华中科技大学闫春泽、方淳，CEJ：快离子传输网络增强型三维锌负极改善锌离子电池性能

快离子传输网络增强型三维锌负极改善锌离子电池性能

探索了三维结构设计对离子扩散-成核行为的影响，从而实现致密均匀的沉积形貌。

3D锌粉负极内的Zn(OTF)₂-PEO水凝胶组分构建了3D离子传输网络，实现了负极内的快速离子传输。

通过构建三维连续富F的SEI层，减轻了比表面积增大导致的腐蚀问题，进一步提高了3D Zn-M负极的电化学性能。

近日，来自华中科技大学的闫春泽教授与方淳副教授合作，在知名期刊Chemical Engineering Journal上发表题为“Fast ion transport network enhanced 3D Zn anode for ultra-stable zinc ion batteries”的文章，提出了一种通过三维结构设计和成分改性来稳定锌负极的改性策略。

作者通过3D打印技术制备了具有快速离子输运网络的3D Zn负极来调节Zn离子的沉积模式。3D结构设计有助于探索几何约束对离子扩散-成核行为的影响，验证成核理论的边界条件，从而实现致密均匀的沉积形貌。在三维锌粉电极内的Zn(OTF)₂-PEO水凝胶组分构建了三维离子传输网络。水凝胶网络通过降低表面能来优化成核过程，从而解决由于表面积增加而引起的腐蚀问题。

图1 3D打印锌基负极示意图

Fig.1. Schematic illustrations of 3D printed Zn based anodes.

图2 (a)锌负极的表面自由能。(b) Zn²⁺电沉积过程的时间-电压曲线。(c)电位为-150 mV时Zn-M和Zn-P负极的i-t曲线（vs. Zn/ Zn²⁺）。(d)离子传导模式示意图。(e) (e1) 2D和（e2） 3D离子扩散过程示意图。(f)二维锌负极和锌电沉积（f1）前（f2）后、三维锌负极和锌电沉积（f3）前（f4）后的电极形貌及对应的锌离子浓度。(g)二维锌负极和锌电沉积（g1）前（g2）后、三维锌负极和锌电沉积（g3）前（g4）后的电极形貌和空间电位。

Fig. 2. (a) Surface free energies of Zn anodes. (b) time-voltage curve during electro-deposition of  Zn²⁺. (c) i-t curves of Zn-M and Zn-P anodes with a potential of -150 mV (vs. Zn/ Zn²⁺). (d) Schematic diagram of ion conduction mode. (e) Schematic illustrations of (e1) 2D and (e2) 3D ion diffusion process. (f) electrode morphology and the corresponding zinc ion concentration of 2D Zn anode (f1) before and (f2) after Zn electrodeposition, 3D anode (f3) before and (f4) after Zn electrodeposition. (g) electrode morphology and the space potential of 2D Zn anode (g1) before and (g2) after Zn electrodeposition, 3D anode (g3) before and (g4) after Zn electrodeposition.

图3 (a)扫描速率为1 mV s^-1的三电极系统在ZnSO₄电解液中测量Zn负极的Tafel图；(b) ZnSO₄电解质中Zn负极的析氢极化曲线。(c)基于Zn//Cu电池和对Zn沉积过程的全面理解的可逆镀锌/剥离行为，（d-f）不同循环下对应的电压分布图；

Fig. 3. (a) The Tafel plots of Zn anodes measured in the ZnSO₄ electrolytes using three-electrode system at a scan rate of 1 mV s^-1; (b) Hydrogen evolution polarization curves for Zn anodes in the ZnSO₄ electrolytes. (c) Reversible Zn plating/stripping behaviors based on Zn//Cu cells and comprehensive understanding for the process of Zn deposition, and (d-f) corresponding voltage profiles at various cycles;

Tafel极化曲线，LSV测试等证明了Zn的腐蚀抑制作用。三维结构表面积的增加使反应活性增加，导致三维Zn-P、三维Zn-M电极的腐蚀电流增大。Zn(OTF)₂-PEO的加入有效地降低了腐蚀电流。

图4 （a-b）基于Zn//Zn的可逆镀锌/剥离行为。（c-f） (c) 3D Zn-M, (d) 2D Zn-P, (e) 2D Zn-M, (f) 1 mA cm^-2电流密度100h下3D Zn-P负极沉积的SEM图。(g)沉积/剥离100h后Zn负极的XRD图谱。(h)对称电池的长期循环性能与最近出版的论文中报道的性能比较。

Fig. 4. (a-b) Reversible Zn plating/stripping behaviors based on Zn//Zn. (c-f) SEM images of (c) 3D Zn-M, (d) 2D Zn-P, (e) 2D Zn-M, (f) 3D Zn-P anodes deposits at current density of 1 mA cm^-2 of 100h. (g) XRD patterns of Zn anode after 100h plating/stripping. (h) Comparison of long-term cycling performance of symmetrical batteries with the performance reported in recent publications.

图5 Zn-NH₄V₄O₁₀电池性能。(a) 2 A g^-1电流密度下的循环稳定性。(b)不同循环时间的GCD曲线和 (c) 0.1、0.2、1、2和5 A g^-1不同电流密度下的倍率容量。(d) 1000次循环后Zn负极的XRD图。(e)循环后电池的DRT图。（f-i）激光扫描共聚焦显微镜循环(f) 2D Zn-P, (g) 2D Zn-M, (h) 3D Zn-P, (i) 3D Zn-M负极和（j-p）相应的粗糙度曲线。

Fig. 5. Performance comparison of Zn-NH₄V₄O₁₀ cells. (a) cycling stabilities comparison under a current density of 2 A g^-1. (b) GCD curves of different cycling time and (c) Rate capacities under different current densities of 0.1, 0.2, 1, 2 and 5 A g^-1. (d) Ex-situ XRD patterns of Zn anode after 1000 cycles. e) DRT plots of cycled anodes. (f-i) Laser scanning confocal microscope images of cycled (f) 2D Zn-P, (g) 2D Zn-M, (h) 3D Zn-P, (i) 3D Zn-M anodes and (j-p) corresponding roughness curve.

图6（a-b）循环1000次后锌负极的XPS光谱。(c) ZnF₂和硫氧化物在SEI膜中的TOF-SIMS深度分布图。(d) TOF-SIMS中氟化物和硫氧化物的三维视图。

Fig. 6. (a-b) XPS spectra of Zn anodes after 1000 cycles. (c) the TOF-SIMS depth profiles for ZnF₂ and sulfur oxide in SEI film. (d) The 3D views of fluoride and sulfur oxide in the TOF-SIMS sputtered volumes.

Fast ion transport network enhanced 3D Zn anode for ultra-stable zinc ion batteries

https://doi.org/10.1016/j.cej.2025.159895

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