化学进展 2022, Vol. 34 Issue (2): 285-300 DOI: 10.7536/PC210116 前一篇   后一篇

• 综述 •


王才威1,2, 杨东杰1,2,*(), 邱学青3,4, 张文礼3,4   

  1. 1 华南理工大学化学与化工学院 广州 510640
    2 广东省绿色精细化学产品工程技术研究开发中心 广州 510640
    3 广东工业大学轻工与化工学院 广州 510006
    4 广东省植物资源生物炼制重点实验室 广州 510006
  • 收稿日期:2021-01-22 修回日期:2021-06-01 出版日期:2022-02-20 发布日期:2021-07-29
  • 通讯作者: 杨东杰
  • 基金资助:
    国家重点研发计划(2018YFB1501503); 国家自然科学基金项目(22038004); 国家自然科学基金项目(21878114); 广东省重点领域研发计划(2020B1111380002); 广东省自然科学基金项目(2017A030308012); 广东省自然科学基金项目(2018B030311052)

Applications of Lignin-Derived Porous Carbons for Electrochemical Energy Storage

Caiwei Wang1,2, Dongjie Yang1,2(), Xueqing Qiu3,4, Wenli Zhang3,4   

  1. 1 School of Chemistry and Chemical Engineering, South China University of Technology,Guangzhou 510640, China
    2 Guangdong Provincial Engineering Research Center for Green Fine Chemicals,Guangzhou 510640, China
    3 School of Chemical Engineering and Light Industry, Guangdong University of Technology,Guangzhou 510006, China
    4 Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, Guangdong University of Technology,Guangzhou 510006, China
  • Received:2021-01-22 Revised:2021-06-01 Online:2022-02-20 Published:2021-07-29
  • Contact: Dongjie Yang
  • Supported by:
    National Key Research and Development Program of China(2018YFB1501503); National Natural Science Foundation of China(22038004); National Natural Science Foundation of China(21878114); Research and Development Program in Key Fields of Guangdong Province(2020B1111380002); Natural Science Foundation of Guangdong Province(2017A030308012); Natural Science Foundation of Guangdong Province(2018B030311052)


Lignin is a renewable resource with the advantages of low cost, high carbon content, high aromaticity and easy collection. Lignin is regarded as one of the most important raw carbonaceous materials for industry to prepare new porous carbon materials in a large scale. It is of great strategic significance to alleviate the consumption of fossil fuel resources and deepen the sustainable development. Porous carbon materials have an extraordinary application prospect in the fields of energy storage materials, because of their high conductivity, high specific surface area, abundant porosity, excellent stability, etc. In this review, the latest research advances and developments for the preparation of lignin-derived porous carbon materials (LPCM) by template, activation and hydrothermal methods are reviewed pivotally. Meanwhile, the influences of pyrolysis parameters on the micro-structure of LPCM are summarized in detail. Furthermore, the applications of LPCM as the electrode materials for lithium-ion batteries, sodium-ion batteries and supercapacitors are illustrated emphatically. However, there exist some bottlenecks that the preparation processes of LPCM are complicated and their energy storage performances are relatively poor. Thus, the optimization of ion/electron diffusion kinetics, the synergistic effect of multiple energy storage mechanisms and the development of the green and facile preparation processes are proposed to conquer these challenges. The development of advanced carbonization techniques to construct the reasonable hierarchical porous structure, precise regulating the suitable interlayer spacing and the highly ordered arrangement of carbon layers, functionally modifying surface microenvironment, and the direct establishment of the relationship between carbonization parameters and electrochemical performance are the research directions to prepare LPCM with the high energy storage performances in the future.


1 Introduction

2 Preparation of lignin-derived porous carbon materials (LPCM)

2.1 Activation methods

2.2 Template methods

2.3 Hydrothermal method

3 Applications of LPCM in energy storage materials

3.1 Lithium-ion batteries

3.2 Sodium-ion batteries

3.3 Supercapacitors

4 Conclusion and outlook

表1 直接炭化和物理活化所制备LPCM结构参数
Table 1 Structural properties of LPCM prepared by direct carbonization and physical activation
表2 化学活化所制备LPCM的结构参数
Table 2 Structural properties of LPCM prepared by chemical activation
图1 硬模板法制备LPCM示意图
Fig. 1 Schematic diagram of LPCM prepared by hard template
图2 片形MgO硬模板制备花状LPCM示意图[37]
Fig. 2 Schematic diagram of flower-like LPCM prepared by hard template using lamellar MgO[37]
图3 软模板法制备LPCM示意图[38]
Fig. 3 Schematic diagram of LPCM prepared by soft template[38]
图4 双模板法制备LPCM示意图[36]
Fig. 4 Schematic diagram of LPCM prepared by dual templates[36]
表3 锂离子电池木质素多孔碳材料负极性能
Table 3 Performances of LPCM anodes in lithium-ion batteries
图5 (a)ZnCO3制备LPCM示意图,(b,c)HLPC-ZnCO3-600透射图,(d)0.2 A/g下HLPC-ZnCO3-600循环性能,(e)HLPC-ZnCO3-600倍率性能[56]
Fig. 5 (a) Schematic diagram of LPCM prepared by ZnCO3, (b, c) TEM images of HLPC-ZnCO3-600, (d) Cycling performance of HLPC-ZnCO3-600 at 0.2 A/g, (e) Rate performance of HLPC-ZnCO3-600[56]
图6 (a)双模板法制备LPCM包覆SiO2示意图,(b,c)LHC/SiO2-21扫描电镜图,(d)LHC/SiO2-21透射电镜图,(e)0.1 A/g下LHC/SiO2-21循环性能,(f)LHC/SiO2-21倍率性能[58]
Fig. 6 (a) Schematic diagram of SiO2@LPCM prepared by dual templates, (b, c) SEM images of LHC/SiO2-21, (d) TEM image of LHC/SiO2-21, (e) Cycling performance of LHC/SiO2-21 at 0.1 A/g, (f) Rate performance of LHC/SiO2-21[58]
表4 钠离子电池木质素硬炭负极性能
Table 4 Performances of lignin-derived hard carbon anodes in sodium-ion batteries
图7 (a)碱木质素及木质素磺酸钠硬炭制备示意图,(b)碱木质素硬炭扫描电镜图,(c)木质素磺酸钠硬炭SEM图,(d)碱木质素硬炭透射电镜图,(e)首次库仑效率,(f)1/10 C下循环性能[68]
Fig. 7 (a) Schematic diagram of hard carbon prepared from alkali lignin and sodium lignosulphonate, (b) SEM image of alkali lignin derived hard carbon, (c) SEM image of sodium lignosulphonate derived hard carbon, (d) TEM image of alkali lignin derived hard carbon, (e) Initial coulombic efficiency, (f) Cycling performances at 1/10 C[68]
图8 (a,b)900 ℃和1300 ℃制得木质素硬炭扫描电镜图及透射电镜图,(c)0.05 A/g下循环性能,(d)倍率性能[69]
Fig.8 (a, b) SEM and TEM images of lignin-derived hard carbon prepared at 900 ℃ and 1300 ℃, (c) Cycling performances at 0.05 A/g, (d) Rate performances[69]
图9 不同热解温度制得硬炭储钠机理的演变[78]
Fig. 9 Evolution of sodium-ion storage mechanisms in hard carbon prepared at different temperature[78]
表5 超级电容器木质素多孔碳材料电极性能
Table 5 Performances of LPCM electrodes in supercapacitors
Raw materials Preparation conditions Specific surface area (m2/g) Total pore
volume (cm3/g)
Capacity (F/g) Scan rate (A/g) Electrolyte ref
Alkali lignin/KOH Carbonization at 600 ℃, 1 h; lignin char:KOH=1:3, activation at 800 ℃, 2 h 2223 1.06 276 1 6 M KOH 84
Alkali lignin/KOH Carbonization at 500 ℃, 1 h; lignin char:KOH=1:4, activation at 800 ℃, 1 h 3775 2.70 287 0.2 6 M KOH 85
Organosolv lignin/
Carbonization at 400 ℃, 1 h; Lignin:KOH=1:3, activation at 700 ℃, 1 h, 10 ℃/min 2265 - 336 1 6 M KOH 86
Enzymatic hydrolysis lignin/KOH Hydrothermal pretreatment at 200 ℃, 24 h; hydrothermally treated lignin:KOH=1:2, activation at 800 ℃, 1 h, 3 ℃/min 2218 - 312 1 6 M KOH 50
Enzymatic hydrolysis lignin/KOH Hydrothermal pretreatment at 180 ℃, 18 h, hydrothermally treated lignin:KOH=1:2, activation at 800 ℃, 1 h, 5 ℃/min 1660 0.78 420 0.1 6 M KOH 87
Sodium lignosulphonate Carbonization at 700 ℃, 1 h, 5 ℃/min 903 0.53 247 0.05 7 M KOH 85
Sodium lignosulphonate Pre-oxidation at 120 ℃, 2 h, 5 ℃/min, 200 ℃, 4 h, 0.5 ℃/min; carbonization at 700 ℃, 1 h, 5 ℃/min 1255 0.87 276 0.1 7 M KOH 89
Alkali lignin Carbonization at 400 ℃, 1 h, 2 ℃/min; 700 ℃, 1 h, 4 ℃/min 1269 0.60 245 0.2 6 M KOH 90
Alkali lignin/F127 Lignin:F127=45:72, Carbonization at 400 ℃, 1 ℃/min; 1000 ℃, 15 min, 2 ℃/min 185 0.28 77.1 - 6 M KOH 88
Alkali lignin/F127/CO2 Lignin:F127=45:72, Carbonization at 400 ℃, 1 ℃/min; 1000 ℃, 15 min, 2 ℃/min, activation at 875 ℃, 4 L/min 624 0.73 102.3 6 M KOH
Alkali lignin/F127/KOH Lignin:F127=45:72, carbonization at 400 ℃, 1 ℃/min; 1000 ℃, 15 min, 2 ℃/min, lignin/F127:KOH=1:2, activation at 1000 ℃, 10 ℃/min 1148 1.00 91.7 6 M KOH
Sodium lignosulphonate/ZnC2O4 Lignin:ZnC2O4=1:2, carbonization at 650 ℃, 2 h, 5 ℃/min 1069 406 320 1 6 M KOH 91
图10 (a)先水热预处理再KOH活化制备LPCM示意图,(b)扫描电镜图,(c)倍率性能,(d)组装成对称超级电容器性能[87]
Fig. 10 (a) Schematic diagram of LPCM prepared by hydrothermal treatment and KOH activation, (b) SEM image, (c) Rate performance, (d) Performance of assembled symmetric supercapacitor[87]
图11 (a)气相剥离和原位ZnO模板法制备LPCM示意图,(b)PLC-650-2扫描电镜图,(c,d)PLC-650-2透射电镜图,(e)倍率性能,(f)组装成对称超级电容器性能[91]
Fig. 11 (a) Schematic diagram of LPCM prepared by gas exfoliation and in-situ ZnO template method, (b) SEM image of PLC-650-2, (c, d ) TEM images of PLC-650-2, (e) Rate performance, (f) Performance of assembled symmetric supercapacitor[91]
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