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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Tuning Li Nucleation by a Hybrid Lithiophilic Protective Layer for High-Performance Lithium Metal Batteries

Kaixin Zhao,Lirong Zhang,Qi Jin,Junpeng Xiao,Lili Wu,Xitian Zhang

Lithium (Li) metal has been recognized as the most promising anode material for next-generation rechargeable batteries. However, the practical application of Li anodes is hampered by the growth of Li dendrites. To address this issue, a robust and uniform Sb-based hybrid lithiophilic protective layer is designed and built by a facile in situ surface reaction approach. As evidenced theoretically and experimentally, the as-prepared hybrid protective layer provides outstanding wettability and fast charge-transfer kinetics. Moreover, the lithiophilic Sb embedded in the protective layer provides a rich site for Li nucleation, which effectively reduces the overpotential and induces uniform Li deposition. Consequently, the symmetric cell exhibits a long lifespan of over 1600 h at 1 mA cm–2 and 1 mAh cm–2 with a low voltage polarization. Furthermore, excellent cycling stability is also obtained in Li–S full cells (60% capacity retention in 800 cycles at 1 C) and Li||LFP full cells (74% capacity retention in 500 cycles at 5 C). This work proposed a facile but efficient strategy to stabilize the Li metal anode.

研究领域: 材料科学 · 电化学
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ELECTROCHIMICA ACTA · 2024 · IF 5.5

Self-assembled monolayer regulates lithium nucleation and growth for stable lithium metal anodes

Shuchen Huang,Chunfeng Meng,Haopeng Chen,Zichuang Jiao,Jian Qiu,Hao Zhu,Fengjian Shi,Aihua Yuan,Hu Zhou

As the “holy grail” anode material for next-generation lithium batteries, the application of lithium metal has been long hindered due to the uncontrolled dendrites. Organic polymer coatings have shown advantages in regulating the ion diffusion and reducing the surface energy of the substrate, with which large lithium nucleis and better cycle stability can be obtained, whereas the electronic insulation property of the thick polymer is adverse for lithium deposition. Hence, self-assembled monolayers (SAMs) are anchored onto the surface of planar copper via a spontaneous thiol-to-copper reaction to obtain the modified current collectors with lower surface energy. The electron/ion transfer and lithiophilicity of the planar copper are adjusted by changing the length of the alkyl length and the ending groups. Therefore, lithium nucleation and growth behaviors are regulated, and large dough-like nucleis are generated on the planar copper grafted with 3-mercaptopropionic acid (Cu-MPA), displaying a nucleation overpotential of 17.6 mV and a reversible Coulombic efficiency of 98.4 % over 250 cycles (0.5 mA cm −2 , 1 mAh cm −2 ). This strategy provides a new avenue to achieve a stable Cu/Li interface and lithium metal anodes since the very beginning of the lithium nucleation.

CAS / MDL: 107-96-0 107-03-9
研究领域: 材料科学 · 电化学
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Understanding the anchoring effect on Li plating with Indium Tin oxide layer functionalized hosts for Li metal anodes

Xiaolin Yan,Fangjun Ye,Yinggan Zhang,Liang Lin,Baisheng Sa,Fang Liu,Junjie Li,Laisen Wang,Jie Lin,Qingshui Xie,Dong-Liang Peng

Li dendrites caused by nonuniform Li plating and locally concentrated ion/electron flux would give rise to poor cycling performance and safety issues of short-circuit and so on. Herein, a functional nanolayer consisting of Indium Tin oxide (ITO) nanoparticles on 3D Cu foam was fabricated as case study to understand the mechanism of metal oxides on anchoring Li metal spots and how initial Li nucleation influences the following dendrites growth. Based on the experimental and theoretical results, it is demonstrated that not only the pristine metal oxides have higher binding energy with Li atom, but also in situ formed alloy phase during alloying process performs a great importance on homogeneous nucleation, thus leading to ordered ion/electron distribution and fast kinetics. Therefore, excellent wettability and even self-propagation behavior between ITO-Cu foam and molten Li are achieved, meanwhile the half cells with ITO-Cu foam electrodes exhibit an ultralow nucleation overpotential of 2 mV under 0.5 mA cm −2 . When the designed ITO-Cu foam@Li anodes is matched with LFP (LiFePO 4 ) cathodes, the constructed full cells can empower superior cycling stability for over 1000 cycles at 5C (3.4 mA cm −2 ), and remarkable specific capacity (149 mAh g −1 ) and capacity retention (80% for 250 cycles) even with ultrahigh mass loading (15.3 mg cm −2 ), which provides an avenue to regulate Li deposition/dissolution for high energy Li metal batteries.

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米科技 · 金属电池
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

One-stone, two birds: One step regeneration of discarded copper foil in zinc battery for dendrite-free lithium deposition current collector

Ting-Ting Lin,Qian Zhang,Xu Zhang,Peng-Jun Ma,Juan Yang,Jiang-Tao Chen,Bing-Jun Yang,Zheng-Yang Xie,Hui Li,Bao Liu

The ever-growing requirement for electrochemical energy storage has exacerbated the production of spent batteries, and the recycling of valuable battery components has recently received a remarkable attention. Among all battery components, copper foil is widely utilized as a current collector for stable zinc platting and stripping in zinc metal batteries (ZMBs) due to the perfect lattice matching of between metal copper and zinc, which is accompanied by the formation of multiple copper-zinc alloy components during the cycling process. Herein, a novel “two birds with one-stone” strategy through a one simple heat treatment step to revive the discarded copper foil in zinc metal battery is reported to further obtain a lithiophilic current collector (Cu x Zn y -Cu) with multiple copper-zinc alloy components on the surface of the discarded copper foil. Such revived Cu x Zn y -Cu current collector greatly reduces the lithium nucleation overpotential and realizes uniform lithium deposition and further inhibits lithium dendrites growth. The formed multiple Cu x Zn y alloy phases on the surface of discarded copper foil exhibit a low Li nucleation overpotential of only 15 mV at 0.5 mA cm −2 for the first cycle. Moreover, such a Cu x Zn y -Cu current collector could achieve stable cycle for 220 cycles at 0.5 mA cm −2 and 110 cycles at 1 mA cm −2 with a Li plating capacity of 1 mAh cm −2 . Theoretical calculations indicate that, compared with pure Cu foil, the formed multiple alloy components of CuZn 5 , CuZn 8 , Cu 0.61 Zn 0.39 and CuZn have low adsorption energy of −2.17, −2.55, −2.16 and −2.35 eV with lithium atoms, respectively, which result in reduced lithium nucleation overpotential. The full cell composed of Cu x Zn y alloy current collector with deposition of 5 mAh cm −2 metal Li anode coupled with LiFePO 4 (LFP) cathode exhibits a reversible capacity of 125.6 mAh/g after 110 cycles at a current of 0.5 C with capacity retention of 85.1 %. This work proposed a promising strategy to regenerate the discarded copper foil in rechargeable batteries.

研究领域: 材料科学 · 电化学 · 能源存储 · 电池回收
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Energy Storage Materials · 2021 · IF 17.789

Spatial confinement of vertical arrays of lithiophilic SnS2 nanosheets enables conformal Li nucleation/growth towards dendrite-free Li metal anode

Dan Xie,Huan-Huan Li,Wan-Yue Diao,Ru Jiang,Fang-Yu Tao,Hai-Zhu Sun,Xing-Long Wu,Jing-Ping Zhang

The development of next-generation lithium metal batteries (LMBs) has been chronically hindered by uncontrollable dendrite growth and infinite dimension change of metal Li. Even though the porous carbon skeletons have been deemed as effective hosting materials to prepare low-stress Li metal anode (LMA), the lithiophobic feature and poor spatial regulation for Li nucleation/growth of carbon skeletons render the achievement of high-stable LMA to be challenging. Herein, vertical-aligned SnS 2 nanosheet arrays (SnS 2 NSA) with intrinsic lithiophilic nature, endowed by in situ formed Li 13 Sn 5 via the alloying reaction of SnS 2 , are uniformly decorated on highly flexible carbon foam (SnS 2 NSA@CF) to overcome the encountered issues of ordinary carbon skeletons. The vertical-aligned SnS 2 nanosheet offers enriched lithiophilic surface area, thereby guiding the thin Li-nuclei layer uniformly deposited on nanosheet. Moreover, the continuous Li growth is proceeded on the initial Li-nuclei layer and spatially confined into the nanochannels of nanoarray to eliminate the volume change of LMA. The well-defined nanochannel effectively reduces the local current density and provides open spacing for quick charge transfer kinetics. Accordingly, the sustainable Li utilization with high Coulombic efficiency and highly stable Li plating/stripping with low polarization is achieved, shedding light on the feasibility of SnS 2 NSA for dendrite-free LMA.

研究领域: 材料科学 · 能源存储 · 电池技术 · 纳米技术
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ACS Applied Energy Materials · 2022 · IF 6.959

Regulating Lithium-Ion Transference Number of a Poly(vinyl alcohol)-Based Gel Electrolyte by the Incorporation of H3BO3 as an Anion Trapper

Lei Wang,Jiawei Yan,Min Zhong,Jiali Zhang,Wenzhuo Shen,Shouwu Guo

Gel electrolytes hold great promise for improving the safety of lithium-ion batteries (LIBs); however, their low lithium-ion transference number (tLi+ < 0.4) remains to be improved. Herein, boron-containing poly(vinyl alcohol) (B-PVA) solutions are prepared based on the simple reaction between PVA and H3BO3 and then electrospun to obtain the B-PVA nanofiber matrices. The gel electrolytes are formed by loading the liquid electrolytes into the as-obtained porous B-PVA matrices. We demonstrate that the tLi+ of B-PVA8 (with 8 wt % H3BO3 added) gel electrolyte can reach 0.81, much higher than that of the conventional PVA gel electrolyte (0.32). The B-PVA8 gel electrolyte also shows the highest Li+ conductivity of 1.81 × 10–3 S cm–1 compared to PVA. The B-PVA8 gel electrolyte enables a small Li nucleation overpotential of 129.8 mV when Li is plated and reduces the concentration polarization of Li||Li batteries. The mesocarbon microbead (MCMB) half-coin cells with the B-PVA8 gel electrolyte exhibit excellent rate capability and exceptional charge/discharge cycling stability.

CAS / MDL: 9002-89-5
研究领域: 材料科学 · 电化学 · 电池技术
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