Li1.5Al0.5Ge1.5(PO4)3基固体复合电解质的制备及锂离子导电行为

doi:10.7503/cjcu20150704

摘要/Abstract

摘要：

将聚氧化乙烯(PEO)和二(三氟甲基磺酰)亚胺锂(LiTFSI)混合(固定EO/Li摩尔比为13)后, 采用溶液浇注法制备了一系列不同Li_1.5Al_0.5Ge_1.5(PO₄)₃(LAGP)与PEO质量比的LAGP-PEO(LiTFSI)固体复合电解质体系. 结合电化学阻抗法、表面形貌表征以及与惰性陶瓷填料(SiO₂, Al₂O₃) 性能的对比分析, 探讨了LAGP在固体复合电解质中的作用机理以及锂离子的导电行为. 结果表明, 在以LAGP为主相的固体复合电解质中, PEO主要处于无定形态, 整个体系主要为PEO与LiTFSI的络合相、 LAGP与PEO(LiTFSI)相互作用形成的过渡相和LAGP晶相. 其中LAGP作为主要的导电基体不仅起到降低PEO结晶度、改善两相导电界面的作用; 同时自身也可以作为离子传输的通道, 降低锂离子迁移的活化能, 从而使离子电导率得到提高. 当LAGP与PEO的质量比为6:4时, 固体复合电解质的成膜性能最好, 离子电导率最高, 在30 ℃时为2.57×10^-5 S/cm, 接近LAGP的水平, 电化学稳定窗口超过5 V.

关键词: 固体复合电解质, Li1.5Al0.5Ge1.5(PO4)3, 聚氧化乙烯, 离子电导率

Abstract:

LAGP-PEO(LiTFSI) solid composite electrolyte were prepared with Li_1.5Al_0.5Ge_1.5(PO₄)₃(LAGP) and LiN(CF₃SO₂)₂(LiTFSI) as conductive components and poly(ethylene oxide)(PEO) as the binder using solution casting method. The molar ratio of EO/Li was 13 when the ratio of PEO to LAGP was varied. The role of LAGP and the transport mechanism of Li-ion in solid composite electrolyte were analyzed using electrochemical impedance spectroscopy and morphology techniques. The results showed that LAGP partially interacted to PEO(LiTFSI) and uniformly distributed in the electrolyte. With the increase of LAGP content, amorphous regions of PEO rises up to a maximum value due to the coordination interactions between LAGP and PEO(LiTFSI). Three phases are generally present, namely a pure crystalline LAGP phase, all amorphous complexion PEO(LiTFSI) phase and a transition phase consisting of lithium salt particles and amorphous PEO(LiTFSI). The electrochemical impedance spectroscopy(EIS) showed that Li⁺ ions can go through the interface between ceramic particles and polymer. Compared with other ceramic fillers(SiO₂, Al₂O₃), the addition of Li⁺conducting LAGP improves the ionic conductivity and electrochemical stability of PEO-based solid composite electrolyte. LAGP glass-ceramic improves solid composite electrolyte conductivity not only by enhancing the amorphous PEO phase, but also via its intrinsic conductivity. The highest ionic conductivity and the processability of LAGP-PEO(LiTFSI) solid electrolyte were obtained when the mass ratio of LAGP to PEO was fixed at 6:4. The optimal ionic conductivity can reach 2.57×10^-5 S/cm at room temperature which is close to that of LAGP. In addition, LAGP-PEO(LiTFSI) solid composite electrolyte shows an enlarged electrochemical stability window(>5 V) in comparison to the PEO(LiTFSI) polymer electrolyte. Solid composite electrolyte based on LAGP-PEO(LiX) has a great prospect in application due to the combination of the fast ion conductor LAGP with high ionic conductivity and the PEO-based polymer electrolyte with good processability.

Key words: Solid composite electrolyte, Li1.5Al0.5Ge1.5(PO4)3(LAGP), Poly(ethylene oxide)(PEO), Ionic conductivity

中图分类号:

O646.2

TrendMD:

余涛, 韩喻, 王珲, 熊仕昭, 谢凯, 郭青鹏. Li_1.5Al_0.5Ge_1.5(PO₄)₃基固体复合电解质的制备及锂离子导电行为. 高等学校化学学报, 2016, 37(2): 306.

YU Tao, HAN Yu, WANG Hui, XIONG Shizhao, XIE Kai, GUO Qingpeng. Preparation and Lithium Ion Transport Behavior for Li_1.5Al_0.5Ge_1.5(PO₄)₃ Based Solid Composite Electrolyte. Chem. J. Chinese Universities, 2016, 37(2): 306.

图/表 13

Fig.1 Model for SS||PEO(LiTFSI)/LAGP/PEO(LiTFSI)||SS cell

Fig.2 XRD patterns of LAGP(a), PEO(LiTFSI)(b) and LAGP-PEO(LiTFSI) solid composite electrolytes m(LAGP)/m(PEO): c. 5:5; d. 6:4; e. 7:3; f. 8:2; g. 9:1.

Fig.3 SEM images of the surface(A) and cross-section(B) of the LAGP-PEO(LiTFSI) solid composite electrolyte

Fig.4 DSC curves(A) and FTIR spectra(B) of the LAGP-PEO(LiTFSI) solid composite electrolytes m(LAGP):m(PEO): a. 6:4; b. 7:3; c. 8:2; d. 9:1; e. LAGP; f. PEO(LAGP); g. PEO(LiTFSI); h. PEO. Peak A: CH2 rocking vibration absorption peak of PEO; peak B: C—O—C stretching vibration absorption peak of PEO.

Fig.5 Ionic conductivity as a function of temperature for the LAGP-PEO(LiTFSI) solid composite electrolytes m(LAGP)/m(PEO): a. 6:4; b. 7:3; c. 8:2; d. 9:1.

Table 1 Thermal property and ionic conductivity of the LAGP-PEO(LiTFSI) solid composite electrolytes with various LAGP contents*

Mass ratio of LAGP to PEO	T_g/℃	T_m/℃	10⁵Conductivity/(S·cm^-1)		E_a/(J·mol^-1)
Mass ratio of LAGP to PEO	T_g/℃	T_m/℃	30 ℃		60 ℃
Pure PEO(LiTFSI)	-33.84	52.56	0.23	1.74	92.74
6:4(without LiTFSI)	-43.81	66.61	0.07	1.10	76.55
5:5	—	—	0.34	2.07	50.22
6:4	-44.43	42.35	2.57	8.96	33.61
7:3	-45.10	39.94	1.44	5.30	36.31
8:2	-45.77	36.53	0.22	1.81	53.38
9:1	-48.17	29.65	0.02	0.12	57.25

Fig.6 Impedance spectra(A) and inoic conductivity as a function of temperature(B) for the PEO(LiTFSI)/LAGP/PEO(LiTFSI) cell

Fig.7 SEM images of the surface and cross-section of the LAGP from the PEO(LiTFSI)/LAGP/PEO(LiTFSI) cell (A) Surface morphology(initial state); (B) surface morphology(60 ℃ activation); (C) surface morphology after measurement; (D) cross-section morphology after measurement.

Table 2 Thermal property and ionic conductivity of the solid composite electrolyte with different cermatic fillers

Solid composite electrolyte	T_g/℃	T_m/℃	10⁵Conductivity/(S·cm^-1)		E_a/(J·mol^-1)
Solid composite electrolyte	T_g/℃	T_m/℃	25 ℃		60 ℃
Pure PEO(LiTFSI)	-33.84	52.56	0.23	1.74	92.74
PEO(LiTFSI)-10%SiO₂	-39.8	45.37	0.40	7.85	70.84
PEO(LiTFSI)-10%Al₂O₃	-40.17	45.45	0.30	5.94	71.00
PEO(LiTFSI)-10%LAGP	-40.37	46.17	0.62	10.14	64.94
PEO(LiTFSI)-10%SiO₂+10%LAGP	-41.50	39.67	0.29	5.09	74.36
PEO(LiTFSI)-20%LAGP	-43.83	48.83	0.41	8.31	71.46

Fig.8 XRD patterns(A), DSC traces(B), FTIR spectra(C) and inoic conductivity as a function of temperature(D) of solid composite electrolyte with different ceramic fillers

Fig.9 Equivalent circuit model(A, B) and fitted impedance results(C, D) of solid composite electrolytes PEO(LiTFSI)-10%inert filler at 30 ℃(A, C) and PEO(LiTFSI)-10%LAGP at 30 ℃(B, D) CPE1 and CPE2: diffusion element; CPE3 and CPE4: constant phase elements; Cl: the capacitance of double layer;C2 and C3: the capacitance of electrolyte.

Table 3 Fitted results of the solid composite electrolyte with different ceramic fillers

Ceramic filler	R₁/Ω	R₂/Ω	R₃/Ω	10⁵Conductivity/(S·cm^-1)
Pure PEO(LiTFSI)	681.5		3638	0.23
PEO(LiTFSI)-10%SiO₂	608.5		1159	0.40
PEO(LiTFSI)-10%Al₂O₃	628.5		1225	0.30
PEO(LiTFSI)-10%LAGP	614.3	81.8	1224	0.62

Fig.10 Transport mechanism of Li-ion of the solid composite electrolyte with different ceramic fillers (A) Inert filler; (B) LAGP.

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Li_1.5Al_0.5Ge_1.5(PO₄)₃基固体复合电解质的制备及锂离子导电行为

Preparation and Lithium Ion Transport Behavior for Li_1.5Al_0.5Ge_1.5(PO₄)₃ Based Solid Composite Electrolyte

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