王友昌^a，b，张晓静^{a. b}，朱宇薇^a，b，李筱璐^a，b，李宇航^a，沈志刚^a，b

北京航空航天大学 a. 航空科学与工程学院， b. 粉体技术研究开发北京市重点实验室，北京 100191

引用格式：

王友昌，张晓静，朱宇薇，等 . 石墨烯基水性导电油墨的制备及低温热管理应用［J］. 中国粉体技术，2024，30（6）：15-26.

WANG Youchang， ZHANG Xiaojing， ZHU Yuwei， et al. Preparation of graphene-based water-based conductive ink and its application in low-temperature thermal management［J］. China Powder Science and Technology，2024，30（6）：15−26.

基金项目：国家自然科学基金项目，编号：U23A20111。

第一作者简介：王友昌（1990—），男，博士生，研究方向为二维纳米材料制备及储能应用。E-mail：by1805149@buaa. edu. cn。

通信作者简介：张晓静（1984—），女，副研究员，博士，硕士生导师，研究方向为二维纳米材料制备及应用。E-mail：zhangxiaojing@buaa.edu. cn；沈志刚（1958—），男，教授，博士，博士生导师，研究方向为二维纳米材料制备及应用。E-mail：shenzhg@buaa. edu。

摘要：【目的】 为了制备环保型的石墨烯基水性导电油墨，印刷高性能柔性电阻加热器（flexible resistive heaters，FRHs），实现锂离子电池的低温热管理。【方法】 采用球磨法制备石墨烯基水性导电油墨；采用扫描电子显微镜和透射电子显微镜表征石墨烯及印刷图案的形貌和结构；采用平板流变仪和四探针电阻仪表征炭黑含量对石墨烯基水性油墨流变性能和印刷图案导电性能的影响；探讨石墨烯基FRHs的响应速率、热稳定性和力学性能，以及其在锂离子电池低温热管理中的应用。【结果】 油墨的静态黏度和黏度恢复率随着炭黑含量的增加而增大，印刷图案的电导率在炭黑质量分数为15%时达到最大，为20 383 S/m；石墨烯基FRHs在8 V的低电压下在30 s快速达到150 ℃，能够实现120次的重复开关循环，在72 h的持久运行后温度仅增加了2. 54%，并且在2 000次的弯折后温度变化小于2. 1%。在电压为6 V时将锂离子电池从-30 ℃预热至20 ℃，并在30 min内实现了80%的充电容量。【结论】 射流空化法产生的高剥离度、完好晶体结构和较大横向尺寸（1 μm）的石墨烯与填充于其中的炭黑使油墨具有合适的流变性，并在印刷图案中构建致密的导电通道，赋予FRHs优异的性能。

关键词：石墨烯；水性油墨；丝网印刷；柔性电阻加热器；热管理

Abstract

Objective Traditional metal heating films used for preheating lithium-ion batteries are often inflexible， dense， and susceptible to corrosion. In contrast， graphene-based flexible resistive heaters （FRHs）， produced through screen printing， demonstrate great potential due to their outstanding conductivity， stability， and lightweight properties. However， replacing toxic， high-boiling-point organic solvents with water remains a substantial challenge. To address this， this paper prepares an environmentally friendly graphene-based ink using a ternary mixed solvent composed of water， ethanol， and ethylene glycol.

Methods High-quality graphene was initially prepared using the jet cavitation method， with its morphology and structure characterized by scanning electron microscopy （SEM） and transmission electron microscopy （TEM）. A simple sand-milling method was then employed to produce graphene-based water-based ink with varying ratios of graphene and carbon black. A parallel-plate rheometer and a four-probe resistivity meter were utilized to assess the rheological properties of the ink and the conductivity of the printed patterns. SEM was used to explore the mechanism by which carbon black influenced the conductivity of the printed patterns. Finally， graphene-based FRHs were fabricated through screen printing， and their electrothermal properties were tested. These FRHs were applied to low-temperature thermal management in lithium-ion batteries.

Results and Discussion The size and quality of graphene had a significant impact on the rheological properties of the ink and the conductivity of the printed patterns. Graphene produced through jet cavitation method exhibited large lateral sizes （~1 μm）and a high degree of exfoliation， as observed in TEM images. The symmetrical hexagonal patterns in electron diffraction images confirmed its excellent crystallinity. These characteristics contributed to its superior conductivity due to minimal obstruction to carrier mobility. However， the rigid connections between two-dimensional graphene sheets created numerous line contacts， limiting the full utilization of graphene’s specific surface area. Introducing zero-dimensional carbon black particles filled the voids between graphene sheets， constructing a dense conductive network that significantly enhanced conductivity by approximately seven times， from ~3. 2×10³ S∙m^-1 to ~2. 04×10⁴ S∙m^-1. Additionally， the large specific surface area and structure of carbon black increased the static viscosity of the ink while maintaining its viscosity（1. 1~1. 2 Pa·s） at a high shear rate （100 s^-1 ）， making it highly suitable for screen-printing process. Moreover， carbon black enhanced the post-printing viscosity recovery rate，optimizing leveling properties on the substrate. Results indicated that at 15% carbon black content， the ink exhibited optimal rheological properties， and the printed patterns achieved maximum conductivity of 20，383 S/m. FRHs prepared through screen printing showed rapid voltage-independent response time， reaching 150 ℃ within 30 seconds at a low voltage of 8 V， while maintaining uniform temperature distribution. The prepared FRHs could undergo 120 repeated switching cycles， with only a 2. 54% temperature increase after 72 hours of continuous operation and less than 2. 1% temperature variation after 2 000 bending cycles. These results demonstrated excellent reliability， long-term stability， and mechanical performance of the printed graphene-based FRHs. When using FRHs to preheat lithium-ion batteries at voltages of 6 V，7 V， and 8 V， the battery surface temperature rose from -30 ℃ to 20 ℃ in 800，400， and 240 s， corresponding to heating rates of 3. 75，7. 5， and 12. 5 ℃·min^-1，respectively. Preheated lithium-ion batteries could be charged and discharged at rates of 2 C and 5 C， respectively. At 6 V， the battery achieved 80% state of charge （SOC） within 24. 2 minutes， and at 7 V，64. 8% SOC within 30 minutes. Graphene-based FRHs screen-printed with G-ink-15 outperformed conventional external preheating methods and showed comparable performance to internal preheating methods.

Conclusion In this paper， an environmentally friendly graphene-based water-based ink was successfully prepared using a ternary mixed solvent of water， ethanol， and ethylene glycol. The ink exhibits excellent rheological properties and produces highly conductive printed patterns. The prepared FRHs demonstrate a fast response time and outstanding stability， indicating significant potential for thermal management applications in lithium-ion batteries.

Keywords：graphene； water-based ink； screen printing； flexible resistive heater； thermal management

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