石榴石型Li6.4La3Zr1.4Ta0.6O12对Si/C负极表面固体电解质中间相的调控机制研究

doi:10.15541/jim20220196

无机材料学报 ›› 2022, Vol. 37 ›› Issue (7): 802-808.DOI: 10.15541/jim20220196 CSTR: 32189.14.10.15541/jim20220196

• 研究快报 • 上一篇

石榴石型Li_6.4La₃Zr_1.4Ta_0.6O₁₂对Si/C负极表面固体电解质中间相的调控机制研究

苏东良(), 崔锦, 翟朋博(), 郭向欣()

青岛大学物理科学学院, 青岛 266071

收稿日期:2022-04-07 修回日期:2022-05-15 出版日期:2022-07-20 网络出版日期:2022-05-27
通讯作者: 翟朋博, 副教授. E-mail: woshizpb@qdu.edu.cn; 郭向欣, 教授. E-mail: xxguo@qdu.edu.cn
作者简介:苏东良(1995-), 男, 硕士研究生. E-mail: 13994381640@163.com

Mechanism Study on Garnet-type Li_6.4La₃Zr_1.4Ta_0.6O₁₂ Regulating the Solid Electrolyte Interphases of Si/C Anodes

SU Dongliang(), CUI Jin, ZHAI Pengbo(), GUO Xiangxin()

College of Physics, Qingdao University, Qingdao 266071, China

Received:2022-04-07 Revised:2022-05-15 Published:2022-07-20 Online:2022-05-27
Contact: ZHAI Pengbo, associate professor. E-mail: woshizpb@qdu.edu.cn; GUO Xiangxin, professor. E-mail: xxguo@qdu.edu.cn
About author:SU Dongliang (1995-), male, Master candidate. E-mail: 13994381640@163.com
Supported by:
National Natural Science Foundation of China(U1932205);Key R&D Program of Shandong Province(2021CXGC010401);Taishan Scholars Program(ts201712035);Project of Qingdao Leading Talents in Entrepreneurship and Innovation

摘要/Abstract

摘要：

硅(Si)负极在充放电过程中巨大的体积变化会导致固态电解质中间相(SEI)破裂和硅颗粒粉化, 进而造成容量快速衰减。本研究报道了一种利用Li_6.4La₃Zr_1.4Ta_0.6O₁₂(LLZTO)固体电解质调节Si/C负极表面SEI成分的策略。将LLZTO层均匀地涂覆在商用化聚丙烯(PP)隔膜表面, 不仅提高了电解液对隔膜的润湿性, 均匀化锂离子通量, 并且增大了SEI中无机组分的比例, 从而增强Si/C负极的界面稳定性。得益于上述优势, 使用LLZTO修饰的PP隔膜所组装的锂离子电池表现出更为优异的循环稳定性和倍率性能。Li-Si/C半电池的可逆容量为876 mAh·g^-1, 在0.3C (1C=1.5 A·g^-1)的倍率下, 200次循环的容量保持率为81%; 而LFP-Si/C全电池的比容量为125 mAh·g^-1, 在0.3C (1C=170 mA·g^-1)的倍率下循环100次后容量保持率为91.8%。该工作中LLZTO固体电解质调节了Si/C负极表面SEI成分, 为开发高性能硅基锂离子电池提供了新思路。

关键词: 固体电解质中间相, 成分调控, 石榴石型固体电解质, Si/C负极, 锂离子电池

Abstract:

The large volume change of silicon anode leads to rupture of the solid electrolyte interface (SEI) and the pulverization of Si electrode during charge-discharge process, which results in uncontrolled capacity loss. In this work, a strategy to regulate the SEI composition of Si/C anodes utilizing Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) solid electrolyte was proposed. LLZTO layer is uniformly coated on the surface of polypropylene (PP) separator, which not only improves wettability of the electrolyte to the separator, thereby homogenizing the lithium-ion flux, but also increases the proportion of inorganic components in SEI and enhances the interfacial stability of Si/C anodes. As a result, Li batteries using the LLZTO coated PP separator exhibit better cycling stability and rate capability. Li-Si/C half cell exhibits a reversible capacity of 876 mAh·g^-1 with 81% capacity retention for more than 200 cycles at 0.3C (1C= 1.5 A·g^-1), and Si/C-LiFePO₄ (LFP) full cell delivers a capacity of 125 mAh·g^-1 with 91.8% capacity retention after 100 cycles at 0.3C (1C=170 mA·g^-1). This work reveals the mechanism of LLZTO solid electrolytes in regulating the SEI of Si/C anodes and sparks new ideas for developing high-performance silicon-based lithium batteries.

Key words: solid electrolyte interphase, composition regulation, garnet-type solid electrolyte, Si/C anode, lithium- ion battery

中图分类号:

TM912

苏东良, 崔锦, 翟朋博, 郭向欣. 石榴石型Li_6.4La₃Zr_1.4Ta_0.6O₁₂对Si/C负极表面固体电解质中间相的调控机制研究[J]. 无机材料学报, 2022, 37(7): 802-808.

SU Dongliang, CUI Jin, ZHAI Pengbo, GUO Xiangxin. Mechanism Study on Garnet-type Li_6.4La₃Zr_1.4Ta_0.6O₁₂ Regulating the Solid Electrolyte Interphases of Si/C Anodes[J]. Journal of Inorganic Materials, 2022, 37(7): 802-808.

图/表 16

Fig. 1 Schematic diagram of PP separator coated by LLZTO

Fig. 2 Structural characterization of PP-10 μm-LLZTO separator (a) XRD patterns of LLZTO powder, bare PP separator, PVDF and PP-10 μm-LLZTO separator; (b) Optical photos of PP-10 μm-LLZTO separator; (c) Photograph of LLZTO-PVDF slurry after stirring; (d) SEM image of LLZTO powder; (e) Cross-sectional SEM image of PP separator; (f) Top-view and (g) cross-sectional SEM images of PP-10 μm-LLZTO separator; Electrolyte contact angles of (h) PP and (i) PP-10 μm-LLZTO separators

Fig. S1 (a) SEM image and corresponding EDS elemental mapping of Si/C particles, (b) EDS spectrum of Si/C particles

Fig. 3 Electrochemical performance of Li-Si/C half cells (a) CV curves of the initial 5 cycles of half-cell using PP-10 μm-LLZTO separator; (b) Rate tests of half-cells using PP and PP-10 μm-LLZTO separators; (c) Charge-discharge curves of Li/Si half-cell using PP-10 μm-LLZTO separator; (d) Stability tests of Li/Si half-cells using PP and PP-10 μm-LLZTO separators with different thicknesses; (e) EIS spectra of half-cells with PP and PP-10 μm-LLZTO separators before cycling. Colorful figures are available on website

Fig. S2 Charge-discharge curves of Li-Si/C half-cell using PP separator

Fig. S3 Cross-sectional SEM images of PP-6 μm-LLZTO separator

Fig. S4 Cross-sectional SEM images of PP-12 μm-LLZTO separator

Fig. S5 Stability test of Li-Si/C half-cell using PP-PVDF separator

Fig. S6 (a) Top-view and (b) cross-sectional SEM images of the Si/C anode of the Li|PP-10 μm-LLZTO|Si/C half-cell after 10 cycles

Fig. S7 Cross-sectional SEM images of (a) Si/C anode, (b) PP-10 μm-LLZTO separator, (c) Si/C anode, (d) PP-10 μm-LLZTO separator after charge

Fig. S8 Equivalent circuit model of bare PP half-cell and PP-10 μm-LLZTO half-cell

Table S1 Bulk resistance and ionic conductivity of PP and PP-10 μm-LLZTO separators

Separator	Bulk resistance/Ω	Interfacial resistance/Ω
Bare PP	3.3	525.5
PP-10 μm-LLZTO	7.0	149.1

Fig. S9 (a, c) C1s and (b, d) F1s for SEI of the half-cells with (a, b) PP and (c, d) PP-10 μm-LLZTO separators after 100 cycles

Fig. S10 CV curves of initial 3 cycles of the LFP|PP-10 μm-LLZTO|Si/C full cell

Fig. S12 Charge-discharge curves of LFP|PP|Si/C full cell

参考文献 28

[1]	LI K, HU X, ZHANG Z, et al. Three-dimensional porous biogenic Si/C composite for high performance lithium-ion battery anode derived from equisetum fluviatile. Journal of Inorganic Materials, 2021, 36(9): 929-935. DOI URL
[2]	CERVERA R B, SUZUKI N, OHNISHI T, et al. High performance silicon-based anodes in solid-state lithium batteries. Energy & Environmental Science, 2014, 7(2): 662-666.
[3]	FENG M Y, TIAN J H, LIU Y Y, et al. Effect of silicon anode additives on lithium ion batteries. Journal of Inorganic Materials, 2015, 30(6): 647-652. DOI URL
[4]	OZANAM F, ROSSO M. Silicon as anode material for Li-ion batteries. Materials Science and Engineering: B, 2016, 213: 2-11. DOI URL
[5]	SUNG J, KIM N, MA J, et al. Subnano-sized silicon anode via crystal growth inhibition mechanism and its application in a prototype battery pack. Nature Energy, 2021, 6(12): 1164-1175. DOI URL
[6]	HUANG X, SUI X, YANG H, et al. HF-free synthesis of Si/C yolk/shell anodes for lithium-ion batteries. Journal of Materials Chemistry A, 2018, 6(6): 2593-2599. DOI URL
[7]	LIU Y, BAI H, ZHAO Q, et al. Storage aging mechanism of LiNi_0.8Co_0.15Al_0.05O₂/graphite Li-ion batteries at high state of charge. Journal of Inorganic Materials, 2021, 36(2): 175-180. DOI URL
[8]	MENG X L, HUO H Y, GUO X X, et al. Influence of film thickness on the electrochemical performance of α-SiO_x thin-film anodes. Journal of Inorganic Materials, 2018, 33(10): 1141-1146. DOI URL
[9]	OHTA N, KIMURA S, SAKABE J. et al. Anode properties of Si nanoparticles in all-solid-state Li batteries. ACS Applied Energy Materials, 2019, 2(10): 7005-7008. DOI URL
[10]	HA J, PAIK U. Hydrogen treated, cap-opened Si nanotubes array anode for high power lithium ion battery. Journal of Power Sources, 2013, 244: 463-468. DOI URL
[11]	KIM H, SEO M, PARK M H, et al. A critical size of silicon nano-anodes for lithium rechargeable batteries. Angewandte Chemie International Edition, 2010, 49(12): 2146-2149. DOI URL
[12]	CHAN C K, PENG H, LIU G, et al. High-performance lithium battery anodes using silicon nanowires. Nature Nanotechnology, 2008, 3(1): 31-35. DOI URL
[13]	WEN Z, LU G, MAO S, et al. Silicon nanotube anode for lithium-ion batteries. Electrochemistry Communications, 2013, 29: 67-70. DOI URL
[14]	ZHANG H, ZONG P, CHEN M, et al. In situ synthesis of multilayer carbon matrix decorated with copper particles: enhancing the performance of Si as anode for Li-ion batteries. ACS Nano, 2019, 13(3): 3054-3062. DOI URL
[15]	WANG G X, AHN J H, YAO J, et al. Nanostructured Si-C composite anodes for lithium-ion batteries. Electrochemistry Communications, 2004, 6(7): 689-692. DOI URL
[16]	SHEN T, XIA X H, XIE D, et al. Encapsulating silicon nanoparticles into mesoporous carbon forming pomegranate- structured microspheres as a high-performance anode for lithium ion batteries. Journal of Materials Chemistry A, 2017, 5(22): 11197-11203. DOI URL
[17]	DU F M, ZHAO N, LI Y Q, et al. All solid state lithium batteries based on lamellar garnet-type ceramic electrolytes. Journal of Power Sources, 2015, 300: 24-28. DOI URL
[18]	ZHAO C Z, CHEN P Y, ZHANG R, et al. An ion redistributor for dendrite-free lithium metal anodes. Science Advances, 2018, 4(11): eaat3446.
[19]	HUO H, LI X, CHEN Y, et al. Bifunctional composite separator with a solid-state-battery strategy for dendrite-free lithium metal batteries. Energy Storage Materials, 2020, 29: 361-366. DOI URL
[20]	LIANG T CAO, J H, LIANG W H, et al. Asymmetrically coated LAGP/PP/PVDF-HFP composite separator film and its effect on the improvement of NCM battery performance. RSC Advances, 2019, 9(70): 41151-41160. DOI URL
[21]	ZHOU X, YIN Y X, WAN L J, et al. Self-assembled nanocomposite of silicon nanoparticles encapsulated in graphene through electrostatic attraction for lithium-ion batteries. Advanced Energy Materials, 2012, 2(9): 1086-1090. DOI URL
[22]	YAO Y, MCDOWELL M T, RYU I, et al. Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life. Nano Letters, 2011, 11(7): 2949-2954. DOI URL
[23]	DHANABALAN A, SONG B F, BISWAL S L, et al. Extreme rate capability cycling of porous silicon composite anodes for lithium- ion batteries. ChemElectroChem, 2021, 8(17): 3318-3325. DOI URL
[24]	ZHANG X, WENG S, YANG G, et al. Interplay between solid-electrolyte interphase and (in) active Li_xSi in silicon anode. Cell Reports Physical Science, 2021, 2(12): 100668.
[25]	LIU J Y, GAO X W, HARTLEY G O, et al. The interface between Li_6.5La₃Zr_1.5Ta_0.5O₁₂ and liquid electrolyte. Joule, 2020, 4(1): 101-108. DOI URL
[26]	JAUMANN T, BALACH J, KLOSE M, et al. SEI-component formation on sub 5 nm sized silicon nanoparticles in Li-ion batteries: the role of electrode preparation, FEC addition and binders. Physical Chemistry Chemical Physics, 2015, 17(38): 24956-24967. DOI URL
[27]	LI Y JIN, B, WANG K, et al. Coordinatively-intertwined dual anionic polysaccharides as binder with 3D network conducive for stable SEI formation in advanced silicon-based anodes. Chemical Engineering Journal, 2022, 429: 132235.
[28]	LÜ L, WANG Y, HUANG W, et al. The effect of cathode type on the electrochemical performance of Si-based full cells. Journal of Power Sources, 2022, 520: 230855.

石榴石型Li_6.4La₃Zr_1.4Ta_0.6O₁₂对Si/C负极表面固体电解质中间相的调控机制研究

Mechanism Study on Garnet-type Li_6.4La₃Zr_1.4Ta_0.6O₁₂ Regulating the Solid Electrolyte Interphases of Si/C Anodes

RichHTML

PDF (PC)