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, n.zhao@qdu.edu.cn Xiangxin Guo, xxguo@qdu.edu.cn
Received Date: 8 May 2023
Revised Date: 6 June 2023
Accepted Date: 6 June 2023
Available Online: 13 June 2023
Fund Project: the Key R&D Program of Shandong Province 2021CXGC010401the National Natural Science Foundation of China U1932205the National Natural Science Foundation of China 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 ℃. 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]
  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 doi: 10.1016/j.joule.2019.03.019
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 doi: 10.1016/j.ensm.2020.11.038
3. [3]
  Jin, F.; Li, J.; Hu, C. J.; Dong, H. C.; Chen, P.; Shen, Y. B.; Chen, L. W. Acta Phys. -Chim. Sin. 2019, 35 (12), 1399. doi: 10.3866/PKU.WHXB201904085
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 doi: 10.1039/D2CS00322H
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 doi: 10.1016/j.ensm.2022.02.048
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 doi: 10.1063/5.0098255
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 doi: 10.1016/j.jpowsour.2022.231939
8. [8]
  Li, W. K.; Zhao, N.; Bi, Z. J.; Guo, X. X. J. Inorg. Mater. 2022, 37 (2), 189. doi: 10.15541/jim20210486 doi: 10.15541/jim20210486
9. [9]
  Wang, H.; An, H. W.; Shan, H. M.; Zhao, L.; Wang, J. J. Acta Phys. -Chim. Sin. 2021, 37 (11), 2007070. doi: 10.3866/PKU.WHXB202007070
10. [10]
  Tufail, M. K.; Zhai, P.; Jia, M.; Zhao, N.; Guo, X. Energy Mater. Adv. 2023, 4, 0015. doi: 10.34133/energymatadv.0015 doi: 10.34133/energymatadv.0015
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 doi: 10.1002/aenm.202200967
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 doi: 10.1016/j.nanoen.2022.107470
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 doi: 10.1002/aenm.201804004
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 doi: 10.1007/s40242-021-1054-1
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 doi: 10.1016/j.nanoen.2016.09.002
16. [16]
  Yu, X. R.; Ma, J.; Mou, C. B.; Cui, G. L. Acta Phys. -Chim. Sin. 2022, 38 (3), 1912061. doi: 10.3866/PKU.WHXB201912061
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 doi: 10.19799/j.cnki.2095-4239.2022.0097
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 doi: 10.1016/j.nanoen.2017.12.037
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 doi: 10.1039/c9ta03395e
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 doi: 10.1016/j.jechem.2020.03.017
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 doi: 10.1021/acsaem.8b01850
22. [22]
  Althues, H.; Henle, J.; Kaskel, S. Chem. Soc. Rev. 2007, 36 (9), 1454. doi: 10.1039/b608177k doi: 10.1039/b608177k
23. [23]
  Shrestha, S.; Wang, B.; Dutta, P. Adv. Colloid Interface Sci. 2020, 279, 16. doi: 10.1016/j.cis.2020.102162 doi: 10.1016/j.cis.2020.102162
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 doi: 10.1021/acsami.0c13434
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 doi: 10.1016/j.progpolymsci.2013.02.003
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 doi: 10.1016/j.compositesa.2010.03.005
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 doi: 10.1021/acs.nanolett.3c00783
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 doi: 10.1016/j.ensm.2019.11.018
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 doi: 10.1016/j.ensm.2022.06.025
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 doi: 10.1016/s1875-5372(12)60024-1
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]
  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 doi: 10.1016/j.jpowsour.2020.229363
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 doi: 10.1007/s00289-009-0045-z
34. [34]
  Yan, B.; Kotobuki, M.; Liu, J. Mater. Technol. 2016, 31 (11), 623. doi: 10.1080/10667857.2016.1196033 doi: 10.1080/10667857.2016.1196033
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 doi: 10.1016/j.electacta.2018.03.101
36. [36]
  Ghadimi, A.; Metselaar, I. H. Exp. Therm. Fluid Sci. 2013, 51, 1. doi: 10.1016/j.expthermflusci.2013.06.001 doi: 10.1016/j.expthermflusci.2013.06.001
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 doi: 10.1016/s0021-9797(02)00176-5
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 doi: 10.1007/s10404-014-1491-y
39. [39]
  Isaac, J. A.; Devaux, D.; Bouchet, R. Nat. Mater. 2022, 21(12), 1412. doi: 10.1038/s41563-022-01343-w doi: 10.1038/s41563-022-01343-w
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 doi: 10.1016/j.mtnano.2020.100075
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 doi: 10.1002/adma.202000399
1. [1]
  Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . Sulfide Solid Electrolyte Synthesized by Liquid Phase Approach and Application in All-Solid-State Lithium Batteries. Acta Physico-Chimica Sinica, 2025, 41(1): 100004-0. doi: 10.3866/PKU.WHXB202309019
2. [2]
  Da Wang , Xiaobin Yin , Jianfang Wu , Yaqiao Luo , Siqi Shi . All-Solid-State Lithium Cathode/Electrolyte Interfacial Resistance: From Space-Charge Layer Model to Characterization and Simulation. Acta Physico-Chimica Sinica, 2024, 40(7): 2307029-0. doi: 10.3866/PKU.WHXB202307029
3. [3]
  Jiandong Liu , Zhijia Zhang , Kamenskii Mikhail , Volkov Filipp , Eliseeva Svetlana , Jianmin Ma . Research Progress on Cathode Electrolyte Interphase in High-Voltage Lithium Batteries. Acta Physico-Chimica Sinica, 2025, 41(2): 2308048-0. doi: 10.3866/PKU.WHXB202308048
4. [4]
  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
5. [5]
  Ke Qiu , Fengmei Wang , Mochou Liao , Kerun Zhu , Jiawei Chen , Wei Zhang , Yongyao Xia , Xiaoli Dong , Fei Wang . A Fumed SiO₂-based Composite Hydrogel Polymer Electrolyte for Near-Neutral Zinc-Air Batteries. Acta Physico-Chimica Sinica, 2024, 40(3): 2304036-0. doi: 10.3866/PKU.WHXB202304036
6. [6]
  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
7. [7]
  Zhuo Han , Danfeng Zhang , Haixian Wang , Guorui Zheng , Ming Liu , Yanbing He . Research Progress and Prospect on Electrolyte Additives for Interface Reconstruction of Long-Life Ni-Rich Lithium Batteries. Acta Physico-Chimica Sinica, 2024, 40(9): 2307034-0. doi: 10.3866/PKU.WHXB202307034
8. [8]
  Zhaoxuan ZHU , Lixin WANG , Xiaoning TANG , Long LI , Yan SHI , Jiaojing SHAO . Application of poly(vinyl alcohol) conductive hydrogel electrolytes in zinc ion batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 893-902. doi: 10.11862/CJIC.20240368
9. [9]
  Changsheng An , Tao Liu . Decoding SEI chemistry at the lithium-metal potential. Acta Physico-Chimica Sinica, 2025, 41(9): 100101-0. doi: 10.1016/j.actphy.2025.100101
10. [10]
  Zhi Dou , Huiyu Duan , Yixi Lin , Yinghui Xia , Mingbo Zheng , Zhenming Xu . High-Throughput Screening Lithium Alloy Phases and Investigation of Ion Transport for Solid Electrolyte Interphase Layer. Acta Physico-Chimica Sinica, 2024, 40(3): 2305039-0. doi: 10.3866/PKU.WHXB202305039
11. [11]
  Xinran Zhang , Siqi Liu , Yichi Chen , Qingli Zou , Qinghong Xu , Yaqin Huang . From Protein to Energy Storage Materials: Edible Gelatin Jelly Electrolyte. University Chemistry, 2025, 40(7): 255-266. doi: 10.12461/PKU.DXHX202408104
12. [12]
  Yu Peng , Jiawei Chen , Yue Yin , Yongjie Cao , Mochou Liao , Congxiao Wang , Xiaoli Dong , Yongyao Xia . Tailored cathode electrolyte interphase via ethylene carbonate-free electrolytes enabling stable and wide-temperature operation of high-voltage LiCoO₂. Acta Physico-Chimica Sinica, 2025, 41(8): 100087-0. doi: 10.1016/j.actphy.2025.100087
13. [13]
  Zeyu Liu , Wenze Huang , Yang Xiao , Jundong Zhang , Weijin Kong , Peng Wu , Chenzi Zhao , Aibing Chen , Qiang Zhang . Nanocomposite Current Collectors for Anode-Free All-Solid-State Lithium Batteries. Acta Physico-Chimica Sinica, 2024, 40(3): 2305040-0. doi: 10.3866/PKU.WHXB202305040
14. [14]
  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
15. [15]
  Caiyun Jin , Zexuan Wu , Guopeng Li , Zhan Luo , Nian-Wu Li . Phosphazene-based flame-retardant artificial interphase layer for lithium metal batteries. Acta Physico-Chimica Sinica, 2025, 41(8): 100094-0. doi: 10.1016/j.actphy.2025.100094
16. [16]
  Jiandong Liu , Xin Li , Daxiong Wu , Huaping Wang , Junda Huang , Jianmin Ma . Anion-Acceptor Electrolyte Additive Strategy for Optimizing Electrolyte Solvation Characteristics and Electrode Electrolyte Interphases for Li||NCM811 Battery. Acta Physico-Chimica Sinica, 2024, 40(6): 2306039-0. doi: 10.3866/PKU.WHXB202306039
17. [17]
  Qianli Ma , Tianbing Song , Tianle He , Xirong Zhang , Huanming Xiong . Sulfur-doped carbon dots: a novel bifunctional electrolyte additive for high-performance aqueous zinc-ion batteries. Acta Physico-Chimica Sinica, 2025, 41(9): 100106-0. doi: 10.1016/j.actphy.2025.100106
18. [18]
  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): 2408007-0. doi: 10.3866/PKU.WHXB202408007
19. [19]
  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
20. [20]
  Yi Yang , Xin Zhou , Miaoli Gu , Bei Cheng , Zhen Wu , Jianjun Zhang . Femtosecond transient absorption spectroscopy investigation on ultrafast electron transfer in S-scheme ZnO/CdIn₂S₄ photocatalyst for H₂O₂ production and benzylamine oxidation. Acta Physico-Chimica Sinica, 2025, 41(6): 100064-0. doi: 10.1016/j.actphy.2025.100064

Get Citation

PDF

XML

Metrics

PDF Downloads(6)
Abstract views(744)
HTML views(116)

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