杂原子掺杂石墨烯在锂离子电池负极中的研究进展

doi:10.19799/j.cnki.2095-4239.2025.0739

摘要/Abstract

摘要：

石墨烯凭借独特的二维结构和优异的性能在锂离子电池负极材料领域备受关注。然而，石墨烯的固有化学惰性和易聚集倾向制约了其应用。杂原子掺杂是优化石墨烯电化学性能的关键策略。本文综述了氮、硼、硫、磷、硅、卤素等不同杂原子掺杂石墨烯的制备方法、储锂机制及性能优势。杂原子掺杂石墨烯根据掺杂元素数量的不同分为单掺杂石墨烯和共掺杂石墨烯。杂原子掺杂效果主要受掺杂原子半径、电负性、元素组合以及掺杂方式等因素的影响。单掺杂石墨烯通过调控电子特性、引入缺陷和活性位点、扩展层间距等策略，可显著提升石墨烯的电化学性能。共掺杂石墨烯通过电子效应、空间效应及稳定性协同作用突破单掺杂石墨烯的性能瓶颈。杂原子掺杂尤其是共掺杂策略，通过多机制协同显著提升石墨烯的储锂容量、倍率性能及循环稳定性，为高性能锂离子电池负极材料的设计与开发提供了重要研究思路与方向。

关键词: 石墨烯, 杂原子掺杂, 单掺杂, 共掺杂, 锂离子电池

Abstract:

Graphene has attracted much attention in the field of lithium-ion battery negative electrode materials due to its unique two-dimensional structure and excellent performance. However, the inherent chemical inertness and tendency to aggregate of graphene limit its applications. Doping with heteroatoms is a key strategy for optimizing the electrochemical performance of graphene. This article reviews the preparation methods, lithium storage mechanisms, and performance advantages of graphene doped with different heteroatoms such as nitrogen, boron, sulfur, phosphorus, silicon, and halogens. Heteroatomic doped graphene is divided into single doped graphene and co doped graphene based on the number of doping elements. The doping effect of heteroatoms is mainly influenced by factors such as doping atom radius, electronegativity, element combination, and doping method. Single doped graphene can significantly enhance its electrochemical performance by regulating electronic properties, introducing defects and active sites, and expanding interlayer spacing. Co doped graphene breaks through the performance bottleneck of single doped graphene through the synergistic effects of electronic effects, spatial effects, and stability. The doping of heteroatoms, especially the co doping strategy, significantly improves the lithium storage capacity, rate performance, and cycling stability of graphene through multi mechanism synergy, providing important research ideas and directions for the design and development of high-performance lithium-ion battery negative electrode materials.

Key words: graphene, heteroatom doping, single doping, co doping, lithium-ion battery

中图分类号:

TM911

王良旺, 刘斌, 肖灵, 何立粮, 文芳, 徐岩岩. 杂原子掺杂石墨烯在锂离子电池负极中的研究进展[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2025.0739.

Liangwang WANG, Bin LIU, Ling XIAO, Liliang HE, Fang WEN, Yanyan XU. Research progress of graphene doped with heteroatoms in the negative electrode of lithium-ion batteries[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2025.0739.

图/表 6

图1

图2

图3

图4

表1

单掺杂石墨烯体系基本特性对比"

掺杂元素	方法典型制备	主要构型/键型	核心作用机制	优势	挑战
N	水热法^[29,31]、热处理法^[30]	吡啶氮、吡咯氮、石墨氮	高电负性增强锂离子吸附；引入拓扑缺陷与活性位点，促进锂离子扩散；N型/P型掺杂，提升导电性	掺杂工艺成熟；电子结构调控效果好；结构稳定性优异	单一掺杂易引发Li₃N生成，持续消耗活性锂
B	热处理法^[38-39]	BC₃，B–C–O	原子半径较大，扩大层间距，降低锂离子扩散势垒；缺电子体，增强锂离子吸附；提升sp3缺陷密度，增加活性位点	锂离子吸附能力强，抑制锂枝晶，倍率性能优异；长循环稳定性优于氮	掺杂效率低；高掺杂量易破坏碳骨架完整性
S	球磨法^[41]，电化学剥离法^[42]	-C=S、-C-S-C-、-C-SOx-C-	原子半径较大，诱导片层扭曲，增加缺陷密度；孤对电子与锂离子形成强配位	层间堆叠抑制效果好；与碳骨架结合稳定（-C-S-C-）	-C-SOx-C-较多时会对电化学性能产生不利影响
P	热处理法^[46]	P-C、P-O、C-P-O	原子半径较大，引发晶格畸变，增加边缘活性位点；N型掺杂，载流子密度提升；C-P-O键增强结构稳定性	缺陷结构可缓解体积膨胀，P-O键抑制电解液副反应，循环性能好。	掺杂难度较大；掺杂量窗口窄（1~2 at%最优）
Si	微波辐射法^[48]	C–Si–O	电子受体提供额外锂存储位点；原子半径较大，引发晶格畸变，增加边缘活性位点	硅锂储存容量高；循环中活性位点持续激活；C-Si-O键抑制硅体积膨胀	掺杂难度较大；在长期循环中仍可能发生局部破裂
I	球磨法^[50]	C-I	高电负性诱导电荷重分布，增强锂离子吸附；碘原子半径较大，扩大层间距；C-I键兼具离子性，提供额外活性位点	具有优异反应动力学和高锂存储容量；层间堆叠抑制效果显著	含氧官能团需精准调控（导致不可逆容量损失）
F	电弧放电法^[51]	C-F、C-F₂、C-F₃	高电负性增强锂离子吸附；嵌锂过程原位形成LiF，增大层间距，并提升界面稳定性，减少不可逆反应	SEI膜稳定性好，循环性能优异；高倍率下容量保持能力强	LiF可致SEI膜局部破裂与重构

表1

表2

共掺杂石墨烯体系基本特性对比"

掺杂元素	典型制备方法	主要构型/键型	核心作用机制	优势	挑战
N，S	热处理法^[56]	吡啶/吡咯氮，噻吩硫（-C-S-C-）	氮硫电子协同，降低锂离子嵌入能垒；硫扩大层间距，氮通过键合稳定构型，实现空间协同；噻吩硫钝化碳表面，抑制电解液副反应	高容量与高倍率兼顾；循环中电极活化，容量上升；比表面积大，活性位点丰富	硫掺杂量低（0.52 at%），协同效应受限；热处理工艺相对复杂
N，B	热处理法^[58]	吡啶/吡咯氮，BC₃	氮硼电子协同，调控电荷分布，提升导电性和锂离子吸附能力；硼扩大层间距，氮提升电荷传输效率，在维持稳定结构同时，保持高活性储锂能力	电荷转移效率高；拥有高比容量与循环稳定性	氮硼掺杂比例需精准调控；钴等催化剂增加成本且存在杂质风险
N，P	热处理法^[59]	吡啶/吡咯/石墨氮，P–C/P–O	氮磷电子协同，减少电荷散射，提升导电性；磷主导层间距扩大和边缘活性位点创造，缺陷密度显著提升；共掺杂键合稳定石墨烯晶格，缓解体积应变、抑制片层堆叠	活化效应显著，循环中容量持续上升；高倍率下长循环无容量衰减	原子半径和化学性质差异可能导致掺杂分布不均
N，O	热处理法^[60]	吡啶/吡咯/石墨氮，C=O/C–O/COOH	氮通过孤对电子增强锂离子吸附，提升导电性；氧原子主导层间距增大；共掺杂极性官能团提升电解液润湿性，抑制电解液过度分解	稳定的SEI膜和碳层结构提升循环性能	首效偏低；氧官能团易引发首次充放电副反应；热处理工艺相对复杂
N，F	水热法^[61]	吡啶/吡咯/石墨氮，C–F	氮通过孤对电子构建亲锂位点，提升导电性，弥补氟掺杂导致的亲锂性不足和导电性下降；氟形成富含LiF的稳定SEI膜，减少Li₃N生成	通过优化锂成核和形成稳定SEI，循环寿命长；高倍率下容量保持率高	氮氟掺杂的作用互补，故掺杂比例需精准调控；氟源腐蚀性强，制备需防泄漏
N，Cl	溶剂热法^[62]	吡啶氮/吡咯氮/石墨氮、C-Cl	氮增强锂离子吸附，提升导电性，增加活性位点；氯扩大层间距，引入结构畸变和缺陷，抑制氧掺杂来减少活性锂消耗；C-Cl共价键增强电容贡献	展现优异的高倍率长循环稳定性；制备工艺温和	首效偏低，需进一步降低氧含量；氯因尺寸大，掺杂均匀性控制较难

表2

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