非化学计量 Cu2-xSe 作为水系锌离子电池阳极的相工程,ACS Nano

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非化学计量 Cu2-xSe 作为水系锌离子电池阳极的相工程
ACS Nano ( IF 15.8 ) Pub Date : 2023-09-14 , DOI: 10.1021/acsnano.3c06361
Jianbo Li ₁ , Yibin Ren ₁ , Zhen Li ₁ , Yunhui Huang ₁

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水系锌离子电池（AZIBs）因其资源丰富、材料成本低、安全性高等优点而受到广泛关注。然而，锌金属阳极对腐蚀和析氢的敏感性限制了其进一步的实际应用。用插层型负极材料代替金属锌并构建摇椅型电池可能是显着延长AZIBs循环寿命的有效方法。在这里，我们通过简单的氧化还原反应呈现出具有不同晶相结构的硒化铜作为AZIBs的阳极。通过比较和分析不同的硒化铜相，发现立方Cu _{2– x} Se表现出优异的结构稳定性和高度可逆的Zn ²⁺存储。理论计算结果进一步表明，立方Cu _{2– x} Se具有更高的电导率、更高的Zn ²⁺吸附能和更低的扩散势垒，从而促进Zn ²⁺离子的储存可逆性和（脱）插动力学。因此，Cu _{2– x} Se 阳极具有超过 15000 次循环的长期使用寿命和令人印象深刻的累积容量。_{此外，用MnO 2} /CNT阴极组装的全电池在6 mA cm ^–2和负/正（N/P）容量比约为1.53的情况下稳定运行超过1500个循环。这项工作提供了一种更理想的无锌金属阳极，有助于推动AZIBs的实际应用。

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Phase Engineering of Nonstoichiometric Cu2–xSe as Anode for Aqueous Zn-Ion Batteries

Aqueous zinc-ion batteries (AZIBs) are receiving widespread attention due to their abundant resources, low material cost, and high safety. However, the susceptibility of Zn metal anodes to corrosion and hydrogen evolution limits their further practical applications. Replacing Zn metal with intercalation-type anode material and constructing rocking-chair-type batteries could be an effective way to significantly prolong the cycle life of AZIBs. Herein, we present copper selenide with different crystal phase structures through a facile redox reaction as an anode for AZIBs. By comparing and analyzing different copper selenide phases, it is found that the cubic Cu_2–xSe shows superior structural stability and highly reversible Zn²⁺ storage. Theoretical calculation results further demonstrate that the cubic Cu_2–xSe possesses an increased electrical conductivity, higher Zn²⁺ adsorption energy, and reduced diffusion barrier, thereby promoting the storage reversibility and (de)intercalation kinetics of the Zn²⁺ ion. Thus, the Cu_2–xSe anode delivers a long-term service life of over 15 000 cycles and impressive cumulative capacity. Furthermore, the full-cells assembled with the MnO₂/CNT cathode operate stably for over 1500 cycles at 6 mA cm^–2 at a negative/positive (N/P) capacity ratio of ∼1.53. This work provides a more ideal Zn-metal-free anode, which helps to push the practical applications of AZIBs.

更新日期：2023-09-14

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