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非热等离子体在能源材料缺陷工程中的应用

解志鹏 ,  张达 ,  梁风

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非热等离子体在能源材料缺陷工程中的应用

解志鹏, 张达, 梁风
物理学报,
doi: 10.7498/aps.74.20251185
cstr: 32037.14.aps.74.20251185

Applications and prospects of non-thermal plasma in defect engineering of energy materials

XIE Zhipeng, ZHANG Da, LIANG Feng
Acta Phys. Sin.,
doi: 10.7498/aps.74.20251185
cstr: 32037.14.aps.74.20251185
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  • 摘要

    非热等离子体 (non-thermal plasma, NTP) 作为一种在接近室温条件下高效实现材料制备与改性的先进技术, 近年来在能源材料领域备受关注. 由于其电子温度高而整体气体温度低, NTP能够在避免热损伤的前提下, 通过引入空位、杂原子掺杂, 调控孔隙率和表面粗糙程度等多尺度缺陷, 显著改善电极材料的电化学性能. 等离子体-材料表面相互作用是一个复杂的体系, 涉及等离子体与材料之间的相互影响规律, 深入理解该作用机制对实现NTP改性精准调控材料缺陷类型、密度、空间分布至关重要. 本综述系统总结了NTP在能源材料刻蚀和掺杂领域的应用, 重点阐述了缺陷的生成及其对等离子体与材料表面相互作用中的影响. 最后, 分析了NTP技术规模化应用过程中面临的主要挑战并对其未来发展进行了展望.

    Abstract

    Non-thermal plasma (NTP), as an advanced technology capable of efficiently synthesizing and modifying materials at near-ambient temperatures, has attracted significant attention in the field of energy materials in recent years. Owing to its high electron temperature and low bulk gas temperature, NTP can significantly enhance the electrochemical performance of electrode materials by creating vacancies, enabling heteroatom doping, and adjusting multiscale defects such as porosity and surface roughness, while preventing thermal damage. The plasma-material surface interaction is a complex system involving mutual influences between the plasma and the material. An in-depth understanding of this mechanism is essential for achieving precise control over defect type, density, and spatial distribution by modifying NTP . This paper systematically summarizes recent advances in the application of NTP for etching and doping energy materials, with special emphasis on the formation mechanisms of defects and their functional role in plasma-surface interactions. The plasma sheath effects, defect generation pathways, and the influence of material morphology on local plasma behavior are discussed in detail. Finally, this paper outlines prospects for future research on NTP-modified energy materials.

  • 图 1  (a) 等离子体鞘层, (b) 空位缺陷, (c) 孔缺陷, (d) 掺杂缺陷示意图

    Fig. 1.  Schematic of (a) plasma sheath, (b) vacancy defect, (c) pore defect, and (d) doping detect.

    下载: 全尺寸图片 幻灯片

    图 2  材料表面结构对等离子体鞘层的影响示意图

    Fig. 2.  Schematic of the influence of material surface structure on the plasma sheath.

    下载: 全尺寸图片 幻灯片

    图 3  (a) 在矩形排列的单个纳米管附近离子通量的分布随等离子体密度和纳米管直径变化. 电子温度Te = 2 eV, 离子通量分布相对于相邻纳米管的方向以暗黄色圆圈表示, S1, S2和S3分别表示位于基底表面上方75, 50和25 nm处的纳米管横截面[23]; (b) 在基于射频等离子体的工艺中生长出的尖且长的碳纳米锥体生长机制和扫描电子显微镜图像[40]; (c) 混合阵列的合成示意图以及模型图案内原子密度和电场的相应数值模拟[41]

    Fig. 3.  (a) The distribution of ion flux near the single nanotubes arranged in a rectangular pattern varies with plasma density and nanotube diameter, the electron temperature Te = 2 eV, the ion flux distribution is indicated by dark yellow circles relative to the direction of the adjacent nanotubes. S1, S2, and S3 respectively represent the cross-sections of nanotubes located 75, 50, and 25 nm above the substrate surface[23]; (b) the growth mechanism and SEM images of sharp, long carbon nanocones grown in a RF plasma-based process[40]; (c) schematic of the synthesis of a mixed array, and corresponding numerical simulations of the adatom density and electric field within the model pattern[41].

    下载: 全尺寸图片 幻灯片

    图 4  (a) Fe—N/C-0和(b) Fe—N/C-120的SEM图像, 等离子体刻蚀对Fe—N/C的结构表征; (c) 拉曼光谱; (d) 氮气吸脱附曲线; (e) 孔径分布; (f) 傅里叶红外光谱[51]

    Fig. 4.  SEM images of (a) Fe—N/C-0 and (b) Fe—N/C-120; (c) Raman spectra; (d) N2 adsorption–desorption curves; (e) pore size distributions; (f) FT-IR spectra[51].

    下载: 全尺寸图片 幻灯片

    图 5  (a) P-Si/C/Bi复合材料的制备工艺及概念设计; (b) NVP的示意图和第一性原理计算; (c) 优化后的NVP-4N中间层中Na原子的吸附构型及吸附Na的电荷密度差, 黄色和青色电子云分别代表电子积累和耗尽; (d) 计算的NVP-0 N和NVP-4N中Na+的扩散势垒分布; (e), (f) NVP-0N和NVP-4N的映射态密度[58]

    Fig. 5.  (a) Fabrication process and conceptual design of P-Si/C/Bi composite; (b) schematic illustration for NVP and first-principles calculation; (c) optimized adsorption configuration and charge density differences of a Na atom in the interlayer: yellow and cyan electron clouds represent electron accumulation and depletion, respectively; (d) calculated diffusion barrier profiles of Na+ for NVP-0N and NVP-4N; (e) pore size distributions, and (e), (f) projected density of states of NVP-0N and NVP-4N[58].

    下载: 全尺寸图片 幻灯片

    图 6  (a) 非热等离子体制备等离子体催化电极的合成工艺流程图; (b) 等离子体制备催化电极的步骤示意图; (c) 氮原子掺杂机理; (d) 含氧官能团的引入过程[72]

    Fig. 6.  (a) The synthesis procedure diagram of the plasma-prepared catalytic electrode by non-thermal plasma; (b) schematic diagram shows the steps of plasma preparing catalytic electrode; (c) doping mechanism of nitrogen atoms; (d) introduction process of oxygen-containing functional groups[72].

    下载: 全尺寸图片 幻灯片
    下载: 全尺寸图片 幻灯片

    表 1  氮掺杂反应中涉及的键能表[72]

    Table 1.  The bond energy table involved in the nitrogen doping reaction[72].

    化学键 键能/eV 化学键 键能/eV
    C—H 3.2—4.7 C—C 2.6—5.2
    N—H 2.1—4.7 C—O 0.95—3.0
    C—N 1.2—3.1 C=C 3.3—7.5
    C=O 5.5 O—H 3.4—5.2
    下载: 导出CSV
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    [20] 汤学峰, 顾 牡, 童宏勇, 梁 玲, 姚明珍, 陈玲燕, 廖晶莹, 沈炳浮, 曲向东, 殷之文, 徐炜新, 王景成. 掺镧PbWO4闪烁晶体的缺陷研究. 物理学报, doi: 10.7498/aps.49.2007
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出版历程
  • 收稿日期:  2025-09-01
  • 修回日期:  2025-09-27
  • 上网日期:  2025-10-10

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