Research progress on element doped biomass carbon materials for electrochemical energy storage

doi:10.16085/j.issn.1000-6613.2022-1797

Abstract

Abstract:

In order to achieve emissions peak and carbon neutrality, the development of new biomass carbon materials and their application in the field of electrochemical energy storage has been attracted extensive attention. Among various methods, element doping can solve the problems of low specific capacity and poor stability, and provide a simple and effective method and strategy to optimized and improve the electrochemical properties of biomass carbon materials. In this review, the precursors of doped biomass carbon materials were introduced from three aspects: plant-based, animal-based and microbial-based. The elemental doped biomass carbon materials were classified as single-element doped and multi-elements co-doped according to the number of doped elements. The applications of elemental doped biomass carbon materials in electrochemical energy storage devices (supercapacitors,lithium-ion batteries, sodium-ion batteries and lithium-sulfur batteries) were reviewed, and the effects of their chemical composition and microstructure on electrochemical performance were analyzed. Finally, the future development and commercialization prospects of element doped biomass carbon materials were prospected. The regulation of types and contents of doped elements, the optimization of preparation methods and processes and the activation of biomass self-doped properties were future development directions and urgent problems to be solved.

Key words: biomass, carbon material, element doped, electrode material, electrochemistry, electrochemical energy storage

摘要：

在“双碳”目标的背景下，新型生物质炭材料的开发及其在电化学储能领域中的应用引起了人们广泛的关注。在各种优化生物质炭材料性能的方法中，元素掺杂能够解决比容量低、稳定性差的问题，为提高生物质炭材料电化学性能提供了一种简单、有效的方法和策略。本文从植物基、动物基和微生物基三方面介绍了元素掺杂生物质炭材料的来源，并根据掺杂元素的种数将元素掺杂生物质炭材料归纳为单元素掺杂和多元素共掺杂。回顾了元素掺杂生物质炭材料在超级电容器、锂离子电池、钠离子电池、锂硫电池等电化学储能器件中的应用，在此基础上分析了其化学组成和微观结构对电化学性能的影响。同时对其今后的发展和商业化前景做出展望，指出掺杂元素的种类和含量的调控、制备方法和工艺的优化、生物质自掺杂属性的激活仍是目前亟待解决的问题和未来的发展方向。

关键词: 生物质, 炭材料, 元素掺杂, 电极材料, 电化学, 电化学储能

CLC Number:

TQ127.1

WANG Shuaiqing, YANG Siwen, LI Na, SUN Zhanying, AN Haoran. Research progress on element doped biomass carbon materials for electrochemical energy storage[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4296-4306.

王帅晴, 杨思文, 李娜, 孙占英, 安浩然. 元素掺杂生物质炭材料在电化学储能中的研究进展[J]. 化工进展, 2023, 42(8): 4296-4306.

Figures/Tables 4

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种类	原料	掺杂种类和试剂	掺杂元素	杂原子含量	形貌结构	应用	电化学性能	参考文献
植物基	豆浆	自掺杂	N	7.15%（原子分数）	炭纳米片	LIBs	0.05A/g下100次循环后1084.2mAh/g	[19]
植物基	甘蔗渣	外源掺杂（尿素）	N	7.58%（原子分数）	多孔炭	Li-S	0.5C下400次循环后571.5mAh/g	[18]
植物基	花粉	外源掺杂（尿素）	N	4.60%（原子分数）	多孔炭	SCs	1A/g下300F/g（6mol/L KOH）	[36]
植物基	菜籽饼	外源掺杂（三聚氰胺）	N	3.48	多孔炭	SCs	0.05A/g下274F/g（6mol/L KOH）	[37]
植物基	竹子	外源掺杂（硫粉）	S	8.28%（原子分数）	棒状纤维	KIBs	0.2A/g下300次循环后203.8mAh/g	[10]
植物基	药渣	外源掺杂（硫代乙酰胺）	S	6.7%（质量分数）	多孔炭	LIBs	0.1A/g下50次循环后710mAh/g	[20]
植物基	棕榈花	外源掺杂（硫脲）	S	9.86%（质量分数）	片状多孔炭	SCs	1A/g下275F/g（1mol/L H₂SO₄）	[21]
植物基	椴木	外源掺杂（植酸）	P	9.24%（原子分数）	多孔炭	SCs	1mA/cm²下206.5F/g（6mol/L KOH）	[23]
植物基	锯末	外源掺杂（磷酸）	P	—	多孔炭	SCs	0.1A/g下292F/g（1mol/L H₂SO₄）	[24]
植物基	向日葵	自掺杂	O	21%（质量分数）	多孔炭	SCs	1A/g下345F/g（6mol/L KOH）	[26]
植物基	玉米秸秆	自掺杂	O	10.68%（原子分数）	多孔炭片	SCs	1A/g下407F/g（1mol/L H₂SO₄）	[25]
植物基	甘蔗渣	外源掺杂（NH₄H₂PO₄）	N、P	1.87%、1.03% （原子分数）	片状多孔炭	LIBs	0.1A/g下50次循环后816.36mAh/g	[27]
植物基	玉米秸秆	外源掺杂（NH₄H₂PO₄）	N、P	0.90%、1.82% （原子分数）	折叠层状	SIBs	0.25C下100次循环后277mAh/g	[38]
植物基	稻壳	外源掺杂（硫脲）	S、N	5.34%、4.85%（质量分数）	多孔炭	LIBs	1A/g下1200次循环后632mAh/g	[39]
植物基	刀豆壳	外源掺杂（NH₄B₅O₈·4H₂O）	N、B	2.03%、3.12% （质量分数）	多孔炭	SCs	1A/g下369F/g（6mol/L KOH）	[29]
植物基	木材	外源掺杂（硼酸、氨水）	B、N	—	多孔炭	SCs	0.2A/g下318F/g（1mol/L H₂SO₄）	[32]
植物基	小麦粉	外源掺杂（尿素、碘化钾）	N、I	1.30%、0.65% （原子分数）	多孔炭	Li-S	0.1C下100次循环后 916.7mAh/g	[40]
植物基	药渣	外源掺杂（三聚氰胺、硫代乙酰胺）	S、N	8.8%、4.6%（质量分数）	多孔炭	LIBs	0.1A/g下50次循环后1060mAh/g	[41]
植物基	淀粉	外源掺杂（尿素、H₂S）	S、N	2.11%、5.22% （原子分数）	多孔炭	SIBs	8A/g下3000次循环后156mAh/g	[42]
植物基	豆渣	自掺杂	N、O	2.02%、8.04%（原子分数）	多孔炭	Li-S	1C下600次循环后435.7mAh/g	[9]
植物基	榕树根	自掺杂	N、O	15.17%、1.0%（质量分数）	层状多孔炭	Li-S	0.1C下200次循环后1047mAh/g	[43]
动物基	甲壳素	自掺杂	N	7.29%（原子分数）	纳米纤维	SIBs	0.05A/g下50次循环后320.6mAh/g	[4]
动物基	乌贼	自掺杂	N	9.72%（原子分数）	纳米球形	LICs	1A/g下1000次循环后218.4mAh/g	[44]
动物基	猪骨	自掺杂	N、P	3.42%、0.25%（质量分数）	多孔炭	LIBs	0.5A/g下500次循环后640mAh/g	[12]
动物基	鱼皮	自掺杂	N、O、S	14.02%、8.18%、2.25% （原子分数）	炭纳米片	SCs	0.1A/g下438F/g（6mol/L KOH）	[34]
动物基	山羊毛	自掺杂	N、O、P	3.70%、5.69%、3.37% （原子分数）	多孔炭	Li-S	0.2C下300次循环后489mAh/g	[33]
动物基	豆虫	自掺杂	N、O、 P、S	4.36%、12.86%、0.21%、0.23%（原子分数）	多孔炭	SCs	0.1A/g下371.8F/g（6mol/L KOH）	[35]
微生物基	浮萍	自掺杂	N	4.31%（原子分数）	多孔炭	LIBs	0.1A/g下100次循环后1071mAh/g	[13]
微生物基	黑曲霉菌	外源掺杂（NH₃）	N	—	管状多孔炭	SCs	1A/g下298F/g（6mol/L KOH）	[14]
微生物基	细菌纤维素	外源掺杂（N₃P₃Cl₆）	N、P	2.82%、2.76%（原子分数）	多孔炭	SIBs	0.1A/g下150次循环后199mAh/g	[15]
微生物基	海带	自掺杂	S、N	9.12%、4.52%（质量分数）	炭纳米片	SIBs	0.1A/g下300次循环后214mAh/g	[45]

种类	原料	掺杂种类和试剂	掺杂元素	杂原子含量	形貌结构	应用	电化学性能	参考文献
植物基	豆浆	自掺杂	N	7.15%（原子分数）	炭纳米片	LIBs	0.05A/g下100次循环后1084.2mAh/g	[19]
植物基	甘蔗渣	外源掺杂（尿素）	N	7.58%（原子分数）	多孔炭	Li-S	0.5C下400次循环后571.5mAh/g	[18]
植物基	花粉	外源掺杂（尿素）	N	4.60%（原子分数）	多孔炭	SCs	1A/g下300F/g（6mol/L KOH）	[36]
植物基	菜籽饼	外源掺杂（三聚氰胺）	N	3.48	多孔炭	SCs	0.05A/g下274F/g（6mol/L KOH）	[37]
植物基	竹子	外源掺杂（硫粉）	S	8.28%（原子分数）	棒状纤维	KIBs	0.2A/g下300次循环后203.8mAh/g	[10]
植物基	药渣	外源掺杂（硫代乙酰胺）	S	6.7%（质量分数）	多孔炭	LIBs	0.1A/g下50次循环后710mAh/g	[20]
植物基	棕榈花	外源掺杂（硫脲）	S	9.86%（质量分数）	片状多孔炭	SCs	1A/g下275F/g（1mol/L H₂SO₄）	[21]
植物基	椴木	外源掺杂（植酸）	P	9.24%（原子分数）	多孔炭	SCs	1mA/cm²下206.5F/g（6mol/L KOH）	[23]
植物基	锯末	外源掺杂（磷酸）	P	—	多孔炭	SCs	0.1A/g下292F/g（1mol/L H₂SO₄）	[24]
植物基	向日葵	自掺杂	O	21%（质量分数）	多孔炭	SCs	1A/g下345F/g（6mol/L KOH）	[26]
植物基	玉米秸秆	自掺杂	O	10.68%（原子分数）	多孔炭片	SCs	1A/g下407F/g（1mol/L H₂SO₄）	[25]
植物基	甘蔗渣	外源掺杂（NH₄H₂PO₄）	N、P	1.87%、1.03% （原子分数）	片状多孔炭	LIBs	0.1A/g下50次循环后816.36mAh/g	[27]
植物基	玉米秸秆	外源掺杂（NH₄H₂PO₄）	N、P	0.90%、1.82% （原子分数）	折叠层状	SIBs	0.25C下100次循环后277mAh/g	[38]
植物基	稻壳	外源掺杂（硫脲）	S、N	5.34%、4.85%（质量分数）	多孔炭	LIBs	1A/g下1200次循环后632mAh/g	[39]
植物基	刀豆壳	外源掺杂（NH₄B₅O₈·4H₂O）	N、B	2.03%、3.12% （质量分数）	多孔炭	SCs	1A/g下369F/g（6mol/L KOH）	[29]
植物基	木材	外源掺杂（硼酸、氨水）	B、N	—	多孔炭	SCs	0.2A/g下318F/g（1mol/L H₂SO₄）	[32]
植物基	小麦粉	外源掺杂（尿素、碘化钾）	N、I	1.30%、0.65% （原子分数）	多孔炭	Li-S	0.1C下100次循环后 916.7mAh/g	[40]
植物基	药渣	外源掺杂（三聚氰胺、硫代乙酰胺）	S、N	8.8%、4.6%（质量分数）	多孔炭	LIBs	0.1A/g下50次循环后1060mAh/g	[41]
植物基	淀粉	外源掺杂（尿素、H₂S）	S、N	2.11%、5.22% （原子分数）	多孔炭	SIBs	8A/g下3000次循环后156mAh/g	[42]
植物基	豆渣	自掺杂	N、O	2.02%、8.04%（原子分数）	多孔炭	Li-S	1C下600次循环后435.7mAh/g	[9]
植物基	榕树根	自掺杂	N、O	15.17%、1.0%（质量分数）	层状多孔炭	Li-S	0.1C下200次循环后1047mAh/g	[43]
动物基	甲壳素	自掺杂	N	7.29%（原子分数）	纳米纤维	SIBs	0.05A/g下50次循环后320.6mAh/g	[4]
动物基	乌贼	自掺杂	N	9.72%（原子分数）	纳米球形	LICs	1A/g下1000次循环后218.4mAh/g	[44]
动物基	猪骨	自掺杂	N、P	3.42%、0.25%（质量分数）	多孔炭	LIBs	0.5A/g下500次循环后640mAh/g	[12]
动物基	鱼皮	自掺杂	N、O、S	14.02%、8.18%、2.25% （原子分数）	炭纳米片	SCs	0.1A/g下438F/g（6mol/L KOH）	[34]
动物基	山羊毛	自掺杂	N、O、P	3.70%、5.69%、3.37% （原子分数）	多孔炭	Li-S	0.2C下300次循环后489mAh/g	[33]
动物基	豆虫	自掺杂	N、O、 P、S	4.36%、12.86%、0.21%、0.23%（原子分数）	多孔炭	SCs	0.1A/g下371.8F/g（6mol/L KOH）	[35]
微生物基	浮萍	自掺杂	N	4.31%（原子分数）	多孔炭	LIBs	0.1A/g下100次循环后1071mAh/g	[13]
微生物基	黑曲霉菌	外源掺杂（NH₃）	N	—	管状多孔炭	SCs	1A/g下298F/g（6mol/L KOH）	[14]
微生物基	细菌纤维素	外源掺杂（N₃P₃Cl₆）	N、P	2.82%、2.76%（原子分数）	多孔炭	SIBs	0.1A/g下150次循环后199mAh/g	[15]
微生物基	海带	自掺杂	S、N	9.12%、4.52%（质量分数）	炭纳米片	SIBs	0.1A/g下300次循环后214mAh/g	[45]

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