Metal phosphides and borides as the catalytic host of sulfur cathode for lithium–sulfur batteries

Abstract

Lithium-sulfur batteries are one of the most competitive high-energy batteries due to their high theoretical energy density of 2600 W·h·kg⁻¹. However, their commercialization is limited by poor cycle stability mainly due to the low intrinsic electrical conductivity of sulfur and its discharged products (Li₂S₂/Li₂S), the sluggish reaction kinetics of sulfur cathode, and the “shuttle effect” of soluble intermediate lithium polysulfides in ether-based electrolyte. To address these challenges, catalytic hosts have recently been introduced in sulfur cathodes to enhance the conversion of soluble polysulfides to the final solid products and thus prevent the dissolution and loss of active-sulfur material. In this review, we summarize the recent progress on the use of metal phosphides and borides of different dimensions as the catalytic host of sulfur cathodes and demonstrate the catalytic conversion mechanism of sulfur cathodes with the help of metal phosphides and borides for high-energy and long-life lithium-sulfur batteries. Finally, future outlooks are proposed on developing advanced catalytic host materials to improve battery performance.

Keywords

lithium-sulfur batteries / sulfur cathode / catalytic host / metal phosphides / metal borides

References

[1] Lu YX, Rong XH, Hu YS, Chen LQ, Li H. Research and development of advanced battery materials in China. Energy Storage Mater., 2019, 23, 144.

[2] M.A. Pope and I.A. Aksay, Structural design of cathodes for Li-S batteries, Adv. Energy Mater., 5(2015), No. 16, art. No. 1500124.

[3] Zuo PJ, Hua JF, He MX, Zhang H, Qian ZY, Ma YL, Du CY, Cheng XQ, Gao YZ, Yin GP. Facilitating the redox reaction of polysulfides by an electrocatalytic layer-modified separator for lithium-sulfur batteries. J. Mater. Chem. A, 2017, 5(22): 10936.

[4] W.J. Deng, J. Phung, G. Li, and X.L. Wang, Realizing high-performance lithium-sulfur batteries via rational design and engineering strategies, Nano Energy, 82(2021), art. No. 105761.

[5] Deng C, Wang ZW, Wang SP, Yu JX. Inhibition of polysulfide diffusion in lithium-sulfur batteries: Mechanism and improvement strategies. J. Mater. Chem. A, 2019, 7(20): 12381.

[6] He F, Wu XJ, Qian JF, Cao YL, Yang HX, Ai XP, Xia DG. Building a cycle-stable sulphur cathode by tailoring its redox reaction into a solid-phase conversion mechanism. J. Mater. Chem. A, 2018, 6(46): 23396.

[7] P. Chen, Z. Wu, T. Guo, Y. Zhou, M.L. Liu, X.F. Xia, J.W. Sun, L.D. Lu, X.P. Ouyang, X. Wang, Y.S. Fu, and J.W. Zhu, Strong chemical interaction between lithium polysulfides and flame-retardant polyphosphazene for lithium-sulfur batteries with enhanced safety and electrochemical performance, Adv. Mater., 33(2021), No. 9, art. No. 2007549.

[8] P. Wang, B.J. Xi, M. Huang, W.H. Chen, J.K. Feng, and S.L. Xiong, Emerging catalysts to promote kinetics of lithium-sulfur batteries, Adv. Energy Mater., 11(2021), No. 7, art. No. 2002893.

[9] Li YJ, Fan JM, Zheng MS, Dong QF. A novel synergistic composite with multi-functional effects for high-performance Li-S batteries. Energy Environ. Sci, 2016, 9(6): 1998.

[10] S.H. Chung, C.H. Chang, and A. Manthiram, Progress on the critical parameters for lithium-sulfur batteries to be practically viable, Adv. Funct. Mater., 28(2018), No. 28, art. No. 1801188.

[11] D.H. Liu, C. Zhang, G.M. Zhou, W. Lv, G.W. Ling, L.J. Zhi, and Q.H. Yang, Catalytic effects in lithium-sulfur batteries: Promoted sulfur transformation and reduced shuttle effect, Adv. Sci., 5(2018), No. 1, art. No. 1700270.

[12] Chen WJ, Li BQ, Zhao CX, Zhao M, Yuan TQ, Sun RC, Huang JQ, Zhang Q. Electrolyte regulation towards stable lithium-metal anodes in lithium-sulfur batteries with sulfurized polyacrylonitrile cathodes. Angew. Chem. Int. Ed., 2020, 59(27): 10732.

[13] K. Mahankali, S. Nagarajan, N.K. Thangavel, S. Rajendran, M. Yeddala, and L.M.R. Arava, Metal-based electrocatalysts for high-performance lithium-sulfur batteries: A review, Catalysts, 10(2020), No. 10, art. No. 1137.

[14] Jin ZS, Lin TN, Jia HF, Liu BQ, Zhang Q, Li L, Zhang LY, Su ZM, Wang CG. Expediting the conversion of Li₂S₂ to Li₂S enables high-performance Li-S batteries. ACS Nano, 2021, 15(4): 7318.

[15] Chen K, Fang RP, Lian Z, Zhang XY, Tang P, Li B, He K, Wang DW, Cheng HM, Sun ZH, Li F. An in situ solidification strategy to block polysulfides in lithium-sulfur batteries. Energy Storage Mater., 2021, 37, 224.

[16] Xiang JW, Guo ZZ, Yi ZQ, Zhang Y, Yuan LX, Cheng ZX, Shen Y, Huang YH. Facile synthesis of sulfurized polyacrylonitrile composite as cathode for high-rate lithium-sulfur batteries. J. Energy Chem., 2020, 49, 161.

[17] L. Zhou, D.L. Danilov, R.A. Eichel, and P.H.L. Notten, Host materials anchoring polysulfides in Li-S batteries reviewed, Adv. Energy Mater., 11(2021), No. 15, art. No. 2001304.

[18] Wang XL, Li G, Li JD, Zhang YN, Wook A, Yu AP, Chen ZW. Structural and chemical synergistic encapsulation of polysulfides enables ultralong-life lithium-sulfur batteries. Energy Environ. Sci., 2016, 9(8): 2533.

[19] Ji XL, Lee KT, Nazar LF. A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries. Nat. Mater., 2009, 8(6): 500.

[20] Wang DW, Zeng QC, Zhou GM, Yin LC, Li F, Cheng HM, Gentle IR, Lu GQM. Carbon-sulfur composites for Li-S batteries: Status and prospects. J. Mater. Chem. A, 2013, 1(33): 9382.

[21] Fu YZ, Su YS, Manthiram A. Sulfur-carbon nanocomposite cathodes improved by an amphiphilic block copolymer for high-rate lithium-sulfur batteries. ACS Appl. Mater. Interfaces, 2012, 4(11): 6046.

[22] L. Wang, G.R. Li, S. Liu, and X.P. Gao, Hollow molybdate microspheres as catalytic hosts for enhancing the electrochemical performance of sulfur cathode under high sulfur loading and lean electrolyte, Adv. Funct. Mater., 31(2021), No. 18, art. No. 2010693.

[23] Zhang Z, Wu DH, Zhou Z, Li GR, Liu S, Gao XP. Sulfur/nickel ferrite composite as cathode with high-volumetric-capacity for lithium-sulfur battery. Sci. China Mater., 2019, 62(1): 74.

[24] Wang L, Song YH, Zhang BH, Liu YT, Wang ZY, Li GR, Liu S, Gao XP. Spherical metal oxides with high tap density as sulfur host to enhance cathode volumetric capacity for lithium-sulfur battery. ACS Appl. Mater. Interfaces, 2020, 12(5): 5909.

[25] Y.T. Liu, S. Liu, G.R. Li, T.Y. Yan, and X.P. Gao, High volumetric energy density sulfur cathode with heavy and catalytic metal oxide host for lithium-sulfur battery, Adv. Sci., 7(2020), No. 12, art. No. 1903693.

[26] K. Xi, D.Q. He, C. Harris, Y.K. Wang, C. Lai, H.L. Li, P.R. Coxon, S.J. Ding, C. Wang, and R.V. Kumar, Enhanced sulfur transformation by multifunctional FeS₂/FeS/S composites for high-volumetric capacity cathodes in lithium-sulfur batteries, Adv. Sci., 6(2019), No. 6, art. No. 1800815.

[27] Chen T, Zhang ZW, Cheng BR, Chen RP, Hu Y, Ma LB, Zhu GY, Liu J, Jin Z. Self-templated formation of interlaced carbon nanotubes threaded hollow Co₃S₄ nanoboxes for high-rate and heat-resistant lithium-sulfur batteries. J. Am. Chem. Soc., 2017, 139(36): 12710.

[28] H. Peng, Y.G. Zhang, Y.L. Chen, J. Zhang, H. Jiang, X. Chen, Z.G. Zhang, Y.B. Zeng, B.S. Sa, Q.L. Wei, J. Lin, and H. Guo, Reducing polarization of lithium-sulfur batteries via ZnS/reduced graphene oxide accelerated lithium polysulfide conversion, Mater. Today Energy, 18(2020), art. No. 100519.

[29] Ma LB, Yuan H, Zhang WJ, Zhu GY, Wang YR, Hu Y, Zhao PY, Chen RP, Chen T, Liu J, Hu Z, Jin Z. Porous-shell vanadium nitride nanobubbles with ultrahigh areal sulfur loading for high-capacity and long-life lithium-sulfur batteries. Nano Lett., 2017, 17(12): 7839.

[30] Liu RQ, Liu WH, Bu Y, Yang WW, Wang C, Priest C, Liu ZW, Wang YZ, Chen JY, Wang YH, Cheng J, Lin XJ, Feng XM, Wu G, Ma YW, Huang W. Conductive porous laminated vanadium nitride as carbon-free hosts for high-loading sulfur cathodes in lithium-sulfur batteries. ACS Nano, 2020, 14(12): 17308.

[31] Z.Q. Ye, Y. Jiang, J. Qian, W.L. Li, T. Feng, L. Li, F. Wu, and R.J. Chen, Exceptional adsorption and catalysis effects of hollow polyhedra/carbon nanotube confined CoP nanoparticles superstructures for enhanced lithium-sulfur batteries, Nano Energy, 64(2019), art. No. 103965.

[32] Yuan HD, Chen XL, Zhou GM, Zhang WK, Luo JM, Huang H, Gan YP, Liang C, Xia Y, Zhang J, Wang JG, Tao XY. Efficient activation of Li₂S by transition metal phosphides nanoparticles for highly stable lithium-sulfur batteries. ACS Energy Lett., 2017, 2(7): 1711.

[33] C.Q. Zhang, R.F. Du, J.J. Biendicho, M.J. Yi, K. Xiao, D.W. Yang, T. Zhang, X. Wang, J. Arbiol, J. Llorca, Y.T. Zhou, J.R. Morante, and A. Cabot, Tubular CoFeP@CN as a mott-schottky catalyst with multiple adsorption sites for robust lithium-sulfur batteries, Adv. Energy Mater., 11(2021), No. 24, art. No. 2100432.

[34] D. Zhang, Y.X. Luo, B. Wu, P. Zeng, C. Xiang, C.K. Zhao, Z. Sofer, M.F. Chen, and X.Y. Wang, A heterogeneous FeP-CoP electrocatalyst for expediting sulfur redox in high-specific-energy lithium-sulfur batteries, Electrochimica Acta, 397(2021), art. No. 139275.

[35] J.R. He, A. Bhargav, and A. Manthiram, Molybdenum boride as an efficient catalyst for polysulfide redox to enable high-energy-density lithium-sulfur batteries, Adv. Mater., 32(2020), No. 40, art. No. 2004741.

[36] C.C. Li, S.Y. Qi, L. Zhu, Y. Zhao, R.Z. Huang, Y.Y. He, W.N. Ge, X.B. Liu, M.W. Zhao, L.Q. Xu, and Y.T. Qian, Regulating polysulfide intermediates by ultrathin Co-Bi nanosheet electrocatalyst in lithium-sulfur batteries, Nano Today, 40(2021), art. No. 101246.

[37] Y.P. Xiao, Y. Li, Z.L. Guo, C.C. Tang, B.S. Sa, N.H. Miao, J. Zhou, and Z.M. Sun, Functionalized Mo₂B₂ MBenes: Promising anchoring and electrocatalysis materials for lithium-sulfur battery, Appl. Surf. Sci., 566(2021), art. No. 150634.

[38] G.R. Li, H.Y. Li, and H.B. Zeng, Recent progress of boron-based materials in lithium-sulfur battery, J. Inorg. Mater., 37(2022), No. 2, art. No. 152.

[39] Y.C. Jiang, H.M.U. Arshad, H.J. Li, S. Liu, G.R. Li, and X.P. Gao, Crystalline multi-metallic compounds as host materials in cathode for lithium-sulfur batteries, Small, 17(2021), No. 22, art. No. 2005332.

[40] Wang ZS, Xu XJ, Liu ZB, Zhang DC, Yuan JJ, Liu J. Multifunctional metal phosphides as superior host materials for advanced lithium-sulfur batteries. Chem. A Eur. J., 2021, 27(54): 13494.

[41] Qin YT, Zhang YC, Zhu XD. Research progress on metal borides as cathode carrier materials for Li-S batteries. Nonferrous Met. Eng., 2021, 11(11): 137

[42] Z.S. Wang, J.D. Shen, J. Liu, X.J. Xu, Z.B. Liu, R.Z. Hu, L.C. Yang, Y.Z. Feng, J. Liu, Z.C. Shi, L.Z. Ouyang, Y. Yu, and M. Zhu, Self-supported and flexible sulfur cathode enabled via synergistic confinement for high-energy-density lithium-sulfur batteries, Adv. Mater., 31(2019), No. 33, art. No. 1902228.

[43] Guan B, Fan LS, Wu X, Wang PX, Qiu Y, Wang MX, Guo ZK, Zhang NQ, Sun KN. The facile synthesis and enhanced lithium-sulfur battery performance of an amorphous cobalt boride (Co₂B)@graphene composite cathode. J. Mater. Chem. A, 2018, 6(47): 24045.

[44] H. Yuan, H.J. Peng, J.Q. Huang, and Q. Zhang, Sulfur redox reactions at working interfaces in lithium-sulfur batteries: A perspective, Adv. Mater. Interfaces, 6(2019), No. 4, art. No. 1802046.

[45] Y.Z. Song, W.L. Cai, L. Kong, J.S. Cai, Q. Zhang, and J.Y. Sun, Rationalizing electrocatalysis of Li-S chemistry by mediator design: Progress and prospects, Adv. Energy Mater., 10(2020), No. 11, art. No. 1901075.

[46] Y.T. Liu, S. Liu, G.R. Li, and X.P. Gao, Strategy of enhancing the volumetric energy density for lithium-sulfur batteries, Adv. Mater., 33(2021), No. 8, art. No. 2003955.

[47] Chen JJ, Dong QF. Research progress of key components in lithium-sulfur batteries. J. Electrochem., 2020, 26(5): 648

[48] Lin Z, Liang CD. Lithium-sulfur batteries: From liquid to solid cells. J. Mater. Chem. A, 2015, 3(3): 936.

[49] Zhang BH, Wu JF, Gu JK, Li S, Yan TY, Gao XP. The fundamental understanding of lithium polysulfides in ether-based electrolyte for lithium-sulfur batteries. ACS Energy Lett., 2021, 6(2): 537.

[50] Y. Li, Z.H. Dong, and L.F. Jiao, Multifunctional transition metal-based phosphides in energy-related electrocatalysis, Adv. Energy Mater., 10(2020), No. 11, art. No. 1902104.

[51] Chen H, Zou XX. Intermetallic borides: Structures, synthesis and applications in electrocatalysis. Inorg. Chem. Front., 2020, 7(11): 2248.

[52] Cui L, Zhang WX, Zheng RK, Liu JQ. Electrocatalysts based on transition metal borides and borates for the oxygen evolution reaction. Chem. A Eur. J., 2020, 26(51): 11661.

[53] Y.H. Yao, Z.Y. Zhang, and L.F. Jiao, Development strategies in transition metal borides for electrochemical water splitting, Energy Environ. Mater., (2021). DOI: https://doi.org/10.1002/eem2.12198

[54] P. Xiao, W. Chen, and X. Wang, A review of phosphide-based materials for electrocatalytic hydrogen evolution, Adv. Energy Mater., 5(2015), No. 24, art. No. 1500985

[55] Li ZF, Zheng Y, Liu QY, Wang YQ, Wang DH, Li ZK, Zheng PL, Liu ZH. Recent advances in nanostructured metal phosphides as promising anode materials for rechargeable batteries. J. Mater. Chem. A, 2020, 8(37): 19113.

[56] Carenco S, Portehault D, Boissière C, Mézailles N, Sanchez C. Nanoscaled metal borides and phosphides: Recent developments and perspectives. Chem. Rev., 2013, 113(10): 7981.

[57] Liu YN, McCue AJ, Li DQ. Metal phosphides and sulfides in heterogeneous catalysis: Electronic and geometric effects. ACS Catal., 2021, 11(15): 9102.

[58] Huang S, Huixiang E, Yang Y, Zhang YF, Ye MH, Li CC. Transition metal phosphides: New generation cathode host/separator modifier for Li-S batteries. J. Mater. Chem. A, 2021, 9(12): 7458.

[59] Yu SL, Cai WL, Chen L, Song LX, Song YZ. Recent advances of metal phosphides for Li-S chemistry. J. Energy Chem., 2021, 55, 533.

[60] Ren JT, Hu ZP, Chen C, Liu YP, Yuan ZY. Integrated Ni₂P nanosheet arrays on three-dimensional Ni foam for highly efficient water reduction and oxidation. J. Energy Chem., 2017, 26(6): 1196.

[61] He MX, Feng CQ, Liao T, Hu SN, Wu HM, Sun ZQ. Low-cost Ni₂P/Ni_0.96S heterostructured bifunctional electrocatalyst toward highly efficient overall urea-water electrolysis. ACS Appl. Mater. Interfaces, 2020, 12(2): 2225.

[62] Dou YY, Li GR, Song J, Gao XP. Nickel phosphide-embedded graphene as counter electrode for dye-sensitized solar cells. Phys. Chem. Chem. Phys., 2012, 14(4): 1339.

[63] Wang S, Xie Y, Shi KY, Zhou W, Xing ZP, Pan K, Cabot A. Monodispersed nickel phosphide nanocrystals in situ grown on reduced graphene oxide with controllable size and composition as a counter electrode for dye-sensitized solar cells. ACS Sustain. Chem. Eng., 2020, 8(15): 5920.

[64] Du ZZ, Ai W, Yang J, Gong YJ, Yu CY, Zhao JF, Dong XC, Sun GZ, Huang W. In situ fabrication of Ni₂P nanoparticles embedded in nitrogen and phosphorus codoped carbon nanofibers as a superior anode for Li-ion batteries. ACS Sustainable Chem. Eng., 2018, 6(11): 14795.

[65] Cheng JH, Zhao D, Fan LS, Wu X, Wang MX, Zhang NQ, Sun KN. Ultra-high rate Li-S batteries based on a novel conductive Ni₂P yolk-shell material as the host for the S cathode. J. Mater. Chem. A, 2017, 5(28): 14519.

[66] Zhang F, Li Z, Cao T, Qin K, Xu QJ, Liu HM, Xia YY. Multishelled Ni₂P microspheres as multifunctional sulfur host 3D-printed cathode materials ensuring high areal capacity of lithium-sulfur batteries. ACS Sustainable Chem. Eng., 2021, 9(17): 6097.

[67] Yu XF, Tian DX, Li WC, He B, Zhang Y, Chen ZY, Lu AH. One-pot synthesis of highly conductive nickel-rich phosphide/CNTs hybrid as a polar sulfur host for high-rate and long-cycle Li-S battery. Nano Res., 2019, 12(5): 1193.

[68] R. Gao, Z. Y. Wang, L. Wang, P. Chen, S. Liu, Z. P. Ma, and G. J. Shao, Ni₂P nanosheets on graphene as a sulfur cathode material for lithium-sulfur batteries, Chinese J. Inorg. Chem., (2022), DOI: https://doi.org/10.11862/CJIC.2022.070

[69] Cheng JH, Zhao D, Fan LS, Wu X, Wang MX, Wu HX, Guan B, Zhang NQ, Sun KN. A conductive Ni₂P nanoporous composite with a 3D structure derived from a metal-organic framework for lithium-sulfur batteries. Chem. A Eur. J, 2018, 24(50): 13253.

[70] J.Q. Liu, X.N. Liu, Q. Zhang, X. Liang, J. Yan, H.H. Tan, Y. Yu, and Y.C. Wu, Integration of nickel phosphide nanodot-enriched 3D graphene-like carbon with carbon fibers as self-supported sulfur hosts for advanced lithium sulfur batteries, Electrochim. Acta, 382(2021), art. No. 138267.

[71] Zhong YR, Yin LC, He P, Liu W, Wu ZS, Wang HL. Surface chemistry in cobalt phosphide-stabilized lithium-sulfur batteries. J. Am. Chem. Soc., 2018, 140(4): 1455.

[72] Li ZY, Zou YL, Duan JL, Long B. Coral-like CoP hollow composites as effective host cathodes for lithium-sulfur batteries. Ionics, 2019, 25(10): 4625.

[73] Zhou JB, Liu XJ, Zhu LQ, Zhou J, Guan Y, Chen L, Niu SW, Cai JY, Sun D, Zhu YC, Du J, Wang GM, Qian YT. Deciphering the modulation essence of p bands in Co-based compounds on Li-S chemistry. Joule, 2018, 2(12): 2681.

[74] K.K. Xiao, Z. Chen, Z. Liu, L.L. Zhang, X.Y. Cai, C.S. Song, Z.F. Fan, X.H. Chen, J.L. Liu, and Z.X. Shen, N-doped carbon sheets arrays embedded with CoP nanoparticles as high-performance cathode for Li-S batteries via triple synergistic effects, J. Power Sources, 455(2020), art. No. 227959.

[75] Cheng Q, Yin ZH, Pan SY, Zhang GZ, Pan ZX, Yu XY, Fang YP, Rao HS, Zhong XH. Enhancing adsorption and reaction kinetics of polysulfides using CoP-coated N-doped mesoporous carbon for high-energy-density lithium-sulfur batteries. ACS Appl. Mater. Interfaces, 2020, 12(39): 43844.

[76] H.Y. Zhang, S.S. Xin, J. Li, H.T. Cui, Y.Y. Liu, Y.Z. Yang, and M.R. Wang, Synergistic regulation of polysulfides immobilization and conversion by MOF-derived CoP-HNC nanocages for high-performance lithium-sulfur batteries, Nano Energy, 85(2021), art. No. 106011.

[77] Sun R, Bai Y, Luo M, Qu MX, Wang ZH, Sun W, Sun KN. Enhancing polysulfide confinement and electrochemical kinetics by amorphous cobalt phosphide for highly efficient lithium-sulfur batteries. ACS Nano, 2021, 15(1): 739.

[78] Yang YX, Zhong YR, Shi QW, Wang ZH, Sun KN, Wang HL. Electrocatalysis in lithium sulfur batteries under lean electrolyte conditions. Angew. Chem. Int. Ed., 2018, 57(47): 15549.

[79] Xia G, Ye JJ, Zheng ZQ, Li XT, Chen CZ, Hu C. Catalytic FeP decorated carbon black as a multifunctional conducting additive for high-performance lithium-sulfur batteries. Carbon, 2021, 172, 96.

[80] Zhang YG, Wang YG, Luo RJ, Yang Y, Lu Y, Guo Y, Liu XM, Cao SX, Kim JK, Luo YS. A 3D porous FeP/rGO modulated separator as a dual-function polysulfide barrier for high-performance lithium sulfur batteries. Nanoscale Horiz., 2020, 5(3): 530.

[81] X.G. Gao, Y. Huang, X. Li, H. Gao, and T.H. Li, SnP0.94 nanodots confined carbon aerogel with porous hollow superstructures as an exceptional polysulfide electrocatalyst and “adsorption nest” to enable enhanced lithium-sulfur batteries, Chem. Eng. J., 420(2021), art. No. 129724.

[82] Z.H. Shen, M.Q. Cao, Z.L. Zhang, J. Pu, C.L. Zhong, J.C. Li, H.X. Ma, F.J. Li, J. Zhu, F. Pan, and H.G. Zhang, Efficient Ni₂Co₄P₃ nanowires catalysts enhance ultrahigh-loading lithium-sulfur conversion in a microreactor-like battery, Adv. Funct. Mater., 30(2020), No. 3, art. No. 1906661.

[83] Wang L, Zhang M, Zhang B, Wang B, Dou JM, Kong Z, Wang CS, Sun XP, Qian YT, Xu LQ. A porous polycrystalline NiCo₂P_x as a highly efficient host for sulfur cathodes in Li-S batteries. J. Mater. Chem. A, 2021, 9(40): 23149.

[84] J.L. Duan, Y.L. Zou, Z.Y. Li, B. Long, and Y.Y. Du, Hollow quasi-polyhedron structure of NiCoP with strong constraint sulfur effect for lithium sulfur battery, J. Electroanal. Chem., 847(2019), art. No. 113187.

[85] Chen Y, Zhang WX, Zhou D, Tian HJ, Su DW, Wang CY, Stockdale D, Kang FY, Li BH, Wang GX. Co-Fe mixed metal phosphide nanocubes with highly interconnected-pore architecture as an efficient polysulfide mediator for lithium-sulfur batteries. ACS Nano, 2019, 13(4): 4731.

[86] Chen XX, Zeng SY, Muheiyati H, Zhai YJ, Li CC, Ding XY, Wang L, Wang DB, Xu LQ, He YY, Qian YT. Double-shelled Ni-Fe-P/N-doped carbon nanobox derived from a Prussian blue analogue as an electrode material for K-ion batteries and Li-S batteries. ACS Energy Lett., 2019, 4(7): 1496.

[87] Wang ZY, Wang HM, Liu S, Li GR, Gao XP. To promote the catalytic conversion of polysulfides using Ni-B alloy nanoparticles on carbon nanotube microspheres under high sulfur loading and a lean electrolyte. ACS Appl. Mater. Interfaces, 2021, 13(17): 20222.

[88] Li CC, Liu XB, Zhu L, Huang RZ, Zhao MW, Xu LQ, Qian YT. Conductive and polar titanium boride as a sulfur host for advanced lithium-sulfur batteries. Chem. Mater, 2018, 30(20): 6969.

[89] Pang Q, Kwok CY, Kundu DP, Liang X, Nazar LF. Lightweight metallic MgB₂ mediates polysulfide redox and promises high-energy-density lithium-sulfur batteries. Joule, 2019, 3(1): 136.

[90] Z.L. Li, P.Y. Li, X.P. Meng, Z. Lin, and R.H. Wang, The interfacial electronic engineering in binary sulfiphilic cobalt boride heterostructure nanosheets for upgrading energy density and longevity of lithium-sulfur batteries, Adv. Mater., 33(2021), No. 42, art. No. 2102338.

[91] Chen XX, Ding XY, Wang CS, Feng ZY, Xu LQ, Gao X, Zhai YJ, Wang DB. A multi-shelled CoP nanosphere modified separator for highly efficient Li-S batteries. Nanoscale, 2018, 10(28): 13694.

[92] L.M. Jin, J. Ni, C. Shen, F.L. Peng, Q. Wu, D.H. Ye, J.S. Zheng, G.R. Li, C.M. Zhang, Z.P. Li, and J.P. Zheng, Metallically conductive TiB₂ as a multi-functional separator modifier for improved lithium sulfur batteries, J. Power Sources, 448(2020), art. No. 227336.

[93] Liu S, Li GR, Gao XP. Lanthanum nitrate as electrolyte additive to stabilize the surface morphology of lithium anode for lithium-sulfur battery. ACS Appl. Mater. Interfaces, 2016, 8(12): 7783.

[94] Zhao BS, Wang L, Liu S, Li GR, Gao XP. High-efficiency hybrid sulfur cathode based on electroactive niobium tungsten oxide and conductive carbon nanotubes for all-solidstate lithium-sulfur batteries. ACS Appl. Mater. Interfaces, 2022, 14(1): 1212.

[95] Yang XF, Luo J, Sun XL. Towards high-performance solid-state Li-S batteries: From fundamental understanding to engineering design. Chem. Soc. Rev., 2020, 49(7): 2140.

[96] L.Y. Tian, Z. Zhang, S. Liu, G.R. Li, and X.P. Gao, High-entropy spinel oxide nanofibers as catalytic sulfur hosts promise the high gravimetric and volumetric capacities for lithium-sulfur batteries, Energy Environ. Meter., (2021). DOI: https://doi.org/10.1002/eem2.12215.

[97] Zheng YN, Yi YK, Fan MH, Liu HY, Li X, Zhang R, Li MT, Qiao ZN. A high-entropy metal oxide as chemical anchor of polysulfide for lithium-sulfur batteries. Energy Storage Mater., 2019, 23, 678.

[98] Xu HF, Hu RM, Zhang YZ, Yan HB, Zhu Q, Shang JX, Yang SB, Li B. Nano high-entropy alloy with strong affinity driving fast polysulfide conversion towards stable lithium sulfur batteries. Energy Storage Mater., 2021, 43, 212.

[99] Z.Y. Wang, H.L. Ge, S. Liu, G.R. Li, and X.P. Gao, High-entropy alloys to activate the sulfur cathode for lithium-sulfur batteries, Energy Environ. Mater., (2022). DOI: https://doi.org/10.1002/eem2.12358.