Preparation and Lithium Ion Transport Behavior for Li1.5Al0.5Ge1.5(PO4)3 Based Solid Composite Electrolyte

doi:10.7503/cjcu20150704

Abstract

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

CLC Number:

O646.2

TrendMD:

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[J]. Chem. J. Chinese Universities, 2016, 37(2): 306.

Figures/Tables 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.

References 26

[1]	Li Y. J., Cao T. P., Sun X. L., Shao C. L., Chem. J. Chinese Universities, 2010, 31(1), 16—19
	(李跃军, 曹铁平, 孙新丽, 邵长路. 高等学校化学学报, 2010, 31(1), 16—19)
[2]	Liu J., Xu J. Y., Lin Y., Li J., Lai Y. Q., Yuan C. F., Zhang J., Zhu K., Acta Chim. Sin., 2013, 71, 869—878
	(刘晋, 徐俊毅, 林月, 李劼, 赖延清, 袁长福, 张锦, 朱凯. 化学学报, 2013, 71, 869—878)
[3]	Young J. N., Sung J. C., Dae Y. O., Jun M. L., Sung Y. K., Jun H. S., Young G. L., Lee Y. S., Yoon S. J., Nano Letters, 2015, 15(5), 3317—3323
[4]	Han F.D., Gao T., Zhu Y. J., Gaskell K. J., Wang C. S., Adv. Mater., 2015, 1—11
[5]	Lin X. M., Zhu L. L., Han J., Liu X. M., Chem. J. Chinese Universities, 2015, 36(1), 61—66
	(林晓敏, 朱丽丽, 韩健, 刘晓梅. 高等学校化学学报, 2015, 36(1), 61—66)
[6]	Arbi K., Bucheli W., Jiménez R., Sanz J., J. Eur. Ceramic Soc., 2015, 35, 1477—1484
[7]	Brian E. F., Conrad R. S., Chem. Mater., 2014, 26, 4741—4749
[8]	Kubansk A., Cast L., Torteta L., Schäf O., Dollé M., Bouchet R., Solid State Ionics, 2014, 266, 44—50
[9]	Xu X. X., Qiu Z. J., Guan Y. B., Huang Z., Jin Y., Energy Storage Science and Technology, 2013, 2(4), 331—341
	(许晓雄, 邱志军, 官亦标, 黄祯, 金翼. 储能科学与技术, 2013, 2(4), 331—341)
[10]	Goodenough B. J., Youngsik K., Chem. Mater., 2010, 22(3), 587—603
[11]	Zhao X. D., Zhu W., Li J. R., Jia Y. B., Mater. Rev., 2014, 28(4), 13—17
	(赵旭东, 朱文, 李镜人, 贾迎宾. 材料导报, 2014, 28(4), 13—17)
[12]	Angdl C. A., Liu C., Sanchez E., Nature, 1993, 362(6416), 137—139
[13]	Xu K., Angell C. A., Electrochim. Acta, 1995, 40(13/14), 2401—2403
[14]	Huang L. Z., Wen Z. Y., Jin J., Liu Y., J. Inorg. Mater., 2012, 27(3), 249—252
	(黄乐之, 温兆银, 靳俊, 刘宇. 无机材料学报, 2012, 27(3), 249—252)
[15]	Wang Y.J., Study on PEO Based Composite Polymer Electrolytes Using Li1.3Al0.3Ti1.7(PO4)3 as Main Component and Filler, Zhejiang University, Hangzhou, 2005
	(王严杰. Li1.3Al0.3Ti1.7(PO4)3作主相和填料相的PEO基聚合物电解质的研究, 杭州: 浙江大学, 2005)
[16]	Croce F., Persi L., Scrosati B., Serraino F., Plichta E., Hendricksonb M. A., Electrochim. Acta, 2001, 46, 2457—2461
[17]	Appetecchi G. B., Zane D., Scrosati B., J. Electroanal. Chem., 2004, 151(9), A1369—A1374
[18]	Marzantowicz M., Dygas J. R., Krok F., Electrochim. Acta, 2008, 53, 741—742
[19]	Wieczorek W., RaduchaD., Zalewska A., Phys. Chem. B, 1998, 102(44), 8725—8731
[20]	Wang Z. X., Gao W. D., Huang X. J., Mo Y. J., Chen L. Q., J. Raman Spectrosc., 2001, 32, 900—905
[21]	Dany B., Donald E. I., Nicholas J. T., Ge'rald P., Marek O., Jacques E. D., Phys. Chem. Chem. Phys., 2002, 4, 6063—6071
[22]	Shen C., Wang J. M., Tan Z., Wan H. J., Lia H. Q., Zhang J. Q., Cao C. N., Electrochim. Acta, 2009, 54, 3490—3494
[23]	Wang C. S., Zhang X. W., John A., J. Electroanal. Chem., 2005, 152(1), A205—A209
[24]	Capiglia C., Mustarelli P., Quartarone E., Tomasi C., Magistris A., Solid State Ionics, 1999, 118, 73—79
[25]	Tan W. Q., Zang. D. Y., Li Y. F., Zhang Y. J., Lu C. J., Li Z. G., Chem. J. Chinese Universities, 2014, 35(1), 85—91
	(谭伟强, 臧渡洋, 李云飞, 张永建, 陆晨君, 栗志广. 高等学校化学学报, 2014, 35(1), 85—91)
[26]	Qian X. M., Gu N. Y., Cheng Z. L., Yang X. R., Wang E. K., Dong S. J., Electrochim. Acta, 2001, 46, 1829—1836

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

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