Al2O3/P2O5摩尔比对动力锂电池封接玻璃结构与性能的影响

doi:10.15541/jim20250283

无机材料学报 ›› 2026, Vol. 41 ›› Issue (5): 611-618.DOI: 10.15541/jim20250283 CSTR: 32189.14.jim20250283

Al₂O₃/P₂O₅摩尔比对动力锂电池封接玻璃结构与性能的影响

王巍巍¹^,²(), 曹欣¹, 刘俊飞¹, 杨小菲³, 韩娜¹, 李幸聪¹, 石丽芬¹()

¹ 中建材玻璃新材料研究院集团有限公司先进玻璃材料全国重点实验室, 蚌埠 233000
² 武汉理工大学材料科学与工程学院, 武汉 430070
³ 安徽凯盛基础材料科技有限公司, 蚌埠 233000

收稿日期:2025-07-06 修回日期:2025-10-28 出版日期:2025-11-11 网络出版日期:2025-11-11
通讯作者: 石丽芬, 教授级高级工程师. E-mail: slf@ctiec.net
作者简介:王巍巍(1988-), 男, 博士研究生. E-mail: wangweiwei@ctiec.net
基金资助:
国家重点研发计划(2021YFB3501103);安徽省自然科学基金(2408085ME138);安徽省重点研究与开发计划(2022a05020026)

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

WANG Weiwei¹^,²(), CAO Xin¹, LIU Junfei¹, YANG Xiaofei³, HAN Na¹, LI Xingcong¹, SHI Lifen¹()

¹ State Key Laboratory of Advanced Glass Materials, CNBM Research Institute for Advanced Glass Materials Group Co., Ltd., Bengbu 233000, China
² School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China
³ Anhui Triumph Basic Material Technology Co., Ltd., Bengbu 233000, China

Received:2025-07-06 Revised:2025-10-28 Published:2025-11-11 Online:2025-11-11
Contact: SHI Lifen, professor. E-mail: slf@ctiec.net
About author:WANG Weiwei (1988-), male, PhD candidate. E-mail: wangweiwei@ctiec.net
Supported by:
National Key R&D Program of China(2021YFB3501103);Natural Science Foundation of Anhui Province(2408085ME138);Anhui Provincial Key R&D Program(2022a05020026)

摘要/Abstract

摘要：

磷酸盐玻璃以其热膨胀系数高、封接温度低等特点而成为玻璃密封领域的研究热点, 但在动力锂电池封接领域的研究并不多见。针对动力锂电池封接玻璃的性能需求, 本研究制备了P₂O₅-Al₂O₃-B₂O₃-R₂O-NaF系高热膨胀系数玻璃, 表征了Al₂O₃/P₂O₅摩尔比对封接玻璃结构、热学性能、封接性能及化学稳定性的影响。结果表明: 随着Al₂O₃/P₂O₅摩尔比由0.35增大至0.76, 玻璃结构中P-O-P桥氧键数量逐渐减少, [AlO₄]四面体含量先增加后减少, 导致磷酸盐玻璃网络结构紧密度先增大后降低, 耐酸性随之变化; 玻璃热膨胀系数先由164.5×10^-7 ℃^-1降至160.0×10^-7 ℃^-1, 再逐渐升高至175.9×10^-7 ℃^-1, 封接温度先升高至588 ℃后又降至549 ℃, 耐酸性先增强后减弱。本研究制备的磷酸盐封接玻璃兼顾了高热膨胀系数、低封接温度与良好的化学稳定性, 为寻求动力锂电池电极的玻璃低温封接工艺提供了理论与技术支撑。

关键词: 动力锂电池, 磷酸盐玻璃, 高热膨胀系数, 封接温度, 耐酸性

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

中图分类号:

TQ171

王巍巍, 曹欣, 刘俊飞, 杨小菲, 韩娜, 李幸聪, 石丽芬. Al₂O₃/P₂O₅摩尔比对动力锂电池封接玻璃结构与性能的影响[J]. 无机材料学报, 2026, 41(5): 611-618.

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.

图/表 13

表1 LBG-1~LBG-6磷酸盐玻璃的配料比(%, 摩尔分数)

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

图1 LBG-1~LBG-6玻璃的XRD图谱

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

图2 (a) LBG-1~LBG-6玻璃的拉曼光谱图和(b) LBG-1在765~1300 cm-1的分峰拟合图

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

表2 LBG-1~LBG-6的拉曼光谱(765~1300 cm-1)分峰参数(波峰位置C和相对面积A)及其所属结构单元

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)

图3 (a) LBG-1~LBG-6玻璃的FT-IR光谱图和(b) LBG-1在785~1250 cm-1的分峰拟合图

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

图4 (a) LBG-1~LBG-6的膨胀-温度曲线和(b)热膨胀系数变化曲线

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

图5 Al2O3/P2O5摩尔比对玻璃Tg和Td的影响

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

图6 LBG-1~LBG-6 (a)在盐酸与氢氟酸溶液中的溶解速率、在盐酸溶液中的pH以及(b)溶解速率随时间的变化曲线

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

图7 玻璃试样在盐酸中侵蚀2 h后的表面SEM照片

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

表3 玻璃试样LBG-1在不同温度下的烧结形貌

Table 3 Sintering morphologies of LBG-1 at different temperatures

Sample	Initial temperature	Corner softening temperature	Hemispheric temperature
LBG-1

图8 LBG-1~LBG-6玻璃的(a)封接温度、半球直径和(b)封接强度

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

图9 LBG-5在不同烧结温度时的XRD图谱

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

表S1 玻璃试样在不同温度下的烧结形貌

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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Al₂O₃/P₂O₅摩尔比对动力锂电池封接玻璃结构与性能的影响

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

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