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ADVANCED FUNCTIONAL MATERIALS · 2024 · IF 18.5

An Electrostripping Strategy for Constructing a 3D Honeycomb-Like Zn Anode Toward Dendrite-Free Zinc-Ion Batteries

Dexin Meng,Xincheng Liang,Qian Liu,Xingfa Chen,Renshu Huang,Lin Peng,Huan Wen,Shibin Yin

The severe dendrite issue of the Zn anode greatly hinders the practical application of aqueous zinc-ion batteries, which demands a prompt solution. This work proposes an electrostripping strategy using sodium citrate (SC) solution as the electrolyte to fabricate a 3D honeycomb-like Zn (3DH-Zn) anode. Theoretical calculations and experimental results reveal that SC preferentially adsorbs on the Zn(100) and Zn(101) planes and exhibits a shielding effect, leading to the major dissolution of Zn atoms from the Zn(002) plane, thus obtaining a honeycomb-like structure. Notably, convinced by morphology characterization and finite element simulation results, Zn 2+ tends to deposit on the lateral sides of the hexagonal holes on the 3DH-Zn anode, resulting in a flat deposition morphology dominated by Zn(101)/Zn(100) planes, which significantly inhibits dendrite formation. As a result, the 3DH-Zn symmetric cell achieves an ultra-long lifespan of 2000 h at 5.0 mA cm −2 and 1.0 mAh cm −2 . Besides, the 3DH-Zn||VO 2 full cell works for 1000 cycles at 1.0 A g −1 with a residual capacity of 123.1 mAh g −1 . This work opens up a new horizon for applying electrostripping strategy in designing advanced Zn anode.

研究领域: 材料科学 · 电化学 · 电池技术
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Modulating solvated structure of Zn2+ and inducing surface crystallography by a simple organic molecule with abundant polar functional groups to synergistically stabilize zinc metal anodes for long-life aqueous zinc-ion batteries

Xiaoqin Zhang,Yijun Zhai,Bin Xie,Min Li,Haoran Lang,Yi Yang,Ji Chen,Yuxiang Chen,Qiaoji Zheng,Yu Huo,Ruyi Zhao,Kwok-Ho Lam,Dunmin Lin

Aqueous zinc-ion batteries (AZIBs) have attracted significant attention owing to their inherent security, low cost, abundant zinc (Zn) resources and high energy density. Nevertheless, the growth of zinc dendrites and side reactions on the surface of Zn anodes during repeatedly plating/stripping shorten the cycle life of AZIBs. Herein, a simple organic molecule with abundant polar functional groups, 2,2,2-trifluoroether formate (TF), has been proposed as a high-efficient additive in the ZnSO 4 electrolyte to suppress the growth of Zn dendrites and side reaction during cycling. It is found that TF molecules can infiltrate the solvated sheath layer of the hydrated Zn 2+ to reduce the number of highly chemically active H 2 O molecules owing to their strong binding energy with Zn 2+ . Simultaneously, TF molecules can preferentially adsorb onto the Zn surface, guiding the uniform deposition of Zn 2+ along the crystalline surface of Zn(0   0   2). This dual action significantly inhibits the formation of Zn dendrites and side reactions, thus greatly extending the cycling life of the batteries. Accordingly, the Zn//Cu asymmetric cell with 2 % TF exhibits stable cycling for more than 3,800 cycles, achieving an excellent average Columbic efficiency (CE) of 99.81 % at 2 mA cm −2 /1 mAh cm −2 . Meanwhile, the Zn||Zn symmetric cell with 2 % TF demonstrates a superlong cycle life exceeding 3,800 h and 2,400 h at 2 mA cm −2 /1 mAh cm −2 and 5 mA cm −2 /2.5 mAh cm −2 , respectively. Simultaneously, the Zn//VO 2 full cell with 2 % TF possesses high initial capacity (276.8 mAh/g) and capacity retention (72.5 %) at 5 A/g after 500 cycles. This investigation provides new insights into stabilizing Zn metal anodes for AZIBs through the co-regulation of Zn 2+ solvated structure and surface crystallography.

研究领域: 材料科学 · 电化学 · 电池技术
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ACS Nano · 2024 · IF 15.8

Missing-Linker Defect Functionalized Metal–Organic Frameworks Accelerating Zinc Ion Conduction for Ultrastable All-Solid-State Zinc Metal Batteries

Xiaobin Hui,Zhen Zhan,Zeyu Zhang,Jingya Yu,Pengyan Jiang,Zhengzheng Dang,Jian Wang,Songhua Cai,Yanming Wang,Zheng-Long Xu

Solid-state polymer electrolytes (SPEs) are promising for high-performance zinc metal batteries (ZMBs), but they encounter critical challenges of low ionic conductivity, limited Zn2+ transference number (tZn2+), and an unstable electrolyte-electrode interface. Here, we present an effective approach involving a missing-linker metallic organic framework (MOF)-catalyzed poly(ethylene glycol) diacrylate (PEGDA)/polyacrylamide (PAM) copolymer SPE for single Zn2+ conduction and seamless electrolyte-electrode contact. The single-Zn2+ conduction is facilitated by the anchoring of the OTF– anions onto the unsaturated metal sites of missing-linker MOF, while the PEGDA and PAM chains in competitive coordination with Zn2+ ions promote rapid Zn ion transport. Our all-solid-state electrolyte simultaneously achieves a superior ionic conductivity of 1.52 mS cm–1 and a high tZn2+ of 0.83 at room temperature, alongside uniform Zn metal deposition (1000 cycles in symmetric cells) and high Zn plating/striping efficiencies (>99% after 600 cycles in asymmetric cells). Applications of our SPE in Zn//VO2 full cells are further demonstrated with a long lifespan of 2000 cycles and an extremely low-capacity degradation rate of 0.012% per cycle. This work provides an effective strategy for using a missing-linker MOF to catalyze competitively coordinating copolymers for accelerating Zn2+ ion conduction, assisting the future design of all-solid-state ZMBs.

研究领域: 材料科学 · 电化学 · 能源存储 · 电池技术
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