高杨氏模量细菌纤维素隔膜有效抑制锂枝晶

doi:10.6023/A24040141

化学学报 ›› 2024, Vol. 82 ›› Issue (8): 849-855.DOI: 10.6023/A24040141 上一篇下一篇

研究论文

高杨氏模量细菌纤维素隔膜有效抑制锂枝晶

苑志祥^a^,^b^,^c^,^d, 张雅岚^b^,^c^,^d, 张浩^b^,^c^,^d, 张仕杰^b^,^c^,^d, 王朵^b^,^c^,^d, 张波涛^a^,^*(), 张建军^b^,^c^,^d^,^*(), 崔光磊^b^,^c^,^d^,^*()

a 青岛大学化学化工学院青岛 266071
b 中国科学院青岛生物能源与过程研究所青岛储能产业技术研究院青岛 266101
c 山东能源研究院青岛 266101
d 青岛新能源山东省实验室青岛 266101

投稿日期:2024-04-22 发布日期:2024-06-26
基金资助:
山东省重大科技创新工程(2022CXGC020301); 国家自然科学基金面上项目(52073298); 国家自然科学基金面上项目(52273221); 中国科学院青年创新促进会(2020217); 青岛新能源山东省实验室开放课题(QNESL OP202312)

Bacterial Cellulose Separator with High Young's Modulus Effectively Inhibits Lithium Dendrites

Zhixiang Yuan^a^,^b^,^c^,^d, Yalan Zhang^b^,^c^,^d, Hao Zhang^b^,^c^,^d, Shijie Zhang^b^,^c^,^d, duo Wang^b^,^c^,^d, Botao Zhang^a^,^*(), Jianjun Zhang^b^,^c^,^d^,^*(), Guanglei Cui^b^,^c^,^d^,^*()

a School of Chemistry and Chemical Engineering, Qingdao University, Qingdao 266071
b Qingdao Industrial Energy Storage Research Institute, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101
c Shandong Energy Institute, Qingdao 266101
d Qingdao New Energy Shandong Laboratory, Qingdao 266101

Received:2024-04-22 Published:2024-06-26
Contact: * E-mail: botaozhang@qdu.edu.cn; zhang_jj@qibebt.ac.cn; cuigl@qibebt.ac.cn; Tel.: 0532-80662746; Fax: 0532-80662744
Supported by:
Key Scientific and Technological Innovation Project of Shandong(2022CXGC020301); National Natural Science Foundation of China(52073298); National Natural Science Foundation of China(52273221); Youth Innovation Promotion Association of CAS(2020217); Qingdao New Energy Shandong Laboratory Open Project(QNESL OP202312)

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1. Supporting Information-A24040141.pdf(1055KB)

摘要/Abstract

隔膜是锂电池的重要组成部分, 其作用尤为重要. 然而, 现有聚烯烃基隔膜对电解液润湿性差, 而且尺寸热稳定性较差, 尤其是其杨氏模量较低无法有效抑制锂枝晶的生长, 严重限制了其在锂金属电池中的应用. 为了解决这些问题, 设计制备出一种具有高杨氏模量、尺寸热稳定性优异、对电解液浸润性好的细菌纤维素隔膜. 实验结果表明, 该细菌纤维素隔膜具有高拉伸强度(144 MPa)、高杨氏模量(8.1 GPa)和优异的尺寸热稳定性(≥300 ℃). 使用该细菌纤维素隔膜并匹配传统有机碳酸酯类电解液的Li/Li对称电池, 可以在0.52 mA•cm⁻²的电流密度以及1.56 mAh•cm⁻²的面容量下实现4000 h的稳定循环. 如此优异的性能归因于该隔膜具有的高杨氏模量以及其可以促进锂金属电极表面形成稳定的固态电解质界面层. 可以预见, 该细菌纤维素隔膜是一种非常有前途的可适用于高能量密度锂金属电池的新型隔膜.

关键词: 细菌纤维素隔膜, 高杨氏模量, 抑制锂枝晶, 锂金属电池, 界面化学

Separators play a critical role in isolating anodes and cathodes for lithium battery. However, commercialized polyolefin-based separators often suffered from poor electrolyte wettability, inferior dimentionally thermal stability, especially the low Young's modulus of polyolefin-based separators cannot effectively inhibit the growth of lithium dendrites, which limits their large-scale practical application in lithium metal batteries. Therefore, a novel separator with high Young's modulus which can be applied to lithium metal batteries is urgently needed. Bacterial cellulose is a porous, nanoscale biopolymer, which is synthesized mainly by micro-organisms such as bacillus xylosus. Compared with plant-derived cellulose, bacterial cellulose exhibits high crystallinity, high thermal stability, high electrolyte absorption, high porosity, and excellent mechanical strength. Considering the above advantages, bacterial cellulose-based bacterial cellulose separators have the potential to be effectively suited in lithium metal batteries. Herein, we demonstrate a novel kind of bacterial cellulose separator. Firstly, the structure of the prepared bacterial cellulose separator is characterized using scanning electron microscopy (SEM), atomic force microspocy (AFM) and X-ray diffraction (XRD), which shows a three-dimensional interpenetrating network structure, suggesting that it is favourable for achieving wetting of the electrolyte and providing more ionic conduction pathways. In addition, this bacterial cellulose separator with high Young's modulus, excellent dimentionally thermal stability and outstanding electrolyte wettability was prepared by a sample process. It is demonstrated that the resultant separator exhibits excellent mechanical strength (144 MPa), high Young's modulus (8.1 GPa) and superior thermal dimentionally stability (≥300 ℃). Meanwhile, Li/Li cells using this bacterial cellulose separator and conventional organic carbonate-based electrolyte can achieve a steady lithium plating/stripping behavior over 4000 h at a current rate of 0.52 mA•cm⁻² and 1.56 mAh•cm⁻². Such improved reliability is chiefly attributed to the high Young's modulus of bacterial cellulose separator and the formed stable solid electrolyte interphase (SEI) which rich in inorganic components such as boron oxides, LiF and Li₂O. More intriguingly, this separator delivers an excellent cycling performance in LiFePO₄/Li battery, stable cycling for 100 cycles with a low capacity loss at 1 C. These fascinating characteristics indicate this separator is a promising material for high-energy-density lithium metal batteries.

Key words: bacterial cellulose separator, high Young's modulus, lithium dendrite inhibition, lithium metal battery, interfacial chemistry

引用此文

苑志祥, 张雅岚, 张浩, 张仕杰, 王朵, 张波涛, 张建军, 崔光磊. 高杨氏模量细菌纤维素隔膜有效抑制锂枝晶[J]. 化学学报, 2024, 82(8): 849-855.

Zhixiang Yuan, Yalan Zhang, Hao Zhang, Shijie Zhang, duo Wang, Botao Zhang, Jianjun Zhang, Guanglei Cui. Bacterial Cellulose Separator with High Young's Modulus Effectively Inhibits Lithium Dendrites[J]. Acta Chimica Sinica, 2024, 82(8): 849-855.

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图/表 5

图1. 细菌纤维素隔膜的(a)表面SEM图像, (b)截面SEM图像, (c)三维AFM图像(高度)和(d)二维XRD图像

Figure 1. (a) Typical SEM image, (b) cross-section SEM image, (c) 3D AFM image (height) and (d) 2D XRD pattern of bacterial cellulose separator

图2. (a) PP隔膜和细菌纤维素隔膜的应力-应变曲线. (b)细菌纤维素隔膜的3D AFM图像(DMT模量). (c) PP隔膜和细菌纤维素隔膜的DSC曲线. (d)细菌纤维素隔膜在25, 50, 100, 150和200 ℃下的XRD谱. PP隔膜和细菌纤维素隔膜的(e)接触角测试和(f)电解液浸润测试

Figure 2. (a) Stress-strain curves of PP separator and bacterial cellulose separator. (b) 3D AFM image (DMT Modulus) of bacterial cellulose separator. (c) DSC curves of PP separator and bacterial cellulose separator. (d) XRD patterns of bacterial cellulose separator at 25, 50, 100, 150 and 200 ℃. (e) Contact angel test and (f) electrolyte immersion characterization of PP separator and bacterial cellulose separator

图3. PP隔膜和细菌纤维素隔膜的(a)电化学阻抗谱和(b)线性扫描伏安曲线. (c)使用PP隔膜和细菌纤维素隔膜组装的锂/锂对称电池在0.52 mA?cm?2 (1.56 mAh?cm?2)下的时间电压曲线

Figure 3. (a) Electrochemical impedance spectroscopy and (b) linear sweep voltammetry obtained for PP separator and bacterial cellulose separator. (c) Time-voltage profiles of Li/Li symmetric cells assembled with PP separator and bacterial cellulose separator at 0.52 mA?cm?2 (1.56 mAh?cm?2)

图4. 原始锂负极的(a)数码照片, (b)截面SEM图像和(c)表面SEM图像. 使用PP隔膜循环500 h后的锂负极的(d)数码照片, (e)截面SEM图像和(f)表面SEM图像. 使用细菌纤维素隔膜循环4000 h后的锂负极的(g)数码照片, (h)截面SEM图像和(i)表面SEM图像

Figure 4. (a) Digital photograph, (b) cross-section SEM image and (c) top SEM image of initial lithium electrode. (d) Digital photograph, (e) cross-section SEM image and (f) top SEM image of lithium electrode in contact with PP separator after 500 h cycling. (g) Digital photograph, (h) cross-section SEM image and (i) top SEM image of lithium electrode in contact with bacterial cellulose separator after 4000 h cycling

图5. 使用PP隔膜(a~c)和细菌纤维素隔膜(d~f)的Li/Li对称电池在经过长时间循环后的锂负极的B 1s、C 1s和Li 1s的XPS光谱. (g)使用PP隔膜和细菌纤维素隔膜的锂沉积/剥离过程的示意图

Figure 5. XPS spectra of B 1s, C 1s, and Li 1s of Li metal from symmetric Li/Li cells using (a~c) PP separator and (d~f) bacterial cellulose separator after long cycling. (g) Schematic diagrams of Li deposition/striping process with PP separator and bacterial cellulose separator

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高杨氏模量细菌纤维素隔膜有效抑制锂枝晶

Bacterial Cellulose Separator with High Young's Modulus Effectively Inhibits Lithium Dendrites

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