Research progress in preparation of graphene by supercritical CO2 exfoliation

doi:10.19491/j.issn.1001-9278.2024.11.021

Abstract

Abstract:

Graphene has attracted extensive attention due to its unique structure and excellent properties. Graphene has achieved industrialization； however， it has not yet gained large⁃scale applications by now. This may be due to the fact that the properties and cost of the graphene obtained from large⁃scale production are difficult to meet a requirement of the practical applications. The development of green， low⁃cost， and high⁃quality graphene is still necessary. As the most easily achievable supercritical fluid， supercritical CO₂， exhibits a number of advantages for the preparation of graphene， such as high product quality， short preparation time， environmental friendliness， low cost， and suitability for large⁃scale production. This review summarized the main research processes in the preparation of graphene through supercritical CO₂ exfoliation in recent years and introduced the corresponding product quality of the resultant graphene. The prospects for future research in the large⁃scale preparation of graphene were also discussed.

Key words: graphene, supercritical carbon dioxide, preparation

CLC Number:

TQ320.6

WANG Xiang. Research progress in preparation of graphene by supercritical CO₂ exfoliation[J]. China Plastics, 2024, 38(11): 124-129.

Figures/Tables 7

References 38

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序号	机械方式	石墨烯产率及质量	参考文献
1	搅拌	10层以下产率约30 %~40 %	［5］
2	搅拌、多次剥离	第一次：47%为6~8层第二次：35%为3~5层，8%为1~2层	［18］
3	搅拌、高压45 MPa	75 %约为3~6层，90 %的横向尺寸小于1.4 μm	［19］
4	超声	使用300 W和120 W的超声功率分别获得了横向尺寸为50~100 nm的单层石墨烯和横向尺寸为0.5~1 μ m的双层石墨烯	［6］
5	超声	24 %为单层、44 %为双层和26 %为3层的石墨烯	［7］
6	超声	剥离率为82.6 %，1~2层的约占60 %	［4］
7	超声	超声功率从12 W增加到240 W，产率从5.2 %增加到21.5 %	［20］
8	超声	100 %的产率	［21］
9	球磨	3~5层	［9］
10	球磨	72 %小于5层，≈98 %少于10层	［10］
11	先球磨再高剪切混合器	90 %小于5层，其中单层和双层分别占7.73 %和24.86 %	［11］
12	流体剪切	1~10层达到 90 % 以上	［12］
13	高剪切混合器和多次剥离	7 次剥离反应后剥离率为63.2 %，5 层以下79 %，单层 27 %，双层 25 %，3层 14 %	［13］
14	微射流装置	3层以下88 %	［14］
15	微射流装置	少于5层68 %，75 %的横向尺寸在1~4 μm	［15］
16	微射流装置	3层以下95 %，2层65 %	［16］
17	微射流装置	少于5层88.6 %，36.6 %横向尺寸大于1 μm	［17］

序号	机械方式	石墨烯产率及质量	参考文献
1	搅拌	10层以下产率约30 %~40 %	［5］
2	搅拌、多次剥离	第一次：47%为6~8层第二次：35%为3~5层，8%为1~2层	［18］
3	搅拌、高压45 MPa	75 %约为3~6层，90 %的横向尺寸小于1.4 μm	［19］
4	超声	使用300 W和120 W的超声功率分别获得了横向尺寸为50~100 nm的单层石墨烯和横向尺寸为0.5~1 μ m的双层石墨烯	［6］
5	超声	24 %为单层、44 %为双层和26 %为3层的石墨烯	［7］
6	超声	剥离率为82.6 %，1~2层的约占60 %	［4］
7	超声	超声功率从12 W增加到240 W，产率从5.2 %增加到21.5 %	［20］
8	超声	100 %的产率	［21］
9	球磨	3~5层	［9］
10	球磨	72 %小于5层，≈98 %少于10层	［10］
11	先球磨再高剪切混合器	90 %小于5层，其中单层和双层分别占7.73 %和24.86 %	［11］
12	流体剪切	1~10层达到 90 % 以上	［12］
13	高剪切混合器和多次剥离	7 次剥离反应后剥离率为63.2 %，5 层以下79 %，单层 27 %，双层 25 %，3层 14 %	［13］
14	微射流装置	3层以下88 %	［14］
15	微射流装置	少于5层68 %，75 %的横向尺寸在1~4 μm	［15］
16	微射流装置	3层以下95 %，2层65 %	［16］
17	微射流装置	少于5层88.6 %，36.6 %横向尺寸大于1 μm	［17］

序号	溶剂/表面活性剂等	石墨烯产率及质量	工艺	参考文献
1	NMP	5~8层，最大生产率为1.44 g/h	高剪切混合器	［24］
2	NMP	石墨烯产品分布在2~3 层，单层石墨烯比例可以达到 12 %~38 %	低温（30~60 ℃） 1 000 r/min带玻璃珠搅拌	［30］
3	NMP	68 %的产物厚度小于2.5 nm，横向尺寸为0.5~3.0 μm	20 MPa下通过三叶片型螺旋桨以1 000 r/min搅拌3 h。空化和喷射的作用下再次剥离，混合物冲出喷嘴，强烈冲击目标网格	［31］
4	NMP	0.653 mg/mL，1~3层约为56.4 %	叶轮和尾水管组合结构	［32］
5	水、乙醇	石墨烯产率超过50 %，93 %的石墨烯为 3 层以下，悬浮液浓度大于2.5 g/L	超声	［25］
6	水、SDBS	1~3层和4~6层的产率分别为40 %和36 %，80 %的石墨烯片不到6层。当转速4 000 r/min时，十字转子和六齿转子产生的石墨烯产率分别34.01 %和33.3 %	高剪切混合器	［33］
7	水、PVP	5层以下石墨烯比例达到 70 %	搅拌式球磨设备	［34］
8	水、PVP	产率70.25 %，而80 %的石墨烯片为单层或寡层，尺寸约为微米	交替的微流体化过程（液相，LP）和超临界CO₂过程（气相，GP），即LP⁃GP⁃LP过程	［35］
9	水、乙醇、PVP	石墨烯纳米片层数在3层以下的比例超过 87.7 %，并且单层和双层石墨烯占72.2 %	搅拌	［26］
10	1⁃乙基⁃3⁃甲基咪唑鎓双（三氟甲基磺酰基）酰亚胺	3.5~5.5 nm的石墨烯约为70 %，横向尺寸约为700~1 100 nm的占70 %	射流冲击	［36］
11	DMF、芘衍生物	1~3层石墨烯82 %，单层石墨烯6 %	搅拌	［27］
12	DMSO、芘聚合物	石墨烯溶液主要由单层、双层或3层和多层（5层）石墨烯片组成，石墨烯片在水中的产率10.2 %，在DMSO中的产率51.8 %	搅拌	［28］
13	2，2，2⁃PTFEMA⁃b⁃PVP	产生了具有5层或5层以上的少层石墨烯	搅拌	［29］

序号	溶剂/表面活性剂等	石墨烯产率及质量	工艺	参考文献
1	NMP	5~8层，最大生产率为1.44 g/h	高剪切混合器	［24］
2	NMP	石墨烯产品分布在2~3 层，单层石墨烯比例可以达到 12 %~38 %	低温（30~60 ℃） 1 000 r/min带玻璃珠搅拌	［30］
3	NMP	68 %的产物厚度小于2.5 nm，横向尺寸为0.5~3.0 μm	20 MPa下通过三叶片型螺旋桨以1 000 r/min搅拌3 h。空化和喷射的作用下再次剥离，混合物冲出喷嘴，强烈冲击目标网格	［31］
4	NMP	0.653 mg/mL，1~3层约为56.4 %	叶轮和尾水管组合结构	［32］
5	水、乙醇	石墨烯产率超过50 %，93 %的石墨烯为 3 层以下，悬浮液浓度大于2.5 g/L	超声	［25］
6	水、SDBS	1~3层和4~6层的产率分别为40 %和36 %，80 %的石墨烯片不到6层。当转速4 000 r/min时，十字转子和六齿转子产生的石墨烯产率分别34.01 %和33.3 %	高剪切混合器	［33］
7	水、PVP	5层以下石墨烯比例达到 70 %	搅拌式球磨设备	［34］
8	水、PVP	产率70.25 %，而80 %的石墨烯片为单层或寡层，尺寸约为微米	交替的微流体化过程（液相，LP）和超临界CO₂过程（气相，GP），即LP⁃GP⁃LP过程	［35］
9	水、乙醇、PVP	石墨烯纳米片层数在3层以下的比例超过 87.7 %，并且单层和双层石墨烯占72.2 %	搅拌	［26］
10	1⁃乙基⁃3⁃甲基咪唑鎓双（三氟甲基磺酰基）酰亚胺	3.5~5.5 nm的石墨烯约为70 %，横向尺寸约为700~1 100 nm的占70 %	射流冲击	［36］
11	DMF、芘衍生物	1~3层石墨烯82 %，单层石墨烯6 %	搅拌	［27］
12	DMSO、芘聚合物	石墨烯溶液主要由单层、双层或3层和多层（5层）石墨烯片组成，石墨烯片在水中的产率10.2 %，在DMSO中的产率51.8 %	搅拌	［28］
13	2，2，2⁃PTFEMA⁃b⁃PVP	产生了具有5层或5层以上的少层石墨烯	搅拌	［29］

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Research progress in preparation of graphene by supercritical CO₂ exfoliation

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