三维锌锡合金设计稳定水系锌离子电池负极-中国粉体技术

三维锌锡合金设计稳定水系锌离子电池负极
3D Zn-Sn alloy design for stabilizing aqueous zinc⁃ion battery anodes

宋仪，李厚祯，康永超，王书华

山东大学晶体材料研究院（晶体材料全国重点实验室），山东济南 250022

摘要：【目的】为了解决水系锌离子电池循环过程中锌负极表面的腐蚀、析氢等不可控副反应和枝晶生长等问题，优化设计锌负极，抑制电池在充放电过程中的腐蚀和析氢反应，均匀锌沉积。【方法】通过多次置换反应和物理辊压制备三维锌锡合金负极；采用扫描电子显微镜和X射线衍射分析三维锌锡合金负极的结构和形貌，在三电极体系下进行电化学测试，研究三维锌锡合金负极的耐腐蚀和抑制析氢及枝晶生长能力。【结果】在电流密度为 0. 5 mA·cm^-2时，三维锌锡合金负极组装的对称电池具有 850 h 的循环寿命；在电流密度为 4 A·g^-1时，ZnSn||钒酸铵（NHVO）全电池的比容量高达182 mA·h·g^-1，循环1 000次后，比Zn||NHVO全电池的比容量高47. 2 mA·h·g^-1。【结论】三维锌锡合金作为水系锌离子电池负极，为实现耐腐蚀、无析氢和枝晶的水系锌离子电池提供了新方案。

关键词：水系锌离子电池；三维锌锡合金负极；耐腐蚀；抑制析氢；锌枝晶

Abstract

Objective Aqueous zinc-ion batteries （AZIBs） are promising candidates for developing large-scale energy storage systems dueto their inherent safety and non-flammability compared to lithium-ion batteries. However， challenges such as corrosion， hydrogen evolution， and dendrite formation hinder their cycling stability and reversibility. To address these issues， the study developed a three-dimensional （3D） Zn-Sn alloy anode， which demonstrated enhanced corrosion resistance， suppressed hydrogenevolution， and dendrite-free Zn deposition， thereby improving the overall performance of AZIBs.

Methods A 3D Zn-Sn alloy anode was fabricated through a series of steps. Firstly， a 5 mM SnF₂ solution was prepared， and the pretreated Zn foil was immersed in it for 3 min， followed by folding and rolling. After repeating the immersion and rolling process 10 times， the obtained electrode was annealed at 500 ℃ for 3 h in an argon atmosphere to obtain a 3D Zn-Sn alloy anode.

Results and Discussion X-ray diffraction （XRD） analysis confirmed the successful doping of Sn into the Zn matrix. Energydispersive spectroscopy （EDS） revealed a uniform Sn distribution with a mass fraction of 11. 31% in the Zn-Sn alloy anode.Electrochemical tests demonstrated that the Zn-Sn alloy anode exhibited a more positive corrosion potential （-0. 962 V vs.-0. 964 V） and a reduced corrosion current density （3. 89 mA·cm^-2vs. 6. 26 mA·cm^-2

）compared to the pure Zn anode， indicating better corrosion resistance. The hydrogen evolution reaction （HER） potential was reduced from -1. 762 V to -1. 819 V at 10 mA·cm^-2， indicating effective HER suppression. The nucleation and deposition behavior of Zn²⁺on the Zn-Sn alloy anode was investigated using a Zn||Cu half-cell. Cyclic voltammetry （CV） results reveal a significantly lower nucleation overpotential of 41 mV on the Zn-Sn alloy anode compared to 103 mV on the Zn anode， indicating a lower nucleation barrier. The lower barrier facilitated the uniform Zn²⁺deposition and effectively eliminated dendrite formation. Additionally， chronoamperometry（CA）analysis exhibited the advantages of uniform Zn²⁺ deposition at the 3D Zn-Sn alloy anode. It showed that Zn²⁺ on the Zn-Sn alloyanode surface transitioned more rapidly into the 3D diffusion stage， shortening the 2D diffusion process that typically leads to theformation of inhomogeneous zinc nuclei. This mechanism effectively prevented dendrite growth， thereby improving the cycling stability and reversibility of the battery. The symmetric cell with 3D Zn-Sn alloy anode reached a cycle life of 850 h at a currentdensity of 0. 5 mA·cm^-1. The Zn-Sn||Cu half-cell maintained an average coulombic efficiency （CE） of 98% after 900 cycles. Infull-cell configurations， the Zn-Sn||NHVO cell obtained a capacity of 182 mAh·g^-1at 4 A·g^-1and retained a 47. 2 mAh·g^-1 higher specific capacity than that of the Zn||NHVO cell after 1 000 cycles.

Conclusion In this paper， a 3D Zn-Sn alloy anode was prepared through a series of processes， including replacement， rolling，and annealing. The morphology， electrochemical properties， and cycling stability of the 3D Zn-Sn alloy anode were characterized and analyzed. The results demonstrated that the use of 3D Zn-Sn alloy anodes enhanced the cycle stability and reversibility of symmetric cells， half-cells， and full cells. This work provides a new approach for preparing high-performance alloy anodes，offering a promising solution to improve the anode performance of zinc-ion batteries and produce high-performance AZIBs.

Keywords：aqueous zinc-ion battery； three-dimensional Zn-Sn alloy anode； corrosion resistance； hydrogen evolution suppression； Zn dendrite

参考文献（References）

［1］HOU Z G， ZHANG X Q， CHEN J W， et al. Towards high-performance aqueous sodium ion batteries： constructing hollow NaTi₂（PO₄）₃@C nanocube anode with Zn metal-induced pre-sodiation and deep eutectic electrolyte［J］. Advanced Energy Materials，2022，12（14）：2104053.

［2］LIU Z X， WANG R， GAO Y C， et al. Low-cost multi-function electrolyte additive enabling highly stable interfacial chemical environment for highly reversible aqueous zinc ion batteries［J］. Advanced Functional Materials，2023，33（49）：2308463.

［3］LEE Y H， JEOUN Y， LEE S H， et al. Byproduct reverse engineering to construct unusually enhanced protection layers for dendrite-free Zn anode［J］. Chemical Engineering Journal，2023，464：142580.

［4］XU H T， YANG W Y， LI M， et al. Advances in aqueous zinc ion batteries based on conversion mechanism： challenges，strategies， and prospects［J］. Small，2024，20（27）：2310972.

［5］CHEN W Y， XIE Z B， CHEN H C， et al. Low-cost aqueous electrolyte with MBA additives for uniform and stable zinc deposition［J］. ACS Applied Materials & Interfaces，2024，16（23）：30580-30588.

［6］WANG J Y， YU Y， CHEN R W， et al. Induced anionic functional group orientation-assisted stable electrode-electrolyte interphases for highly reversible zinc anodes［J］. Advanced Science，2024，11（25）：2402821.

［7］TIAN H J， FENG G X， WANG Q， et al. Three-dimensional Zn-based alloys for dendrite-free aqueous Zn battery in dualcation electrolytes［J］. Nature Communications，2022，13（1）：7922.

［8］CHEN P， YUAN X H， XIA Y B， et al. An artificial polyacrylonitrile coating layer confining zinc dendrite growth for highly reversible aqueous zinc-based batteries［J］. Advanced Science，2021，8（11）：2100309.

［9］ZHANG J J， MAO L H， XIA Z G， et al. Zincophilic design for highly stable and dendrite-free zinc metal anodes in aqueous zinc-ion batteries［J］. Advanced Functional Materials，2024：2412547.

［10］ZHAO X， WANG Y， HUANG C， et al. Tetraphenylporphyrin-based chelating ligand additive as a molecular sieving interfacial barrier toward durable aqueous zinc metal batteries［J］. Angewandte Chemie International Edition，2023，62（46）：e202312193.

［11］HUANG C， ZHAO X， HAO Y S， et al. Stabilizing Zn metal anodes by 4-hydroxybenzaldehyde as the H* scavenger［J］.Energy Storage Materials，2024，65：103158.

［12］CAO J， WU H Y， ZHANG D D， et al. In⁃situ ultrafast construction of zinc tungstate interface layer for highly reversible zinc anodes［J］. Angewandte Chemie International Edition，2024，63（29）： e202319661.

［13］LI Y M， WANG Z W， LI W H， et al. Trinary nanogradients at electrode/electrolyte interface for lean zinc metal batteries［J］. Energy Storage Materials，2023，61：102873.

［14］WANG S W， ZHENG H Y， DING J W， et al. A coaxial zinc-tin vertically oriented array-based anode for achieving ultra⁃high areal current and capacity up to 80 mA·cm⁻²and 80 mA·h·cm⁻²［J］. Journal of Materials Chemistry A，2022，10（4）：1919-1927.

［15］ZHOU M， FU C Y， QIN L P， et al. Intrinsic structural optimization of zinc anode with uniform second phase for stable zinc metal batteries［J］. Energy Storage Materials，2022，52：161-168.

［16］LI J W， ZHOU S， CHEN Y N， et al. Self-smoothing deposition behavior enabled by beneficial potential compensating for highly reversible Zn-metal anodes［J］. Advanced Functional Materials，2023，33（52）：2307201.

［17］LI M， LI Z L， WANG X P， et al. Comprehensive understanding of the roles of water molecules in aqueous Zn-ion batter⁃ies： from electrolytes to electrode materials［J］. Energy & Environmental Science，2021，14（7）：3796-3839.

［18］CHEN S W， WANG H B， ZHU M Y， et al. Revitalizing zinc-ion batteries with advanced zinc anode design［J］. Nanoscale Horizons，2022，8（1）：29-54.

［19］CHEN R W， ZHANG W， HUANG Q B， et al. Trace amounts of triple-functional additives enable reversible aqueous zincion batteries from a comprehensive perspective［J］. Nano-Micro Letters，2023，15（1）：81.

［20］WANG G L， YAO Q， DONG J J， et al. In situ construction of multifunctional surface coatings on zinc metal for advanced aqueous zinc-iodine batteries［J］. Advanced Energy Materials，2024，14（5）：2303221.

［21］GUO W， ZHANG Y， TONG X， et al. Multifunctional tin layer enabled long-life and stable anode for aqueous zinc-ion bat⁃teries［J］. Materials Today Energy，2021，20：100675.

［22］DONG W T， DU M， ZHANG F， et al. In situ electrochemical transformation reaction of ammonium-anchored heptavana⁃date cathode for long-life aqueous zinc-ion batteries［J］. ACS Applied Materials & Interfaces，2021，13（4）：5034-5043.

三维锌锡合金设计稳定水系锌离子电池负极3D Zn-Sn alloy design for stabilizing aqueous zinc⁃ion battery anodes

三维锌锡合金设计稳定水系锌离子电池负极
3D Zn-Sn alloy design for stabilizing aqueous zinc⁃ion battery anodes