Citation: Hanmei Lü, Xin Chen, Qifu Sun, Ning Zhao, Xiangxin Guo. Uniform Garnet Nanoparticle Dispersion in Composite Polymer Electrolytes[J]. Acta Physico-Chimica Sinica, ;2024, 40(3): 230501. doi: 10.3866/PKU.WHXB202305016 shu

Uniform Garnet Nanoparticle Dispersion in Composite Polymer Electrolytes

College of Physics, Qingdao University, Qingdao 266071, Shandong Province, China

Corresponding author: Ning Zhao, Xiangxin Guo,
Received Date: 8 May 2023
Revised Date: 6 June 2023
Accepted Date: 6 June 2023

Fund Project: The project was supported by the Key R&D Program of Shandong Province (2021CXGC010401) and the National Natural Science Foundation of China (U1932205, 52002197).

Solid-state lithium batteries (SSLBs) have the potential to further boost the energy density of Li-ion batteries and improve their safety by facilitating the use of Li-metal anodes and limiting flammability, respectively. Solid electrolytes, as key SSLB materials, significantly impact battery performance, among which composite polymer/garnet electrolytes are promising materials for manufacturing SSLBs on a large scale, owing to polymer electrolyte processing ease in combination with the thermal stabilities and high ionic conductivities of garnet electrolytes, both of which are beneficial. Uniformly dispersing garnet particles in the polymer matrix is important for ensuring a highly ionically conductive composite polymer electrolyte. However, high nanoparticle surface energies and incompatible organic–inorganic interfaces lead to garnet particle agglomeration in the polymer matrix and a poorly ionically conductive composite electrolyte. With the aim of promoting Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) particle dispersion in both solvents and polymer matrices, in this study, we introduced the 3-glycidyloxypropyl trimethoxy silane (GPTMS) coupling agent onto the LLZTO surface. A 5-nm-thick GPTMS shell was constructed on each LLZTO nanoparticle by covalently bonding GPTMS molecules on the surface of the nanoparticle. The lipophilic epoxy group in GPTMS enables the uniform dispersion of GPTMS-modified LLZTO nanoparticles (LLZTO@GPTMS) in organic solvents, such as acetonitrile, N-methylpyrrolidone, and N,N-dimethylformamide. Particle-size-distribution experiments reveal that LLZTO-nanoparticle dispersity is positively correlated with solvent polarity. Well-dispersed LLZTO suspensions led to superior polyethylene-oxide-based (PEO-based) composite polymer electrolyte ionic conductivities of 2.31 × 10^-4 S·cm^-1 at 30 °C. Both symmetric lithium batteries and SSLBs that use LiFePO₄ (LFP) cathodes, lithium-metal anodes, and the optimal PEO: LLZTO@GPTMS electrolyte exhibited prolonged cycling lives. Moreover, the polyethylene separator was homogeneously coated with LLZTO nanoparticles following GPTMS modification. LFP|Li batteries with LLZTO@GPTMS-coated PE separators exhibited better cycling stabilities than those of batteries with unmodified LLZTO/PE. This study demonstrated that GPTMS effectively improves LLZTO-nanoparticle dispersibility in both organic solvents and polymer matrices, which is also instructive for other organic–inorganic composite systems.
- Solid-state Li battery,
- Garnet electrolyte,
- Composite solid electrolyte,
- Silane coupling agent,
- Nanoparticle dispersion
1. [1]
  (1) Zhao, N.; Khokhar, W.; Bi, Z. J.; Shi, C.; Guo, X. X.; Fan, L. Z.; Nan, C. W. Joule 2019, 3 (5), 1190. doi:10.1016/j.joule.2019.03.019
2. [2]
  (2) Bi, Z. J.; Mu, S.; Zhao, N.; Sun, W. H.; Huang, W. L.; Guo, X. X. Energy Storage Mater. 2021, 35, 512. doi:10.1016/j.ensm.2020.11.038
3. [3]
4. [4]
  (4) Hu, X.; Zuo, D.; Cheng, S.; Chen, S.; Liu, Y.; Bao, W.; Deng, S.; Harris, S. J.; Wan, J. Chem. Soc. Rev. 2023, 52 (3), 1103. doi:10.1039/D2CS00322H
5. [5]
  (5) Mi, J.; Ma, J.; Chen, L.; Lai, C.; Yang, K.; Biao, J.; Xia, H.; Song, X.; Lv, W.; Zhong, G.; et al. Energy Storage Mater. 2022, 48, 375. doi:10.1016/j.ensm.2022.02.048
6. [6]
  (6) Li, W. K.; Zhao, N.; Bi, Z. J.; Guo, X. X. Appl. Phys. Lett. 2022, 121 (3), 7. doi:10.1063/5.0098255
7. [7]
  (7) Chen, X.; Jia, Z. Q.; Lv, H. M.; Wang, C. G.; Zhao, N.; Guo, X. X. J. Power Sources 2022, 545, 6. doi:10.1016/j.jpowsour.2022.231939
8. [8]
  (8) Li, W. K.; Zhao, N.; Bi, Z. J.; Guo, X. X. J. Inorg. Mater. 2022, 37 (2), 189. doi:10.15541/jim20210486
9. [9]
10. [10]
  (10) Tufail, M. K.; Zhai, P.; Jia, M.; Zhao, N.; Guo, X. Energy Mater. Adv. 2023, 4, 0015. doi:10.34133/energymatadv.0015
11. [11]
  (11) Zhai, P. B.; Yang, Z. L.; Wei, Y.; Guo, X. X.; Gong, Y. J. Adv. Energy Mater. 2022, 12 (42), 13. doi:10.1002/aenm.202200967
12. [12]
  (12) Chen, L. K.; Gu, T.; Ma, J. B.; Yang, K.; Shi, P. R.; Biao, J.; Mi, J. S.; Liu, M.; Lv, W.; He, Y. B. Nano Energy 2022, 100, 10. doi:10.1016/j.nanoen.2022.107470
13. [13]
  (13) Huo, H. Y.; Chen, Y.; Luo, J.; Yang, X. F.; Guo, X. X.; Sun, X. L. Adv. Energy Mater. 2019, 9 (17), 8. doi:10.1002/aenm.201804004
14. [14]
  (14) Mu, S.; Bi, Z. J.; Gao, S. H.; Guo, X. X. Chem. Res. Chin. Univ. 2021, 37 (2), 246. doi:10.1007/s40242-021-1054-1
15. [15]
  (15) Zhang, J. X.; Zhao, N.; Zhang, M.; Li, Y. Q.; Chu, P. K.; Guo, X. X.; Di, Z. F.; Wang, X.; Li, H. Nano Energy 2016, 28, 447. doi:10.1016/j.nanoen.2016.09.002
16. [16]
17. [17]
  (17) Zhai, P. B.; Chang, D. M.; Bi, Z. J.; Zhao, N.; Guo, X. X. Energy Storage Sci. Technol. 2022, 11 (9), 2847. doi:10.19799/j.cnki.2095-4239.2022.0097
18. [18]
  (18) Chen, L.; Li, Y. T.; Li, S. P.; Fan, L. Z.; Nan, C. W.; Goodenough, J. B. Nano Energy 2018, 46, 176. doi:10.1016/j.nanoen.2017.12.037
19. [19]
  (19) Huang, Z. Y.; Pang, W. Y.; Liang, P.; Jin, Z. H.; Grundish, N.; Li, Y. T.; Wang, C. A. J. Mater. Chem. A 2019, 7 (27), 16425. doi:10.1039/c9ta03395e
20. [20]
  (20) Li, L. S.; Deng, Y. F.; Chen, G. H. J. Energy Chem. 2020, 50, 154. doi:10.1016/j.jechem.2020.03.017
21. [21]
  (21) Zagorski, J.; del Amo, J. M. L.; Cordill, M. J.; Aguesse, F.; Buannic, L.; Llordes, A. ACS Appl. Energ. Mater. 2019, 2 (3), 1734. doi:10.1021/acsaem.8b01850
22. [22]
  (22) Althues, H.; Henle, J.; Kaskel, S. Chem. Soc. Rev. 2007, 36 (9), 1454. doi:10.1039/b608177k
23. [23]
  (23) Shrestha, S.; Wang, B.; Dutta, P. Adv. Colloid Interface Sci. 2020, 279, 16. doi:10.1016/j.cis.2020.102162
24. [24]
  (24) Jia, M. Y.; Zhao, N.; Bi, Z. J.; Fu, Z. Q.; Xu, F. F.; Shi, C.; Guo, X. X. ACS Appl. Mater. Interfaces 2020, 12 (41), 46162. doi:10.1021/acsami.0c13434
25. [25]
  (25) Kango, S.; Kalia, S.; Celli, A.; Njuguna, J.; Habibi, Y.; Kumar, R. Prog. Polym. Sci. 2013, 38 (8), 1232. doi:10.1016/j.progpolymsci.2013.02.003
26. [26]
  (26) Xie, Y. J.; Hill, C. A. S.; Xiao, Z. F.; Militz, H.; Mai, C. Compos. Pt. A-Appl. Sci. Manuf. 2010, 41 (7), 806. doi:10.1016/j.compositesa.2010.03.005
27. [27]
  (27) Li, C.; Liang, Z.; Li, Z.; Cao, D.; Zuo, D.; Chang, J.; Wang, J.; Deng, Y.; Liu, K.; Kong, X.; et al. Nano Lett. 2023, 23 (9), 4014. doi:10.1021/acs.nanolett.3c00783
28. [28]
  (28) Yan, C. Y.; Zhu, P.; Jia, H.; Du, Z.; Zhu, J. D.; Orenstein, R.; Cheng, H.; Wu, N. Q.; Dirican, M.; Zhang, X. W. Energy Storage Mater. 2020, 26, 448. doi:10.1016/j.ensm.2019.11.018
29. [29]
  (29) Zhang, Z. Y.; Zhang, S.; Geng, S. X.; Zhou, S. B.; Hu, Z. L.; Luo, J. Y. Energy Storage Mater. 2022, 51, 19. doi:10.1016/j.ensm.2022.06.025
30. [30]
  (30) Li, X. X.; Zheng, B. Y.; Xu, L. M.; Wu, D. D.; Liu, Z. L.; Zhang, H. C. Rare Metal Mat. Eng. 2012, 41 (1), 24. doi:10.1016/s1875-5372(12)60024-1
31. [31]
  (31) Li, H.; Wang, C. A.; Guo, Z. H.; Wang, H. R.; Zhang, Y. X.; Hong, R.; Peng, Z. R. Effects of Silane Coupling Agents on the Electrical Properties of Silica/Epoxy Nanocomposites, In IEEE International Conference on Dielectrics (ICD), Montpellier, France July 03-07; IEEE:Montpellier, France, 2016; pp. 1036.
32. [32]
  (32) Jia, M. Y.; Bi, Z. J.; Shi, C.; Zhao, N.; Guo, X. X. J. Power Sources 2021, 486, 7. doi:10.1016/j.jpowsour.2020.229363
33. [33]
  (33) Gu, J.; Zhang, Q.; Dang, J.; Zhang, J.; Chen, S. Polym. Bull. 2009, 62 (5), 689. doi:10.1007/s00289-009-0045-z
34. [34]
  (34) Yan, B.; Kotobuki, M.; Liu, J. Mater. Technol. 2016, 31 (11), 623. doi:10.1080/10667857.2016.1196033
35. [35]
  (35) Song, S. D.; Chen, B. T.; Ruan, Y. L.; Sun, J.; Yu, L. M.; Wang, Y.; Thokchom, J. Electrochim. Acta 2018, 270, 501. doi:10.1016/j.electacta.2018.03.101
36. [36]
  (36) Ghadimi, A.; Metselaar, I. H. Exp. Therm. Fluid Sci. 2013, 51, 1. doi:10.1016/j.expthermflusci.2013.06.001
37. [37]
  (37) Jiang, L. Q.; Gao, L.; Sun, J. J. Colloid Interface Sci. 2003, 260 (1), 89. doi:10.1016/s0021-9797(02)00176-5
38. [38]
  (38) Sadeghi, R.; Etemad, S. G.; Keshavarzi, E.; Haghshenasfard, M. Microfluid. Nanofluid. 2015, 18 (5-6), 1023. doi:10.1007/s10404-014-1491-y
39. [39]
  (39) Isaac, J. A.; Devaux, D.; Bouchet, R. Nat. Mater. 2022, 21(12), 1412. doi:10.1038/s41563-022-01343-w
40. [40]
  (40) Huang, W. L.; Zhao, N.; Bi, Z. J.; Shi, C.; Guo, X. X.; Fan, L. Z.; Nan, C. W. Mater. Today Nano 2020, 10, 100075. doi:10.1016/j.mtnano.2020.100075
41. [41]
  (41) Pan, K. C.; Zhang, L.; Qian, W. W.; Wu, X. K.; Dong, K.; Zhang, H. T.; Zhang, S. J. Adv. Mater. 2020, 32 (17), 8. doi:10.1002/adma.202000399
1. [1]
  Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . 液相法制备硫化物固体电解质及其在全固态锂电池中的应用. Acta Physico-Chimica Sinica, 2025, 41(1): 2309019-. doi: 10.3866/PKU.WHXB202309019
2. [2]
  Jiandong Liu , Zhijia Zhang , Mikhail Kamenskii , Filipp Volkov , Svetlana Eliseeva , Jianmin Ma . Research Progress on Cathode Electrolyte Interphase in High-Voltage Lithium Batteries. Acta Physico-Chimica Sinica, 2025, 41(2): 100011-. doi: 10.3866/PKU.WHXB202308048
3. [3]
  Tao Jiang , Yuting Wang , Lüjin Gao , Yi Zou , Bowen Zhu , Li Chen , Xianzeng Li . Experimental Design for the Preparation of Composite Solid Electrolytes for Application in All-Solid-State Batteries: Exploration of Comprehensive Chemistry Laboratory Teaching. University Chemistry, 2024, 39(2): 371-378. doi: 10.3866/PKU.DXHX202308057
4. [4]
  Jiahe LIU , Gan TANG , Kai CHEN , Mingda ZHANG . Effect of low-temperature electrolyte additives on low-temperature performance of lithium cobaltate batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 719-728. doi: 10.11862/CJIC.20250023
5. [5]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
6. [6]
  Aoyu Huang , Jun Xu , Yu Huang , Gui Chu , Mao Wang , Lili Wang , Yongqi Sun , Zhen Jiang , Xiaobo Zhu . Tailoring Electrode-Electrolyte Interfaces via a Simple Slurry Additive for Stable High-Voltage Lithium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100037-. doi: 10.3866/PKU.WHXB202408007
7. [7]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
8. [8]
  Yi Yang , Xin Zhou , Miaoli Gu , Bei Cheng , Zhen Wu , Jianjun Zhang . S型ZnO/CdIn₂S₄光催化剂制备H₂O₂偶联苄胺氧化的超快电子转移飞秒吸收光谱研究. Acta Physico-Chimica Sinica, 2025, 41(6): 100064-. doi: 10.1016/j.actphy.2025.100064
9. [9]
  Shuang Yang , Qun Wang , Caiqin Miao , Ziqi Geng , Xinran Li , Yang Li , Xiaohong Wu . Ideological and Political Education Design for Research-Oriented Experimental Course of Highly Efficient Hydrogen Production from Water Electrolysis in Aerospace Perspective. University Chemistry, 2024, 39(11): 269-277. doi: 10.12461/PKU.DXHX202403044
10. [10]
  Wenqi Gao , Xiaoyan Fan , Feixiang Wang , Zhuojun Fu , Jing Zhang , Enlai Hu , Peijun Gong . Exploring Nernst Equation Factors and Applications of Solid Zinc-Air Battery. University Chemistry, 2024, 39(5): 98-107. doi: 10.3866/PKU.DXHX202310026
11. [11]
  Xuanzhu Huo , Yixi Liu , Qiyu Wu , Zhiqiang Dong , Chanzi Ruan , Yanping Ren . Integrated Experiment of “Electrolytic Preparation of Cu₂O and Gasometric Determination of Avogadro’s Constant: Implementation, Results, and Discussion: A Micro-Experiment Recommended for Freshmen in Higher Education at Various Levels Across the Nation. University Chemistry, 2024, 39(3): 302-307. doi: 10.3866/PKU.DXHX202308095
12. [12]
  Yanan Liu , Yufei He , Dianqing Li . Preparation of Highly Dispersed LDHs-based Catalysts and Testing of Nitro Compound Reduction Performance: A Comprehensive Chemical Experiment for Research Transformation. University Chemistry, 2024, 39(8): 306-313. doi: 10.3866/PKU.DXHX202401081
13. [13]
  Zhenhua Wang , Haoyang Feng , Xiaoyang Shao , Wenru Fan . Vitamins in Solid Propellants: Controlled Synthesis of Neutral Macromolecular Bonding Agents. University Chemistry, 2025, 40(4): 1-9. doi: 10.3866/PKU.DXHX202401007
14. [14]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . 氢电极支撑可逆固体氧化物电池性能及电化学不对称性优化. Acta Physico-Chimica Sinica, 2025, 41(1): 2309037-. doi: 10.3866/PKU.WHXB202309037
15. [15]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
16. [16]
  Yongmei Liu , Lisen Sun , Zhen Huang , Tao Tu . Curriculum-Based Ideological and Political Design for the Experiment of Methanol Oxidation to Formaldehyde Catalyzed by Electrolytic Silver. University Chemistry, 2024, 39(2): 67-71. doi: 10.3866/PKU.DXHX202308020
17. [17]
  Feiya Cao , Qixin Wang , Pu Li , Zhirong Xing , Ziyu Song , Heng Zhang , Zhibin Zhou , Wenfang Feng . Magnesium-Ion Conducting Electrolyte Based on Grignard Reaction: Synthesis and Properties. University Chemistry, 2024, 39(3): 359-368. doi: 10.3866/PKU.DXHX202308094
18. [18]
  Jiaxuan Zuo , Kun Zhang , Jing Wang , Xifei Li . 锂离子电池Ni-Co-Mn基正极材料前驱体的形核调控及机制. Acta Physico-Chimica Sinica, 2025, 41(1): 2404042-. doi: 10.3866/PKU.WHXB202404042
19. [19]
  Zunxiang Zeng , Yuling Hu , Yufei Hu , Hua Xiao . Analysis of Plant Essential Oils by Supercritical CO₂Extraction with Gas Chromatography-Mass Spectrometry: An Instrumental Analysis Comprehensive Experiment Teaching Reform. University Chemistry, 2024, 39(3): 274-282. doi: 10.3866/PKU.DXHX202309069
20. [20]
  Bowen Yang , Rui Wang , Benjian Xin , Lili Liu , Zhiqiang Niu . C-SnO₂/MWCNTs Composite with Stable Conductive Network for Lithium-based Semi-Solid Flow Batteries. Acta Physico-Chimica Sinica, 2025, 41(2): 100015-. doi: 10.3866/PKU.WHXB202310024

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(605)
HTML views(109)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142