锂离子电池用碳纳米管导电剂产业化应用研究进展

doi:10.19799/j.cnki.2095-4239.2025.0864

摘要/Abstract

摘要：

碳纳米管(CNTs)是由sp²杂化碳原子构成的一维纳米材料，具有卓越的本征电导率和力学性能，通过“线接触-线桥接”协同机制在锂离子电池(LIBs)电极中构建高效三维导电网络，可显著提升电池的能量密度、倍率特性及循环稳定性，已成为高能量密度电池体系的核心材料。目前，多壁碳纳米管(MWCNTs)与炭黑复合导电体系已在高端锂电领域实现规模化应用，但单壁碳纳米管(SWCNTs)仍面临宏量制备技术不成熟、分散工艺复杂及综合成本较高等产业化挑战。本文系统综述CNTs导电剂产业化应用的最新进展：阐述CNTs构建长效电子传导路径、稳定电极/电解质界面和缓冲电极体积应变的微观机理；重点剖析流化床CVD技术对CNTs宏量制备的调控策略，以及纯化、表面修饰(如-COOH、N/B掺杂)和干燥工艺对电化学性能的优化机制；评述CNTs在磷酸铁锂(LFP)、高镍三元、硅基负极及全固态电池(ASSBs)等体系中的适配性，并提出基于性能、成本与应用场景的综合选型原则。综合分析表明，未来CNTs导电剂的性能突破需依托跨尺度制备技术整合(如催化剂逆向设计与AI工艺调控)、绿色低成本分散工艺开发(如生物基分散剂与干法电极技术适配)以及SWCNTs工程应用瓶颈突破(如多金属协同催化降本)三大路径，推动CNTs从"辅助导电材料"向"多功能核心材料"的战略转型，为下一代高能量密度、高安全性储能系统提供关键材料支撑与理论指导。

关键词: 锂离子电池, 碳纳米管, 导电剂, 储能材料

Abstract:

Carbon nanotubes (CNTs), one-dimensional nanomaterials composed of sp²-hybridized carbon atoms, possess exceptional intrinsic electrical conductivity and mechanical properties. They construct highly efficient three-dimensional conductive networks within lithium-ion battery (LIB) electrodes through a synergistic "line-contact to bridging" mechanism, significantly enhancing energy density, rate capability, and cycling stability. Consequently, CNTs have emerged as a critical material for high-energy-density battery systems. While multi-walled CNTs (MWCNTs) combined with carbon black have been widely adopted in high-end LIBs, the industrialization of single-walled CNTs (SWCNTs) remains challenging due to immature mass-production techniques, intricate dispersion processes, and high overall costs. This review systematically examines recent advances in the industrial application of CNT-based conductive agents. It elaborates on the microscopic mechanisms by which CNTs facilitate long-range electron conduction, stabilize electrode/electrolyte interfaces, and buffer electrode volume strain. The review further analyzes strategies for scalable CNT synthesis via fluidized bed chemical vapor deposition (CVD), alongside the performance optimization achieved through purification, surface functionalization (e.g., carboxylation, N/B doping), and drying processes. The compatibility of CNTs with various electrode systems—including lithium iron phosphate (LFP), high-nickel ternary cathodes, silicon-based anodes, and all-solid-state batteries (ASSBs)—is critically assessed, with practical selection guidelines proposed based on performance, cost, and application scenarios. Comprehensive analysis indicates that future breakthroughs depend on three key pathways: the integration of cross-scale manufacturing technologies (e.g., inverse catalyst design and AI-assisted process control), the development of green and low-cost dispersion methods (e.g., bio-based dispersants and adaptation for dry electrode technology), and overcoming the engineering bottlenecks of SWCNTs (e.g., cost reduction via multi-metal synergistic catalysis). These advancements are expected to propel the strategic evolution of CNTs from auxiliary conductive additives to multifunctional core components, providing crucial material support and theoretical guidance for next-generation high-energy-density and high-safety energy storage systems.

Key words: lithium-ion batteries, carbon nanotubes, conductive agents, energy storage materials

中图分类号:

TM912

李连平, 梁波, 侯明泰, 左昭贵. 锂离子电池用碳纳米管导电剂产业化应用研究进展[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2025.0864.

Lianping LI, Bo LIANG, Mingtai HOU, Zhaogui ZUO. Research progress on the industrial application of carbon nanotube conductive agents for lithium-ion batteries[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2025.0864.

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性能参数	SWCNTs	MWCNTs	导电炭黑(如N990)
直径(nm)	~0.7-3.0	~1.3-100	20-50(一次粒径)
电导率(S/cm)	10⁶~10⁸	~10⁵	~10²
热导率(W/m·K)	~3000-6000	~2000-3000	0.1-0.5
比表面积(m²/g)	400-1300	200-400	50-1500
拉伸强度(GPa)	~120	~10-60	-(非连续相)
添加量(wt%)	0.2-1.0	0.5-1.5	2-5
分散性	极难	良好	优异
导电机制	一维(优异)	一/三维混合(良好)	点接触(一般)

性能参数	三元正极(NCM/NCA)		硅基负极(SiOx/C)		LFP		ASSBs
性能参数	CNTs	传统炭基	CNTs	传统炭基	CNTs	传统炭基	SWCNTs	特殊导电剂
添加量(wt%)	0.5-1.0	2.0-3.0	1.0-1.5	3.0-5.0	0.8-1.2	2.0-3.0	0.2-0.5	1.5-2.5
内阻(Ω)	8-10	12-15	10-12	18-22	5-7	8-10	8-10	15-18
倍率性能(%)	105-108	82-85	105-110	75-78	102-105	85-88	115-120	78-82
循环寿命(次)	1350-1450	800-1000	600-700	300-400	3500-4000	2500-3000	250-350	100-200
能量密度(Wh/kg)	265-275	240-250	450-480	380-400	165-170	155-160	340-360	280-300

企业名称	主要产品	产能(万吨/年)	技术优势	客户群体
天奈科技	MW/SWCNTs浆料	12.5	连续化纯化	CATL、比亚迪、LG化学
OCSiAl	TUBALL^TM系列	0.08	SWCNTs分散	全球高端电池
卡博特	ENTACET^TM系列	8.2	复合导电剂	国际高端客户
LG化学	MWCNTs浆料	4.5	原位生长	自供为主，部分外销
青岛昊鑫	MWCNTs浆料	4.8	低成本制备	比亚迪、国轩高科

正极类型	CNTs类型	添加量(wt%)	关键性能提升
LFP	MWCNTs/CB复合	0.8-1.5	0.5 C容量146.32 mAh/g；循环2165周容量保持率91.78%
NCM	CNT-COOH/CB复合	0.5-1.2	1 C循环200次容量保持率73.8%；10 C容量保持率53.1%
LMO	(8,0)型SWCNTs	0.3-0.8	5 C放电容量保持率提升至82%(抑制Mn溶出)
NMCA	COF/CNTs	1.0-2.0	比容量314 mAh/g；10000次循环容量保持率88%
LRLO	N-S-CNTs	1.0-2.5	提高导电性，改善充放电性能
P_0.02-nrNCM	体相掺杂协同CNTs	-	1 C容量166.07 mAh/g，100次循环容量保持率92.4%

性能指标	Super P	MWCNTs	SWCNTs	核心作用机制
首次放电比容量(mAh/g)	1200-1500	1500-1800	1800-2200	CNTs构建的三维网络增强电子传导
100次循环容量保持率(%)	55-65	60-70	70-80	CNTs的网状结构缓冲体积膨胀
平均库仑效率(%)	97.0-98.0	99.0-99.3	99.5-99.8	CNTs形成SEI膜，减少不可逆锂消耗
电极膨胀率(%)	300-400	150-200	100-150	CNTs有效抑制整体膨胀
界面阻抗(Ω)	80-100	40-50	30-40	CNTs增强界面耦合与离子传输