原位聚合制备PDOL基固态电解质及其在锂金属电池中的应用

doi:10.19799/j.cnki.2095-4239.2024.0712

储能科学与技术 ›› 2025, Vol. 14 ›› Issue (1): 1-12.doi: 10.19799/j.cnki.2095-4239.2024.0712

• 储能材料与器件 • 下一篇

原位聚合制备PDOL基固态电解质及其在锂金属电池中的应用

江训昌¹^,²(), 喻科霖³, 杨大祥¹^,²^,⁴(), 廖敏会⁵, 周洋⁵

^1.重庆交通大学绿色航空技术研究院
^2.重庆交通大学
^3.重庆市育才中学
^4.绿色航空能源动力重庆市重点实验室，重庆 400000
^5.重庆长安新能源汽车有限公司，重庆 400074

收稿日期:2024-07-29 修回日期:2024-08-08 出版日期:2025-01-28 发布日期:2025-02-25
通讯作者: 杨大祥 E-mail:2641996850@qq.com;6669203@qq.com
作者简介:江训昌（1998—），男，硕士研究生，从事固态电解质研究，E-mail：2641996850@qq.com；
基金资助:
重庆市自然科学基金面上项目(CSTB2022NSCQ-MSX0479)

Preparation of PDOL-based solid electrolyte by in-situ polymerization and its application in lithium metal batteries

Xunchang JIANG¹^,²(), Kelin YU³, Daxiang YANG¹^,²^,⁴(), Minhui LIAO⁵, Yang ZHOU⁵

^1.The Green Aeromechanics Research Institute of Chongqing Jiaotong University
^2.Chongqing Jiaotong University
^3.Chongqing Yucai Middle School
^4.Chongqing Key Laboratory of Green Aviation Energy and Power, Chongqing 400000, China
^5.Chongqing Chang'an New Energy Automobile corporation, Chongqing 400074, China

Received:2024-07-29 Revised:2024-08-08 Online:2025-01-28 Published:2025-02-25
Contact: Daxiang YANG E-mail:2641996850@qq.com;6669203@qq.com

摘要/Abstract

摘要：

通过同轴静电纺丝工艺，制备出在聚偏氟乙烯(PVDF)纳米纤维表面包覆了氧化钇稳定氧化锆(YSZ)纳米颗粒的YPVDF纳米纤维膜，并以1,3-二氧戊环(DOL)为聚合物前驱体单体，三(三氟磺酸)铝[Al(OfT)₃]为引发剂，双三氟甲基磺酰亚胺锂(LiTFSI)为锂盐，氟代碳酸乙烯酯(FEC)为SEI膜添加剂，采用原位聚合工艺，在高比表面积的YPVDF纳米纤维基膜中原位聚合生成PDOL基复合固态电解质，PDOL与YPVDF纤维表面的YSZ形成大量的YSZ/PDOL有机-无机离子快速传输界面，制备出的PDOL@YPVDF-CSE在室温下拥有0.94×10^-4 S/cm的离子电导率；YPVDF纤维上YSZ的Lewis酸位点(Zr⁴⁺、Y³⁺、氧空位)能够吸附LiTFSI中的阴离子，促进LiTFSI解离出Li⁺，从而使得PDOL@YPVDF-CSE具有0.78的锂离子迁移数，同时YSZ提供的Lewis酸位点可以协同Al(OfT)₃促进DOL开环聚合，使DOL单体的转化率达到98.2%。此外，YPVDF纳米纤维的引入使得PDOL@YPVDF-CSE的耐热分解温度提升至312 ℃。以PDOL@YPVDF-CSE组装的Li|PDOL@YPVDF-CSE|Li锂对称电池，能够稳定循环1500 h以上；组装的LFP|PDOL@YPVDF-CSE|Li电池在0.5C倍率下循环800次以后，容量保持率为97.4%，在2 C倍率下循环500次后，容量保持率为96.8%。同时，以LiNi_0.6Co_0.2Mn_0.2O₂(NCM622)为正极组装的NCM622|PDOL @YPVDF-CSE|Li电池在1 C倍率下循环150次后，容量保持率为96.2%。

关键词: 同轴静电纺丝, 聚(1,3-二氧戊环), 原位聚合, 电化学性能, 复合固态电解质

Abstract:

YPVDF nanofiber membranes coated with yttria-stabilized zirconia (YSZ) nanoparticles on the surface of polyvinylidene fluoride (PVDF) nanofibers were prepared by a coaxial electrospinning process. In this process, 1,3-dioxolane (DOL) was used as the polymer precursor monomer; tris (trifluoromethanesulfonic acid) aluminum (Al(OfT)₃) was used as the initiator; LiTFSI was used as the lithium salt; and FEC was used as the SEI film additive. In situ polymerization was performed on the YPVDF nanofiber base film with a high surface area to generate PDOL. PDOL formed a large number of YSZ/PDOL organic-inorganic rapid-ion-transport interfaces with YSZ on the surface of YPVDF fibers. PDOL@YPVDF-CSE has an ionic conductivity of 0.94 × 10^-4 S/cm at room temperature. The Lewis acid sites (Zr⁴⁺, Y³⁺, and oxygen vacancies) of the YSZ on the YPVDF fibers facilitate the adsorption of anions from LiTFSI, thus promoting the dissociation of Li⁺ from LiTFSI. Therefore, PDOL@YPVDF-CSE YSZ has a lithium ion migration number of 0.78, and the Lewis acid sites provided by YSZ can synergistically promote the ring opening polymerization of DOL with Al (OfT)₃, resulting in a DOL monomer conversion rate of 98.2%. In addition, because of the introduction of YPVDF nanofibers, the heat-resistant decomposition temperature of PDOL@YPVDF-CSE increased to 312 ℃. A symmetric lithium battery assembled as Li| PDOL@YPVDF-CSE |Li was capable of stable cycling for over 1500 h. An assembled LiFeO₄| PDOL@YPVDF-CSE | battery subjected to 800 cycles at a rate of 0.5C had a capacity retention rate of 97.4%, and after 500 cycles at a rate of 2C, the capacity retention rate was 96.8%. Meanwhile, the NCM622 | PDOL @ YPVDF-CSE | Li battery assembled with LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) as the positive electrode had a capacity retention rate of 96.2% after 150 cycles at a rate of 1C.

Key words: coaxial electrospinning, poly(1,3-dioxolane), in situ polymerization, electrochemical performance, composite solid electrolyte

中图分类号:

O 63

江训昌, 喻科霖, 杨大祥, 廖敏会, 周洋. 原位聚合制备PDOL基固态电解质及其在锂金属电池中的应用[J]. 储能科学与技术, 2025, 14(1): 1-12.

Xunchang JIANG, Kelin YU, Daxiang YANG, Minhui LIAO, Yang ZHOU. Preparation of PDOL-based solid electrolyte by in-situ polymerization and its application in lithium metal batteries[J]. Energy Storage Science and Technology, 2025, 14(1): 1-12.

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参考文献 28

1	LU Y X, RONG X H, HU Y S, et al. Research and development of advanced battery materials in China[J]. Energy Storage Materials, 2019, 23: 144-153. DOI: 10.1016/j.ensm.2019.05.019.
2	SUN C W, LIU J, GONG Y D, et al. Recent advances in all-solid-state rechargeable lithium batteries[J]. Nano Energy, 2017, 33: 363-386. DOI: 10.1016/j.nanoen.2017.01.028.
3	DOUX J M, NGUYEN H, TAN D H S, et al. Stack pressure considerations for room-temperature all-solid-state lithium metal batteries[J]. Advanced Energy Materials, 2020, 10(1): 1903253. DOI: 10.1002/aenm.201903253.
4	IHRIG M, FINSTERBUSCH M, TSAI C L, et al. Low temperature sintering of fully inorganic all-solid-state batteries-Impact of interfaces on full cell performance[J]. Journal of Power Sources, 2021, 482: 228905. DOI: 10.1016/j.jpowsour.2020.228905.
5	LIANG J N, HWANG S, LI S, et al. Stabilizing and understanding the interface between nickel-rich cathode and PEO-based electrolyte by lithium niobium oxide coating for high-performance all-solid-state batteries[J]. Nano Energy, 2020, 78: 105107. DOI: 10.1016/j.nanoen.2020.105107.
6	XIAO Y R, TURCHENIUK K, NARLA A, et al. Electrolyte melt infiltration for scalable manufacturing of inorganic all-solid-state lithium-ion batteries[J]. Nature Materials, 2021, 20(7): 984-990. DOI: 10.1038/s41563-021-00943-2.
7	ATES T, KELLER M, KULISCH J, et al. Development of an all-solid-state lithium battery by slurry-coating procedures using a sulfidic electrolyte[J]. Energy Storage Materials, 2019, 17: 204-210. DOI: 10.1016/j.ensm.2018.11.011.
8	LIU F Q, WANG W P, YIN Y X, et al. Upgrading traditional liquid electrolyte via in situ gelation for future lithium metal batteries[J]. Science Advances, 2018, 4(10): eaat5383. DOI: 10.1126/sciadv.aat5383.
9	LIU C Y, WANG S, WU X Y, et al. In situ construction of zwitterionic polymer electrolytes with synergistic cation-anion regulation functions for lithium metal batteries[J]. Advanced Functional Materials, 2024, 34(1): 2307248. DOI: 10.1002/adfm.202307248.
10	HUO S D, SHENG L, XUE W D, et al. Challenges of stable ion pathways in cathode electrode for all-solid-state lithium batteries: A review[J]. Advanced Energy Materials, 2023, 13(15): 2204343. DOI: 10.1002/aenm.202204343.
11	MI Y Q, DENG W, HE C H, et al. In situ polymerized 1, 3-dioxolane electrolyte for integrated solid-state lithium batteries[J]. Angewandte Chemie (International Ed), 2023, 62(12): e202218621. DOI: 10.1002/anie.202218621.
12	苑志祥, 张浩, 胡思伽, 等. 离子聚合原位固态化构建高安全锂电池固态聚合物电解质的研究进展[J]. 化学学报, 2023, 81(8): 1064-1080.
	YUAN Z X, ZHANG H, HU S J, et al. Research progress of ion-initiated in situ generated solid polymer electrolytes for high-safety lithium batteries[J]. Acta Chimica Sinica, 2023, 81(8): 1064-1080.
13	DENG B, JING M X, LI L X, et al. Nano-zirconia boosting the ionic conductivity and lithium dendrite inhibition ability of a poly(1, 3-dioxolane) solid electrolyte for high-voltage solid-state lithium batteries[J]. Sustainable Energy & Fuels, 2021, 5(21): 5461-5470. DOI: 10.1039/D1SE01132D.
14	REN W H, ZHANG Y F, LV R X, et al. In-situ formation of quasi-solid polymer electrolyte for improved lithium metal battery performances at low temperatures[J]. Journal of Power Sources, 2022, 542: 231773. DOI: 10.1016/j.jpowsour.2022.231773.
15	ZHU J, ZHANG J P, ZHAO R Q, et al. In situ 3D crosslinked gel polymer electrolyte for ultra-long cycling, high-voltage, and high-safety lithium metal batteries[J]. Energy Storage Materials, 2023, 57: 92-101. DOI: 10.1016/j.ensm.2023.02.012.
16	GENG Z, HUANG Y L, SUN G C, et al. In-situ polymerized solid-state electrolytes with stable cycling for Li/LiCoO₂ batteries[J]. Nano Energy, 2022, 91: DOI: 10.1016/j.nanoen.2021.106679.
17	YANG H, ZHANG B, JING M X, et al. In situ catalytic polymerization of a highly homogeneous PDOL composite electrolyte for long-cycle high-voltage solid-state lithium batteries[J]. Advanced Energy Materials, 2022, 12(39): DOI: 10.1002/aenm.202201762.
18	王其钰, 褚赓, 张杰男, 等. 锂离子扣式电池的组装, 充放电测量和数据分析[J]. 储能科学与技术, 2018, 7(2): 327-344.
	WANG Q Y, CHU G, ZHANG J N, et al. The assembly, charge-discharge performance measurement and data analysis of lithium-ion button cell[J]. Energy Storage Science and Technology, 2018, 7(2): 327-344.
19	BODKHE S, RAJESH P S M, KAMLE S, et al. Beta-phase enhancement in polyvinylidene fluoride through filler addition: Comparing cellulose with carbon nanotubes and clay[J]. Journal of Polymer Research, 2014, 21(5): 434. DOI: 10.1007/s10965-014-0434-3.
20	LIU R, YANG Z, LI J, et al. Study on the mechanism of action of various metal ions on the surface of monazite[J]. Physicochemical Problems of Mineral Processing, 2024, 60(2): DOI:10.37190/ppmp/185901.
21	MA Q, YUE J P, FAN M, et al. Formulating the electrolyte towards high-energy and safe rechargeable lithium-metal batteries[J]. Angewandte Chemie (International Ed), 2021, 60(30): 16554-16560. DOI: 10.1002/anie.202103850.
22	ZHOU J Q, QIAN T, LIU J, et al. High-safety all-solid-state lithium-metal battery with high-ionic-conductivity thermoresponsive solid polymer electrolyte[J]. Nano Letters, 2019, 19(5): 3066-3073. DOI: 10.1021/acs.nanolett.9b00450.
23	ZHAO Y, ZHOU T, BASTER D, et al. Targeted functionalization of cyclic ether solvents for controlled reactivity in high-voltage lithium metal batteries[J]. ACS Energy Letters, 2023, 8(7): 3180-3187.
24	ABDELMAOULA A E, SHU J, CHENG Y, et al. Core-shell MOF-in-MOF nanopore bifunctional host of electrolyte for high-performance solid-state lithium batteries[J]. Small Methods, 2021, 5(8): e2100508. DOI: 10.1002/smtd.202100508.
25	TANG W J, TANG S, GUAN X Z, et al. High-performance solid polymer electrolytes filled with vertically aligned 2D materials[J]. Advanced Functional Materials, 2019, 29(16): 1900648. DOI: 10.1002/adfm.201900648.
26	ZHANG X Q, CHENG X B, CHEN X, et al. Fluoroethylene carbonate additives to render uniform Li deposits in lithium metal batteries[J]. Advanced Functional Materials, 2017, 27(10): 1605989. DOI: 10.1002/adfm.201605989.
27	梁大宇, 包婷婷, 高田慧, 等. 锂离子电池固态电解质界面膜(SEI)的研究进展[J]. 储能科学与技术, 2018, 7(3): 418-423. DOI: 10.12028/j.issn.2095-4239.2018.0059.
	LIANG D Y, BAO T T, GAO T H, et al. Research progress of lithium ion battery solid-electrolyte interface(SEI)[J]. Energy Storage Science and Technology, 2018, 7(3): 418-423. DOI: 10.12028/j.issn.2095-4239.2018.0059.
28	LIANG H M, WANG Z X, GUO H J, et al. Improvement in the electrochemical performance of LiNi_0.8Co_0.1Mn_0.1O₂ cathode material by Li₂ZrO₃ coating[J]. Applied Surface Science, 2017, 423: 1045-1053. DOI: 10.1016/j.apsusc.2017.06.283.

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原位聚合制备PDOL基固态电解质及其在锂金属电池中的应用

Preparation of PDOL-based solid electrolyte by in-situ polymerization and its application in lithium metal batteries

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