•  
  •  
 

Corresponding Author

Wei-Kun Wang(wangweikun2002@163.com);
Ming Yao(Yaoming@mail.buct.edu.cn);
Ya-Qin Huang(huangyq@mail.buct.edu.cn)

Abstract

Sulfurized polyacrylonitrile (SPAN) is regarded as an attractive cathode candidate of lithium-sulfur (Li-S) batteries for its non-dissolution mechanism and effective alleviation of polysulfides shuttling issue in Li-S batteries, displaying high utilization of cathode active material, outstanding cycle stability and structural stability. However, the relation between cyclization degree and cycle stability of SPAN is still unveiled. In this work, SPAN-C-V composites were synthesized by co-introduction of CuSO4 and zinc n-ethyl-n-phenyldithiocarbamate (ZDB) in the co-heating of sulfur and polyacrylonitrile. The co-introduction of CuSO4 and ZDB reduced the cyclization reaction onset temperature of PAN while increased the C—C/C=C within SPAN-C-V, thus led to an increase in the degree of cyclization of SPAN-C-V, achieving excellent electrochemical performance by simultaneously improving the cyclization degree and increasing the content of sulfur. The SPAN-C-V exhibited an initial reversible capacity of 805 mAh·g-1 and 601 mAh·g-1 after 100 cycles with the capacity retention rate of 93% at 0.2 C (1 C = 600 mAh·g-1). The focus on the cyclization degree of SPAN provides an enlightenment of advanced cathode material.

Graphical Abstract

Keywords

sulfurized polyacrylonitrile, CuSO4, zinc n-ethyl-n-phenyldithiocarbamate, cyclization degree, lithium-sulfur battery

Publication Date

2022-12-28

Online Available Date

2022-11-14

Revised Date

2022-10-06

Received Date

2022-09-15

References

[1] Seh Z W, Sun Y, Zhang Q, Cui Y. Designing high-energy lithium-sulfur batteries[J]. Chem. Soc. Rev., 2016, 45(20): 5605-5634.
pmid: 27460222

[2] Manthiram A, Fu Y, Chung S H, Zu C, Su Y S. Rechargeable lithium-sulfur batteries[J]. Chem. Rev., 2014, 114(23): 11751-11787.
doi: 10.1021/cr500062v pmid: 25026475

[3] Wang L, Zhao J S, He X M, Wan C R. Kinetic investigation of sulfurized polyacrylonitrile cathode material by electrochemical impedance spectroscopy[J]. Electrochim. Acta, 2011, 56(14): 5252-5256.
doi: 10.1016/j.electacta.2011.03.009 URL

[4] Ji X, Lee K T, Nazar L F. A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries[J]. Nat. Mater., 2009, 8(6): 500-506.
doi: 10.1038/nmat2460 URL

[5] Takeuchi T, Kojima T, Kageyama H, Mitsuhara K, Ogawa M, Yamanaka K, Ohta T, Kobayashi H, Nagai R, Ohta A. High capacity sulfurized alcohol composite positive electrode materials applicable for lithium sulfur batteries[J]. J. Electrochem. Soc., 2016, 164(1): A6288-A6293.
doi: 10.1149/2.0501701jes URL

[6] He X M, Pu W H, Ren J G, Wang L, Wang J L, Jiang C Y, Wan C R. Charge/discharge characteristics of sulfur composite cathode materials in rechargeable lithium batteries[J]. Electrochim. Acta, 2007, 52(25): 7372-7376.
doi: 10.1016/j.electacta.2007.06.016 URL

[7] Yun J H, Kim J H, Kim D K, Lee H W. Suppressing polysulfide dissolution via cohesive forces by interwoven carbon nanofibers for high-areal-capacity lithium-sulfur batteries[J]. Nano Lett., 2017, 18(1): 475-481.
doi: 10.1021/acs.nanolett.7b04425 URL

[8] Wang J L, Yang J, Wan C R, Du K, Xie J Y, Xu N X. Sulfur composite cathode materials for rechargeable lithium batteries[J]. Adv. Funct. Mater., 2003, 13(6): 487-492.
doi: 10.1002/adfm.200304284 URL

[9] Zhang T, Hong M, Yang J, Xu Z X, Wang J L, Guo Y S, Liang C D. A high performance lithium-ion-sulfur battery with a free-standing carbon matrix supported Li-rich alloy anode[J]. Chem. Sci., 2018, 9(47): 8829-8835.
doi: 10.1039/c8sc02897d pmid: 30627400

[10] Yang H J, Chen J H, Yang J, Wang J L. Prospect of sulfurized pyrolyzed poly(acrylonitrile) (S@pPAN) cathode materials for rechargeable lithium batteries[J]. Angew. Chem. Int. Edit., 2020, 59(19): 7306-7318.
doi: 10.1002/anie.201913540 URL

[11] Ahmed M S, Lee S, Agostini M, Jeong M G, Jung H G, Ming J, Sun Y K, Kim J, Hwang J Y. Multiscale understanding of covalently fixed sulfur-polyacrylonitrile composite as advanced cathode for metal-sulfur batteries[J]. Adv. Sci., 2021, 8(21): e2101123.

[12] Wang L, He X M, Li J J, Gao J, Fang M, Tian G Y, Wang J L, Fan S S. Graphene-coated plastic film as current collector for lithium/sulfur batteries[J]. J. Power Sources, 2013, 239: 623-627.
doi: 10.1016/j.jpowsour.2013.02.008 URL

[13] Chen H W, Wang C H, Hu C J, Zhang J S, Gao S, Lu W, Chen L W. Vulcanization accelerator enabled sulfurized carbon material for high capacity high stability lithium-sulfur batteries[J]. J. Mater. Chem. A, 2015, 3: 1392.
doi: 10.1039/C4TA05938G URL

[14] Wang Y, Shuai Y, Chen K H. Diphenyl guanidine as vulcanization accelerators in sulfurized polyacrylonitrile for high performance lithium-sulfur battery[J]. Chem. Eng. J., 2020, 388: 124378.
doi: 10.1016/j.cej.2020.124378 URL

[15] Wang Y, Zhang Y P, Shuai Y, Chen K H. Diphenyl guanidine vulcanization accelerators enable sulfurized polyacrylonitrile cathode for high capacity and ether-compatible by fast kinetic[J]. Energy, 2021, 233: 121160.
doi: 10.1016/j.energy.2021.121160 URL

[16] Jin J, van Swaaij A P J, Noordermeer J W M, Blume A, Dierkes W K. On the various roles of 1,3-DIPHENYL Guanidine in silica/silane reinforced sbr/br blends[J]. Polym. Test., 2021, 93: 106858.
doi: 10.1016/j.polymertesting.2020.106858 URL

[17] Liu R G, Xu J. Recent progress in high performance PAN based carbon fibers[J]. Sci. Tech. review, 2018, 36(19): 32-42.

[18] KO T H, Huang L C. Preparation of high-performance carbon fibres from PAN fibres modified with cobaltous chloride[J]. J. Mater. Sci., 1992, 27(9): 2429-2436.
doi: 10.1007/BF01105054 URL

[19] Li J M. The effect of cuprous salt on polyacrylonitrile fiber(PAN) during thermostablization[J]. J. China Textile University, 1992, 18(4): 22-29.

[20] Zhang W X, Wang Y Z, Wang Y X, Cai H S, Li M S. Effect of NiSO4 on the structure and properties of PAN precursors and resultant carbon fibres[J]. Acta Polym. Sin., 2001, (5): 670-673.

[21] Ma S B, Zhang Z G, Wang Y, Yu Z J, Cui C, He M X, Huo H, Yin G P, Zuo P J. Iodine-doped sulfurized polyacrylonitrile with enhanced electrochemical performance for lithium sulfur batteries in carbonate electrolyte.[J]. Chem. Eng. J., 2021, 418: 129410.
doi: 10.1016/j.cej.2021.129410 URL

[22] Wang J, He Y S, Yang J. Sulfur-based composite cathode materials for high-energy rechargeable lithium batteries[J]. Adv. Mater., 2015, 27(3): 569-575.
doi: 10.1002/adma.201402569 URL

[23] Dou T, Qin Y, Zhang F Z, Lei X D. CuS nanosheet arrays for electrochemical CO2 reduction with surface reconstruction and the effect on selective formation of formate[J]. ACS Appl. Energy Mater., 2021, 4(5): 4376-4384.
doi: 10.1021/acsaem.0c03190 URL

[24] Jin Z Q, Liu Y G, Wang W K, Wang A B, Hu B W, Shen M, Gao T, Zhao P C, Yang Y S. A new insight into the lithium storage mechanism of sulfurized polyacrylonitrile with no soluble intermediates[J]. Energy Storage Mater., 2018, 14: 272-278.

[25] Ratanavaraporn J, Soontornvipart K, Shuangshoti S, Shuangshoti S, Damrongsakkul S. Localized delivery of curcumin from injectable gelatin/Thai silk fibroin microspheres for anti-inflammatory treatment of osteoarthritis in a rat model[J]. Inflammopharmacology, 2017, 25(2): 211-221.
doi: 10.1007/s10787-017-0318-3 pmid: 28251487

[26] Wang Y S, Xu L H, Wang M Z, Pang W M, Ge X W. Structural identification of polyacrylonitrile during thermal treatment by selective 13C labeling and solid-state 13C NMR spectroscopy[J]. Macromolecules, 2014, 47(12): 3901-3908.
doi: 10.1021/ma500727n URL

[27] Yuan Z, Peng H J, Hou T Z, Huang J Q, Chen C M, Wang D W, Cheng X B, Wei F, Zhang Q. Powering lithium-sulfur battery performance by propelling polysulfide redox at sulfiphilic hosts[J]. Nano Lett., 2016, 16(1): 519-527.
doi: 10.1021/acs.nanolett.5b04166 pmid: 26713782

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.