Preparation and performance of EVOLi-OMMT separator material for lithium ion battery
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摘要: 以聚(乙烯-乙烯醇)(EVOH)，锂基蒙脱土(Li-OMMT)为主要原料，先合成了一种离子型树脂，后与锂基蒙脱土复合以制备一种全新的有机-无机杂化材料EVOLi-OMMT。采用高压静电纺丝法，将其制成锂离子电池用无纺布隔膜。先用红外表征了杂化材料的键接结构，又用SEM表征了隔膜的微观结构，后将合成的两种复合隔膜与Celgard 隔膜进行了吸液率、孔隙率、热性能和电性能的对比。结果表明，EVOLi与OMMT之间生成了新的化学键，形成了插层交联结构，隔膜力学强度比EVOLi提升了68.12%，隔膜孔径均一，改性后的隔膜孔隙率和吸液率分别达457%和73%，初始温度较高，可达270℃，可耐175℃不发生皱缩；电化学测试结果表明改性过后的隔膜离子界面迁移阻抗小，可低至96.59 Ω；100次0.1 C循环以后容量保持率可达93.4%，并在循环测试中表现出优异的倍率性能。
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关键词:
- 锂离子电池 /
- 隔膜 /
- 杂化材料 /
- 静电纺丝 /
- 聚(乙烯-乙烯醇)(EVOH) /
- 锂基蒙脱土(Li-OMMT)
Abstract: Using Poly (ethylene-vinyl alcohol) (EVOH) and Lithium montmorillonite (Li-OMMT), an ionic resin is synthesized first, and then compounded with the lithium montmorillonite to prepare a new organic-inorganic hybrid material EVOLi-OMMT. Electrospinning is used to make it into a non-woven fabric separator for lithium-ion batteries. The bonding structure of the hybrid material was first characterized by infrared, and the microstructure of the diaphragm was characterized by SEM. Then the two composite diaphragms synthesized were compared with the Celgard diaphragm for liquid absorption, porosity, thermal performance and electrical performance. The results show that a new chemical bond is formed between EVOLi and OMMT to form an intercalation cross-linked structure. The mechanical strength of the diaphragm is 68.12% higher than that of EVOLi. The pore diameter of the diaphragm is uniform. The modified diaphragm has a porosity and liquid absorption rate of 457% and 73% respectively, the initial temperature is higher, up to 270℃, and can withstand 175℃ without shrinkage; the electrochemical test results show that the modified membrane has a small ion interface migration resistance, which can be as low as 96.59 Ω; 100 times 0.1 C After the cycle, the capacity retention rate can reach 93.4%, and it shows excellent rate performance in the cycle test. -
图 1 EVOLi-OMMT合成原理及插层示意图
Figure 1. Synthetic principle and schematic diagram of intercalation of EVOLi-OMMT
LTB—Lithium tert-butoxide; 1, 3-PS—1, 3-Propane sultone; EVOH—Ethylene vinyl alcohol copolymer; OMMT—Organic montmorillonite; EVOLi—Lithium-ionized ethylene vinyl alcohol
图 3 EVOLi隔膜与EVOLi-OMMT隔膜的SEM图像：(a)纯EVOLi；(b) 3% OMMT掺杂的EVOLi
Figure 3. SEM images of EVOLi and EVOLi-OMMT separator: (a) Pure EVOLi; (b) 3% OMMT doped EVOLi
图 4 Celgard 2400、EVOLi、EVOLi-OMMT隔膜的吸液率和孔隙率
Figure 4. Uptaken and porosity rate of Celgard 2400, EVOLi and EVOLi-OMMT separator
图 5 Celgard 2400、EVOLi、EVOLi-OMMT隔膜的TGA曲线 (a) 和Celgard 2400、EVOLi、EVOLi-OMMT隔膜的热收缩照片 (b)
Figure 5. TGA curves of Celgard 2400、EVOLi、EVOLi-OMMT、separator (a) and thermal shrinkage photos of Celgard 2400, EVOLi and EVOLi-OMMT separators (b)
图 6 Celgard 2400、EVOLi、EVOLi-OMMT隔膜的界面阻抗谱 (a) 和等效电路图 (b)
Figure 6. equivalent circuit diagrams of Celgard 2400, EVOLi, EVOLi-OMMT (a) and AC impedance spectroscopy (b)
Rs—Electrolyte and electrode resistance; Cdl—Hole electrode interface electric double layer capacitance; Ret—Electron transfer resistance; CPE—Constant phase angle element; Zw—Warburg impedance during diffusion
图 7 Celgard 2400、EVOLi和EVOLi-OMMT隔膜的循环性能曲线(a)和倍率性能曲线(b)
Figure 7. Cycle performance curves (a) and rate performance curves (b) of Celgard 2400, EVOLi and EVOLi-OMMT separator
表 1 隔膜的力学性能数据
Table 1. Mechanics performance data of separator
Separator name Elongation at break/% Tensile strength/MPa Celgard 2400 30.00 134.15 EVOLi 42.13 2.76 EVOLi-OMMT 38.15 4.64 Notes: Celgard 2400—Commercial single-layer polypropylene (PP) separator; EVOLi—Lithium ionized ethylene vinyl alcohol copolymer; EVOLi-OMMT—Lithium ionized ethylene vinyl alcohol copolymer grafted with montmorillonite. 
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