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

XIE Zhipeng; ZHANG Da; LIANG Feng

doi:10.7498/aps.74.20251185

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.

Keywords:
non-thermal plasma /

plasma-material surface interaction /

defects /

energy materials
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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

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

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图 2 材料表面结构对等离子体鞘层的影响示意图

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

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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T_e= 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]

Figure 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 T_e= 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].

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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]

Figure 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].

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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]

Figure 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].

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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]

Figure 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].

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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

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

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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

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

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