<strong>PHCN</strong>准固态电解质的制备和性能

doi:10.11901/1005.3093.2025.092

材料研究学报

2025, Vol. 39

Issue (12): 935-944 DOI: 10.11901/1005.3093.2025.092

研究论文

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PHCN准固态电解质的制备和性能

梁洪华¹, 陈江超¹, 郑文育¹, 吴海宁¹, 黄亦聪¹, 易卓彦¹, 庞大志¹, 蒋坤朋¹, 朱归胜¹(

), 徐华蕊¹^,²

^1.电子信息材料与器件教育部工程研究中心广西信息材料重点实验室桂林电子科技大学材料科学与工程学院桂林 541004
^2.北部湾大学石油与化工学院钦州 535011

Synthesis and Performance of a Novel Quasi-solid-state Electrolyte PHCN Based on Polyvinylidene Fluoride-hydrogenated Acrylate Incorparated with Mesoporous Spherical g-C₃N₄

LIANG Honghua¹, CHEN Jiangchao¹, ZHENG Wenyu¹, WU Haining¹, HUANG Yicong¹, YI Zhuoyan¹, PANG Dazhi¹, JIANG Kunpeng¹, ZHU Guisheng¹(

), XU Huarui¹^,²

^1.Engineering Research Center of Electronic Information Materials and Devices, Guangxi Key Laboratory of Information Materials, School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004, China
^2.College of Petroleum and Chemical Engineering, Beibu Gulf University, Qinzhou 535011, China

引用本文:

梁洪华, 陈江超, 郑文育, 吴海宁, 黄亦聪, 易卓彦, 庞大志, 蒋坤朋, 朱归胜, 徐华蕊. PHCN准固态电解质的制备和性能[J]. 材料研究学报, 2025, 39(12): 935-944.
Honghua LIANG, Jiangchao CHEN, Wenyu ZHENG, Haining WU, Yicong HUANG, Zhuoyan YI, Dazhi PANG, Kunpeng JIANG, Guisheng ZHU, Huarui XU. Synthesis and Performance of a Novel Quasi-solid-state Electrolyte PHCN Based on Polyvinylidene Fluoride-hydrogenated Acrylate Incorparated with Mesoporous Spherical g-C₃N₄[J]. Chinese Journal of Materials Research, 2025, 39(12): 935-944.

全文: PDF(10656 KB) HTML

摘要:

将介孔球状g-C₃N₄引入PVDF-HFP基质制备出PHCN系列准固态电解质。这种准固态电解质其独特的“拉丝”与“驿站式”结构，提高了离子传导性能和降低了聚合物结晶度。其中的PHCN-3性能优异，在30 ℃其离子电导率为2.62 × 10^-3 S·cm^-1，t_Li⁺迁移数为0.71，电化学窗口拓展至约4.6 V。在电流密度为0.2 mA·cm^-2条件下用PHCN准固态电解质组装的锂对称电池的稳定循环超过2000 h，LiFePO₄/PHCN-3-LiPF₆/Li电池在0.5C倍率条件下循环200次后其容量保持率仍保持88.33%。

关键词 ：无机非金属材料, 准固态电解质, 锂离子电池, 介孔球状g-C₃N₄, “拉丝”结构, “驿站”式结构

Abstract：

Quasi-solid-state electrolytes have garnered significant attention in lithium-ion battery research due to their potential to overcome the safety risks of liquid electrolytes and the low room-temperature ionic conductivity of solid-state electrolytes. In this work, a novel series of quasi-solid-state electrolytes named PHCN (namely PHCN-1, PHCN-2, PHCN-3, and PHCN-4) was fabricated by incorporating mesoporous spherical g-C₃N₄ into a poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix. The resulting PHCN electrolytes feature unique stationary and "instantaneous" structures, which contribute to enhanced ionic conductivity and reduced polymer crystallinity. The optimized sample, PHCN-3 (with 3% g-C₃N₄), exhibits outstanding performance: an ionic conductivity of 2.62 × 10^-3 S·cm^-1 at 30 ^oC, a Li⁺ transference number of 0.71, and a widened electrochemical stability window of approximately 4.6 V. A lithium symmetric cell employing the PHCN-3 electrolyte demonstrated exceptional cycling stability for over 2000 h at a current density of 0.2 mA·cm^-2. Furthermore, a LiFePO₄/PHCN-3-LiPF₆/Li cell maintained a high capacity retention of 88.33% after 200 cycles at a 0.5C rate. These findings indicate that the PHCN quasi-solid-state electrolytes present a promising path for the development of high-performance and safe lithium-ion batteries.

Key words： inorganic non-metallic materials quasi-solid electrolyte lithium-ion battery mesoporous spherical g-C₃N₄ “brushed” structure “stationary” structure

收稿日期: 2025-02-27

ZTFLH:

TB332

基金资助:广西科技基地和人才专项(桂科AD23023013);桂林市科学研究与技术开发计划(20220120-1)

通讯作者: 朱归胜，教授，zhuguisheng@guet.edu.cn，研究方向为纳米光电材料，能源材料及器件等

Corresponding author: ZHU Guisheng, Tel: 13507730539, E-mail: zhuguisheng@guet.edu.cn

作者简介: 梁洪华，男，1999年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2025.092 或 https://www.cjmr.org/CN/Y2025/V39/I12/935

图1 PHCN QSE的制造工艺示意图

图2 介孔球状g-C3N4的SEM图像和EDS能谱、多通道PVDF-HFP的SEM图像、PHCN-3的SEM图像、拉丝状结构以及横截面SEM图像

图3 介孔球状g-C3N4的N2吸附脱附曲线和孔径分布、介孔球状g-C3N4的XRD谱、PHCN-X和PVDF-HFP的XRD谱、FTIR光谱、应力-应变曲线、吸液率、热重分析以及DSC分析

图4 温度为30 ℃时Nyquist图、阿伦尼乌斯曲线、活化能曲线、PHCN-3在30 ℃极化前后的电池极化曲线和阻抗图、PHCN-3和PVDF-HFP准固态电解质在30 ℃、扫描速率为10 mV·s-1的LSV曲线

图5 用PVDF-HFP和PHCN-3组装的锂对称电池的恒电流循环曲线以及PHCN-3的临界电流密度曲线

图6 LiFePO4/PHCN-3-LiPF6/Li电池的倍率性能和在不同循环速率下的首次充放电曲线、PHCN-3和PVDF-HFP在0.5C和30 ℃下的循环稳定性

图7 LiFePO4/PHCN-3-LiPF6/Li电池循环500圈后锂片的表面形貌

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