doi:10.11777/j.issn1000-3304.2019.19097

引用本文: 张建军, 杨金凤, 吴瀚, 张敏, 刘亭亭, 张津宁, 董杉木, 崔光磊. 二次电池用原位生成聚合物电解质的研究进展[J]. 高分子学报, 2019, 50(9): 890-914. doi: 10.11777/j.issn1000-3304.2019.19097 shu

Citation: Jian-jun Zhang, Jin-feng Yang, Han Wu, Min Zhang, Ting-ting Liu, Jin-ning Zhang, Shan-mu Dong and Guang-lei Cui. Research Progress of in situ Generated Polymer Electrolyte for Rechargeable Batteries[J]. Acta Polymerica Sinica, 2019, 50(9): 890-914. doi: 10.11777/j.issn1000-3304.2019.19097 shu

二次电池用原位生成聚合物电解质的研究进展

1.
青岛储能产业技术研究院中国科学院青岛生物能源与过程研究所　青岛 266101
2.
中国科学院大学材料与光电研究中心　北京 100049
3.
中南大学化学化工学院　长沙 410083

通讯作者: 崔光磊, E-mail: cuigl@qibebt.ac.cn

摘要: 聚合物电解质可以在很大程度上缓解甚至解决二次电池所面临的电解液泄漏、挥发、燃烧和爆炸等潜在安全问题. 但传统聚合物电解质成型工艺繁琐冗赘，且制备过程中存在溶剂挥发污染环境等缺点，原位生成聚合物电解质除可以有效解决上述安全问题外，还可以在二次电池内部形成稳定的固体电解质界面，实现界面融合，减少固/固界面阻抗，有利于提高二次电池循环寿命，具有很好的应用前景. 基于此，本综述从有无引发剂添加、引发剂种类等多角度重点阐述了原位生成聚合物电解质的制备工艺、形成机理、聚合物电解质类型及其在锂(钠、镁)等二次电池中应用的主要研究进展和现状. 最后对二次电池用原位生成聚合物电解质存在的挑战和未来可能发展趋势进行了展望.

关键词:

English

Research Progress of in situ Generated Polymer Electrolyte for Rechargeable Batteries

1.
Qingdao Industrial Energy Storage Research Institute, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101
2.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049
3.
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083

Corresponding author:

Received Date: 2019-05-09
Accepted Date: 2019-06-08
Available Online: 2019-09-01

Abstract: Rechargeable batteries, which are among the most promising energy storage devices, have become a research hotspot related to energy-storage and energy-convert systems. While the rechargeable batteries based on liquid electrolytes commonly possess serious safety risks such as electrolyte leakage, volatilization, combustion, and explosion, polymer electrolytes display great potentials in ameliorating and addressing these problems. Conventional polymer electrolytes are generally prepared by the solution casting method, which is difficult to implement in actual production owing to its complicated operation and harsh conditions. In addition, the poor electrolyte/electrode interfacial contact in solid-state lithium batteries is also a common issue, mainly originating from the ex situ assembly technique of solid-state electrolyte. These drawbacks hinder their large-scale promotion and application. In this context have emerged the in situ generated polymer electrolytes, which aim at solving the above mentioned problems effectively. The general process of in situ preparation of the polymer electrolytes is as follows: a precursor solution consisting of monomers, lithium salts, and initiators is injected into the battery to fully wet the electrode channels and gaps, and the monomers are then polymerized in situ under certain external conditions to afford a gel/solid polymer rechargeable battery in one step. Compared to the traditional routes to polymer electrolytes, such in situ polymerization simplifies the preparation process, facilitates favorable solid electrolyte interface, and enables the electrode and electrolyte to form an integrated structure for better interfacial contact. These advantages are beneficial to an improved performance of rechargeable batteries and endow the technique with a promising application prospect. For more efficient development, it is an urgent task to review the existing process routes, reaction principles, types of polymer electrolytes, and the practical applications of in situ generated polymer electrolytes in rechargeable batteries (such as lithium, sodium, magnesium, etc.). Herein, we summarize the research progress of in situ polymerization in significantly stabilizing the electrode/electrolyte interface and inhibiting the diffusion of intermediates. Further, we discuss the challenges and development treads of in situ generated polymer electrolytes, including the prospects of quasi-solid polymer electrolytes. We believe this review paper will serve as a valuable reference and theoretical guidance for researchers engaged in polymer electrolytes.

Key words:

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Figure 1. Comparisons of preparation methods, advantages, and disadvantages of polymer electrolytes by (a) solution-casting and (b) in situ method

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Figure 2. (a) Rate performance of LFMP/PVCA-LSnPS/Li cell at the rates of 0.1, 0.3, 0.5, and 1 C, and cycle performance at the rate of 0.5 C at room temperature; (b) Element mapping analysis of PVCA-LSnPS composite after cycling; (c) Possible complex structures in PVCA-LSnPS composite after cycling based on element mapping analysis and the DFT calculation results (Reprinted with permission from Ref.[41]; Copyright (2018) American Chemical Society)

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Figure 3. Scheme of “Shuangjian hebi” reaction (Reprinted with permission from Ref.[47]; Copyright (2017) American Chemical Society)

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Figure 4. In situ polymerization of GPE (Reprinted with permission from Ref.[52]; Copyright (2018) Wiley-VCH Verlag GmbH & Co. KGaA)

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Figure 5. Schematic illustration for the in situ synthesis route to nesting doll-like HPILSE (Reprinted with permission from Ref.[56]; Copyright (2017) Elsevier)

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Figure 6. Polymerization mechanism of PVA-CN in electrolyte solvents (Reprinted with permission from Ref.[57]; Copyright (2014) The Royal Society of Chemistry)

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Figure 7. Schematic illustration for the in situ synthesis route to SEN (Reprinted with permission from Ref.[81]; Copyright (2015) Wiley-VCH Verlag GmbH & Co. KGaA)

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Figure 8. Schematic diagram of cationic polymerization of divinyl ethers (Reprinted with permission from Ref.[58]; Copyright (2010) Elsevier)

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Figure 9. (a) The optical images of PEGDE solution with LiDFOB and (b) crosslinked solid electrolyte pure C-PEGDE; (c) The cationic polymerization mechanism initiated by BF₃ (Reprinted with permission from Ref.[60]; Copyright (2017) Wiley-VCH Verlag GmbH & Co. KGaA)

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Figure 10. (a) Schematic model of the polymerization mechanism of DOL induced by LiPF₆; (b) Optical photographs of LE and GPE (Reprinted with permission from Ref.[62]; Copyright (2019) Elsevier)

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Figure 11. (a) Schematic illustrating the ex situ and in situ syntheses of SPEs; (b) Reaction mechanism illustrating how Al(OTf)₃ initiates polymerization of DOL (Reprinted with permission from Ref.[83]; Copyright (2019) Springer Nature) (The online version is colorful.)

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Figure 12. The schematic diagram of in situ formed polymerization process of PTHF electrolyte (Reprinted with permission from Ref.[62]; Copyright (2019) Elsevier)

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Figure 13. (a) Schematic illustration of in situ preparation of PTB@GF-GPE and the cell assembly procedure; (b) The synthetic route to PTB-GPE based on the reaction of Mg(BH₄)₂, MgCl₂, and PTHF (Reprinted with permission from Ref.[63]; Copyright (2019) Wiley-VCH Verlag GmbH & Co. KGaA)

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Figure 14. (a) Schematic diagram depicting transformation from liquid into a gel electrolyte; (b) Schematic representation of the polymerization mechanism of PVFM-based GPE (Reprinted with permission from Ref.[64]; Copyright (2014) Elsevier)

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Figure 15. (a) Charge/Discharge curves of LiNi_0.5Mn_1.5O₄/Li in the 5^th, 30^th, 60^th, and 100^th cycles; (b) Cycling behavior of the LiNi_0.5Mn_1.5O₄/PECAGPE/Li batteries at the rate of 1 C; (c) Anionic polymerization mechanism initiated by metal Li (Reprinted with permission from Ref.[65]; Copyright (2017) American Chemical Society)

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Figure 16. The G4 gel formation process: (a – d) photographs of EDA/G4 solution with Li sheet after different days and (e) the separated Li sheet with a gel on the surface; Chemical mechanism of the gel formation by cross-linking reaction: (f) the reaction between Li metal and EDA and (g) cross-linking reactions between G4 and LiEDA^. (Reprinted with permission from Ref.[66]; Copyright (2018) Wiley-VCH Verlag GmbH & Co. KGaA)

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Figure 17. (a) A photograph of the vacuum-degassed solid-state electrolyte pellet; (b) The first to fifth charge-discharge profiles of all-solid-state LiCoO₂/Li battery (Reprinted with permission from Ref.[69]; Copyright (2012) Elsevier)

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Figure 18. Bond lengths (Å) of (a) free TFSI anions (C1 and C2) and (b) interacted TFSI anions with TiO₂ nanoparticle (Reprinted with permission from Ref.[67]; Copyright (2015) Wiley-VCH Verlag GmbH & Co. KGaA)

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Figure 19. Reaction scheme for synthesis of a cross-linked polymer network: (a) fluorinated carbamate synthesised from the reaction between PEI and FEC; (b) cross-linked polymer network obtained by ring-opening reaction between fluorinated carbamate and PEGDE (Reprinted with permission from Ref.[70]; Copyright (2014) Elsevier) (The online version is colorful.)

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Figure 20. (a) Schematic illustration of the preparation of the PDMP-Li GPE; (b) Detailed charge/discharge curves of the pouch-type cell with the PDMP-Li GPE (Reprinted with permission from Ref.[72]; Copyright (2017) The Royal Society of Chemistry) (The online version is colorful.)

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Figure 21. Prospects for the future development of in situ generated polymer electrolyte

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Table 1. Parameters and properties of PVC-based polymer electrolytes generated in situ by free radical polymerization

Precursor	Initiator and initiation conditions	Electrolyte state	Ionic conductivity at 25 °C (S cm⁻¹)	Lithium-ion transference number (t_Li⁺)	Electrochemical window (V)	Ref.
LiDFOB/VC/AIBN	AIBN, 60 °C 24 h or 80 °C 10 h	Solid	2.23 × 10⁻⁵	0.57	4.5	[40]
LSnPS/LiDFOB/ VC/AIBN	AIBN, 60 °C 120 h	Solid	2 × 10⁻⁴	0.60	4.5	[41]
LiDFOB/EC/DEC/ VC/AIBN	AIBN, 60 °C 24 h or 80 °C 2 h	Gel	5.59 × 10⁻⁴	0.34	4.8	[42]

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沈阳化工大学材料科学与工程学院沈阳 110142

二次电池用原位生成聚合物电解质的研究进展

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Research Progress of in situ Generated Polymer Electrolyte for Rechargeable Batteries

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