Ti基MXene及其复合材料在金属离子电池中的进展

刘浩; 姚卫棠

doi:10.13801/j.cnki.fhclxb.20200717.001

Ti基MXene及其复合材料在金属离子电池中的进展

doi: 10.13801/j.cnki.fhclxb.20200717.001

刘浩,
姚卫棠^,

西南科技大学　国防科技学院，绵阳 621000

基金项目: 国家自然科学基金(21671160)

详细信息

通讯作者:
姚卫棠，博士，教授，博士生导师，研究方向为能源材料储存与转换　E-mail：wtyao@ustc.edu.cn

中图分类号: TB34；TM912
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- HTML全文浏览量: 660
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- 被引次数: 0
出版历程
- 收稿日期: 2020-05-21
- 录用日期: 2020-07-08
- 网络出版日期: 2020-07-17
- 刊出日期: 2020-12-15

Research progress of Ti-based MXene and its composites in metal-ion batteries

LIU Hao,
YAO Weitang^,

School of National Defense Science and Technology SWUST, Southwest University of Science and Technology, Mianyang 621000, China

摘要

摘要: 二维过渡金属碳(氮或碳氮)化物MXene自2011年首次报告后，其家族成员不断增加，目前已有超过20种MXene被成功合成。凭借独特的层状结构，出色的物理化学性质和可设计的表面官能团特性，MXene被认为是极具潜力的电极材料。近年来，MXene及其复合材料在储能领域进展显著。为此，本文综述了Ti基MXene及其复合材料在Li离子电池和Na离子电池中的研究进展，并结合其制备方法和特性，详细介绍了电池性能提升策略或机制。最后，指出了MXene及其复合材料构建高性能电池面临的挑战，并对未来前景进行了展望。
- MXene /
- 能量储存 /
- Li离子电池 /
- Na离子电池 /
- 电极材料 /
- 能源材料
Abstract: Since two-dimensional transition metal carbides (nitrides or carbonitrides) MXenes was first reported in 2011, its family members have been increasing. At present, more than 20 MXenes have been successfully synthesized. With unique layered structure, excellent physicochemical properties and designable surface functional group characteristics, MXenes are considered as promising electrode material. In recent years, some remarkable progress of MXenes and its composite materials are achieved in energy storage. To this end, this review presents the research progress of Ti-based MXenes and its composite materials in Lithium-ion batteries and Sodium-ion batteries. Combined with the preparation methods and characteristics of MXenes, the strategies or mechanisms of improving battery performance are introduced in detail. Finally, the challenges and prospects of MXenes and its composite materials in fabricating high-performance batteries are pointed out.
- MXene /
- energy storage /
- Li-ion battery /
- Na-ion battery /
- electrode material /
- energy material

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图 1 层状M₃AX₂晶体结构(a)、单层M₃X₂的侧视图 (b)和俯视图(c)^[21]

Figure 1. Crystal structure of layered M₃AX₂ solid phase (a), side (b) and top (c) views of M₃X₂ monolayer^[21]

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图 2 MXene“粘土”合成及电极制备原理图^[30]

Figure 2. Schematic of MXene clay synthesis and electrode preparation^[30]

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图 3 蚀刻和分层示意图(a)、电化学电池的配置(b)、块状Ti₃AlC₂(c)、Ti₃C₂T_x在水中的分散液(d)、Ti₃AlC₂、Ti₃C₂T_x和Ti₃C₂T_x薄膜的XRD图谱(e)^[31]

Figure 3. Schematic of the etching and delamination process (a), configuration of electrochemical cell (b), optical image of the as-received bulk Ti₃AlC₂(c), aqueous dispersion of delaminated Ti₃C₂T_x(d), XRD patterns of Ti₃AlC₂, Ti₃C₂T_x and Ti₃C₂T_x(e)^[31]

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图 4 MXene平行排列的离子迁移(a)、MXene竖直排列的离子迁移(b)^[75]

Figure 4. Ion transport in horizontally stacked (a) and vertically aligned (b) Ti₃C₂T_x MXene films^[75]

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图 5 Ti₃C₂纳米带合成过程(a)及Ti₃AlC₂(b)、 Ti₃C₂纳米片(c)、三维多孔Ti₃C₂(d)的SEM图像^[80]

Figure 5. Schematic of synthesis of Ti₃C₂ nanoribbons (a) and SEM images of the corresponding Ti₃AlC₂(b) , Ti₃C₂ nanosheets (c) andTi₃C₂ nanoribbons (d)^[80]

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图 6 Ti₃C₂T_x皱缩后SEM图像(a)、Ti₃C₂T_x加入NaOH后引起结絮(b)^[80]、3D多孔MXene泡沫制备过程(c)^[81]

Figure 6. SEM images of Ti₃C₂T_x flocculated networks (a), photographs of Ti₃C₂T_x MXene colloidal suspensions (b)^[80], schematic illustration of the preparation process of 3D porous MXene foam (c)^[81]

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图 7 碳纳米纤维(CNF)“桥接”Ti₃C₂T_x片(a)^[83]、多孔Ti₃C₂T_x-CNT俯视SEM图像(b)和截面SEM图像(c)、Na⁺和电子在多孔Ti₃C₂T_x-CNT中迁移(d)^[84]

Figure 7. Schematic showing the preparation of MXene/carbon nanofiber (CNF) hybrid particles (a), top view (b) and cross-sectional (c) SEM images of porous Ti₃C₂T_x-CNT, Na⁺ diffusion and electron transfer within porous Ti₃C₂T_x-CNT electrodes (d)^[84]

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图 8 MXene、rGO和MXene-rGO的合成示意图(a) 、Ti₃C₂-RGO复合材料倍率性能(b)、Ti₃C₂-RGO复合材料长循环性能(c)^[85]

Figure 8. Schematic illustration of the fabrication of the MXene, rGO, and MXene-rGO films (a), rate capability of different samples (b), cycle performance of different samples at 1 A·g⁻¹(c)^[85]

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图 9 GeO_x@MXene不同倍率下长循环性能(a)、0.2 C下GeO_x@MXene不同温度容量(b)、 −40、−20和60℃时的循环性能(c)、在0.5 C下100次循环后GeO_x@MXene电极的TEM图像和Ge、O、Ti、C、F的元素映射(d)^[88]

Figure 9. Cycling performance of the battery with GeOx@MXene (a), GeO_x@MXene at differenttemperatures under 0.2 C (b), corresponding cyclingperformance at −40, −20 and 60℃, respectively (c), TEM images and element mappings of Ge, O, Ti, C and F of the GeO_x@MXene electrode after 100 cycles at 0.5 C (d)^[88]

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图 10 SiO₂/MXene微球制备过程(a)、SiO₂/MXene微球的SEM图像(b)

Figure 10. Schematic diagram for the synthesis process of SiO₂/MXene microspheres (a), SEM image of SiO₂/MXene (b)

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图 11 Ti 2p的XPS图谱(a)、Ti 2p的XPS对应的定量分析结果 (b)、Ti₃C₂的Bader电荷计算结果(c)、Co₃O₄@Ti₃C₂T_x的Bader电荷结果(d)^[94]

Figure 11. XPS spectra of Ti 2p (a), percentages of various atomic Ti species (Ti, Ti²⁺, Ti³⁺ and Ti—O) of the m-Ti₃C₂T_x, f-Ti₃C₂T_x and H-4(Co₃O₄@Ti₃C₂T_x) (b), bader charge results of two-layer bare Ti₃C₂ (c) and Co₃O₄@Ti₃C₂T_x(d)^[94]

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图 12 Fe₃O₄@Ti₃C₂T_x电极分别经过30次循环(a)、300次循环(b)、1 000次循环(c)的SEM图像和经循环后Fe₃O₄@Ti₃C₂T_x电极原位XRD图谱(d)^[95]

Figure 12. SEM images of the Fe₃O₄@Ti₃C₂T_x electrode after 30 cycles (a), 300 cycles (b) , and 1000 cycles (c) and ex-situ XRD pattern of Fe₃O₄@Ti₃C₂T_x electrode after 30, 300 and 1000 cycles (d)^[95]

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图 13 Li在 MoS₂(a)和MoS₂/Mo₂TiC₂O_x(b)上的吸附位点、对应吸附位点的结合能(c)、MoS₂/Mo₂TiC₂T_x倍率性能(d)、MoS₂(e)和 Mo₂TiC₂O₂(f)上最稳定的吸附构型和结合能、MoS₂/Mo₂TiC₂T_x制备过程(g)^[96]

Figure 13. Adsorption sites for Li on MoS₂ (a) and MoS₂/Mo₂TiC₂O_x (b), binding energies of Li on the surface of MoS₂ and MoS₂/Mo₂TiC₂O_x(c), rate performance for MoS₂/Mo₂TiC₂T_x(d), the most stable adsorption configurations and binding energies of Li₂S on MoS₂ (e) and Mo₂TiC₂O₂(f), schematic illustration of the preparation of MoS₂/Mo₂TiC₂T_x (g)^[96]

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图 14 真空辅助抽滤合成MXene/SnS₂(a)、不同比例MXene/SnS₂的循环性能(b)和倍率性能(c)^[98]

Figure 14. Schematic illustration of the preparation of MXene/SnS₂ composite by vacuum-assisted filtration(a), cycling performance (b) and rate performance (c) of MXene/SnS₂ 10∶1, 5∶1, 2∶1 and MXene^[98]

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图 15 BPQD/Ti₃C₂合成过程(a)、BPQD/Ti₃C₂倍率性能(b)和循环性能(c)、BPQD/Ti₃C₂电极放电过程中的DMES机制(d)^[101]

Figure 15. Schematic illustration of the formation process of the BPQD/Ti₃C₂ composite (a), rate performance of the BPQD/Ti₃C₂ composite electrode followed with a cycling performance at 100 mA·g ⁻¹ (b), long cycling performance of the BPQD/Ti₃C₂ composite electrode at a high current rate of 1 000 mA·g ⁻¹(c), schematic illustration showing the DMES mechanism involved in the discharge process of the BPQD/Ti₃C₂ electrodes (d)^[101]

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图 16 BP/Ti₃C₂T_x倍率性能(a)、 BP/Ti₃C₂T_x长循环性能(b)^[102]

Figure 16. Rate performances of BP/Ti₃C₂T_x(a), cycling performance of BP/Ti₃C₂T_x(b)^[102]

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图 17 NaTi_1.5O_8.3制备过程^[105](a)、TiS₂@C_PVP制备过程(b)、TEM图像(c)、倍率性能(d)和循环性能(e)^[106]

Figure 17. Schematic of the fabrication of NaTi_1.5O_8.3^[105](a), schematic of the synthesis of PVP derived carbon confined TiS₂ nanosheets (b), TEM image (c), rate capability (d) and long cycling performance (e) of TiS₂@C_PVP^[106]

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图 18 CoO/Co₂Mo₃O₈@MXene的制备过程(a)、倍率性能(b)和长循环性能(c)^[109]

Figure 18. Schematic illustration showing the synthesis of CoO/Co₂Mo₃O₈@MXene (a) , rate capabilities (b) and cycling behaviors (c) of CoO/Co₂Mo₃O₈@MXene^[109]

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