液相剥离法高效制备石墨烯的研究进展

doi:10.16085/j.issn.1000-6613.2023-1595

摘要/Abstract

摘要：

石墨烯是一种具有优良物理化学性质的二维纳米材料，广泛应用于电池、催化、传感器、印刷、生物医药等领域。然而，石墨烯及其衍生产品的应用与发展面临着巨大挑战——低成本、高品质、规模化生产。本文综述了液相剥离法高效制备石墨烯的研究进展，重点探讨了电化学插层法、溶剂插层法、高温膨胀法和微波膨胀法等液相剥离的前处理方法原理以及对石墨烯剥离效果的影响；分析了水基溶剂、有机溶剂和混合溶剂等剥离溶剂的优缺点与选取原则；对比了超声、高剪切和微通道等过程强化设备的剥离原理和优缺点；简述了离心分离的后处理方法以及分离效果；最后对液相剥离法宏量制备石墨烯的发展趋势进行了展望：通过结合人工智能等方法进行多目标优化，开发无残留的功能化插层剂并匹配温和快速的膨胀方法，寻找低毒、低沸点、高分散的溶剂体系，精确调控液相剥离设备作用机理，设计连续化梯级离心设备，实现液相剥离制备石墨烯的连续化、规模化、低成本快速制备。

关键词: 石墨烯, 液相剥离, 二维纳米材料, 高剪切, 微通道, 高效制备

Abstract:

Graphene, a two-dimensional nanomaterial with excellent physical and chemical properties, is widely used in batteries, catalysis, sensors, printing, biomedicine and other fields. However, the application and development of graphene and its derivatives face great challenges in achieving low-cost, high-quality and large-scale production. Herein, the progress of large-scale preparation of graphene by liquid-phase exfoliation was reviewed. The focus was on exploring the principles of pretreatment methods for liquid-phase exfoliation, including electrochemical intercalation, solvent intercalation, high-temperature expansion and microwave expansion, and their effects on the exfoliation effect of graphene. Subsequently, the advantages/disadvantages and selection principles of exfoliation solvents, such as water-based solvents, organic solvents and mixed solvents, were analyzed. The exfoliation principles and advantages/disadvantages of process intensification equipment, such as ultrasonic, high-shear and microchannel, were compared. Then, the post-processing method and separation effect of centrifugal separation on graphene were briefly described. Finally, the efficient production of graphene by liquid-phase exfoliation was being improved through multi-objective optimization techniques by integrating artificial intelligence. This included experimenting with residual-free functional intercalation agents and combining them with gentle and rapid expansion methods; exploring solvent systems with properties such as low toxicity, low boiling points and high dispersion characteristics; accurately regulating the liquid-phase exfoliation mechanism and engineering cascaded centrifugation equipment to achieve continuous, large-scale and cost-effective rapid production of graphene.

Key words: graphene, liquid-phase exfoliation, two-dimensional nanomaterial, high-shear, microchannel, efficient preparation

中图分类号:

TQ127.1

李文鹏, 刘晴, 杨志荣, 高展鹏, 王景涛, 周鸣亮, 张金利. 液相剥离法高效制备石墨烯的研究进展[J]. 化工进展, 2024, 43(1): 215-231.

LI Wenpeng, LIU Qing, YANG Zhirong, GAO Zhanpeng, WANG Jingtao, ZHOU Mingliang, ZHANG Jinli. Advances in efficient preparation of graphene by liquid-phase exfoliation[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 215-231.

图/表 24

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108	AMRI Amun, BERTILSYA HENDRI Yola, YIN Chunyang, et al. Very-few-layer graphene obtained from facile two-step shear exfoliation in aqueous solution[J]. Chemical Engineering Science, 2021, 245: 116848.
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年份	插层方法	插层剂	插层效果	石墨烯产品		文献
年份	插层方法	插层剂	插层效果	厚度/nm	尺寸/μm	文献
2023	化学氧化插层	浓硫酸（H₂SO₄）、过硫酸钾（K₂S₂O₈）	层间距明显变大，呈手风琴状结构	—	—	[21]
2023	电化学插层	硫酸铵	石墨层间距离迅速扩大	4~6层	1~10	[22]
2022	化学氧化插层	过氧化氢、过氧乙酸（PAA）	石墨层片迅速膨胀剥落	5~8层	—	[23]
2022	电化学插层	六氟磷酸锂	—	单层；<1	约1	[24]
2022	电化学插层	六氟磷酸锂	—	多层；<4	约1	[24]
2021	电化学插层	硫酸、磷酸	石墨晶粒尺寸急剧减小	3~7层	—	[25]
2020	电化学插层	高铼酸	—	—	—	[26]
2020	溶剂插层	钠萘、N,N-二甲基乙酰胺（DMAC）	—	—	—	[27]
2019	电化学插层	季铵盐、高氯酸盐	短时间内剧烈膨胀	1~3层	1~5	[28]
2019	溶剂插层	碳酸氢铵	层与层之间的距离变大	—	—	[29]
2018	溶剂插层	氨溶液	大大提高石墨烯的剥离效果	2.3	约3	[30]
2018	溶剂插层	尿素（Urea）	增加石墨层间的间距	1	>2	[31]
2018	化学氧化插层	浓硫酸、高锰酸钾	石墨颗粒减少	约1.2	—	[32]
2017	干球磨插层	碳酸氢铵	—	5~8层	0.4~0.8	[33]
2017	电化学插层	四氟硼酸四丁铵	石墨显著膨胀	4~6层	0.4~1.5	[34]

年份	插层方法	插层剂	插层效果	石墨烯产品		文献
年份	插层方法	插层剂	插层效果	厚度/nm	尺寸/μm	文献
2023	化学氧化插层	浓硫酸（H₂SO₄）、过硫酸钾（K₂S₂O₈）	层间距明显变大，呈手风琴状结构	—	—	[21]
2023	电化学插层	硫酸铵	石墨层间距离迅速扩大	4~6层	1~10	[22]
2022	化学氧化插层	过氧化氢、过氧乙酸（PAA）	石墨层片迅速膨胀剥落	5~8层	—	[23]
2022	电化学插层	六氟磷酸锂	—	单层；<1	约1	[24]
2022	电化学插层	六氟磷酸锂	—	多层；<4	约1	[24]
2021	电化学插层	硫酸、磷酸	石墨晶粒尺寸急剧减小	3~7层	—	[25]
2020	电化学插层	高铼酸	—	—	—	[26]
2020	溶剂插层	钠萘、N,N-二甲基乙酰胺（DMAC）	—	—	—	[27]
2019	电化学插层	季铵盐、高氯酸盐	短时间内剧烈膨胀	1~3层	1~5	[28]
2019	溶剂插层	碳酸氢铵	层与层之间的距离变大	—	—	[29]
2018	溶剂插层	氨溶液	大大提高石墨烯的剥离效果	2.3	约3	[30]
2018	溶剂插层	尿素（Urea）	增加石墨层间的间距	1	>2	[31]
2018	化学氧化插层	浓硫酸、高锰酸钾	石墨颗粒减少	约1.2	—	[32]
2017	干球磨插层	碳酸氢铵	—	5~8层	0.4~0.8	[33]
2017	电化学插层	四氟硼酸四丁铵	石墨显著膨胀	4~6层	0.4~1.5	[34]

年份	原料	膨胀预处理条件	膨胀方法	膨胀效果	石墨烯产品		文献
年份	原料	膨胀预处理条件	膨胀方法	膨胀效果	厚度/nm	尺寸/μm	文献
2023	片状石墨（FG）	不同比例的FG∶H₂SO₄∶K₂S₂O₈	微波辅助氧化5min，800W 功率下微波辐照40s	膨胀体积（EV）值至455mL/g	—	—	[21]
2023	废石墨（SG）	硫磷酸和高锰酸钾氧化膨胀	80℃干燥6h，900℃马弗炉15s	层间距由0.338nm 增加到0.392nm	—	—	[36]
2022	天然石墨	石墨粉与浓硫酸氧化，KMnO₄和过氧化氢混合物	800~900℃与水混合1∶3压缩、1200W、30kHz超声	—	7~10层	—	[37]
2022	FG	FG与27mL PAA和3mL过氧化氢混合，室温静置10h	50℃下真空干燥12h，700W微波照射30s	层间距在0.332~0.335nm内	5~8层	—	[23]
2020	六方石墨	硝酸、硫酸处理12h	950℃处理	—	3~5层	—	[39]
2019	高定向裂解石墨	季铵盐、高氯酸盐电化学插层	800℃处理数秒	膨胀1000倍	1~3层	1~5	[28]
2019	插层石墨	商业购买	800℃处理180s	—	—	—	[40]
2019	天然石墨	石墨、高锰酸钾、高氯酸、乙酸酐质量比1∶0.5∶1∶0.4混合10s	720W、2.45GHz微波处理40s	膨胀至300mL/g	—	—	[41]
2018	可膨胀石墨	—	750W微波处理1min	—	3.6	—	[42]
2018	普通石墨	—	微波处理10s，冷却20s，循环处理30min	层间距增至0.3378nm	2.3	约3	[30]
2017	天然石墨	硫酸、过硫酸铵超声混合5min，再加入石墨搅拌30s	室温静置12h	膨胀225倍	—	—	[38]
2016	EG	石墨、甲苯质量比2∶1超声5min	600W微波照射10min、冷却	—	3~12层	约10	[43]
2016	六方石墨	75℃真空干燥2h后加入饱和硫酸、硝酸处理12h	800℃处理数秒	—	<5	—	[44]

年份	原料	膨胀预处理条件	膨胀方法	膨胀效果	石墨烯产品		文献
年份	原料	膨胀预处理条件	膨胀方法	膨胀效果	厚度/nm	尺寸/μm	文献
2023	片状石墨（FG）	不同比例的FG∶H₂SO₄∶K₂S₂O₈	微波辅助氧化5min，800W 功率下微波辐照40s	膨胀体积（EV）值至455mL/g	—	—	[21]
2023	废石墨（SG）	硫磷酸和高锰酸钾氧化膨胀	80℃干燥6h，900℃马弗炉15s	层间距由0.338nm 增加到0.392nm	—	—	[36]
2022	天然石墨	石墨粉与浓硫酸氧化，KMnO₄和过氧化氢混合物	800~900℃与水混合1∶3压缩、1200W、30kHz超声	—	7~10层	—	[37]
2022	FG	FG与27mL PAA和3mL过氧化氢混合，室温静置10h	50℃下真空干燥12h，700W微波照射30s	层间距在0.332~0.335nm内	5~8层	—	[23]
2020	六方石墨	硝酸、硫酸处理12h	950℃处理	—	3~5层	—	[39]
2019	高定向裂解石墨	季铵盐、高氯酸盐电化学插层	800℃处理数秒	膨胀1000倍	1~3层	1~5	[28]
2019	插层石墨	商业购买	800℃处理180s	—	—	—	[40]
2019	天然石墨	石墨、高锰酸钾、高氯酸、乙酸酐质量比1∶0.5∶1∶0.4混合10s	720W、2.45GHz微波处理40s	膨胀至300mL/g	—	—	[41]
2018	可膨胀石墨	—	750W微波处理1min	—	3.6	—	[42]
2018	普通石墨	—	微波处理10s，冷却20s，循环处理30min	层间距增至0.3378nm	2.3	约3	[30]
2017	天然石墨	硫酸、过硫酸铵超声混合5min，再加入石墨搅拌30s	室温静置12h	膨胀225倍	—	—	[38]
2016	EG	石墨、甲苯质量比2∶1超声5min	600W微波照射10min、冷却	—	3~12层	约10	[43]
2016	六方石墨	75℃真空干燥2h后加入饱和硫酸、硝酸处理12h	800℃处理数秒	—	<5	—	[44]

年份	剥离方法	DSA	DSA用量/mg·mL^-1	剥离浓度/mg·mL^-1	石墨烯产品		文献
年份	剥离方法	DSA	DSA用量/mg·mL^-1	剥离浓度/mg·mL^-1	厚度/nm	尺寸/μm	文献
2021	超声	MCC	石墨质量的一半	8.54	约6	约0.15	[52]
2019	微通道	十二烷基硫酸钠（SDS）	4	1.19	0.8~1.2	约0.54	[51]
2019	微通道	F127	4	1.52	0.8~1.2	约0.58	[51]
2019	微通道	TW80	4	1.71	0.8~1.2	约0.67	[51]
2019	微通道	SMA	10	0.522	5层	0.5~0.9	[54]
2019	微通道	SC	1	0.5	0.52~0.92	0.3	[55]
2018	超声	羧甲基纤维素（CMC）	2	0.1	—	<1	[56]
2018	高剪切	NaOH	0.4	50	<1	0.5~5	[53]
2017	高剪切	SC	4	1.1	5层	约0.5	[57]
2017	高剪切	PVP	20	0.7	5层	约0.5	[57]
2017	超声	PTCA	0.6	0.8	1.5~3	约5	[58]