Gel polymer electrolytes for lithium sulfur batteries: synthesis and advanced characterization techniques
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摘要: 凝胶聚合物电解质(GPE)的应用为改善锂硫电池的安全性和抑制穿梭效应提供一种有希望的方案。凝胶聚合物电解质能够改善全固态电解质与双电极之间存在的高界面阻抗所带来的电荷转移受阻、锂沉积不均匀等问题，有效解决容量衰减快、循环稳定性差等缺陷。本文针对锂硫电池中制备凝胶聚合物电解质所采用的原位聚合和非原位聚合两种不同的工艺手段进行介绍，通过阐述不同合成工艺改进凝胶聚合物电解质基底的方法，重点分析不同工艺所带来的“收益”，并介绍了具有实时性和精准性的原位表征仪器在锂硫电池中的应用，指出原位先进表征技术对锂硫电池电极材料设计的指导作用，并供科研工作者开发研究更适宜产业化的凝胶聚合物电解质的合成工艺，展望未来锂硫电池凝胶聚合物电解质合成设计的发展方向。Abstract: The application of Gel-polymer electrolyte (GPE) provides a promising scheme for improving the safety of lithium-sulfur batteries and inhibiting the shuttle effect. The gel polymer electrolyte can improve the charge transfer obstruction and uneven lithium deposition caused by the high interface impedance between the all-solid electrolyte and the double electrode, and effectively solve the defects such as fast capacity decay and poor cycle stability. In this paper, two different technological means, in-situ polymerization and non-in-situ polymerization, are introduced for the preparation of gel polymer electrolytes in lithium-sulfur batteries. The methods of improving the gel polymer electrolyte base by different synthetic processes are described, and the "benefits" brought by different processes are analyzed, and the application of real-time and accurate in-situ characterization instruments in lithium-sulfur batteries is introduced. It is pointed out that in situ advanced characterization technology can guide the electrode material design of lithium sulfur battery and provide researchers with more suitable synthesis technology of gel polymer electrolyte for industrialization.
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图 1 锂硫电池凝胶聚合物电解质(GPE)的不同合成工艺及其先进表征技术
Figure 1. Different synthesis techniques and advanced characterization techniques of lithium-sulfur battery gel-polymer electrolyte (GPE)
图 2 (a) TOC晶体结构及PVFH-TOC-PEG电解质合成示意图[32] (b) PVDF - HFP@m-Co3O4(s)-NH2的合成路线示意图[33] (c) PEO-PAN-LLZO GPE在Li-S电池中的性能提升机制示意图[35] (d) 聚合物凝胶形成机制示意图[36]
Figure 2. (a) Crystal structure of TOC and schematic illustration for the synthesis of the PVFH-TOC-PEG electrolyte[32] (b) Schematic illustration of the synthesis route of PVDF−HFP@m-Co3O4(s)-NH2[33] (c) Schematic illustration for the performance improvement mechanisms of PEO-PAN-LLZO CGPE applied in the Li-S battery[35] (d) Schematic diagram of formation mechanism for the polymer gel polymer[36]
图 4 (a)倍率为0.1 C时Li-TAA/S/C电池的充放电循环曲线 (b) Li-TAA/S/C和Li-S/C电池的倍率性能 (c) Li-TAA/S/C和Li-S/C电池的循环性能(倍率为0.1 C)[38]
Figure 4. (a) Charge and discharge cycle curve of Li-TAA/S/C battery at 0.1 C rate (b) Rate performance of Li-TAA/S/C and Li-S/ C cells (c) Cycling performance of Li-TAA/S/C and Li-S/C cells (rate: 0.1 C)[38]
图 5 (a) DOL与PVA-CN合成IPN-GPE的两步反应机制 (b)具有非对称GPE网络的Li|IPN-GPE|S电池示意图[39] (c) 高离子导电性SHGP凝胶电解质的原理图和工作原理 (d) PEGDE与PEI聚合合成方案[40] (e) 采用CNT/Mo2 C/S正极和GPE的电池中的性能提升机制示意图[41] (f) 当与锂箔静态接触时，LE、PDOL和PDOL@InPc的原理图和光学图像[42]
Figure 5. (a) The two-step reaction mechanisms of DOL and PVA-CN to form the IPN-GPE (b) Schematic diagram of the LijIPN-GPEjS battery with the asymmetric GPE network[39] (c) The schematic illustration and the working principle of high ionic conductive SHGP gel electrolyte (d) Synthesis scheme of the polar polymer by polymerization of PEGDE and PEI[40] (e) Schematic illustration for the performance improvement mechanisms of The cells with CNT/Mo2C/S cathodes and GPE[41] (f) Schematic and optical images of LE, PDOL, and PDOL@InPc when in static contact with lithium foil[42]
图 7 (a) Li2S2和Li2S的成核、生长、沉积、溶解等动态过程[50] (b) 可溶性多硫化锂的in-situ UV-Vis光谱 (c) 硫正极上Li2Sx的动态分布情况[53] (d) 有/无 BSOC的Li/S电池负极侧的原位S K-edge XAS 光谱[54]
Figure 7. (a) Dynamic processes of nucleation, growth, deposition, and dissolution of Li2S2 and Li2S[50] (b) in-situ UV-Vis spectra of soluble lithium polysulfide (c) Dynamic distribution of Li2Sx on the positive sulfur electrode[53] (d) In situ/operando S K-edge XAS observations at the anodic side of Li/S cells with/without BSOC layer[54]
表 1 运用不同合成工艺GPE的优点及其组装锂硫电池的性能参数
Table 1. The advantages of using different synthetic processes GPE and the performance parameters of assembling lithium-sulfur batteries
合成工艺 优点 GPE 离子电导率 面载量 放电比容量 循环性能 非原位聚合法 合成凝胶流程简便，容易在分子水平进行修饰，兼容性更好，易于整合多种材料的优点 PVFH-TOC-PEG 8×10−3 S·cm−1(25℃) 5 mg·cm−2 1103 mA·h·g−1
(2 mA·cm−1)8 mA·cm−2, 650次循环后放电比容量680 mA·h·g−1 PVDF-HFP-m-Co3O4-NH3 3.23×10−3 S·cm−1
(室温)2 mg·cm−2 - 0.5 C, 150次循环后放电比容量620 mA·h·g−1 PVDF-HFP-Al2O3 1.85×10−3 S·cm−1
(室温)1 mg·cm−2 1233 mA·h·g−1
(0.1 C)0.1 C, 150次循环后放电比容量841.5 mA·h·g−1 PEO-PAN-Li7La3Zr2O2 2.1×10−3 S·cm−1(30℃) 2±0.3 mg·cm−2 1459 mA·h·g−1
(0.1 C)1 C, 300次循环后放电比容量575 mA·h·g−1 PI10 6.22×10−3 S·cm−1
(室温)1 mg·cm−2 - 0.2 C, 450次循环后放电比容量1154.3 mA·h·g−1 原位界面聚合法 在硫正极到锂负极间形成固化程度不同的GPE，解决正极/GPE界面稳定性较差的问题 PDOL 5.56×10−3 S·cm−1
(室温)2 mg·cm−2 1102 mA·h·g−1
(0.1 C)0.1 C, 200次循环后放电比容量805 mA·h·g−1 PDOL - 1.5 mg·cm−2 760 mA·h·g−1
(0.5 C)0.1 C, 200次循环后放电比容量645 mA·h·g−1 原位溶液聚合法 扬弃了传统GPE合成过程中的聚合物材料溶解、干燥涂膜等复杂工序，制取便捷、操作安全 PVA-CN/PDOL 3.23×10−3 S·cm−1(25℃) 1.5 mg·cm−2 - 0.5 C, 500次循环后放电比容量807 mA·h·g−1 SHGP 0.75×10−3 S·cm−1(30℃) 2.5 mg·cm−2 950 mA·h·g−1
(0.2 C)0.5 C, 100次循环后放电比容量715 mA·h·g−1 PDOL 2.5×10−2 S·cm−1
(室温)1 mg·cm−2 1024 mA·h·g−1
(0.05 C)0.5 C, 100次循环后放电比容量521 mA·h·g−1 PDOL@InPc 3.7×10−3 S·cm−1
(室温)1.5±0.02 mg·cm−2 1194.7 mA·h·g−1
(0.2 C)0.2 C, 260次循环后放电比容量673.5 mA·h·g−1 Notes: GPE are the gel polymer electrolyte; PVFH-TOC-PEG are the Polyvinylidene fluoride - hexafluoropropylene -Ti32O16(OCH2CH2O)32(RCOO)16(EGH)16(R:t-CH3CH2CH2CH2-, EGH:-OCH2CH2OH)- polyethylene glycol; PVDF-HFP-m-Co3O4-NH3 are the Polyvinylidene fluoride - cohexafluoropropylene - ammoniated mesoporous cobalt tetroxide; PVDF-HFP-Al2O3 are the Polyvinylidene fluoride - total hexafluoropropylene - aluminum oxide; PEO-PAN-Li7La3Zr2O2 are the Polyethylene oxide - polyacrylonitrile - lithium lanthanum zirconium oxygen; PI10 are the polyimide10; PDOL are the Poly (1, 3-dioxopentylene); PVA-CN/PDOL are the Cyanopolyvinyl alcohol/ Poly (1, 3-dioxopentylene); SHGP are the novel gel polymer synthesized from polyethylene glycol diglycidyl ester and branched polyethylene imide; PDOL@InPc is indium phthalocyanine added to poly1, 3-dioxopentane. 
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表 2 不同原位表征方法及其用途
Table 2. Different in situ characterization methods and their uses
原位表征方法 特点 测试对象 在锂硫电池中的用途 in-situ TEM 提供电化学反应过程中电极在高空间分辨率下的实时综合信息，探究锂硫电池中的微观结构演变和化学组成变化 锂硫电池循环过程中的固态产物 观测锂硫电池中Li2S的结晶状态及其演变 in-situ AFM 结合模拟电池环境条件，并跟踪这种环境下观测物的形貌演变 固体材料表面结构(包括绝缘体) 观测正极侧不溶性Li2S及Li2S2演变过程和负极侧SEI形成及演变途径
元素表征in-situ Raman及
in-situ UV-Vis根据拉曼散射光谱和紫外吸收光谱的不同来确定不同分子的组成结构 锂硫电池循环过程中产生的多硫化物 观测锂硫电池体系中，正极/电解质界面处多硫化锂的分布情况 in-situ XAS 不依赖长程有序结构而对目标原子近邻结构敏感，能够得到材料局部几何结构和电子结构信息 催化剂及多硫化物 定量测定硫中几种含硫物种的含量，研究材料与多硫化物相互作用
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