Improving sulfur transformation of lean electrolyte lithium–sulfur battery using nickel nanoparticles encapsulated in N-doped carbon nanotubes
Ze Zhang, Yuqing Xu, Donggen Xiong, Ji Yu, Jianxin Cai, Yizhong Huang, Zhenyu Yang
Improving sulfur transformation of lean electrolyte lithium–sulfur battery using nickel nanoparticles encapsulated in N-doped carbon nanotubes
Efficient redox reactions of lean electrolyte lithium–sulfur (Li–S) batteries highly rely on rational catalyst design. Herein, we report an electrocatalyst based on N-doped carbon nanotubes (CNT)-encapsulated Ni nanoparticles (Ni@NCNT) as kinetics regulators for Li–S batteries to propel the polysulfide-involving multiphase transformation. Moreover, such a CNT-encapsulation strategy greatly prevents the aggregation of Ni nanoparticles and enables the extraordinary structural stability of the hybrid electrocatalyst, which guarantees its persistent catalytic activity on sulfur redox reactions. When used as a modified layer on a commercial separator, the Ni@NCNT interlayer contributes to stabilizing S cathode and Li anode by significantly retarding the shuttle effect. The corresponding batteries with a 3.5 mg cm-2 sulfur loading achieve the promising cycle stability with ∼85% capacity retention at the electrolyte/sulfur ratios of 5 and 3 µL mg-1. Even at a high loading of 12.2 mg cm-2, the battery affords an areal capacity of 7.5 mA h cm-2.
kinetics regulator / lean electrolyte / lithium-sulfur battery / metal nickel nanoparticles / N-doped CNT-encapsulated
[1] |
CaoGQ, DuanRX, LiXF. Controllable catalysis behavior for high performance lithium sulfur batteries: from kinetics to strategies. Inside Energy. 2023;5(1):100096.
CrossRef
Google scholar
|
[2] |
YousafM, NaseerU, LiYJ, et al. A mechanistic study of electrode materials for rechargeable batteries beyond lithium ions by in situ transmission electron microscopy. Energy Environ Sci. 2021;14(5):2670-2707.
CrossRef
Google scholar
|
[3] |
WangY, ZhuLF, WangJX, Zhang Z, YuJ, YangZY. Enhanced chemisorption and catalytic conversion of polysulfides via CoFe@NC nanocubes modified separator for superior Li-S batteries. Chem Eng J. 2022;433:133792.
CrossRef
Google scholar
|
[4] |
TianLY, ZhangZ, LiuS, LiGR, GaoXP. High-entropy perovskite oxide nanofibers as efficient bidirectional electrocatalyst of liquid-solid conversion processes in lithium-sulfur batteries. Nano Energy. 2023;106:108037.
CrossRef
Google scholar
|
[5] |
FangRP, ZhaoSY, SunZH, Wang DW, ChengHM, LiF. More reliable lithium-sulfur batteries: status, solutions and prospects. Adv Mater. 2017;29(48):1606823.
CrossRef
Google scholar
|
[6] |
ChenT, ZhangZW, ChengBR, et al. 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):12710-12715.
CrossRef
Google scholar
|
[7] |
ShiLL, Anderson CS, MishraL, et al. Early failure of lithium–sulfur batteries at practical conditions: crosstalk between sulfur cathode and lithium anode. Adv Sci. 2022;9(21):2201640.
CrossRef
Google scholar
|
[8] |
ZhongY, ChaoDL, DengSJ, et al. Confining sulfur in integrated composite scaffold with highly porous carbon fibers/vanadium nitride arrays for high-performance lithium–sulfur batteries. Adv Funct Mater. 2018;28(38):1706391.
CrossRef
Google scholar
|
[9] |
HeJR, Bhargav A, AslHY, ChenYF, Manthiram A. 1T′-ReS2 nanosheets in situ grown on carbon nanotubes as a highly efficient polysulfide electrocatalyst for stable Li–S batteries. Adv Energy Mater. 2020;10(23):2001017.
CrossRef
Google scholar
|
[10] |
MaF, Srinivas K, ZhangXJ, et al. Mo2N quantum dots decorated N-doped graphene nanosheets as dual-functional interlayer for dendrite-free and shuttle-free lithium-sulfur batteries. Adv Funct Mater. 2022;32(40):2206113.
CrossRef
Google scholar
|
[11] |
LiuFJ, ZhuYT, LiuLQ, et al. Defect-rich W/Mo-doped V2O5 microspheres as a catalytic host to boost sulfur redox kinetics for lithium–sulfur batteries. Inorg Chem. 2023;62(13):5219-5228.
CrossRef
Google scholar
|
[12] |
ZhaoQN, WangRH, WenJ, et al. Separator engineering toward practical Li-S batteries: targeted electrocatalytic sulfur conversion, lithium plating regulation, and thermal tolerance. Nano Energy. 2023;95:106982.
CrossRef
Google scholar
|
[13] |
YuB, ChenDJ, WangZG, et al.Mo2C quantum dots@graphene functionalized separator toward high-current-density lithium metal anodes for ultrastable Li-S batteries Chem Eng J. 2020;399:125837.
CrossRef
Google scholar
|
[14] |
WangL, HuaWX, WanX, et al. Design rules of a sulfur redox electrocatalyst for lithium–sulfur batteries. Adv Mater. 2022;34(14):2110279.
CrossRef
Google scholar
|
[15] |
ZhangZ, BasuS, ZhuPP, et al. Highly sulfiphilic Ni-Fe bimetallic oxide nanoparticles anchored on carbon nanotubes enable effective immobilization and conversion of polysulfides for stable lithium-sulfur batteries. Carbon. 2019;142:32-39.
CrossRef
Google scholar
|
[16] |
WangJ, YangG, ChenJ, et al. Lithium–sulfur batteries: flexible and high-loading lithium–sulfur batteries enabled by integrated three-in-one fibrous membranes. Adv Energy Mater. 2019;9(38):1902001.
CrossRef
Google scholar
|
[17] |
HeJR, LuoL, ChenYF, Manthiram A. Yolk–shelled C@Fe3O4 nanoboxes as efficient sulfur hosts for high-performance lithium–sulfur batteries. Adv Mater. 2017;29(34):1702707.
CrossRef
Google scholar
|
[18] |
ChengZB, PanH, ChenJQ, Meng XP, WangRH. Separator modified by cobalt-embedded carbon nanosheets enabling chemisorption and catalytic effects of polysulfides for highenergy- density lithium-sulfur batteries. Adv Energy Mater. 2019;9(32):1901609.
CrossRef
Google scholar
|
[19] |
ChaE, PatelMD, ParkJ, et al. 2D MoS2 as an efficient protective layer for lithium metal anodes in high-performance Li–S batteries. Nat Nanotechnol. 2018;13(4):337-344.
CrossRef
Google scholar
|
[20] |
MaF, ChenZ, SrinivasK, et al. VN quantum dots anchored Ndoped carbon nanosheets as bifunctional interlayer for highperformance lithium-metal and lithium-sulfur batteries. Chem Eng J. 2023;459:141526.
CrossRef
Google scholar
|
[21] |
HeJR, Hartmann G, LeeM, HwangGS, ChenYF, ManthiramA. Freestanding 1T MoS2/graphene heterostructures as a highly efficient electrocatalyst for lithium polysulfides in Li–S batteries. Energy Environ Sci. 2019;12(1):344-350.
CrossRef
Google scholar
|
[22] |
ZhaoM, LiBQ, ZhangXQ, Huang JQ, ZhangQ. A perspective toward practical lithium–sulfur batteries. ACS Cent Sci. 2020;6(7):1095-1104.
CrossRef
Google scholar
|
[23] |
TianLY, ZhangZ, LiuS, LiGR, GaoXP. High-entropy spinel oxide nanofibers as catalytic sulfur hosts promise the high gravimetric and volumetric capacities for lithium–sulfur batteries. Energy Environ Mater. 2022;5(2):645-654.
CrossRef
Google scholar
|
[24] |
ZhaoFL, XueJH, ShaoW, Yu H, HuangW, XiaoJ. Toward high-sulfur-content, high-performance lithium-sulfur batteries: review of materials and technologies. J Energy Chem. 2023;80:625-657.
CrossRef
Google scholar
|
[25] |
DorflerS, Althues H, HartelP, AbendrothT, SchummB, KaskelS. Challenges and key parameters of lithium-sulfur batteries on pouch cell level. Joule. 2020;4(3):539-554.
CrossRef
Google scholar
|
[26] |
ZhangZ, XiongDG, ShaoAH, et al. Integrating metallic cobalt and N/B heteroatoms into porous carbon nanosheets as efficient sulfur immobilizer for lithium-sulfur batteries. Carbon. 2020;167:918-929.
CrossRef
Google scholar
|
[27] |
JanML, XuR, ChengXB, et al. Rational design of two-dimensional nanomaterials for lithium–sulfur batteries. Energy Environ Sci. 2020;13(4):1049-1075.
CrossRef
Google scholar
|
[28] |
ShiMJ, ZhangS, JiangYT, et al. Sandwiching sulfur into the dents between N, O Co-doped graphene layered blocks with strong physicochemical confinements for stable and high-rate Li–S batteries. Nano-Micro Lett. 2020;12(1):146.
CrossRef
Google scholar
|
[29] |
ChenL, SunYJ, WeiXJ, et al. Dual-functional V2C MXene assembly in facilitating sulfur evolution kinetics and Li-ion sieving toward practical lithium-sulfur batteries. Adv Mater. 2023;35(26):2300771.
CrossRef
Google scholar
|
[30] |
ZhangW, LiYF, LvHF, et al. A comparison study of the electrocatalytic sulfur reduction activity on heteroatomdoped graphene for Li–S battery. Small Struct. 2023;4(3):2200244.
CrossRef
Google scholar
|
[31] |
YangW, WangXY, ShanJW, et al. Atomic-level design rules of metal-cation-doped catalysts: manipulating electron affinity/ionic radius of doped cations for accelerating sulfur redox kinetics in Li–S batteries. Energy Environ Sci. 2023;16(6):2669-2683.
CrossRef
Google scholar
|
[32] |
YuB, HuangAJ, SrinivasK, et al. Outstanding catalytic effects of 1t′-MoTe2 quantum Dots@3D graphene in shuttle-free Li–S batteries. ACS Nano. 2021;15(8):13279-13288.
CrossRef
Google scholar
|
[33] |
ZhangZ, WangJN, ShaoAH, et al. Recyclable cobaltmolybdenum bimetallic carbide modified separator boosts the polysulfide adsorption-catalysis of lithium sulfur battery. Sci China Mater. 2020;63(12):2443-2455.
CrossRef
Google scholar
|
[34] |
LiZ, QiCY, ChangQ, Jin J, LuY, WenZY. TiC nanoparticles supported on free-standing carbon nanofibers enabled high-performance Lithium–Sulfur batteries. Composites Part B. 2023;257:110679.
CrossRef
Google scholar
|
[35] |
YuB, HuangA, ChenDJ, et al. In situ construction of Mo2C quantum dots-decorated CNT networks as a multifunctional electrocatalyst for advanced lithium–sulfur batteries. Small. 2021;17(23):2100460.
CrossRef
Google scholar
|
[36] |
LiYY, WuHW, WuDH, et al. High-density oxygen doping of conductive metal sulfides for better polysulfide trapping and Li2S-S8 redox kinetics in high areal capacity lithium–sulfur batteries. Adv Sci. 2022;9(17):2200840.
CrossRef
Google scholar
|
[37] |
ChenT, MaLB, ChengBR, et al. Metallic and polar Co9S8 inlaid carbon hollow nanopolyhedra as efficient polysulfide mediator for lithium–sulfur batteries. Nano Energy. 2017;38:239-248.
CrossRef
Google scholar
|
[38] |
HeJR, ChenYF, ManthiramA. Metal sulfide-decorated carbon sponge as a highly efficient electrocatalyst and absorbant for polysulfide in high-loading Li2S batteries. Adv Energy Mater. 2019;9(20):1900584.
CrossRef
Google scholar
|
[39] |
ShenJD, XuXJ, LiuJ, et al. Mechanistic understanding of metal phosphide host for sulfur cathode in high-energydensity lithium–sulfur batteries. ACS Nano. 2019;13(8):8986-8996.
CrossRef
Google scholar
|
[40] |
SunZH, WuXL, PengZQ, et al. Compactly coupled nitrogendoped carbon nanosheets/molybdenum phosphide nanocrystal hollow nanospheres as polysulfide reservoirs for highperformance lithium–sulfur chemistry. Small. 2019;15(40):1902491.
CrossRef
Google scholar
|
[41] |
YuB, MaF, ChenDJ, et al. MoP QDs@graphene as highly efficient electrocatalyst for polysulfide conversion in Li-S batteries. J Mater Sci Technol. 2021;90:37-44.
CrossRef
Google scholar
|
[42] |
XieYH, ZhengWR, AoJ, et al. Multifunctional Ni-doped CoSe2 nanoparticles decorated bilayer carbon structures for polysulfide conversion and dendrite-free lithium toward high-performance Li-S full cell. Energy Storgae Mater. 2023;62:102925.
CrossRef
Google scholar
|
[43] |
CaiD, LiuBK, ZhuDH, et al. Lithium-sulfur batteries: ultrafine Co3Se4 nanoparticles in nitrogen-doped 3D carbon matrix for high-stable and long-cycle-life lithium sulfur batteries. Adv Energy Mater. 2020;10(19):1904273.
CrossRef
Google scholar
|
[44] |
ChenZX, ChengQ, LiXY, et al. Cathode kinetics evaluation in lean-electrolyte lithium–sulfur batteries. J Am Chem Soc. 2023;145(30):16449-16457.
CrossRef
Google scholar
|
[45] |
LiuFJ, LuoWL, ZhangZ, Yu J, CaiJX, YangZY. Cation-doped V2O5 microsphere as a bidirectional catalyst to activate sulfur redox reactions for lithium-sulfur batteries. Chem Eng J. 2023;456:140948.
CrossRef
Google scholar
|
[46] |
ChenWJ, LiBQ, ZhaoCX, et al. Electrolyte regulation towards stable lithium-metal anodes in lithium–sulfur batteries with sulfurized polyacrylonitrile cathodes. Angew Chem Int Ed. 2020;59(27):10732-10745.
CrossRef
Google scholar
|
[47] |
ZhangXX, ZhuYT, MiaoZR, et al. Dual confining polysulfides by growing NiCo2S4 nanosheets on porous carbon nanoboxes to accelerate redox kinetics for efficient lithium-sulfur batteries. Electrochim Acta. 2023;441:141864.
CrossRef
Google scholar
|
[48] |
LvXX, LeiTY, WangBJ, et al. An efficient separator with low Li-ion diffusion energy barrier resolving feeble conductivity for practical lithium–sulfur batteries. Adv Energy Mater. 2019;9(40):1901800.
CrossRef
Google scholar
|
[49] |
ZuoYZ, ZhaoM, RenPJ, et al. An efficient polysulfide trapper of an nitrogen and nickel-decorating amylum scaffold-coated separator for ultrahigh performance in lithium–sulfur batteries. J Mater Chem A. 2020;8(3):1238-1246.
CrossRef
Google scholar
|
[50] |
ZhangZ, KongLL, LiuS, LiGR, GaoXP. A high-efficiency sulfur/carbon composite based on 3D graphene nanosheet@carbon nanotube matrix as cathode for lithium–sulfur battery. Adv Energy Mater. 2017;7(11):1602543.
CrossRef
Google scholar
|
[51] |
FangRP, ZhaoSY, PeiSF, et al. An integrated electrode/separator with nitrogen and nickel functionalized carbon hybrids for advanced lithium/polysulfide batteries. Carbon. 2016;109:719-726.
CrossRef
Google scholar
|
[52] |
ZouXX, HuangXX, GoswamiA, et al. Cobalt-embedded nitrogen-rich carbon nanotubes efficiently catalyze hydrogen evolution reaction at all pH values. Angew Chem Int Ed. 2014;126(17):4461-4465.
CrossRef
Google scholar
|
[53] |
XuHF, JiangQB, ZhangBK, Chen C, LinZ. Integrating conductivity, immobility, and catalytic ability into high-N carbon/graphene sheets as an effective sulfur host. Adv Mater. 2019;32(7):1906357.
CrossRef
Google scholar
|
[54] |
YuanH, PengHJ, LiBQ, et al. Conductive and catalytic triplephase interfaces enabling uniform nucleation in high-rate lithium–sulfur batteries. Adv Energy Mater. 2018;9(1):1802768.
CrossRef
Google scholar
|
[55] |
YeHL, SunJG, ZhangSL, et al. Stepwise electrocatalysis as a strategy against polysulfide shuttling in Li–S batteries. ACS Nano. 2019;13(12):14208-14216.
CrossRef
Google scholar
|
[56] |
ZhangLL, LiuDB, MuhammadZ, et al. Single nickel atoms on nitrogen-doped graphene enabling enhanced kinetics of lithium–sulfur batteries. Adv Mater. 2019;31(40):1903955.
CrossRef
Google scholar
|
[57] |
TaoXY, WangJG, LiuC, et al. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design. Nat Commun. 2016;7(1):11203.
CrossRef
Google scholar
|
[58] |
ZhangZ, ShaoAH, XiongDG, Yu J, KoratkarN, YangZY. Efficient polysulfide redox enabled by lattice-distorted Ni3Fe intermetallic electrocatalyst-modified separator for lithium–sulfur batteries. ACS Appl Mater Interfaces. 2020;12(17):19572-19580.
CrossRef
Google scholar
|
[59] |
LiZ, ZhangF, TangLB, et al. High areal loading and long-life cycle stability of lithium-sulfur batteries achieved by a dual=function ZnS-modified separator. Chem Eng J. 2020;390:124653.
CrossRef
Google scholar
|
[60] |
YuZ, WangBL, LiaoXB, et al. Boosting polysulfide redox kinetics by graphene-supported Ni nanoparticles with carbon coating. Adv Energy Mater. 2020;10(25):2000907.
CrossRef
Google scholar
|
[61] |
BhargavA, HeJR, GuptaA, Manthiram A. Lithium-sulfur batteries: attaining the critical metrics. Joule. 2020;4(2):285-291.
CrossRef
Google scholar
|
[62] |
LiuXW, LiZH, LiaoXB, et al. A three-dimensional nitrogendoped graphene framework decorated with an atomic layer deposited ultrathin V2O5 layer for lithium sulfur batteries with high sulfur loading. J Mater Chem A. 2020;8(24):12106-12113.
CrossRef
Google scholar
|
[63] |
XiongDG, ZhangZ, HuangXY, et al. Boosting the polysulfide confinement in B/N–codoped hierarchically porous carbon nanosheets via Lewis acid–base interaction for stable Li–S batteries. J Energy Chem. 2020;51:90-100.
CrossRef
Google scholar
|
[64] |
ShaoAH, ZhangZ, XiongDG, Yu J, KoratkarN, YangZY. Facile synthesis of a “two-in-one”sulfur host featuring metalliccobalt- embedded N-doped carbon nanotubes for efficient lithium-sulfur batteries. ACS Appl Mater Interfaces. 2020;12(5):5968-5978.
CrossRef
Google scholar
|
[65] |
WangJN, YiSS, LiuJW, et al. Suppressing the shuttle effect and dendrite growth in lithium–sulfur batteries. ACS Nano. 2020;14(8):9819-9831.
CrossRef
Google scholar
|
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