Halogen-bond chemistry-rectified hypervalent tellurium redox kinetics towards high-energy Zn batteries,Energy & Environmental Science

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Halogen-bond chemistry-rectified hypervalent tellurium redox kinetics towards high-energy Zn batteries
Energy & Environmental Science ( IF 32.4 ) Pub Date : 2024-12-03 , DOI: 10.1039/d4ee04806g
Jintu Qi ₁ , Yongchao Tang _{1,

2} , Yue Wei ₃ , Guigui Liu ₁ , Jianping Yan ₁ , Zhenfeng Feng ₁ , Zixin Han ₁ , Minghui Ye ₁ , Wencheng Du _{2,

4} , Qi Yang ₅ , Yufei Zhang _{1,

2} , Zhipeng Wen _{1,

2} , Xiaoqing Liu _{1,

2} , Cheng Chao Li _{1,

2}

Affiliation

Hypervalent Te redox (Te⁰/Te⁴⁺) in ionic liquid electrolytes (ILEs) is promising for energetic Zn batteries. However, the energy contribution of Te⁰/Te⁴⁺ is only one-third of the total redox-amphoteric conversion, so the contribution should be maximized for energy upgradation. The underlying kinetics-limited factor is vital but usually overlooked in previous explorations. Herein, we unlock a halogen-bond chemistry-rectified Te⁰/Te⁴⁺ redox with an almost maximized contribution for 700 W h kg_Te⁻¹ Zn batteries. The Zn–X bond barriers in ZnX₄²⁻ (X = Cl, Br) species from ILEs play crucial roles in rectifying the Te⁰/Te⁴⁺ redox kinetics, especially in localized concentrated ILEs, resulting in sharply different redox conversion depths. When ZnBr₄²⁻ with a weak Zn–Br bond (34.96 kcal mol⁻¹) is used as the activator, the Te⁰/Te⁴⁺ redox contribution can be maximized to ∼90.0% over 5000 cycles at 5 A g⁻¹, 1.8-fold higher than that with the ZnCl₄²⁻ activator via the strong Zn–Cl bond (102.81 kcal mol⁻¹), and surpassing those in most aqueous systems (ca. 33.0%). This work decodes the halogen-bond chemistry-rectified kinetics to maximize the hypervalent redox contribution towards high-energy Zn batteries, which could apply to other chalcogen conversion batteries.

中文翻译：

卤素键化学整流的高价碲氧化还原动力学对高能 Zn 电池的分析

离子液体电解质（ILE）中的高价 Te^氧化还原（Te 0/Te⁴⁺）在高能锌电池中很有前景。然而，Te⁰/Te⁴⁺ 的能量贡献仅为总氧化还原-两性转换的三分之一，因此对于能量升级，该贡献应最大化。潜在的动力学限制因素至关重要，但在以前的探索中通常被忽视。在此，我们解锁了卤素键化学整流的 Te⁰/Te⁴⁺ 氧化还原，对 700 W h kg ^Te-1 Zn 电池的贡献几乎最大。来自 LITE 的 ZnX₄²⁻ （X = Cl， Br）物种中的 Zn-X 键阻挡层在纠正 Te⁰/Te⁴⁺ 氧化还原动力学中起着至关重要的作用，尤其是在局部浓缩的 ILE 中，导致氧化还原转化深度截然不同。当使用具有弱 Zn-Br 键（34.96 kcal ^mol-1）的 ZnBr₄²⁻ 作为活化剂时，在 5 A ^g-1 下，Te⁰/Te⁴⁺ 氧化还原贡献可以在 5000 次循环中最大化至 ∼90.0%，比使用 ZnCl₄²⁻ 活化剂通过强 Zn-Cl 键（102.81 kcal mol^-1），并超过了大多数水性体系中的那些（约 33.0%）。这项工作解码卤素键化学整流动力学，以最大限度地提高高价氧化还原对高能 Zn 电池的贡献，这可能适用于其他硫族元转换电池。

更新日期：2024-12-03

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