体积能量密度189.41 Wh/L
  • V₂O₅正极配合,能量密度76.89 Wh/kg,体积能量密度236.62 Wh/L

柔性展示(图S26-29):

  • 电池可反复180°折叠成纸飞机,仍正常供电
  • 剪刀剪碎后仍能点亮LED
  • 三节串联集成到表带中,为手表供电;为智能手机充电

5 | 锌金属电池的电化学性能a)基于深共晶水凝胶电解质的比纸还薄的Zn||I₂电池的结构示意图。(b)在0.510 A/g电流密度下,Zn||深共晶水凝胶电解质||I₂Zn||深共晶液体电解质||I₂电池的倍率性能(N/P18.50-55.50)。(c-e)在不同温度下,以5 A/g电流密度循环的Zn||I₂电池的长期循环稳定性:(c20℃、(d-40℃和(e80℃N/P18.50-55.50)。(fZn||深共晶水凝胶电解质||I₂Zn||深共晶水凝胶电解质||V₂O₅与近期报道的其他锌金属电池在比能量和体积能量密度方面的比较。

04 机理:为什么这么能抗低温?

传统水凝胶低温失效的原因是自由水结冰,阻断离子通道。deep-eutectic-HE通过三重机制解决:

  1. UR与水的氢键UR-NH-C=OH₂O形成强氢键,破坏冰晶成核所需的规整水分子排列(MD模拟显示氢键数量显著降低,图2j)。
  2. 纳米限域10-30 nm的相分离孔道将水分子限制在纳米空间内,冰点大幅下降。
  3. 高盐浓度Zn(ClO₄)₂浓度高,ClO₄⁻作为离液阴离子,进一步扰乱水分子氢键网络。

高温稳定性则源于氢键网络和纳米孔道对水分子的锚定,抑制了蒸发和结构塌陷。

05 普适性验证

除了I₂正极,团队还组装了Zn||V₂O₅软包电池,同样获得优异性能(图5f),证明该电解质体系具有普适性,不局限于特定正极材料。

06 结语

这项研究通过纳米相分离+深共晶溶剂+氢键网络的协同设计,将水凝胶电解质的厚度、强度、电导率、温域、循环寿命等看似矛盾的性能指标统一到了一起。

正如论文通讯作者金钟所言:

通过分子设计、相调控和工艺工程的协同整合,我们建立了一个可行的方法论框架,用于开发兼具高能量密度和恶劣环境耐受性的先进柔性电池。

6 μm的超薄厚度到36000圈的循环寿命,从-40℃的极寒到80℃的高温,这款深共晶水凝胶电解质为柔性可穿戴电子设备提供了真正实用的能源解决方案。

论文信息Shen, T., Chen, ZJ., Yang, Y. et al. Thinner-than-paper and broad-temperature-adaptive zinc-iodine batteries enabled by nanophase separated deep-eutectic hydrogel electrolytes. 

Nat. Commun. (2026). https://doi.org/10.1038/s41467-026-71312-3

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  1. CONNECT:[ UseTime:0.000651s ] mysql:host=127.0.0.1;port=3306;dbname=b460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.000924s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000363s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000323s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000522s ]
  6. SELECT * FROM `set` [ RunTime:0.000204s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000553s ]
  8. SELECT * FROM `article` WHERE `id` = 530614 LIMIT 1 [ RunTime:0.001724s ]
  9. UPDATE `article` SET `lasttime` = 1776647943 WHERE `id` = 530614 [ RunTime:0.006371s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 65 LIMIT 1 [ RunTime:0.000266s ]
  11. SELECT * FROM `article` WHERE `id` < 530614 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.000545s ]
  12. SELECT * FROM `article` WHERE `id` > 530614 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.000546s ]
  13. SELECT * FROM `article` WHERE `id` < 530614 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.000722s ]
  14. SELECT * FROM `article` WHERE `id` < 530614 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.000728s ]
  15. SELECT * FROM `article` WHERE `id` < 530614 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.000926s ]
0.086814s