P-MXene Ti3C2Tx/CNT多孔微球硫载体复合材料的制备及电化学性能研究

doi:10.11949/0438-1157.20251027

摘要/Abstract

摘要：

为解决锂硫电池（Li-S）正极材料存在的低导电、高膨胀和穿梭效应的不足，本文借助超声辅助、冷冻干燥、喷雾干燥等手段，设计制备出P-MXene Ti₃C₂T_x/CNT（PMC）硫载体。将PMC与升华硫（S）在高温烧结下制备出正极材料P-MXene Ti₃C₂T_x/CNT/S（PMC/S），二者都具有多孔球状形貌，且存在丰富的介孔、大孔，同时也证实了S被均匀地负载在PMC上。将PMC/S正极组装成扣式半电池，对性能测试，PMC/S在0.1 C下具有1271.90 mAh·g^-1的高比容量，循环500次后仍具有531.1 mAh·g^-1的比容量。利用PMC硫载体进行可视化吸附实验以及对称电池的组装，对比于二维片层碳化钛（MXene Ti₃C₂T_x），PMC硫载体对多硫化锂（LiPSs）的吸附作用和催化转化能力均有显著提高。研究结果揭示了MXene Ti₃C₂T_x与碳纳米管（CNT）的协同作用是 PMC具备优异性能的内在原因。

关键词: 锂硫电池, 正极硫载体, MXene, 碳纳米管, 复合材料, 电化学性能

Abstract:

To overcome the inherent limitations of lithium–sulfur (Li–S) batteries—including the poor electrical conductivity of sulfur, large volume variation during cycling, and the polysulfide shuttle effect—a porous P-MXene Ti₃C₂T_x/CNT (PMC) host was rationally designed and synthesized via a combined process of ultrasonication, freeze-drying, and spray-drying. The P-MXene Ti₃C₂T_x/CNT/S (PMC/S) composite cathode was subsequently fabricated through melt-infusion of sulfur (S) into the porous scaffold under thermal treatment. Structural analysis revealed that both PMC and PMC/S exhibit a well-defined spherical architecture with a hierarchical porous structure, containing abundant mesopores and macropores, and confirmed the uniform distribution of sulfur within the PMC matrix. Electrochemical evaluation in coin-type half-cells demonstrated that the PMC/S cathode delivers a high initial discharge capacity of 1271.90 mAh·g^-1 at 0.1 C and maintains a reversible capacity of 531.1 mAh·g^-1 after 500 cycles, highlighting its excellent cycling stability. Furthermore, visual adsorption experiments and symmetric cell tests revealed that the PMC host markedly enhances the chemisorption of lithium polysulfides (LiPSs) and facilitates their catalytic conversion, outperforming conventional two-dimensional titanium carbide nanosheets (MXene Ti₃C₂T_x). These results underscore the critical role of the synergistic interaction between MXene Ti₃C₂T_x and carbon nanotubes (CNT) in promoting polysulfide confinement and redox kinetics, which collectively contribute to the superior electrochemical performance of the PMC/S cathode.

Key words: lithium-sulfur battery, cathode sulfur host, MXene, carbon nanotube, composite material, electrochemical performance

中图分类号:

TM912

彭瑞, 李伟, 曹钰媛, 刘峥, 郭容婷. P-MXene Ti₃C₂T_x/CNT多孔微球硫载体复合材料的制备及电化学性能研究[J]. 化工学报, DOI: 10.11949/0438-1157.20251027.

Rui PENG, Wei LI, Yuyuan CAO, Zheng LIU, Rongting GUO. Preparation and Electrochemical Performance of P-MXene Ti₃C₂T_x/CNT Porous Microsphere Sulfur Host Composite Materials[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251027.

图/表 16

图1 用于拟合EIS数据的等效电路图

Figure 1 Equivalent circuit diagram used for fitting the EIS data

图2(a) 少层MXene Ti3C2Tx分散液的丁达尔效应图，(b, c) 少层多孔PM的SEM图

Figure 2 (a) Tyndall effect of the few-layer MXene Ti3C2Tx dispersion, (b, c) SEM images of the few-layer porous PM

图3 PMC-2、MXene Ti3C2Tx和CNT的XRD图谱

Figure 3 XRD patterns of PMC-2, MXene Ti3C2Tx, and CNT

图4 (a,b)PMC的SEM图像，(c,d,e)PMC的EDS元素面分布图，(f,g)PMC的TEM图像

Figure 4 (a,b)SEM images of PMC，(c,d,e)EDS elemental mapping of PMC，(f,g)TEM images of PMC

图5 （a-c）PMC的XPS谱图，（d）MXene Ti3C2Tx的Ti 2p精细谱图

Figure 5 (a-c) XPS spectra of PMC, (d) Ti 2p fine spectrum of MXene Ti3C2Tx

图6 PMC和MXene Ti3C2Tx的N2吸/脱附等温线

Figure 6 N2 adsorption-desorption isotherms of PMC and MXene Ti3C2Tx

图7 （a）PMC/S的SEM图像，（b-d）PMC/S的EDS元素面分布图

Figure 7 （a）SEM images of PMC/S，（b-d）EDS elemental mapping of PMC/S

图8 PMC/S的XRD图谱

Figure 8 XRD patterns of PMC/S

图9 (a) PMC-2/S的热重分析曲线，(b) PMC/S的N2吸/脱附等温线

Figure 9 (a) Thermogravimetry curve of PMC-2/S, (b) N2 adsorption-desorption isotherm of PMC/S

图10 含一系列PMC/S正极（包括PMC-1/S、PMC-2/S、PMC-3/S）的（a）倍率性能、（b）0.1 C循环性能;，（c）在不同倍率下PMC-2/S的充电-放电曲线，（d）在0.1 C下PMC-2/S、MXene Ti3C2Tx/S的充电-放电曲线平台电位差的比较和PMC-2/S在1 C下的长循环性能（e）

Figure 10 (a) rate performance and (b) 0.1 C cycle performance of a series of PMC/S (including PMC-1/S, PMC-2/S and PMC-3/S), (c) the charge-discharge curves of PMC-2/S at different current densities; (d) the comparison of the platform difference of the charge-discharge curve of PMC-2/S and MXene Ti3C2Tx/S at 0.1 C and(e)Long cycle performance of PMC-2/S at 1 C

图11 （a，b）PMC/S和MXene Ti3C2Tx/S的CV曲线，（c-f）0.1-0.5 mV·s-1PMC/S和MXene Ti3C2Tx/S的CV曲线及对应的氧化还原电流峰值与扫描速率之间的相应线性关系

Figure 11 (a, b) CV curves of PMC/S and MXene Ti3C2Tx/S, (c-f) CV curves of PMC/S and MXene Ti3C2Tx/S at 0.1-0.5 mV·s-1, and the corresponding linear relationship between the peak REDOX current and the scanning rate

图12（a） PMC/S、（b） MXene Ti3C2Tx/S循环100圈前后的EIS图（插图为对应的等效电路图）

Figure 18 EIS before and after 100 cycles of (a) PMC/S, (b) MXene Ti3C2Tx/S (The illustration is the corresponding equivalent circuit diagram)

表1 PMC/S和 MXene Ti3C2Tx/S循环100圈前后的EIS图拟合结果

Table 1 EIS fitting results before and after 100 cycles of PMC/S and MXene Ti3C2Tx/S

Samples	Before cycling		After 100th cycle
Samples	Rs (ohm)	Rct (ohm)	Rs (ohm)	Rct (ohm)
MXene Ti₃C₂Tx/S	6.632	27.970	13.060	9.782
PMC/S	2.711	7.638	6.777	10.470

图13（a） PMC硫载体对Li2S6的吸附结果图，（b）对应样品的上清液紫外-可见光光谱测试，（c）吸附Li2S6后的样品的XPS图谱

Figure 13 (a) The adsorption of PMC sulfur host on Li2S6, (b) the UV-visible spectrum test results of the supernatant of the corresponding sample, and (c) the XPS spectrum of the sample after adsorption of Li2S6

图14 10 mV·s-1的MXene Ti3C2Tx和PMC的对称电池的CV曲线

Figure 14 CV curves of MXene Ti3C2Tx and PMC symmetrical cells at 10 mV·s-1

图15 由PMC/S半电池驱动的串灯实物图

Figure 15 Digital photograph of string lights powered by the PMC/S half-cell

参考文献 46

[1]	Zhang Y Z, Sun C W. Composite lithium protective layer formed in situ for stable lithium metal batteries[J]. ACS Applied Materials & Interfaces, 2021, 13(10): 12099-12105.
[2]	Akhtar N, Sun X G, Akram M Y, et al. A gelatin-based artificial SEI for lithium deposition regulation and polysulfide shuttle suppression in lithium-sulfur batteries[J]. Journal of Energy Chemistry, 2021, 52: 310-317.
[3]	Zhao Y Y, Ye Y S, Wu F, et al. Anode interface engineering and architecture design for high-performance lithium–sulfur batteries[J]. Advanced Materials, 2019, 31(12): 1806532.
[4]	Lin Y L, Huang S, Zhong L, et al. Organic liquid electrolytes in Li-S batteries: actualities and perspectives[J]. Energy Storage Materials, 2021, 34: 128-147.
[5]	Zhang X, Li J, Gao C, et al. Promoting the conversion of Li₂S by functional additives phenyl diselenide in Lithium–Sulfur batteries[J]. Journal of Power Sources, 2021, 482: 228967.
[6]	Chen S R, Wang D W, Zhao Y M, et al. Superior performance of a lithium–sulfur battery enabled by a dimethyl trisulfide containing electrolyte[J]. Small Methods, 2018, 2(6): 1800038.
[7]	Fan L, Chen S H, Zhu J Y, et al. Simultaneous suppression of the dendrite formation and shuttle effect in a lithium–sulfur battery by bilateral solid electrolyte interface[J]. Advanced Science, 2018, 5(9): 1700934.
[8]	Bai Y, Zhao Y B, Li W D, et al. Organic-inorganic multi-scale enhanced interfacial engineering of sulfide solid electrolyte in Li-S battery[J]. Chemical Engineering Journal, 2020, 396: 125334.
[9]	Shao D S, Yang L, Luo K L, et al. Preparation and performances of the modified gel composite electrolyte for application of quasi-solid-state lithium sulfur battery[J]. Chemical Engineering Journal, 2020, 389: 124300.
[10]	Lei D N, Shi K, Ye H, et al. Progress and perspective of solid-state lithium–sulfur batteries[J]. Advanced Functional Materials, 2018, 28(38): 1707570.
[11]	Phuc N H H, Hikima K, Muto H, et al. Recent developments in materials design for all-solid-state Li–S batteries[J]. Critical Reviews in Solid State and Materials Sciences, 2022, 47(3): 283-308.
[12]	Zhang X Z, Chen Z H, Shui L L, et al. The fabrication of a 3D current collector with bitter melon-like TiO₂–NCNFs for highly stable lithium–sulfur batteries[J]. Nanoscale Advances, 2019, 1(2): 527-531.
[13]	Pei F, Fu A, Ye W B, et al. Robust lithium metal anodes realized by lithiophilic 3D porous current collectors for constructing high-energy lithium–sulfur batteries[J]. ACS Nano, 2019, 13(7): 8337-8346.
[14]	Yuan W, Qiu Z Q, Wang C, et al. Design and interface optimization of a sandwich-structured cathode for lithium-sulfur batteries[J]. Chemical Engineering Journal, 2020, 381: 122648.
[15]	Shin D, Song Y, Nam D, et al. High-capacity sulfur copolymer cathode with metallic fibril-based current collector and conductive capping layer[J]. Journal of Materials Chemistry A, 2021, 9(4): 2334-2344.
[16]	Zhou C, He Q, Li Z H, et al. A robust electrospun separator modified with in situ grown metal-organic frameworks for lithium-sulfur batteries[J]. Chemical Engineering Journal, 2020, 395: 124979.
[17]	Cheng P, Guo P Q, Sun K, et al. CeO₂ decorated graphene as separator modification material for capture and boost conversion of polysulfide in lithium-sulfur batteries[J]. Journal of Membrane Science, 2021, 619: 118780.
[18]	Chen P, Wang Z X, Zhang B Y, et al. Multi-functional TiO₂ nanosheets/carbon nanotubes modified separator enhanced cycling performance for lithium-sulfur batteries[J]. International Journal of Energy Research, 2020, 44(4): 3231-3240.
[19]	Liu X, Ma H, Hu C C, et al. Tg-C₃N₄-coated functional separator as polysulfide barrier of high-performance lithium-sulfur batteries[J]. Nanotechnology, 2021, 32(47): 475401.
[20]	Li H T, Jin Q, Li D M, et al. Mo2C-embedded carambola-like N,S-rich carbon framework as the interlayer material for high-rate lithium–sulfur batteries in a wide temperature range[J]. ACS Applied Materials & Interfaces, 2020, 12(20): 22971-22980.
[21]	Fan Z H, Zhang C, Hua W X, et al. Enhanced chemical trapping and catalytic conversion of polysulfides by diatomite/MXene hybrid interlayer for stable Li-S batteries[J]. Journal of Energy Chemistry, 2021, 62: 590-598.
[22]	Xu Z, Wang Z, Wang M R, et al. Large-scale synthesis of Fe₉S₁₀/Fe₃O₄@C heterostructure as integrated trapping-catalyzing interlayer for highly efficient lithium-sulfur batteries[J]. Chemical Engineering Journal, 2021, 422: 130049.
[23]	Zhu D M, Long T, Xu B, et al. Recent advances in interlayer and separator engineering for lithium-sulfur batteries[J]. Journal of Energy Chemistry, 2021, 57: 41-60.
[24]	Ji X L, Lee K T, Nazar L F. A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries[J]. Nature Materials, 2009, 8(6): 500-506.
[25]	Park J, Yu S H, Sung Y E. Design of structural and functional nanomaterials for lithium-sulfur batteries[J]. Nano Today, 2018, 18: 35-64.
[26]	Zhang L L, Wang Y J, Niu Z Q, et al. Advanced nanostructured carbon-based materials for rechargeable lithium-sulfur batteries[J]. Carbon, 2019, 141: 400-416.
[27]	Fang R P, Chen K, Yin L C, et al. The regulating role of carbon nanotubes and graphene in lithium-ion and lithium–sulfur batteries[J]. Advanced Materials, 2019, 31(9): 1800863.
[28]	Shulaker M M, Hills G, Patil N, et al. Carbon nanotube computer[J]. Nature, 2013, 501(7468): 526-530.
[29]	Ma L B, Wu J X, Li Y, et al. Rational design of carbon nanotube architectures for lithium–chalcogen batteries: Advances and perspectives[J]. Energy Storage Materials, 2021, 42: 723-752.
[30]	Ye X M, Ma J, Hu Y S, et al. MWCNT porous microspheres with an efficient 3D conductive network for high performance lithium–sulfur batteries[J]. Journal of Materials Chemistry A, 2016, 4(3): 775-780.
[31]	Feng J N, Liu W D, Shi C, et al. Enabling fast diffusion/conversion kinetics by thiourea-induced wrinkled N, S Co-doped functional MXene for lithium-sulfur battery[J]. Energy Storage Materials, 2024, 67: 103328.
[32]	Xiong D B, Huang S Z, Fang D L, et al. Porosity engineering of MXene membrane towards polysulfide inhibition and fast lithium ion transportation for lithium–sulfur batteries[J]. Small, 2021, 17(34): 2007442.
[33]	Bian R J, He G L, Zhi W Q, et al. Ultralight MXene-based aerogels with high electromagnetic interference shielding performance[J]. Journal of Materials Chemistry C, 2019, 7(3): 474-478.
[34]	Kumar V S, Kummari S, Catanante G, et al. A label-free impedimetric immunosensor for zearalenone based on CS-CNT-Pd nanocomposite modified screen-printed disposable electrodes[J]. Sensors and Actuators B: Chemical, 2023, 377: 133077.
[35]	Zhang Y G, Li G R, Wang J Y, et al. "Sauna" activation toward intrinsic lattice deficiency in carbon nanotube microspheres for high-energy and long-lasting lithium–sulfur batteries[J]. Advanced Energy Materials, 2021, 11(26): 2100497.
[36]	Zhang N N, Huang S, Yuan Z S, et al. Direct self-assembly of MXene on Zn anodes for dendrite-free aqueous zinc-ion batteries[J]. Angewandte Chemie International Edition, 2021, 60(6): 2861-2865.
[37]	Zhang J, Yang L, Wang H B, et al. In situ hydrothermal growth of TiO₂ nanoparticles on a conductive Ti₃C₂T_X MXene nanosheet: a synergistically active Ti-based nanohybrid electrocatalyst for enhanced N₂ reduction to NH₃ at ambient conditions[J]. Inorganic Chemistry, 2019, 58(9): 5414-5418.
[38]	Zhang Y, Huang Y Y, Srot V, et al. Enhanced pseudo-capacitive contributions to high-performance sodium storage in TiO₂/C nanofibers via double effects of sulfur modification[J]. Nano-Micro Letters, 2020, 12(1): 165.
[39]	Li W L, Chen K, Xu Q C, et al. Mo₂C/C hierarchical double-shelled hollow spheres as sulfur host for advanced Li-S batteries[J]. Angewandte Chemie International Edition, 2021, 60(39): 21512-21520.
[40]	Wang S Z, Feng S P, Liang J W, et al. Insight into MoS₂–MoN heterostructure to accelerate polysulfide conversion toward high-energy-density lithium–sulfur batteries[J]. Advanced Energy Materials, 2021, 11(11): 2003314.
[41]	Liu P, Zhong W, Du W Y, et al. Suppressed shuttling effect of polysulfides using three-dimensional nickel hydroxide polyhedrons for advanced lithium-sulfur batteries[J]. Journal of Colloid and Interface Science, 2021, 593: 89-95.
[42]	Li Z, Zhang F, Cao T, et al. Highly stable lithium–sulfur batteries achieved by a SnS/porous carbon nanosheet architecture modified celgard separator[J]. Advanced Functional Materials, 2020, 30(48): 2006297.
[43]	Park G D, Kang Y C. Aerosol-assisted synthesis of porous and hollow carbon-carbon nanotube composite microspheres as sulfur host materials for high-performance Li-S batteries[J]. Applied Surface Science, 2019, 495: 143637.
[44]	Shi T Y, Zhao C Y, Yin C, et al. Incorporation ZnS quantum dots into carbon nanotubes for high-performance lithium–sulfur batteries[J]. Nanotechnology, 2020, 31(49): 495406.
[45]	Zhang L, Bi J Y, Zhao Z K, et al. Sulfur@Self-assembly 3D MXene hybrid cathode material for lithium-sulfur batteries[J]. Electrochimica Acta, 2021, 370: 137759.
[46]	Zhao J, Qi Y R, Yang Q J, et al. Chessboard structured electrode design for Li-S batteries Based on MXene nanosheets[J]. Chemical Engineering Journal, 2022, 429: 131997.

P-MXene Ti₃C₂T_x/CNT多孔微球硫载体复合材料的制备及电化学性能研究

Preparation and Electrochemical Performance of P-MXene Ti₃C₂T_x/CNT Porous Microsphere Sulfur Host Composite Materials

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 16

参考文献 46

相关文章 15

编辑推荐

Metrics

本文评价

[1]	赵维, 邢文乐, 韩朝旭, 袁兴中, 蒋龙波. g-C₃N₄基非金属异质结光催化降解水中有机污染物的研究进展[J]. 化工学报, 2025, 76(9): 4752-4769.
[2]	郭铮铮, 赵一丹, 王辅强, 裴璐, 靳彦岭, 任芳, 任鹏刚. 异质结构MoS₂/RGO/NiFe₂O₄复合材料的构筑及电磁波吸收性能研究[J]. 化工学报, 2025, 76(7): 3719-3732.
[3]	郭乃胜, 朱小波, 王双, 陈平, 褚召阳, 王志臣. 聚氨酯改性沥青高低温性能及影响因素的研究进展[J]. 化工学报, 2025, 76(6): 2505-2523.
[4]	何军, 李勇, 赵楠, 何孝军. 碳负载硒掺杂硫化钴在锂硫电池中的性能研究[J]. 化工学报, 2025, 76(6): 2995-3008.
[5]	石孟琪, 王欢, 王守娟, 席跃宾, 孔凡功. 木质素基炭材料的制备及其在锂硫电池中的研究进展[J]. 化工学报, 2025, 76(4): 1463-1483.
[6]	马钟琛, 魏子杰, 朱明涛, 叶恒棣, 郭学益, 谭磊. 一步氧化法制备锰酸锂正极材料用电池级四氧化三锰[J]. 化工学报, 2025, 76(3): 1363-1374.
[7]	李远华, 凌思棋, 封科军, 冯颖, 郭于菁, 谢世桓. 基于cMOFs的固定化脂肪酶微反应器的构筑及其扁桃酸催化应用[J]. 化工学报, 2025, 76(3): 1170-1179.
[8]	肖俊兵, 邹博, 任建地, 刘昌会, 贾传坤. 基于相图分析的氯化物复合熔盐储热性能研究[J]. 化工学报, 2025, 76(3): 963-974.
[9]	肖俊兵, 钟湘宇, 任建地, 钟芳芳, 刘昌会, 贾传坤. 基于生物碳材料强化的硬脂酸相变材料储热性能研究[J]. 化工学报, 2025, 76(3): 1312-1322.
[10]	刘彦贝, 王若名, 刘娟, Raza Taimoor, 陆玉正, Raza Rizwan, 朱斌, 李松波, 安胜利, 云斯宁. CeO₂@La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ 电解质的制备及半导体离子燃料电池性能研究[J]. 化工学报, 2025, 76(3): 1353-1362.
[11]	肖志华, 房浩楠, 郑方植, 孙冬, 陶丽达, 李永峰, 徐春明, 马新龙. NaCl辅助构筑高性能沥青基硬炭负极材料[J]. 化工学报, 2025, 76(2): 846-857.
[12]	李文宝, 胡锦鹏, 杜淼, 潘鹏举, 单国荣. 强韧P（SBMA-co-AAc）/SiO₂复合水凝胶海洋防污减阻涂层[J]. 化工学报, 2025, 76(2): 787-796.
[13]	王芾涵, 王慧儒, 赵成卓, 刘振宇, 刘伟军, 卞宏友. 石蜡/TPMS结构多孔AlSi10Mg合金复合相变材料蓄热性能实验研究[J]. 化工学报, 2025, 76(10): 5414-5425.
[14]	周池楼, 李治宇, 郑益然. 高压氢环境下丁腈橡胶密封件氢致鼓泡断裂研究[J]. 化工学报, 2025, 76(10): 5262-5276.
[15]	徐子易, 席阳, 宋泽文, 周海骏. 碳纳米材料在锌离子电池中的应用研究进展[J]. 化工学报, 2025, 76(1): 40-52.