无机材料学报 ›› 2019, Vol. 34 ›› Issue (4): 373-378.DOI: 10.15541/jim20180236
收稿日期:
2018-05-21
修回日期:
2018-09-06
出版日期:
2019-04-20
网络出版日期:
2019-04-15
作者简介:
李亚东(1993-), 男, 硕士研究生. E-mail: liyadong@nimte.ac.cn
基金资助:
Ya-Dong LI1,Wei-Ping LI1,Qin WANG1,Dao-Guang ZHENG1,Jian-Xin WANG2()
Received:
2018-05-21
Revised:
2018-09-06
Published:
2019-04-20
Online:
2019-04-15
Supported by:
摘要:
锂硫电池作为极具潜力的下一代二次电池受到广泛关注。然而, 对于含硫正极的研究仍处于实验探索阶段, 商业化的碳纤维毡应用于硫正极鲜有报道。本研究制备了锂硫电池用碳纤维支撑柔性碳硫复合电极, 并对其进行了物性及电池性能的研究。结果发现, 碳纤维毡具有多孔隙的三维网络结构, 与具有微孔结构的多孔碳共同构成正极支撑体, 能够物理固定正极材料, 有助于提高电池的能量密度和锂硫正极的导电性, 界面电阻由原来的97.9 Ω降到22.6 Ω。进一步研究表明, 碳纤维毡做集流体的样品在首圈0.05C倍率下, 具有996.7 mAh/g的放电比容量, 在2C高倍率下循环140圈后仍保持666.7 mAh/g的放电比容量, 而铝箔样品仅为772.9和471.6 mAh/g。同时, 本研究使用的LA132水系粘结剂、super-P导电剂价格低廉, 球磨制备工艺可规模化生产、安全环保, 可以为锂硫电池工业化生产和应用提供参考。
中图分类号:
李亚东, 李伟平, 王琴, 郑道光, 王建新. 碳纤维支撑柔性碳硫复合电极的制备、物性及电池性能研究[J]. 无机材料学报, 2019, 34(4): 373-378.
Ya-Dong LI, Wei-Ping LI, Qin WANG, Dao-Guang ZHENG, Jian-Xin WANG. Flexible Carbon-fiber Supported Carbon-sulfur Electrode: Preparation, Physical Property and Electrochemical Performance[J]. Journal of Inorganic Materials, 2019, 34(4): 373-378.
Sample | Surface area/(m2?g-1) | Volume/(cm3?g-1) | Average pore diameter/nm | ||||
---|---|---|---|---|---|---|---|
SBET | Smicro | Sexternal | Vtotal | Vmicro | BJH | ||
Porous carbon | 1734.7242 | 1041.1364 | 693.5878 | 0.848649 | 0.472287 | 2.2930 | |
CSv | 7.4587 | 1.3661 | 6.0926 | 0.008040 | 0.000438 | 7.1043 |
表1 多孔碳的结构特性
Table 1 Texture properties of porous carbon
Sample | Surface area/(m2?g-1) | Volume/(cm3?g-1) | Average pore diameter/nm | ||||
---|---|---|---|---|---|---|---|
SBET | Smicro | Sexternal | Vtotal | Vmicro | BJH | ||
Porous carbon | 1734.7242 | 1041.1364 | 693.5878 | 0.848649 | 0.472287 | 2.2930 | |
CSv | 7.4587 | 1.3661 | 6.0926 | 0.008040 | 0.000438 | 7.1043 |
图4 (a)~(c)碳纤维毡、(d)多孔碳、(e) CS、(f)~(g) CSv的SEM照片; (h)~(i) 250 ℃处理碳硫粉的EDX图谱以及(j)表面元素含量((g)中标识区域)
Fig. 4 SEM images of (a-c) CFF, (d) porous carbon, (e) CS, and (f-g) CSv, and EDX elemental maps of (h) carbon, (i) sulfur, and (j) the corresponding mass percentage in the area marked with a rectangle in (g)
图7 碳纤维毡和铝箔分别做集流体的电池阻抗, 插图为等效电路图
Fig. 7 Electrochemical impedance plots of the batteries with Al/CSv and CFF/CSv as the current collectors with inset showing equivalent circuit
图8 碳纤维毡和铝箔分别做集流体的电池在(a)0.2C~5C和(b)2C下的循环性能曲线; 不同硫负载量碳纤维毡做集流体的电池在(c)0.2C下的循环性能曲线和(d)首圈0.05C下的充放电曲线
Fig. 8 Cycle performance of CFF/CSv and Al/CSv batteries at (a) 0.2C-5C rates and (b) 2C rate, (c) Cycle performance of CFF/CSv batteries with different S load at 0.2C rate, and (d) charge-discharge performance of the CFF/CSv batteries with different S load at 0.05C rate
[1] | YANG Y, ZHENG G Y, CUI Y . Nanostructured sulfur cathodes. Chemical Society Reviews, 2013,42(7):3018-3032. |
[2] | ROSENMAN A, MARKEVICH E, SALITRA G , et al. Review on Li-sulfur battery systems: an integral perspective. Advanced Energy Materials, 2015, 5(11): 1500212-1-21. |
[3] | ZHANG R, CHENG X B, ZHAO C Z , et al. Conductive nanostructured scaffolds render low local current density to inhibit lithium dendrite growth. Advanced Material, 2016,28(11):2155-2162. |
[4] | CHENG X B, ZHANG R, ZHAO C Z , et al. A review of solid electrolyte interphases on lithium metal anode. Advanced Material, 2016, 3(3): 1500213-1-20. |
[5] | MARMORSTEIN D, YU T H, STRIEBEL K A , et al. Electrochemical performance of lithium/sulfur cells with three different polymer electrolytes. Journal of Power Sources, 2000,89(2):219-226. |
[6] | LI W Y, ZHENG G Y, CUI Y , et al. Sulphur-TiO2 yolk-shell nanoarchitecture with internal void space for long-cycle lithium- sulphur batteries. Nature Communications, 2013, 4(4): 1331-1-6. |
[7] | CHEN H W, DONG W L, WANG C , et al. Ultrafine sulfur nanoparticles in conducting polymer shell as cathode materials for high performance lithium/sulfur batteries. Scientific Reports, 2013, 3(5): 1910-1-6. |
[8] | WU F, CHENG J Z, CHENG R J , et al. Polyethylene-glycol-doped polypyrrole increases the rate performance of the cathode in lithium- sulfur batteries. ChemSusChem, 2013,6(8):1438-1444. |
[9] | DIRLAM P T, CHAR K, PYUN J , et al. The use of polymers in Li-S batteries: a review. Journal of Polymer Science A: Polymer Chemistry, 2017,55:1635-1668. |
[10] | PENG H J, HUANG J Q, WEU F , et al. Nanoarchitectured graphene/ CNT@porous carbon with extraordinary electrical conductivity and interconnected micro/mesopores for lithium-sulfur batteries. Advanced Functional Materials, 2014,24(19):2772-2781. |
[11] | ZHANG Z, KONG L L, LIU S , et al. A high-efficiency sulfur/ carbon composite based on 3D graphene nanosheet@carbon nanotube matrix as cathode for lithium-sulfur battery. Advanced Energy Materials, 2017, 7(11): 1602543-1-12. |
[12] | ZENG L C, YAO Y, YU Y , et al. A flexible S1-xSex@porous carbon nanofibers (x≤0.1) thin film with high performance for Li-S batteries and room-temperature Na-S batteries. Energy Storage Materials, 2016,5:50-57. |
[13] | HANG S C, SONG M S, LEE J Y , et al. Effect of multiwalled carbon nanotubes on electrochemical properties of lithium/sulfur rechargeable batteries. Journal of Electrochemical Society, 2003,150(7):A889-A893. |
[14] | CHANG Z, DING B, DOU H , et al. Hierarchically porous multilayered carbon barriers for high-performance Li-S batteries. Chemistry, 2018,24(15):3768-3775. |
[15] | LI G R, LEI W, CHEN Z W , et al. 3D porous carbon sheets with multidirectional ion pathways for fast and durable lithium-sulfur batteries. Advanced Energy Materials, 2018, 8(8): 1702381-1-10. |
[16] | CHUNG S H, MANTHIRAM A . Low-cost, porous carbon current collector with high sulfur loading for lithium-sulfur batteries. Electrochemistry Communications, 2014,38:91-95. |
[17] | HU M M, HU T, LI Z J , et al. Surface functional groups and interlayer water determine the electrochemical capacitance of Ti3C2Tx MXene. ACS Nano, 2018,12(4):3578-3586. |
[18] | YANG W, SONG A L, SUN G , et al. 3D interconnected porous carbon nanosheets/carbon nanotubes as a polysulfide reservoir for high performance lithium-sulfur batteries. Nanoscale, 2018,10(2):816-824. |
[19] | ZHAO Z X, QING D, WANG S , et al. Fabrication of high conductive S/C cathode by sulfur infiltration into hierarchical porous carbon/ carbon fiber weave-structured materials via vapor-melting method. Electrochimica Acta, 2014,127:123-131. |
[20] | LI X, WANG L J, XIA, LIU Z , et al. Catalytic oxidation of toluene over copper and manganese based catalysts: effect of water vapor. Catalysis Communications, 2011,14(1):15-19. |
[21] | CUI X L, SHAN Z Q, CUI L , et al. Enhanced electrochemical performance of sulfur/carbon nanocomposite material prepared via chemical deposition with a vacuum soaking step. Electrochimica Acta, 2013,105(26):23-30. |
[22] | SCHUSTER J, YIM T, NAZAR L F , et al. Spherical ordered mesoporous carbon nanoparticles with high porosity for lithium- sulfur batteries. Angewandte Chemie International Edition, 2012,51(15):3591-3595. |
[23] | NAZAR L F, JI X L, LEE K T . A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries. Nature Materials, 2009,8(6):500-506. |
[24] | OSCHATZ M, THIEME S, BORCHARDT L , et al. A new route for the preparation of mesoporous carbon materials with high performance in lithium-sulphur battery cathodes. Chemical Communications, 2013,49(52):5832-5834. |
[25] | YI L L, WANG X Y, WANG G , et al. Improved electrochemical performance of spherical Li2FeSiO4/C cathode materials via Mn doping for lithium-ion batteries. Electrochimica Acta, 2016,222:1354-1364. |
[26] | LI G C, HU J J, LI G R , et al. Sulfur/activated-conductive carbon black composites as cathode materials for lithium/sulfur battery. Journal of Power Sources, 2013,240(31):598-605. |
[27] | YAMIN H, GORENSHTEIN A, PENCINER J , et al. Lithium sulfur battery: oxidation/reduction mechanisms of polysulfides in THF solutions. Journal of Electrochemical Society, 1988,19(33):1045-1048. |
[28] | RAUH R D, ABRAHAM K M, PEARSON G F , et al. A lithium/ dissolved sulfur battery with an organic electrolyte. Journal of Electrochemical Society, 1979,126(4):523-527. |
[29] | KOLOSNITYN V S, KUZMINA E V, KARASEVA S E , et al. A study of the electrochemIcal processes in lithium-sulphur cells by impedance spectroscopy. Journal of Power Sources, 2011,196(3):1478-1482. |
[30] | XIE J, YANG J, ZHOU X , et al. Preparation of three-dimensional hybrid nanostructure-encapsulated sulfur cathode for high-rate lithium sulfur batteries. Journal of Power Sources, 2014,253(5):55-63. |
[1] | 杨洋, 崔航源, 祝影, 万昌锦, 万青. 柔性神经形态晶体管研究进展[J]. 无机材料学报, 2023, 38(4): 367-377. |
[2] | 李高然, 李红阳, 曾海波. 硼基材料在锂硫电池中的研究进展[J]. 无机材料学报, 2022, 37(2): 152-162. |
[3] | 李婷婷, 张阳, 陈加航, 闵宇霖, 王久林. 锂硫电池S@pPAN正极用柔性黏结剂研究[J]. 无机材料学报, 2022, 37(2): 182-188. |
[4] | 刘丹, 赵亚欣, 郭锐, 刘艳涛, 张志东, 张增星, 薛晨阳. 退火条件对磁控溅射MgO-Ag3Sb-Sb2O4柔性薄膜热电性能的影响[J]. 无机材料学报, 2022, 37(12): 1302-1310. |
[5] | 罗艺, 夏书海, 牛波, 张亚运, 龙东辉. 柔性有机硅气凝胶的制备及其高温无机化转变研究[J]. 无机材料学报, 2022, 37(12): 1281-1288. |
[6] | 金高尧, 何海传, 吴杰, 张梦源, 李亚娟, 刘又年. 锂硫电池正极用钴掺杂空心多孔碳载体材料[J]. 无机材料学报, 2021, 36(2): 203-209. |
[7] | 方华靖, 赵泽天, 武文婷, 汪宏. 柔性电致变色器件研究进展[J]. 无机材料学报, 2021, 36(2): 140-151. |
[8] | 汤嘉伟, 王永邦, 马成, 杨海潇, 王际童, 乔文明, 凌立成. 甲基萘沥青基有序中孔炭的制备及电化学性能[J]. 无机材料学报, 2021, 36(10): 1031-1038. |
[9] | 徐海丰,侯成义,张青红,李耀刚,王宏志. 碲纳米线柔性薄膜的制备及其热电性能[J]. 无机材料学报, 2020, 35(9): 1034-1040. |
[10] | 蒋浩,吴淏,侯成义,李耀刚,肖茹,张青红,王宏志. 切割方向对桦木衍生的取向微通道生物质炭锂硫电池隔膜性能的影响[J]. 无机材料学报, 2020, 35(6): 717-723. |
[11] | 王佳宁, 靳俊, 温兆银. α-MoC1-x纳米晶富集碳球修饰隔膜对锂硫电池性能的影响[J]. 无机材料学报, 2020, 35(5): 532-540. |
[12] | 杨以娜, 王冉冉, 孙静. MXenes在柔性力敏传感器中的应用研究进展[J]. 无机材料学报, 2020, 35(1): 8-18. |
[13] | 吕喜庆, 张环宇, 李瑞, 张梅, 郭敏. Nb2O5包覆对TiO2纳米阵列/上转换发光复合结构柔性染料敏化太阳能电池性能的影响[J]. 无机材料学报, 2019, 34(6): 590-598. |
[14] | 李鹏, 聂晓蕾, 田烨, 方文兵, 魏平, 朱婉婷, 孙志刚, 张清杰, 赵文俞. Bi0.5Sb1.5Te3/环氧树脂柔性复合热电厚膜的制备及其面内制冷性能[J]. 无机材料学报, 2019, 34(6): 679-684. |
[15] | 肖敏, 孙睿智, 李艳芳, 康同同, 秦俊, 杨润, 毕磊. 基于MoS2/SiO2范德华异质结的VO2薄膜转移打印研究[J]. 无机材料学报, 2019, 34(11): 1161-1166. |
阅读次数 | ||||||
全文 |
|
|||||
摘要 |
|
|||||