<p>Crystallographic engineering of Zn anodes to favor the exposure of (002) planes is an effective approach for improving stability in aqueous electrolytes. However, achieving non-epitaxial electrodeposition with a pronounced (002) texture and maintaining this orientation during extended cycling remains challenging. This study questions the prevailing notion that a single (002)-textured Zn anode inherently ensures superior stability, showing that such anodes cannot sustain their texture in ZnSO<sub>4</sub> electrolytes. We then introduced a novel electrolyte additive, benzyltriethylammonium chloride (TEBAC), which preserves the (002) texture over prolonged cycling. Furthermore, we successfully converted commercial Zn foils into highly crystalline (002)-textured Zn without any pretreatment. Experiments and theoretical calculations revealed that the cationic TEBA<sup>+</sup> selectively adsorbs onto the anode surface, promoting the exposure of the Zn(002) plane and suppressing dendrite formation. A critical discovery was the pitting corrosion caused by chloride ions from TEBAC, which we mitigated by anion substitution. This modification leads to a remarkable lifespan of 375 days for the Zn||Zn symmetric cells at 1&#xa0;mA&#xa0;cm<sup>−2</sup> and 1&#xa0;mAh&#xa0;cm<sup>−2</sup>. Furthermore, a TEBA<sup>+</sup>-modified Zn||VO<sub>2</sub> full cell demonstrates high specific capacity and robust cycle stability at 10.0&#xa0;A&#xa0;g<sup>−1</sup>. These results provide valuable insights and strategies for developing long-life Zn ion batteries.</p>

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Breaking Performance Limits of Zn Anodes in Aqueous Batteries by Tailoring Anion and Cation Additives

  • Zhaoxu Mai,
  • Yuexing Lin,
  • Jingying Sun,
  • Chenhui Wang,
  • Gongzheng Yang,
  • Chengxin Wang

摘要

Crystallographic engineering of Zn anodes to favor the exposure of (002) planes is an effective approach for improving stability in aqueous electrolytes. However, achieving non-epitaxial electrodeposition with a pronounced (002) texture and maintaining this orientation during extended cycling remains challenging. This study questions the prevailing notion that a single (002)-textured Zn anode inherently ensures superior stability, showing that such anodes cannot sustain their texture in ZnSO4 electrolytes. We then introduced a novel electrolyte additive, benzyltriethylammonium chloride (TEBAC), which preserves the (002) texture over prolonged cycling. Furthermore, we successfully converted commercial Zn foils into highly crystalline (002)-textured Zn without any pretreatment. Experiments and theoretical calculations revealed that the cationic TEBA+ selectively adsorbs onto the anode surface, promoting the exposure of the Zn(002) plane and suppressing dendrite formation. A critical discovery was the pitting corrosion caused by chloride ions from TEBAC, which we mitigated by anion substitution. This modification leads to a remarkable lifespan of 375 days for the Zn||Zn symmetric cells at 1 mA cm−2 and 1 mAh cm−2. Furthermore, a TEBA+-modified Zn||VO2 full cell demonstrates high specific capacity and robust cycle stability at 10.0 A g−1. These results provide valuable insights and strategies for developing long-life Zn ion batteries.