Solid-State Transformations of Active Materials in the Pores of Sulfurized-Polyacrylonitrile Fiber Membranes via Nucleophilic Reactions for High-Loading and Free-Standing Lithium–Sulfur Battery Cathodes

Abstract

Sulfurized polyacrylonitrile (SPAN) has emerged as an excellent cathode material for lithium–sulfur batteries (LiSBs), and it addresses the shuttle effect through a solid‒solid reaction. However, the actual sulfur loadings in SPAN often remain below 40 wt%. Due to the susceptibility of polysulfides-to-nucleophilic reactions with electrolytes, achieving physical encapsulation of elemental sulfur is a challenging task. In this study, a free-standing cathode material with a high sulfur/selenium (S/Se) loading of 55 wt% was fabricated by introducing SeS _x into the unique lotus root-like pores of porous SeS _xPAN nanofiber membranes by electrospinning and a two-step heat treatment. Insoluble compounds were formed due to nucleophilic interactions between lithium polyselenosulfides (LiSeS _x) and the electrolyte, which potently blocked the existing lotus root-like pores and facilitated the creation of a thin cathode–electrolyte interphase on the fiber surface. This dual functionality of LiSeS _x safeguarded the active material embedded within the porous structure. The SeS₁₅PAN cathode exhibited remarkable cycling stability with almost no degradation after 200 cycles at 0.2 C, along with a high discharge capacity of 580 mAh/g. This approach presents a solution for addressing the insufficient sulfur content in SPAN.

Keywords

Lithium–sulfur batteries / Sulfurized polyacrylonitrile / Cathode–electrolyte interphase / High active material content / Nucleophilic reactions

References

[1.] Zhou GM, Chen H, Cui Y. Formulating energy density for designing practical lithium–sulfur batteries. Nat Energy, 2022, 7: 312,

[2.] Ahmed MS, Lee S, Agostini M, Jeong MG, Jung HG, Ming J, Sun YK, Kim J, Hwang JY. Multiscale understanding of covalently fixed sulfur-polyacrylonitrile composite as advanced cathode for metal-sulfur batteries. Adv Sci, 2021, 8: 2101123,

[3.] Huang L, Li JJ, Liu B, Li YH, Shen SH, Deng SJ, Lu CW, Zhang WK, Xia Y, Pan GX, Wang XL, Xiong QQ, Xia XH, Tu JP. Electrode design for lithium–sulfur batteries: problems and solutions. Adv Funct Mater, 2020, 30: 1910375,

[4.] Liu M, Deng NP, Ju JG, Fan LL, Wang LY, Li ZJ, Zhao HJ, Yang G, Kang WM, Yan J, Cheng BW. A review: electrospun nanofiber materials for lithium–sulfur batteries. Adv Funct Mater, 2019, 19: 1905467,

[5.] Zhang YS, Zhang XL, Silva SRP, Ding B, Zhang P, Shao GS. Lithium–sulfur batteries meet electrospinning: recent advances and the key parameters for high gravimetric and volume energy density. Adv Sci, 2022, 9: 2103879,

[6.] Wang YK, Li ZM, Hou YP, Hao ZM, Zhang Q, Ni YX, Lu Y, Yan ZH, Zhang K, Zhao Q, Li FL, Chen J. Emerging electrolytes with fluorinated solvents for rechargeable lithium-based batteries. Chem Soc Rev, 2023, 52: 2713,

[7.] Chen Y, Wang TY, Tian HJ, Su DW, Zhang Q, Wang GX. Advances in lithium–sulfur batteries: from academic research to commercial viability. Adv Mater, 2020, 33: 2003666,

[8.] Yang LW, Li HT, Li Q, Wang Y, Chen YX, Wu ZG, Liu YX, Wang GK, Zhong BH, Xiang W, Zhong YJ, Guo XD. Research progress on improving the sulfur conversion efficiency on the sulfur cathode side in lithium–sulfur batteries. Ind Eng Chem Res, 2020, 59: 20979-21000,

[9.] Hua WX, Li H, Pei C, Xia JY, Sun YF, Zhang C, Lv W, Tao Y, Jiao Y, Zhang B, Qiao SZ, Wan Y, Yang QH. Selective catalysis remedies polysulfide shuttling in lithium–sulfur batteries. Adv Mater, 2021, 33: 2101006,

[10.] Chen JH, Zhang HM, Yang HJ, Lei JY, Naveed A, Yang J, Nuli YN, Wang JJ. Towards pactical Li–S battery with dense and flexible electrode containing lean electrolyte. Energy Storage Mater, 2020, 27: 307,

[11.] Rafie A, Kim JW, Sarode KK, Kalra V. A review on the use of carbonate-based electrolytes in li-s batteries: a comprehensive approach enabling solid–solid direct conversion reaction. Energy Storage Mater, 2022, 50: 197,

[12.] Xin S, Gu L, Zhao NH, Yin YX, Zhou LJ, Guo YG, Wan LJ. Smaller sulfur molecules promise better lithium–sulfur batteries. J Am Chem Soc, 2012, 134: 18510,

[13.] Wang J, Yang J, Wan C, Du K, Xie J, Xu N. Sulfur composite cathode materials for rechargeable lithium batterie. Adv Funct Mater, 2003, 13: 487,

[14.] He B, Rao ZX, Cheng ZX, Liu DD, He DQ, Chen J, Miao ZY, Yuan LX, Li Z, Huang YH. Rationally design a sulfur cathode with solid-phase conversion mechanism for high cycle-stable Li–S batteries. Adv Energy Mater, 2021, 11: 2003690,

[15.] Wang J, Yang J, Xie J, Xu N. A novel conductive polymer sulfur composite cathode material for rechargeable lithium batteries. Adv Mater, 2002, 14: 963,

[16.] Haridas AK, Heo JW, Li XY, Ahn HJ, Zhao XH, Deng Z, Agostini M, Matic A, Ahn JH. A flexible and free-standing FeS/sulfurized polyacrylonitrile hybrid anode material for high-rate sodium-ion storage. Chem Eng J, 2020, 385: 123453,

[17.] Luo FQ, Feng XS, Zeng LX, Lin LX, Li XY, Kang BY, Xiao LR, Chen QH, Qian QR. In situ simultaneous encapsulation of defective MoS₂ nanolayers and sulfur nanodots into SPAN fibers for high-rate sodium-ion batteries. Chem Eng J, 2020, 404: 126430,

[18.] Yang HL, Zhou S, Zhang BW, Chu SQ, Guo HP, Gu HF, Liu HW, Lei YJ, Konstantinov K, Wang SL, Chou SL, Liu HK, Dou SX. Architecting freestanding sulfur cathodes for superior room-temperature Na–S batteries. Adv Funct Mater, 2021, 31: 2102280,

[19.] Lei JY, Chen JH, Zhang HM, Naveed A, Yang J, Nuli Y, Wang JL. High molecular weight polyacrylonitrile precursor for S@pPAN composite cathode materials with high specific capacity for rechargeable lithium batteries. ACS Appl Mater Interfaces, 2020, 12: 33702-33709,

[20.] Xiao QHQ, Yang JL, Wang XD, Deng YR, Han P, Yuan N, Zhang L, Feng M, Wang CA, Liu RP. Carbon-based flexible self-supporting cathode for lithium–sulfur batteries: progress and perspective. Carbon Energy, 2021, 3: 271,

[21.] Wang XF, Qian YM, Wang LN, Yang H, Li HL, Zhao Y, Liu TX. Sulfurized polyacrylonitrile cathodes with high compatibility in both ether and carbonate electrolytes for ultrastable lithium–sulfur batteries. Adv Funct Mater, 2019, 29: 1902929,

[22.] Razzaq AA, Chen GW, Zhao XH, Yuan XT, Hu JP, Li ZW, Chen YF, Xu JB, Shah R, Zhong J, Peng Y, Deng Z. Cobalt coordination with pyridines in sulfurized polyacrylonitrile cathodes to form conductive pathways and catalytic M-N4S sites for accelerated Li–S kinetics. J Energy Chem, 2021, 61: 170,

[23.] Xu GL, Sun H, Luo C, Estevez L, Zhuang MH, Gao H, Amine R, Wang H, Zhang XY, Sun CJ, Liu YZ, Ren Y, Heald SM, Wang CS, Chen ZH. Solid-state lithium/selenium–sulfur chemistry enabled via a robust solid-electrolyte interphase. Adv Energy Mater, 2018, 9: 1802235,

[24.] He B, Liu D, Cheng Z, Miao Z, Rao Z, Zhang H, Yuan L, Huang Y. Enabling selenium-rich Se _xS _y cathodes to work in carbonate-based electrolytes. Adv Energy Mater, 2021, 12: 2270001,

[25.] Huang CJ, Lin KY, Hsieh YC, Su WN, Wang CH, Brunklaus G, Winter M, Jiang JC, Hwang BJ. New insights into the N–S bond formation of a sulfurized-polyacrylonitrile cathode material for lithium–sulfur batteries. ACS Appl Mater Interfaces, 2021, 13: 14230,

[26.] Delley B. From molecules to solids with the DMol3 approach. J Chem Phys, 2000, 113: 7756,

[27.] Delley B. An all-electron numerical method for solving the local density functional for polyatomic molecules. J Chem Phys, 1990, 92: 508,

[28.] He B, Rao ZX, Cheng ZX, Liu DD, He DQ, Miao ZY, Yuan LX, Li Z, Huang YH. Rationally design a sulfur cathode with solid-phase conversion mechanism for high cycle-stable Li–S batteries. Adv Energy Mater, 2021, 11: 2003690,

[29.] Chen X, Peng LF, Wang LH, Yang JQ, Hao ZX, Xiang JW, Yuan K, Huang YH, Shan BM, Yuan LX, Xie J. Ether-compatible sulfurized polyacrylonitrile cathode with excellent performance enabled by fast kinetics via selenium doping. Nat Commun, 2019, 10: 1021, pmcid: 6399341

[30.] Pham HV, Boscoboinik JA, Stacchiola DJ, Self EC, Manikandan P, Nagarajan S, Wang YX, Pol VG, Nanda J, Paek E, Mitlin D. Selenium-sulfur (SeS) fast charging cathode for sodium and lithium metal batteries. Energy Storage Mater, 2019, 20: 71,

[31.] Wei SY, Ma L, Hendrickson KE, Tu ZY, Archer LA. Metal–sulfur battery cathodes based on PAN–sulfur composites. J Am Chem Soc, 2015, 37: 12143,

[32.] Xu GL, Sun H, Luo C, Estevez L, Zhuang MH, Gao H, Amine R, Chen ZH, Amine K. Solid-state lithium/selenium–sulfur chemistry enabled via a robust solid-electrolyte interphase. Adv Energy Mater, 2018, 9: 1802235,

[33.] Xue WY, Xu WC, Wang W, Gao GX, Wang L. Iodine-doped fibrous sulfurized polyacrylonitrile with accelerated reaction kinetics. Compos Commun, 2022, 30: 101078,

[34.] Li HL, Xue WY, Wang LN, Liu TX. Two competing reactions of sulfurized polyacrylonitrile produce high-performance lithium–sulfur batteries. ACS Appl Mater Interfaces, 2021, 13: 25002,

[35.] Liu Y, Haridas AK, Lee YK, Cho KK, Ahn JH. Freestanding porous sulfurized polyacrylonitrile fiber as a cathode material for advanced lithium sulfur batteries. Appl Surf Sci, 2019, 472: 135,

[36.] Razzaq AA, Yao YZ, Shah R, Qi PW, Miao LX, Chen MZ, Zhao XH, Peng Y, Deng Z. High-performance lithium sulfur batteries enabled by a synergy between sulfur and carbon nanotubes. Energy Storage Mater, 2019, 16: 194,

[37.] Huang XY, Liu J, Huang ZX, Ke Z, Liu XY, Wang NG, Liu JP, Guo ZP, Yang Y, Shi ZC. Flexible free-standing sulfurized polyacrylonitrile electrode for stable Li/Na storage. Electrochim Acta, 2020, 333: 135493,

[38.] Hu XR, Jiang HL, Hou M, Yu M, Jiang XB, He GH, Li XC. Scalable SPAN membrane cathode with high conductivity and hierarchically porous framework for enhanced ion transfer and cycling stability in Li–S batteries. ACS Mater Lett, 2023, 5: 2047,

[39.] Wang WX, Cao Z, Elia GA, Wahyudi W, Emwas AH, Cavallo L, Li LJ, Ming J. Recognizing the mechanism of sulfurized polyacrylonitrile cathode materials for Li–S batteries and beyond in Al–S batteries. ACS Energy Lett, 2018, 3: 2899,

[40.] Weret MA, Kuo CF, Zeleke TS, Beyene TT, Tsau MC, Huang CJ, Berhe GB, Su WN, Wang HBJ. Mechanistic understanding of the sulfurized-poly(acrylonitrile) cathode for lithium–sulfur batteries. Energy Storage Mater, 2020, 16: 483,

[41.] Oyakhire ST, Gong HX, Cui Y, Bao ZN, Bent SF. An X-ray photoelectron spectroscopy primer for solid-electrolyte interphase characterization in lithium metal anodes. ACS Energy Lett, 2022, 7: 2540,

[42.] Yim T, Park MS, Yu JS, Kim KJ, Im KY, Kim JH, Jeong G, Kim YJ. Effect of chemical reactivity of polysulfide toward carbonate-based electrolyte on the electrochemical performance of Li–S batteries. Electrochim Acta, 2013, 107: 454,

[43.] Ling M, Zhang L, Zheng TY, Feng J, Guo JH, Mai LQL. Nucleophilic substitution between polysulfides and binders unexpectedly stabilizing lithium sulfur battery. Nano Energy, 2017, 38: 82,

[44.] Steudel R, Chivers T. The role of polysulfide dianions and radical anions in the chemical, physical and biological sciences, including sulfur-based batteries. Chem Soc Rev, 2019, 48(12): 3279-3319,

[45.] Qiu CD, Hu YC, Cao KW, Wu XJ, Huang BH, Liu J, Wang YX, Luo LB, Gu D, Ai XP, Cao YL, Chen SL, Ke FS. Engineering peculiar cathode electrolyte interphase toward sustainable and high-rate Li–S batteries. Adv Energy Mater, 2023, 13: 2300229,

[46.] Zhang XH, Gao PY, Wu ZH, Engelhard MH, Cao X, Jia H, Xu YB, Liu HD, Wang CM, Liu J, Zhang JG, Liu P, Xu W. Pinned electrode/electrolyte interphase and its formation origin for sulfurized polyacrylonitrile cathode in stable lithium batteries. ACS Appl Mater Interfaces, 2022, 14: 52046,

Funding

The New Materials Research Key Program of Tianjin(18ZXJMTG00110)