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

doi:10.6023/A24040141

Acta Chimica Sinica ›› 2024, Vol. 82 ›› Issue (8): 849-855.DOI: 10.6023/A24040141 Previous Articles Next Articles

Article

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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Abstract

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

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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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Fig. & Tab. 5

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

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

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)

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

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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