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基于苯乙烯-丙烯酸橡胶胶乳粘结剂的粉状LiNiMnCoO电极在高电压下的电化学性能

Electrochemical Properties of Powdery LiNiMnCoO Electrodes with Styrene-Acrylic-Rubber-Based Latex Binders at High Voltage.

作者信息

Yin Lu, Tatara Ryoichi, Nakamoto Kosuke, Yamazaki Shogo, Takaishi Rena, Shiiyama Eisuke, Matsuyama Takashi, Komaba Shinichi

机构信息

Department of Applied Chemistry, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku, Tokyo 162-8601, Japan.

NIPPON A&L INC, 3-1-98 Kasugadenaka, Konohanaku, Osaka 554-8558, Japan.

出版信息

ACS Appl Mater Interfaces. 2024 Dec 11;16(49):67577-67586. doi: 10.1021/acsami.4c11185. Epub 2024 Nov 25.

Abstract

Efforts to improve the energy density and cycling stability of lithium-ion batteries have focused on replacing LiCoO in cathodes with LiNiMnCoO. However, reliance on polyvinylidene fluoride (PVdF) as the binder limits the application of the LiNiMnCoO composite electrode for lithium-ion batteries. Here, we evaluate the electrochemical properties of a LiNiMnCoO (NMC111) powder electrode formed using a waterborne-styrene-acrylic-rubber (SAR) latex binder combined with sodium carboxymethylcellulose. The composite electrodes prepared with the SAR-based binder copolymerized with the butyl acrylate monomer and styrene exhibited high adhesive strength and excellent cyclability and rate capability. The results of surface analysis via X-ray photoelectron spectroscopy suggested that the electrode with the SAR-based binder is more resistant to electrolyte decomposition during charge and discharge cycling compared with the NMC111 electrode comprising the conventional PVdF binder. The SAR-derived passivation resulted in enhanced capacity retention during long-term cycling tests of both half- and full-cells (NMC111//graphite). An electrode with a higher Ni content, LiNiMnCoO (NMC622), fabricated using the SAR-based binder, retained 87.1% of its capacity after 50 cycles at 4.6 V and exhibited excellent cycling stability.

摘要

提高锂离子电池能量密度和循环稳定性的努力主要集中在使用LiNiMnCoO替代阴极中的LiCoO。然而,依赖聚偏二氟乙烯(PVdF)作为粘合剂限制了LiNiMnCoO复合电极在锂离子电池中的应用。在此,我们评估了使用水性苯乙烯 - 丙烯酸 - 橡胶(SAR)胶乳粘合剂与羧甲基纤维素钠组合形成的LiNiMnCoO(NMC111)粉末电极的电化学性能。用与丙烯酸丁酯单体和苯乙烯共聚的基于SAR的粘合剂制备的复合电极表现出高粘合强度、优异的循环性能和倍率性能。通过X射线光电子能谱进行的表面分析结果表明,与包含传统PVdF粘合剂的NMC111电极相比,基于SAR粘合剂的电极在充放电循环过程中对电解质分解更具抗性。SAR衍生的钝化作用导致在半电池和全电池(NMC111//石墨)的长期循环测试中容量保持率提高。使用基于SAR的粘合剂制造的具有较高镍含量的电极LiNiMnCoO(NMC622)在4.6 V下50次循环后保留了其87.1%的容量,并表现出优异的循环稳定性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1958/11647888/78e1958765c1/am4c11185_0001.jpg

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