微反应器内环酯类锂电池添加剂合成研究进展

doi:10.11949/0438-1157.20230653

摘要/Abstract

摘要：

锂电池电解液添加剂是一类在锂电池中用量不大，但对改善锂电池高低温性能，提高使用寿命和循环次数等方面发挥重要作用的高附加值电子化学品。随着锂电池等下游应用长期向好地发展，添加剂的需求量不断增长，但传统的釜式反应器由于传递性能不佳导致产品质量稳定性较差且污染严重。微反应器在微米尺度对流体有着高效分散和混合的优势，能显著提高生产效率、降低生产成本，在锂电池添加剂合成方面受到越来越广泛的关注。本文结合微反应器优异的传递性能，系统综述了微反应器在环酯类锂离子电池电解液添加剂合成中的应用进展，并对添加剂的微化工合成领域的研究方向进行了展望。

关键词: 微反应器, 合成, 传递, 锂电池电解液添加剂, 电子化学品

Abstract:

Lithium battery electrolyte additives are a class of high value-added electronic chemicals that are not used in large amounts in lithium batteries, but play an important role in improving the high and low temperature performance of lithium batteries, increasing their service life and cycle times. With the long-term development of downstream applications such as lithium batteries, the demand for additives continues to grow. However, the poor transfer performance of traditional kettle reactors results in unsatisfactory product quality stability and severe pollution. Microreactors have the advantage of efficient dispersion and mixing of fluids at the micron scale, which is an effective means to improve production efficiency and reduce production costs, and have received increasing attention in the synthesis of lithium battery additives. In this paper, based on the excellent transfer performance of microreactors, the application of microreactors in the synthesis of cyclic ester lithium-ion battery electrolyte additives is reviewed, and the research direction in the field of microchemical synthesis of additives is prospected.

Key words: microreactor, synthesis, transport, electrolyte additives of lithium battery, electronic chemical

中图分类号:

TQ 225.24

王婷, 王忠东, 项星宇, 何呈祥, 朱春英, 马友光, 付涛涛. 微反应器内环酯类锂电池添加剂合成研究进展[J]. 化工学报, 2024, 75(1): 95-109.

Ting WANG, Zhongdong WANG, Xingyu XIANG, Chengxiang HE, Chunying ZHU, Youguang MA, Taotao FU. Advances in synthesis of cyclic ester additives for lithium batteries in microreactors[J]. CIESC Journal, 2024, 75(1): 95-109.

图/表 19

图1 微反应器内锂电池添加剂合成进展

Fig.1 Advances in synthesis of lithium battery additives in microreactors

图2 硫酸乙烯酯的反应式

Fig.2 Reaction equation of DTD

图3 微混合器示意图[39-41]

Fig.3 Schematic diagram of micromixers[39-41]

图4 硫酸乙烯酯的生产系统[44]

Fig.4 Production system of DTD[44]

图5 亚硫酸乙烯酯的反应式

Fig.5 Reaction equations of ES

图6 微通道反应器结构示意图[51]

Fig.6 Schematic diagram of microchannel reactor structure[51]

图7 亚硫酸乙烯酯的连续反应装置及混合结构示意图[52]

Fig.7 Schematic diagram of continuous reaction device and mixing structure of ES[52]

图8 碳酸乙烯酯的反应式

Fig.8 Reaction equations of EC

图9 碳酸乙烯酯连续生产工艺流程图[56]

Fig.9 Flow chart of continuous production process of EC[56]

图10 氯代碳酸乙烯酯的反应式

Fig.10 Reaction equation of CEC

图11 光化学微反应器[65-68]

Fig.11 Photochemical microreactors[65-68]

图12 光催化氯代碳酸乙烯酯连续流反应器[69]

Fig.12 Continuous flow reactor of photocatalytic CEC[69]

图13 氯代碳酸乙烯酯的连续生产装置示意图[70]

Fig.13 Schematic diagram of continuous production equipment of CEC[70]

图14 增强传质型微通道反应器示意图[71]

Fig.14 Schematic diagram of enhanced mass transfer microchannel reactor[71]

图15 碳酸亚乙烯酯的反应式

Fig.15 Reaction equation of VC

图16 康宁G1玻璃微反应器示意图[76]

Fig.16 Schematic diagram of Corning G1 glass microreactor[76]

图17 氟代碳酸乙烯酯的反应式

Fig.17 Reaction equation of FEC

图18 氟化微反应器的俯视图和侧视图[87]

Fig.18 Top and side views of the fluoride microreactor[87]

图19 Corning微通道反应器系统装置图[92]

Fig.19 Device diagram of Corning microchannel reactor system[92]

参考文献 94

1	任海. 中国新能源汽车用锂电池产业现状及发展趋势[J]. 当代化工研究, 2021(6): 14-15.
	Ren H. Current status and development trend of lithium battery industry for new energy vehicles in China[J]. Modern Chemical Research, 2021(6): 14-15.
2	周璇. 锂电池在新能源汽车中的应用[J]. 南方农机, 2020, 51(22): 140-141.
	Zhou X. Application of lithium batteries in new energy vehicles[J]. China Southern Agricultural Machinery, 2020, 51(22): 140-141.
3	Dileepan V M, Jayakumar J. Performance analysis of lithium batteries[C]//2017 International Conference on Innovations in Electrical, Electronics, Instrumentation and Media Technology (ICEEIMT). Coimbatore, India: IEEE, 2017: 330-333.
4	张金龙, 佟微, 漆汉宏. 锂电池发展浅谈[J]. 电源技术, 2017, 41(9): 1377-1379.
	Zhang J L, Tong W, Qi H H. Discussion of lithium battery development[J]. Chinese Journal of Power Sources, 2017, 41(9): 1377-1379.
5	Reddy M V, Mauger A, Julien C M, et al. Brief history of early lithium-battery development[J]. Materials, 2020, 13(8): 1884.
6	胡华坤, 薛文东, 霍思达, 等. 锂离子电池电解液SEI成膜添加剂的研究进展[J]. 化工学报, 2022, 73(4): 1436-1454.
	Hu H K, Xue W D, Huo S D, et al. Review of SEI film forming additives for electrolyte of lithium ion battery[J]. CIESC Journal, 2022, 73(4): 1436-1454.
7	方黎锋. 锂离子电池电解液导电添加剂的研究进展[J]. 电池, 2023, 53(4):462-465.
	Fang L F. Research progress in conductive additives of electrolyte for Li-ion battery[J]. Battery Bimonthly, 2023, 53(4):462-465.
8	苏金然, 刘萍. 锂离子动力电池电解液添加剂的研究进展[J]. 电源技术, 2019, 43(9): 1551-1553, 1567.
	Su J R, Liu P. Research progress of electrolyte additives for lithium ion batteries[J]. Chinese Journal of Power Sources, 2019, 43(9): 1551-1553, 1567.
9	张千玉. 锂离子电池过充保护添加剂的研究[D]. 上海: 复旦大学, 2010.
	Zhang Q Y. Study on overcharge protection additives for lithium ion batteries[D]. Shanghai: Fudan University, 2010.
10	宋林虎, 李世友, 王洁, 等. 锂离子电池电解液除酸除水添加剂的研究进展[J]. 应用化学, 2022, 39(5): 697-706.
	Song L H, Li S Y, Wang J, et al. Research progress of additives for acid and water removal in electrolyte of lithium ion battery[J]. Chinese Journal of Applied Chemistry, 2022, 39(5): 697-706.
11	贾铭勋, 吴桐, 杨道通, 等. 锂硫电池电解液多功能添加剂:作用机制及先进表征[J]. 储能科学与技术, DOI: 10.19799/j.cnki.2095-4239.2023.0327 .
	Jia M X, Wu T, Yang D T, et al. Electrolyte multifunctional additives of lithium-sulfur battery: mechanism of action and advanced characterization[J]. Energy Storage Science and Technology, DOI: 10.19799/j.cnki.2095-4239.2023.0327 .
12	Yue J. Multiphase flow processing in microreactors combined with heterogeneous catalysis for efficient and sustainable chemical synthesis[J]. Catalysis Today, 2018, 308: 3-19.
13	Pohar A, Plazl I. Process intensification through microreactor application[J]. Chemical & Biochemical Engineering Quarterly, 2009, 23(4): 537-544.
14	荀涛, 蔡旺锋, 张旭斌. 微通道中气-液-液三相流流型及传质研究[J]. 化学工业与工程, 2017, 34(6): 81-87.
	Xun T, Cai W F, Zhang X B. The flow pattern and mass transfer of gas-liquid-liquid three phase flow in microchannel[J]. Chemical Industry and Engineering, 2017, 34(6): 81-87.
15	王栋, 夏晓露, 刘汇洋, 等. 毛细管微反应器降解亚甲基蓝废水试验研究[J]. 化学工业与工程, 2022, 39(4): 65-70.
	Wang D, Xia X L, Liu H Y, et al. Experimental study on degradation of methylene blue wastewater by capillary microreactor[J]. Chemical Industry and Engineering, 2022, 39(4): 65-70.
16	Lee J, Mudawar I. Two-phase flow in high-heat-flux micro-channel heat sink for refrigeration cooling applications(part Ⅱ): Heat transfer characteristics[J]. International Journal of Heat and Mass Transfer, 2005, 48(5): 941-955.
17	李维平. 几种锂电池电解液添加剂的合成工艺研究[D]. 青岛: 青岛科技大学, 2013.
	Li W P. Study on synthesis technology of several electrolyte additives for lithium batteries [D]. Qingdao: Qingdao University of Science & Technology, 2013.
18	Assmann N, Ładosz A, von Rohr P R. Continuous micro liquid-liquid extraction[J]. Chemical Engineering & Technology, 2013, 36(6): 921-936.
19	Kashid M N, Gerlach I, Goetz S, et al. Internal circulation within the liquid slugs of a liquid-liquid slug-flow capillary microreactor[J]. Industrial & Engineering Chemistry Research, 2005, 44(14): 5003-5010.
20	Susanti, Winkelman J G M, Schuur B, et al. Lactic acid extraction and mass transfer characteristics in slug flow capillary microreactors[J]. Industrial & Engineering Chemistry Research, 2016, 55(16): 4691-4702.
21	郭戎威, 付涛涛, 朱春英, 等. 微通道内气-液两相流及并行放大的研究进展[J]. 化学工业与工程, 2021, 38(6): 74-86.
	Guo R W, Fu T T, Zhu C Y, et al. Research progress on gas-liquid two-phase flow and numbering-up strategy in microchannel[J]. Chemical Industry and Engineering, 2021, 38(6): 74-86.
22	武帅. 几种磺内酯类锂电池电解液添加剂的合成工艺研究[D]. 武汉: 武汉工程大学, 2020.
	Wu S. Study on synthesis technology of several sulfonlactone electrolyte additives for lithium batteries[D]. Wuhan: Wuhan Institute of Technology, 2020.
23	贠娇娇, 刘红梅, 郑会元, 等. 无机添加剂用于锂离子电池电解液的研究进展[J]. 储能科学与技术, 2014, 3(6): 584-589.
	Yun J J, Liu H M, Zheng H Y, et al. Research progress on inorganic additives for lithium-ion battery electrolytes[J]. Energy Storage Science and Technology, 2014, 3(6): 584-589.
24	Kozak J A, Wu J, Su X, et al. Bromine-catalyzed conversion of CO₂ and epoxides to cyclic carbonates under continuous flow conditions[J]. Journal of the American Chemical Society, 2013, 135(49): 18497-18501.
25	贾国文, 朱振涛, 王卫江, 等. 一种二氟磷酸锂的制备方法: 115650201A[P]. 2023-01-31.
	Jia G W, Zhu Z T, Wang W J, et al. A preparation method of lithium difluorophosphate: 115650201A[P]. 2023-01-31.
26	岳敏, 李斌, 曾益平, 等. 一种硫酸乙烯酯的制备方法及制备设备: 114591288B[P]. 2023-04-25.
	Yue M, Li B, Zeng Y P, et al. Preparation method and preparation equipment of ethylene sulfate: 114591288B[P]. 2023-04-25.
27	任凡, 王亮, 宋文超, 等. 一种电子级硫酸乙烯酯的生产工艺: 115724822A[P]. 2023-03-03.
	Ren F, Wang L, Song W C, et al. Production process of electronic grade ethylene sulfate: 115724822A[P]. 2023-03-03.
28	王刚, 彭智敏, 张振华. 一种环状硫酸酯的制备方法: 107353277B[P]. 2020-01-31.
	Wang G, Peng Z M, Zhang Z H. Preparation method of cyclic sulfate: 107353277B[P]. 2020-01-31.
29	姜飞, 陈雪君, 陈群, 等. 一种硫酸乙烯酯的合成方法: 112679466A[P]. 2021-04-20.
	Jiang F, Chen X J, Chen Q, et al. Synthesis method of ethylene sulfate: 112679466A[P]. 2021-04-20.
30	武显峰, 姜勇, 周济仓, 等. 一种硫酸乙烯酯的制备方法及其应用: 108822073B[P]. 2021-02-02.
	Wu X F, Jiang Y, Zhou J C, et al. Preparation method and application of ethylene sulfate: 108822073B[P]. 2021-02-02.
31	Tice J D, Lyon A D, Ismagilov R F. Effects of viscosity on droplet formation and mixing in microfluidic channels[J]. Analytica Chimica Acta, 2004, 507(1): 73-77.
32	Wang K, Lu Y C, Xu J H, et al. Determination of dynamic interfacial tension and its effect on droplet formation in the T-shaped microdispersion process[J]. Langmuir, 2009, 25(4): 2153-2158.
33	Wang K, Lu Y C, Xu J H, et al. Generation of micromonodispersed droplets and bubbles in the capillary embedded T-junction microfluidic devices[J]. AIChE Journal, 2011, 57(2): 299-306.
34	Xu J H, Li S W, Tan J, et al. Controllable preparation of monodisperse O/W and W/O emulsions in the same microfluidic device[J]. Langmuir, 2006, 22(19): 7943-7946.
35	Li Q, Angeli P. Intensified Eu(Ⅲ) extraction using ionic liquids in small channels[J]. Chemical Engineering Science, 2016, 143: 276-286.
36	Cai G Z, Xue L, Zhang H L, et al. A review on micromixers[J]. Micromachines, 2017, 8(9): 274.
37	Gidde R R, Pawar P M. Flow feature analysis of T-junction wavy micromixer for mixing application[J]. International Journal of Chemical Reactor Engineering, 2019, 17(9): 20180306.
38	Li G X, Shang M J, Song Y, et al. Characterization of liquid–liquid mass transfer performance in a capillary microreactor system[J]. AIChE Journal, 2018, 64(3): 1106-1116.
39	Ahmed D, Mao X L, Juluri B K, et al. A fast microfluidic mixer based on acoustically driven sidewall-trapped microbubbles[J]. Microfluidics and Nanofluidics, 2009, 7(5): 727-731.
40	Cha J, Kim J, Ryu S K, et al. A highly efficient 3D micromixer using soft PDMS bonding[J]. Journal of Micromechanics and Microengineering, 2006, 16(9): 1778-1782.
41	Knight J B, Vishwanath A, Brody J P, et al. Hydrodynamic focusing on a silicon chip: mixing nanoliters in microseconds[J]. Physical Review Letters, 1998, 80(17): 3863-3866.
42	朱性宇, 贾风雷, 郭建军, 等. 连续制备硫酸乙烯酯的方法: 108707095B[P]. 2021-03-05.
	Zhu X Y, Jia F L, Guo J J, et al. Method of continuously preparing ethylene sulfate: 108707095B[P]. 2021-03-05.
43	赵建, 庞宝华, 谢栋, 等. 利用微通道反应器制备硫酸乙烯酯的方法: 107973774B[P]. 2020-07-17.
	Zhao J, Pang B H, Xie D, et al. Method for preparing ethylene sulfate by using microchannel reactor: 107973774B[P]. 2020-07-17.
44	宋朝阳, 杨磊, 陈静, 等. 一种硫酸乙烯酯生产系统: 211562910U[P]. 2020-09-25.
	Song C Y, Yang L, Chen J, et al. Ethylene sulfate production system: 211562910U[P]. 2020-09-25.
45	杨明霞. 亚硫酸乙烯酯的制备工艺研究[J]. 河南化工, 2022, 39(12): 35-37.
	Yang M X. Study on preparation technology of vinvy sulfite[J]. Henan Chemical Industry, 2022, 39(12): 35-37.
46	黄永强, 黄紫晏, 陶正录, 等. 一种亚硫酸乙烯酯的制备方法: 115745952A[P]. 2023-03-07.
	Huang Y Q, Huang Z Y, Tao Z L, et al. Preparation method of ethylene sulfite: 115745952A[P]. 2023-03-07.
47	Chen X Y, Shen J N. Simulation and experimental analysis of a SAR micromixer with F-shape mixing units[J]. Analytical Methods, 2017, 9(12): 1885-1890.
48	Garstecki P, Fischbach M A, Whitesides G M. Design for mixing using bubbles in branched microfluidic channels[J]. Applied Physics Letters, 2005, 86(24): 244108.
49	Su Y H, Chen G W, Zhao Y C, et al. Intensification of liquid-liquid two-phase mass transfer by gas agitation in a microchannel[J]. AIChE Journal, 2009, 55(8): 1948-1958.
50	王海陶. 一种微通道反应器制备亚硫酸乙烯酯的方法: 114539210A[P]. 2022-05-27.
	Wang H T. Method for preparing ethylene sulfite by using microchannel reactor: 114539210A[P]. 2022-05-27.
51	丁全有, 董延增, 陈彦冰, 等. 微通道反应器制备无溶剂体系的亚硫酸乙烯酯的方法: 115785059A[P]. 2023-03-14.
	Ding Q Y, Dong Y Z, Chen Y B, et al. Method for preparing ethylene sulfite of solvent-free system by using microchannel reactor: 115785059A[P]. 2023-03-14.
52	岳敏, 李斌, 杨涛. 一种亚硫酸乙烯酯的连续反应装置: 217431674U[P]. 2022-09-16.
	Yue M, Li B, Yang T. Continuous reaction device for ethylene sulfite: 217431674U[P]. 2022-09-16.
53	陈艳梅, 王健沛, 朱志庆, 等. 氧化锌催化尿素与乙二醇合成碳酸乙烯酯[J]. 石油化工, 2016, 45(8): 920-924.
	Chen Y M, Wang J P, Zhu Z Q, et al. Synthesis of ethylene carbonate from urea and ethylene glycol over zinc oxide catalyst[J]. Petrochemical Technology, 2016, 45(8): 920-924.
54	刘阳庆, 韩粉女, 许琦. 环状碳酸酯的绿色合成方法[J]. 化工管理, 2021(32): 15-16.
	Liu Y Q, Han F N, Xu Q. Green synthesis of cyclic carbonate[J]. Chemical Engineering Management, 2021(32): 15-16.
55	魏伟, 孙予罕, 闻霞, 等. 二氧化碳资源化利用的机遇与挑战[J]. 化工进展, 2011, 30(1): 216-224.
	Wei W, Sun Y H, Wen X, et al. Opportunities and challenges of carbon dioxide utilization as a resource[J]. Chemical Industry and Engineering Progress, 2011, 30(1): 216-224.
56	丁云成, 李蓝, 王祁宁, 等. 一种连续制备碳酸乙烯酯的方法: 110878077A[P]. 2020-03-13.
	Ding Y C, Li L, Wang Q N, et al. Method for continuously preparing ethylene carbonate: 110878077A[P]. 2020-03-13.
57	Peng J, Yang H J, Geng Y C, et al. Novel, recyclable supramolecular metal complexes for the synthesis of cyclic carbonates from epoxides and CO₂ under solvent-free conditions[J]. Journal of CO₂ Utilization, 2017, 17: 243-255.
58	Gao N N, Wang J X, Shao L, et al. Removal of carbon dioxide by absorption in microporous tube-in-tube microchannel reactor[J]. Industrial & Engineering Chemistry Research, 2011, 50(10): 6369-6374.
59	Niu H N, Pan L W, Su H J, et al. Flow pattern, pressure drop, and mass transfer in a gas-liquid concurrent two-phase flow microchannel reactor[J]. Industrial & Engineering Chemistry Research, 2009, 48(3): 1621-1628.
60	Su H J, Wang S D, Niu H N, et al. Mass transfer characteristics of H₂S absorption from gaseous mixture into methyldiethanolamine solution in a T-junction microchannel[J]. Separation and Purification Technology, 2010, 72(3): 326-334.
61	Yue J, Chen G W, Yuan Q, et al. Hydrodynamics and mass transfer characteristics in gas-liquid flow through a rectangular microchannel[J]. Chemical Engineering Science, 2007, 62(7): 2096-2108.
62	贺同强, 李明燃, 蒋宾伟, 等. 应用微反应器合成碳酸丙烯酯的工艺与模拟[J]. 精细化工, 2023, 40(2): 441-447.
	He T Q, Li M R, Jiang B W, et al. Process and simulation of synthesizing propylene carbonate by microreactor[J]. Fine Chemicals, 2023, 40(2): 441-447.
63	黄存影, 张文敏, 马德龙, 等. 氯代碳酸乙烯酯的合成工艺研究[J]. 山东化工, 2023, 52(7): 32-35.
	Huang C Y, Zhang W M, Ma D L, et al. Study on the synthesis technology of vinyl chlorocarbonate[J]. Shandong Chemical Industry, 2023, 52(7): 32-35.
64	Mlakić M, Šalić A, Bačić M, et al. Photocatalytic oxygenation of heterostilbenes—batch versus microflow reactor[J]. Catalysts, 2021, 11(3): 395.
65	Siopa F, António J P M, Afonso C A M. Flow-assisted synthesis of bicyclic aziridines via photochemical transformation of pyridinium salts[J]. Organic Process Research & Development, 2018, 22(4): 551-556.
66	Corcoran E B, McMullen J P, Lévesque F, et al. Photon equivalents as a parameter for scaling photoredox reactions in flow: translation of photocatalytic C—N cross-coupling from lab scale to multikilogram scale[J]. Angewandte Chemie International Edition, 2020, 59(29): 11964-11968.
67	Escribà-Gelonch M, Halpin A, Noël T, et al. Laser-mediated photo-high-p,T intensification of vitamin D3 synthesis in continuous flow[J]. ChemPhotoChem, 2018, 2(10): 922-930.
68	Fabry D C, Ho Y A, Zapf R, et al. Blue light mediated C—H arylation of heteroarenes using TiO₂ as an immobilized photocatalyst in a continuous-flow microreactor[J]. Green Chemistry, 2017, 19(8): 1911-1918.
69	高翔, 舒鑫琳, 李娜. 一种光催化连续流反应系统及氯代碳酸乙烯酯的连续流合成方法: 115845769A[P]. 2023-03-28.
	Gao X, Shu X L, Li N. Photocatalytic continuous flow reaction system and continuous flow synthesis method of chloroethylene carbonate: 115845769A[P]. 2023-03-28.
70	周龙, 王小龙, 卢正, 等. 一种氯代碳酸乙烯酯连续生产工艺: 115611845A[P]. 2023-01-17.
	Zhou L, Wang X L, Lu Z, et al. Continuous production process of chloroethylene carbonate: 115611845A[P]. 2023-01-17.
71	许国荣, 庞宝华, 孙西船, 等. 一种微通道反应制备氯代碳酸乙烯酯的方法: 106810528A[P]. 2017-06-09.
	Xu G R, Pang B H, Sun X C, et al. Method using microchannel reaction to prepare chloroethylene carbonate: 106810528A[P]. 2017-06-09.
72	陈先进, 李晶, 韦伟, 等. 碳酸亚乙烯酯的合成方法综述[J]. 浙江化工, 2023, 54(2): 9-12.
	Chen X J, Li J, Wei W, et al. Review on synthesis methods of vinylene carbonate[J]. Zhejiang Chemical Industry, 2023, 54(2): 9-12.
73	王爱红, 黄革, 李建丰, 等. 碳酸亚乙烯酯合成[J]. 塑料助剂, 2019(2): 26-29.
	Wang A H, Huang G, Li J F, et al. Synthesis of vinylene carbonate[J]. Plastics Additives, 2019(2): 26-29.
74	胡翼飞, 罗朝辉. 一种碳酸亚乙烯酯的制备方法: 101210006B[P]. 2010-11-17.
	Hu Y F, Luo C H. Method for preparing vinylene carbonate: 101210006B[P]. 2010-11-17.
75	张朋, 贾风雷, 杨文兵, 等. 一种即时分离的碳酸亚乙烯酯合成方法: 116003374A[P]. 2023-04-25.
	Zhang P, Jia F L, Yang W B, et al. Real-time separation method for the synthesis of vinylene carbonate: 116003374A[P]. 2023-04-25.
76	陈光, 王艳华. 制备碳酸亚乙烯酯的方法: 115850230A[P]. 2023-03-28.
	Chen G, Wang Y H. Method for preparing vinylene carbonate: 115850230A[P]. 2023-03-28.
77	孔令文, 许国荣, 孙西船, 等. 一种微通道反应制备碳酸亚乙烯酯的方法: 106749155B[P]. 2019-04-26.
	Kong L W, Xu G R, Sun X C, et al. Method for preparing vinylene carbonate through micro channel reaction: 106749155B[P]. 2019-04-26.
78	Shao H W, Lu Y C, Wang K, et al. Liquid-liquid flow and mass transfer characteristics in micro-sieve array device with dual-sized pores[J]. Chemical Engineering Journal, 2012, 193/194: 96-101.
79	Burns J R, Ramshaw C. The intensification of rapid reactions in multiphase systems using slug flow in capillaries[J]. Lab on a Chip, 2001, 1(1): 10-15.
80	Bai L, Zhao S F, Fu Y H, et al. Experimental study of mass transfer in water/ionic liquid microdroplet systems using micro-LIF technique[J]. Chemical Engineering Journal, 2016, 298: 281-290.
81	杨志荣, 张晶, 朱修洋, 等. 一种微通道连续合成碳酸亚乙烯酯或/和氟代碳酸乙烯酯的方法: 114874179A[P]. 2022-08-09.
	Yang Z R, Zhang J, Zhu X Y, et al. Method for continuously synthesizing vinylene carbonate or/and fluoroethylene carbonate through microchannel: 114874179A[P]. 2022-08-09.
82	吴毅杰, 陈志峰, 林刚, 等. 一种氟代碳酸乙烯酯的快速连续流合成工艺: 113620924A[P]. 2021-11-09.
	Wu Y J, Chen Z F, Lin G, et al. Rapid continuous flow synthesis process of fluoroethylene carbonate: 113620924A[P]. 2021-11-09.
83	Hasegawa M, Ishii H, Fuchigami T. Electroorganic synthesis under solvent-free conditions. Highly regioselective anodic monofluorination of cyclic ethers, lactones, and a cyclic carbonate[J]. Tetrahedron Letters, 2002, 43(8): 1503-1505.
84	苏振东. 一种氟代碳酸乙烯酯的制备方法: 108033943B[P]. 2020-12-01.
	Su Z D. Preparation method of fluoroethylene carbonate: 108033943B[P]. 2020-12-01.
85	张呈平, 胡儒柱, 贾晓卿, 等. 气相连续制备氟代碳酸乙烯酯或/和碳酸亚乙烯酯的方法: 108329293A[P]. 2018-07-27.
	Zhang C P, Hu R Z, Jia X Q, et al. Method for continuously preparing fluoroethylene carbonate and/or vinylene carbonate by gas phase: 108329293A[P]. 2018-07-27.
86	Amii H, Nagaki A, Yoshida J I. Flow microreactor synthesis in organo-fluorine chemistry[J]. Beilstein Journal of Organic Chemistry, 2013, 9: 2793-2802.
87	Chambers R D, Spink R C H. Microreactors for elemental fluorine[J]. Chemical Communications, 1999(10): 883-884.
88	Turnbull M D, Carter N B, Dennison S, et al. Microfluidics-based reactors for safe fluorinations using elemental fluorine[J]. CHIMIA, 2004, 58(3): 159-162.
89	McPake C B, Sandford G. Selective continuous flow processes using fluorine gas[J]. Organic Process Research & Development, 2012, 16(5): 844-851.
90	de Mas N, Günther A, Schmidt M A, et al. Increasing productivity of microreactors for fast gas-liquid reactions: the case of direct fluorination of toluene[J]. Industrial & Engineering Chemistry Research, 2009, 48(3): 1428-1434.
91	夏永高, 王天桃. 一种微通道生产氟代碳酸乙烯酯的方法: 113121491A[P]. 2021-07-16.
	Xia Y G, Wang T T. Method for producing fluoroethylene carbonate through micro-channel: 113121491A[P]. 2021-07-16.
92	肖恒侨, 章祺, 倪航, 等. 一种氟代碳酸乙烯酯的连续制备方法: 111285838A[P]. 2020-06-16.
	Xiao H Q, Zhang Q, Ni H, et al. Continuous preparation method of fluoroethylene carbonate: 111285838A[P]. 2020-06-16.
93	马兵, 潘帅. 一种氟代碳酸乙烯酯的快速连续流合成工艺: 108250176A[P]. 2018-07-06.
	Ma B, Pan S. Rapid continuous flow synthesis process of fluoroethylene carbonate: 108250176A[P]. 2018-07-06.
94	Kundu S, Bhangale A S, Wallace W E, et al. Continuous flow enzyme-catalyzed polymerization in a microreactor[J]. Journal of the American Chemical Society, 2011, 133(15): 6006-6011.

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