Li-SGO掺杂半互穿网络型多孔单离子传导聚合物复合电解质的制备
收稿日期: 2020-04-16
修回日期: 2020-07-01
网络出版日期: 2020-07-01
基金资助
科技部重点研发计划项目(2018YFB1502903);国家自然科学基金项目(21603197)
Preparation and Performance Investigation of Li-SGO doped Semi-IPNs Porous Single Ion Conducting Polymer electrolyte
Received date: 2020-04-16
Revised date: 2020-07-01
Online published: 2020-07-01
本文成功制备了磺酸锂功能化石墨烯,通过原位聚合方式成功将其添加到单离子传导聚合物电解质中制备出磺酸锂功能化石墨烯改性半互穿网络型多孔单离子传导聚合物复合电解质。与未掺杂磺酸锂功能化石墨烯半互穿网络型多孔单离子传导聚合物电解质相比,该电解质具有更高的孔隙率、吸液率、机械拉伸强度和离子电导率。电化学测试结果表明,掺杂磺酸锂功能化石墨烯后,单离子传导聚合物电解质表现出与电极界面更好的相容性,组装的Li|LiFePO4锂离子电池表现出良好的循环性能和更高的倍率性能。对氧化石墨烯磺酸锂功能化可应用于对单离子传导聚合物电解质的改性,有助于提升单离子传导聚合物电解质的综合性能,获得更高的电池性能。
关键词： 锂离子电池; 单离子传导聚合物电解质; 孔隙率; 离子电导率; 磺化氧化石墨烯
张运丰 , 董佳明 , 谭畅 , 霍士康 , 王佳颖 , 何阳 , 王雅莹 . Li-SGO掺杂半互穿网络型多孔单离子传导聚合物复合电解质的制备[J]. 电化学, 2021 , 27(1) : 108 -117 . DOI: 10.13208/j.electrochem.200409
Herein, the lithiated sulfonated graphene oxide (Li-SGO) was successfully prepared via three steps by sulfonation of graphene oxide with 3-merraptnpropylt rimethnxysilane, oxidation of thiol into sulfonate with hydrogen peroxide and lithiation of sulfonate with aqueous lithium hydroxide. The as-prepared Li-SGO was then introduced into the semi-interpenetrating networks of single ion conducting polymer electrolyte (Li-SGO-FPAS) and poly vinylidenefluoride-hexafluoro propylene (PVDF-HFP) binder by in-situ polymerization to fabricate the porous single ion conducting polymer electrolyte membrane (Li-SGO-po-FPAS) generated from the poor compatibility between aromatic Li-SGO-FPAS and aliphatic PVDF-HFP binder. The key properties such as morphology, porosity, solvent uptake, mechanical strength, flexibility, lithium ion transference number, ionic conductivity and rate-capacity were successfully investigated. In addition, the neat single ion polymer electrolyte membrane without Li-SGO (FPAS) (po-FPAS) was prepared for comparison. The Li-SGO-po-FPAS possessed the high porosity of 55.9% and electrolyte uptake of 139.3wt.%, which are much higher than the values derived from the PP separator. As a result, the enhanced ionic conductivities of 0.23 mS·cm-1 and 1.84 mS·cm-1 were obtained at room temperature and 80℃, respectively, comparing to those of 0.14 mS·cm-1 and 1.20 mS·cm-1 for the po-FPA membrane. Furthermore, the mechanical strength of 9.9 MPa was obtained for the Li-SGO-po-FPAS, which is acceptable for the application in Li-ion batteries. The electrochemical characterizations indicate the better compatibility between the single ion conducting polymer electrolyte and the electrode interface after doping with the Li-SGO. The Li-SGO-po-FPAS showed the lithium ion transference number of 0.91 and electrochemical window of 4.6 V vs. Li+/Li. The Li|LiFePO4 Li-ion battery assembled from the Li-SGO-po-FPAS exhibited good cyclability and higher C-rate capacity. The results suggest that the treatment of GO by lithiation and sulfonation processes is useful for application in single ion conducting polymer electrolyte, and it is also favorable for improving the comprehensive performance of single ion conducting polymer electrolyte, subsequently superior battery performance.
| [1] | Hu J(胡静), Huang B B(黄碧斌), Jiang L P(蒋莉萍), Feng K H(冯凯辉), Li Q H(李琼慧), Xu Z(许钊). Application and major issues of electrochemical energy storage under the environment of power market[J]. Electric Power (中国电力), 2020,53(1):100-107. |
| [2] | Lee K T, Jeong S, Cho J. Roles of surface chemistry on safety and electrochemistry in lithium ion batteries[J]. Accounts Chem. Res, 2012,46(5):1161-1170. |
| [3] | Chen W, Lei T Y, Wu C Y, Deng M, Gong C H, Hu K, Ma Y C, Dai L P, Lü W Q, He W D, Liu X J, Xiong J, Yan C L. Designing safe electrolyte systems for a high-stability lithium-sulfur battery[J]. Adv. Energy Mater., 2018,8(10):1702348. |
| [4] | Li H, Wu D B, Wu J, Dong L Y, Zhu Y J, Hu X. Flexible, high-wettability and fire-resistant separators based on hydroxyapatite nanowires for advanced lithium-ion batteries[J]. Adv. Mater., 2017,29(44):1703548-n/a. |
| [5] | Zhang H, Li C M, Piszcz M, Coya E, Rojo T, Rodriguez-Martinez L M, Armand M, Zhou Z B. Single lithium-ion conducting solid polymer electrolytes: advances and perspectives[J]. Chem. Soc. Rev., 2017,46(3):797-815. |
| [6] | Zhang Y F, Pan M Z, Liu X P, Li C C, Dong J M, Sun Y B, Zeng D L, Yang Z H, Cheng H S. Overcoming the ambient-temperature operation limitation in lithium-ion batteries by using a single-ion polymer electrolyte fabricated by controllable molecular design[J]. Energy Technol., 2018,6(2):289-295. |
| [7] | Zhang J W, Wang S J, Han D M, Xiao M, Sun L Y, Meng Y Z. Lithium (4-styrenesulfonyl) (trifluoromethanesulfonyl) imide based single-ion polymer electrolyte with superior battery performance[J]. Energy Storage Mater., 2020,24:579-587. |
| [8] | Shin D M, Bachman J E, Taylor M K, Kamcev J, Park J G, Ziebel M E, Velasquez E, Jarenwattananon N N, Sethi G K, Long J R. A single-ion conducting borate network polymer as a viable quasi-solid electrolyte for lithium metal batteries[J]. Adv. Mater., 2020,32(10):1905771. |
| [9] | Liu J C, Pickett P D, Park B, Upadhyay S P, Orski S V, Schaefer J L. Non-solvating, side-chain polymer electrolytes as lithium single-ion conductors: synjournal and ion transport characterization[J]. Polym. Chem., 2020,11(2):461-471. |
| [10] | Deng K R, Zeng Q G, Wang D, Liu Z, Qiu Z P, Zhang Y F, Xiao M, Meng Y Z. Single-ion conducting gel polymer electrolytes: design, preparation and application[J]. J. Mater. Chem. A , 2020,8(4):1557-1577. |
| [11] | Chen Y Z, Elangovan A, Zeng D L, Zhang Y F, Ke H Z, Li J, Sun Y B, Cheng H S. Vertically aligned carbon nanofibers on Cu foil as a 3D current collector for reversible Li plating/stripping toward high-performance Li-S batteries[J]. Adv. Funct. Mater., 2020,30(4):1906444. |
| [12] | Zhang Y F, Liu Y, Liu X P, Li C C, Dong J M, Sun Y B, Zeng D L, Yang Z H, Cheng H S. Fluorene-containing cardo and fully aromatic single ion conducting polymer electrolyte for room temperature, high performance lithium ion batteries[J]. ChemistrySelect, 2017,2(26):7904-7908. |
| [13] | Zhang Y F, Cai W W, Rohan R, Pan M Z, Liu Y, Liu X P, Li C C, Sun Y B, Cheng H S. Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte[J]. J. Power Sources, 2016,306:152-161. |
| [14] | Zhang Y F, Lim C A, Cai W W, Rohan R, Xu G D, Sun Y B, Cheng H S. Design and synjournal of a single ion conducting block copolymer electrolyte with multifunctionality for lithium ion batteries[J]. RSC Adv., 2014,4(83):43857-43864. |
| [15] | Zhang Y F, Xu G D, Sun Y B, Han B, Teguh B W T, Chen Z X, Rohan R, Cheng H S. A class of sp3 boron-based single-ion polymeric electrolytes for lithium ion batteries[J]. RSC Adv., 2013,3(35):14934-14937. |
| [16] | Li Z, Yao Q M, Zhang Q, Zhao Y Q, Gao D X, Li S S, Xu S M. Creating ionic channels in single-ion conducting solid polymer electrolyte by manipulating phase separation structure[J]. J. Mater. Chem. A, 2018,6(48):24848-24859. |
| [17] | Rohan R, Sun Y B, Cai W W, Pareek K, Zhang Y F, Xu G D, Cheng H S. Functionalized meso/macro-porous single ion polymeric electrolyte for applications in lithium ion batteries[J]. J. Mater. Chem. A, 2014,2(9):2960-2967. |
| [18] | Wu P(吴鹏), Li Z L(李忠伦), Y Z(余智), Liu P B(刘鹏波). Preparation of porous polyimide film with low dielectric constant by nonsolvent induced phase separation[J]. Polym. Mater. Sci. Eng. (高分子材料科学与工程), 2018,34(3):132-137. |
| [19] | Wang J Y, He Y, Wu Q, Zhang Y F, Li Z Y, Liu Z H, Huo S K, Dong J M, Zeng D L, Cheng H S. A facile non-solvent induced phase separation process for preparation of highly porous polybenzimidazole separator for lithium metal battery application[J]. Sci. Rep., 2019,9:19320. |
| [20] | Dong J M, Zhang Y F, Wang J Y, Yang Z H, Sun Y B, Zeng D L, Liu Z H, Cheng H S. Highly porous single ion conducting polymer electrolyte for advanced lithium-ion batteries via facile water-induced phase separation process[J]. J. Membr. Sci. , 2018,568:22-29. |
| [21] | Zan L N(昝丽娜). Comprehensive experimental design of preparation of multiwalled carbon nanotubes/polyvinyl alcohol composite fiber by electrospining[J]. Chin. J. Chem. Edu. (化学教育(中英文)), 2020,41(2):76-80. |
| [22] | Zhang Y F, Rohan R, Cai W W, Xu G D, Sun Y B, Lin A, Cheng H S. Influence of chemical microstructure of single-ion polymeric electrolyte membranes on performance of lithium-ion batteries[J]. ACS Appl. Mater. Interfaces, 2014,6(20):17534-17542. |
| [23] | Zhang Y F, Chen Y Z, Liu Y, Qin B S, Yang Z H, Sun Y B, Zeng D L, Varzi A, Passerini S, Liu Z H, Cheng H S. Highly porous single-ion conductive composite polymer electrolyte for high performance Li-ion batteries[J]. J. Power Sources, 2018,397:79-86. |
| [24] | Liu X P, Yang Z H, Zhang Y F, Li C C, Dong J M, Liu Y, Cheng H S. Electrospun multifunctional sulfonated carbon nanofibers for design and fabrication of SPEEK composite proton exchange membranes for direct methanol fuel cell application[J]. Int. J. Hydrog. Energy, 2017,42(15):10275-10284. |
| [25] | Yang J(杨娟), Lang J W(郎俊伟), Zhang P(张鹏), Liu B(刘宝). Preparations of nanostructural MnO-porous graphene hybrid material by thermally-driven etching of MnO for lithium-air batteries[J]. J. of Electrochem. (电化学), 2019,25(5):621-630. |
| [26] | Hu X L(胡晓兰), Zhou C(周川), Dai S W(代少伟), Liu W J(刘文军), Li W D(李伟东), Zhou Y J(周玉敬), Qiu H(邱虹), Bai H(白华). Micro-structures and dynamic thermal mechanical properties of graphene oxide modified carbon fiber/epoxy resin composites with different fiber surface properties[J]. Acta Mater. Compos. Sin. (复合材料学报), 2020: 37(5):1070-1080. |
| [27] | Zhang Y F, Ting J W Y, Rohan R, Cai W W, Li J, Xu G D, Chen Z X, Lin A, Cheng H S. Fabrication of a proton exchange membrane via blended sulfonimide functionalized polyamide[J]. J. Mater. Sci. , 2014,49(9):3442-3450. |
| [28] | Li C C, Zhang Y F, Liu X P, Dong J M, Wang J Y, Yang Z H, Cheng H S. Cross-linked fully aromatic sulfonated polyamide as a highly efficiency polymeric filler in SPEEK membrane for high methanol concentration direct methanol fuel cells[J]. J. Mater. Sci., 2018,53(7):5501-5510. |
| [29] | Liu Y, Zhang Y F, Pan M Z, Liu X P, Li C C, Sun Y B, Zeng D L, Cheng H S. A mechanically robust porous single ion conducting electrolyte membrane fabricated via self-assembly[J]. J. Membr. Sci. , 2016,507:99-106. |
| [30] | Zhai C X, Zhou H H, Gao T, Zhao L L, Lin S C. Electrostatically tuned microdomain morphology and phase-dependent ion transport anisotropy in single-ion conducting block copolyelectrolytes[J]. Macromolecules, 2018,51(12):4471-4483. |
| [31] | Nguyen H D, Kim G T, Shi J L, Paillard E, Judeinstein P, Lyonnard S, Bresser D, Iojoiu C. Nanostructured multi-block copolymer single-ion conductors for safer high-performance lithium batteries[J]. Energy Environ. Sci., 2018,11(11):3298-3309. |
| [32] | Kamal A Z, ?elik S ü, Bozkurt A. Single ion conducting blend polymer electrolytes based on LiPAAOB and PPEGMA[J]. J. Inorg. Organomet. Polym. Mater., 2018,28(4):1616-1623. |
| [33] | Zhang Y F, Rohan R, Sun Y B, Cai W W, Xu G D, Lin A, Cheng H S. A gel single ion polymer electrolyte membrane for lithium-ion batteries with wide-temperature range operability[J]. RSC Adv., 2014,4(40):21163-21170. |
| [34] | Hu M F, Yuan Y, Liu Y J, Tian L Y, Zhang Y Y, Long D H. Progressively providing ionic inhibitor via functional nanofiber layer to stabilize lithium metal anode[J]. Electrochim. Acta, 2019,302:301-309. |
| [35] | Deng K R, Qin J X, Wang S J, Ren S, Han D M, Xiao M, Meng Y Z. Effective suppression of lithium dendrite growth using a flexible single-ion conducting polymer electrolyte[J]. Small, 2018,14(31):1801420. |
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