Effect of Al2O3/P2O5 Molar Ratio on Structure and Properties of Sealing Glass for Power Lithium Batteries

doi:10.15541/jim20250283

Abstract

Abstract:

This study presents a new kind of sealing glass based on P₂O₅-Al₂O₃-B₂O₃-R₂O-NaF system, which exhibits a high coefficient of thermal expansion (CTE) suitable for sealing power lithium batteries. The effects of Al₂O₃/P₂O₅ molar ratio on the structure, thermal properties, sealing performance and chemical stability of the sealing glass were characterized. The results show that as the Al₂O₃/P₂O₅ molar ratio increases from 0.35 to 0.76, the number of P-O-P bridge oxygen bonds within the glass structure gradually decreases, and the content of [AlO₄] tetrahedra initially increases and then decreases, leading to an initial increase in the compactness of the phosphate glass network structure, followed by a decrease. Correspondingly, the CTE of the glass firstly decreases from 164.5×10^-7 ℃^-1 to 160.0×10^-7 ℃^-1, and then gradually increases to 175.9×10^-7 ℃^-1, while the sealing temperature initially rises to 588 ℃ and subsequently falls to 549 ℃. The acid resistance of the glass also follows this trend, initially improving and then deteriorating. The phosphate sealing glass prepared in this study displays proper balance among high CTE, low sealing temperature and excellent chemical stability, providing theoretical and technical support for the development of a low-temperature sealing process for the electrodes of power lithium batteries.

Key words: power lithium battery, phosphate glass, high thermal expansion coefficient, sealing temperature, acid resistance

CLC Number:

TQ171

WANG Weiwei, CAO Xin, LIU Junfei, YANG Xiaofei, HAN Na, LI Xingcong, SHI Lifen. Effect of Al₂O₃/P₂O₅ Molar Ratio on Structure and Properties of Sealing Glass for Power Lithium Batteries[J]. Journal of Inorganic Materials, 2026, 41(5): 611-618.

Figures/Tables 13

Table 1 Chemical composition of LBG-1-LBG-6 phosphate glasses (%, in molar)

Component	LBG-1	LBG-2	LBG-3	LBG-4	LBG-5	LBG-6
P₂O₅	32.3	30.8	29.3	27.8	26.3	24.8
Al₂O₃	11.4	12.9	14.4	15.9	17.4	18.9
B₂O₃	13.6	13.6	13.6	13.6	13.6	13.6
Na₂O	13	13	13	13	13	13
K₂O	11.2	11.2	11.2	11.2	11.2	11.2
NaF	10.2	10.2	10.2	10.2	10.2	10.2
TiO₂	6	6	6	6	6	6
SiO₂	2.3	2.3	2.3	2.3	2.3	2.3

Fig. 1 XRD patterns of LBG-1-LBG-6 glasses

Fig. 2 (a) Raman spectra of LBG-1-LBG-6 and (b) Gaussian deconvolution of LBG-1 within 765-1300 cm-1 range

Table 2 Deconvolution parameters (band center C and relative area A) of Raman spectra between 765-1300 cm-1 and band assignments of structural units of LBG-1-LBG-6

LBG-1		LBG-2		LBG-3		LBG-4		LBG-5		LBG-6		Assignment
C/cm^-1	A	C/cm^-1	A	C/cm^-1	A	C/cm^-1	A	C/cm^-1	A	C/cm^-1	A	Assignment
840	1.5	835	2.1	832	2.0	831	1.9	829	1.8	826	1.6	ν_b [AlO₄]
939	18.5	941	15.6	938	16.7	939	17.9	938	18.6	937	19.8	ν_as (Q⁰)
1037	52.6	1032	51.4	1028	50.2	1025	49.6	1022	49.2	1019	48.4	ν_s (Q¹)
1141	18.7	1136	18.1	1133	16.8	1131	15.3	1129	13.6	1128	12.7	ν_s (Q²)
1205	8.8	1203	8.6	1198	8.2	1194	7.3	1292	6.5	1290	5.6	ν_as (Q²)

Fig. 3 (a) FT-IR spectra of LBG-1-LBG-6 and (b) Gaussian deconvolution of LBG-1 within 785-1250 cm-1 range

Fig. 4 (a) Expansion-temperature curves and (b) variation of thermal expansion coefficient of LBG-1-LBG-6

Fig. 5 Effects of Al2O3/P2O5 molar ratio on Tg and Td of glasses

Fig. 6 (a) Dissolution rate in HCl and HF, pH in HCl, and (b) dissolution rate varied with immersing time for LBG-1-LBG-6

Fig. 7 Surface SEM images of glasses after being corroded in HCl for 2 h (a) LBG-1; (b) LBG-2; (c) LBG-3; (d) LBG-4; (e) LBG-5; (f) LBG-6

Table 3 Sintering morphologies of LBG-1 at different temperatures

Sample	Initial temperature	Corner softening temperature	Hemispheric temperature
LBG-1

Fig. 8 (a) Sealing temperature, hemispherical diameter and (b) sealing strength of LBG-1-LBG-6 glasses

Fig. 9 XRD patterns of LBG-5 sintered at different temperatures

Table S1 Sintering morphologies of glasses at different temperatures

Sample	Initial temperature	Corner softening temperature	Hemispheric temperature
LBG-1
LBG-2
LBG-3
LBG-4
LBG-5
LBG-6

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Effect of Al₂O₃/P₂O₅ Molar Ratio on Structure and Properties of Sealing Glass for Power Lithium Batteries

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