亲锌聚阴离子交联聚合物薄膜与铜刻蚀协同稳定锌负极

doi:10.6023/A24010006

摘要/Abstract

可充电水系锌基电池具有高容量、高能量密度、低氧化还原电位、低成本、安全性好等优点, 被认为是一种可替代的能源存储器件. 然而, 在镀锌/剥离过程中, 锌金属负极不可控的枝晶生长和复杂的副反应极大地降低了库伦效率, 其可逆性较差, 阻碍锌基电池的实际应用. 在此, 开发了一种简单、可控且有效的方法, 首先利用电化学沉积法在锌箔上沉积了一种由聚苯乙烯磺酸钠(PSS)与氯化锌反应得到孔道丰富的聚阴离子交联聚合物薄膜(记为PZ, 其中P代表PSS、Z代表ZnCl₂), 然后再利用置换反应引入亲锌的化学惰性金属铜, 得到亲锌聚阴离子交联聚合物与铜刻蚀保护层(记为PZC, 其中C代表Cu). PZC@Zn具有丰富的磺酸根官能团促进[Zn(H₂O)₆]²⁺脱溶, 提高Zn²⁺界面传输速率, 排斥SO₄^2-与锌负极接触. 通过重建铜刻蚀层, 铜的高亲锌性促进了沉积动力学, 铜的化学惰性抑制了副反应的发生. 结果表明, 在5 mA•cm^-2的高电流密度下, PZC@Zn//PZC@Zn对称电池寿命高达4055 h(比裸锌对称电池提高了31倍), 累积电镀容量达到10.14 Ah•cm^-2, Ti//PZC@Zn半电池库伦效率(CE)为98.28%, 可以实现稳定且可逆的镀锌/剥离. YP-50F//PZC@Zn锌离子混合超级电容器在2 A•g^-1下稳定循环15000次, 放电比容量高达82.35 mAh•g^-1. α-MnO₂//PZC@Zn水系锌离子电池在1 A•g^-1下循环2000次后放电比容量高达103.57 mAh•g^-1, CE为99.58%. 这项工作为设计先进的无枝晶锌金属负极提供了一种新方法.

关键词: 电化学沉积, 薄膜, 铜刻蚀, 脱溶, 无枝晶锌负极

Rechargeable aqueous zinc-based batteries offer several advantages, including high capacity, high energy density, low redox potential, low cost-effectiveness, and good safety, making them a viable option for energy storage alternatives. However, the dendrite growth and side reactions on the zinc metal anode during the galvanization/stripping process significantly decrease the Coulombic Efficiency (CE), reversibility and hinder their practical application. Therefore, we have developed a simple, and effective method to solve this problem. Firstly, a polyanionic crosslinked polymer film (referred to as PZ, where P represents PSS and Z represents ZnCl₂) was deposited on zinc foil using an electrochemical deposition method, resulting from the reaction of sodium polystyrene sulfonate (PSS) and zinc chloride. Secondly, a displacement reaction is employed to introduce the chemically inert copper metal that is zinophilic, resulting in a cross-linked polymer with zinophilic polyanion and a copper etching protective layer (denoted as PZC, where C represents Cu). The rich sulfonate acid groups can promote the exsolution of [Zn(H₂O)₆]²⁺, improve the interface transfer of Zn²⁺, and repel the contact between SO₄^2- and the zinc anode. Through reconstructing the copper etching protective layer, the high zinc affinity of copper promotes deposition kinetics, while the chemical inertness of copper suppresses the occurrence of side reactions. The results indicate that at a high current density of 5 mA•cm^-2, PZC@Zn//PZC@Zn symmetric cells have a lifespan of up to 4055 h (31-fold enhancement over the performance of the bare zinc symmetric cells), and a cumulative electroplating capacity of 10.14 Ah•cm^-2. In addition, Ti//PZC@Zn half-cell demonstrates a CE of 98.28%, showcasing stable and reversible galvanization/stripping process. Furthermore, the YP-50F//PZC@Zn zinc-ion hybrid supercapacitor display stable cycling performance with 15000 cycles at 2 A•g^-1 and deliver a discharge specific capacity of up to 82.35 mAh•g^-1. The α-MnO₂//PZC@Zn aqueous zinc-ion batteries exhibit a discharge-specific capacity of 103.57 mAh•g^-1 after 2000 cycles at 1 A•g^-1 with a CE of 99.58%. This study gives a novel approach to design advanced dendrite-free zinc metal anodes and presents promising implications for future development.

Key words: electrochemical deposition, membrane, copper etching, exsolution, dendrite-free Zn anode

引用此文

郝再涛, 赵健飞, 李慧同, 李展, 潘朗, 李江. 亲锌聚阴离子交联聚合物薄膜与铜刻蚀协同稳定锌负极[J]. 化学学报, 2024, 82(4): 416-425.

Zaitao Hao, Jianfei Zhao, Huitong Li, Zhan Li, Lang Pan, Jiang Li. Stable Zinc Anodes through Synergistic Copper Etching and Zincophilic Polyanionic Crosslinking Membrane[J]. Acta Chimica Sinica, 2024, 82(4): 416-425.

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图/表 8

图1. PZC@Zn电极的制备方案示意图

Figure 1. Synthetic scheme of PZC@Zn electrodes

图2. (a)裸锌、(b) PZ@Zn和(c) PZC@Zn的SEM图与相应的接触角测试图; (d) PZC@Zn的SEM图与(e~g)相应的元素映射图; (h) PZ@Zn和(i) PZC@Zn的SEM截面图; (j)裸锌、PZ@Zn和PZC@Zn的XRD图

Figure 2. SEM images and corresponding contact angle measurements images of (a) Bare Zn, (b) PZ@Zn and (c) PZC@Zn; (d) SEM images of PZC@Zn and (e~g) corresponding element mappings; cross-sectional SEM of (h) PZ@Zn and (i) PZC@Zn; (j) XRD patterns of Bare Zn, PZ@Zn and PZC@Zn

图3. (a) PZ@Zn的XPS测量扫描光谱和(b) C 1s、(c) S 2p、(d) Zn 2p高分辨率XPS光谱; (e) PZC@Zn的XPS测量扫描光谱和(f) Cu 2p高分辨率XPS光谱

Figure 3. (a) XPS survey scan spectra and high-resolution XPS spectra for (b) C 1s, (c) S 2p, and (d) Zn 2p of PZ@Zn; (e) XPS survey scan spectra and high-resolution XPS spectra for (f) Cu 2p of PZC@Zn

图4. 裸锌、PZ@Zn和PZC@Zn对称电池的循环性能和选定循环下的电压分布: (a) 0.5 mA?cm-2, 0.25 mAh?cm-2; (b) 5 mA?cm-2, 1 mAh?cm-2. (c) 固定容量为1 mAh?cm-2的倍率性能; (d) PZC@Zn负极与一些以前报道的负极的循环性能和电流密度的比较

Figure 4. Cycling performance and voltage profiles at selected cycles of the Bare Zn, PZ@Zn and PZC@Zn symmetric cells: (a) 0.5 mA?cm-2, 0.25 mAh?cm-2; (b) 5 mA?cm-2, 1 mAh?cm-2. (c) Rate performance at a fixed capacity of 1 mAh?cm-2; (d) comparison of cycle performance and current densitiy of the PZC@Zn anodes with some previously reported anodes

图5. 裸锌、PZ@Zn和PZC@Zn对称电池的(a)电化学阻抗(Electrochemical Impedance Spectroscopy, EIS)曲线、(b)塔菲尔极化曲线、(c)计时电流曲线、(d)使用阿伦尼乌斯方程计算脱溶能图、(e)在5 mA?cm-2下沉积锌的电压-容量曲线和(f)不同电流密度下的锌成核过电位图

Figure 5. (a) EIS curves, (b) Tafel polarization curves, (c) chronoamperometry curves, (d) exsolution energy calculated by Arrhenius equation, (e) voltage-capacity curves for Zn deposition at 5 mA?cm-2 and (f) Zn nucleation overpotentials at different current densities of the Bare Zn, PZ@Zn and PZC@Zn symmetric cells

图6. (a, c, e)裸锌、PZ@Zn和PZC@Zn对称电池在3 mA?cm-2, 1 mAh?cm-2下不同循环次数后的SEM图和(b, d, f)相应的XRD结果

Figure 6. (a, c, e) SEM images and (b, d, f) corresponding XRD results of the Bare Zn, PZ@Zn and PZC@Zn anodes with different numbers of cycle at 3 mA?cm-2 with 1 mAh?cm-2

图7. (a) Ti//Bare Zn、Ti//PZ@Zn和Ti//PZC@Zn半电池在1 mA?cm-2, 0.5 mAh?cm-2下镀锌/剥离的库伦效率; (b) Ti//PZC@Zn半电池的电压分布; (c)在1 mA?cm-2下的电压-时间曲线; (d)在1 mV?s-1下的CV曲线; (e) 40次循环后的SEM图和(f)相应的XRD图

Figure 7. (a) CEs of Zn plating/stripping for Ti//Bare Zn, Ti//PZ@Zn and Ti//PZC@Zn half-cells at 1 mA?cm-2 with 0.5 mAh?cm-2; (b) voltage profiles of Ti//PZC@Zn half-cells; (c) voltage-time curves at 1 mA?cm-2; (d) CV curves at 1 mV?s-1; (e) SEM images after 40 cycles test and (f) corresponding XRD images

图8. YP-50F//Bare Zn、YP-50F//PZ@Zn和YP-50F//PZC@Zn锌离子混合超级电容器(a)在80 mV?s-1下的CV曲线和(b) EIS谱; (c) YP-50F//PZC@Zn锌离子混合超级电容器的电压-容量曲线; YP-50F//Bare Zn、YP-50F//PZ@Zn和YP-50F//PZC@Zn锌离子混合超级电容器的(d)倍率性能、(e)长期循环性能和(f) 4000次循环后的SEM图; (g) YP-50F//PZC@Zn锌离子混合超级电容器点亮的“CHD”LED灯牌

Figure 8. (a) CV curves at 80 mV?s-1 and (b) EIS curves of YP-50F//Bare Zn, YP-50F//PZ@Zn and YP-50F//PZC@Zn ZHSCs; (c) voltage-capacity curves of YP-50F//PZC@Zn ZHSCs; (d) rate performance, (e) long-term cycling performance and (f) SEM images after 4000 cycles test of YP-50F//Bare Zn, YP-50F//PZ@Zn and YP-50F//PZC@Zn ZHSCs; (g) “CHD” LED lit by the YP-50F//PZC@Zn ZHSCs

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