植物基多孔炭材料在超级电容器中的应用

doi:10.3866/PKU.WHXB201903055

Abstract

Abstract:

Supercapacitors have been widely used in various fields because of their high power density, long cycle life, and cost-effectiveness. Plant-based porous carbon continues to be the most suitable alternative for manufacturing the commercial electrode materials of supercapacitors because of its good electrochemical performance, simple preparation process, high availability, and low cost. Although plant-based porous carbon prepared using physical activation has been widely used in commercial supercapacitors, its performance is severely restricted because of its low value of specific surface area and highly microporous structure. With a view to achieving high values of specific gravimetric/volumetric capacitances and outstanding rate performance in supercapacitors, this review summarizes the recently developed methods for preparing plant-based ultrahigh specific surface area porous carbon materials, mesoporous carbon materials, hierarchical porous carbon materials, and nitrogen-doped porous carbon materials. The factors affecting the electrochemical performance of plant-based porous carbon are also discussed. We also summarize some novel strategies to improve the volumetric electrochemical performance of plant-based porous carbon materials, such as preparing dense and porous carbon materials, performing heteroatom doping, and combining the carbon with pseudocapacitive materials (conductive polymers or metal oxides). Finally, the challenges and perspectives of using plant-based porous carbon in supercapacitors are also proposed. In brief, when used as the electrode material for supercapacitors, the ultrahigh surface area porous carbon prepared by KOH activation shows high value of specific capacitance at low current densities. However, the tortuous and deep micropores in the plant-based porous carbon result in its sluggish ion-transport kinetics and high value of equivalent series resistance, which, in turn, result in poor rate performance. To improve the rate performance, tremendous efforts have been made to introduce mesopores in the carbon as ion-transport channels. However, this strategy usually involves the coalescence of a large number of micropores, resulting in the reduced surface area as well as energy storage ability of the carbon. Hence, many researchers have utilized the inherent porous structure and inorganic templates of plants to prepare hierarchical porous carbon both with high specific surface area and high mesopore volume for use in devices with high capacitance and power. In addition to altering the surface area and pore structure of the carbon, doping with nitrogen is another promising approach to enhance the capacitance and electronic conductivity of the plant-based porous carbon. Surface nitrogen can be introduced by the direct carbonization/activation of nitrogen-rich plant precursors or by the reaction of the carbon with nitrogen-containing reagents. Porous carbon with large specific area and with developed mesoporous structure may exhibit superior gravimetric capacitance but inferior volumetric capacitance because of the trade-off between its well-developed microporous structure and packing density. To improve the volume performance, some methods, such as preparing dense and porous carbon with reasonably porous structure, using heteroatom-doped carbon, and incorporating the carbon with pseudocapacitive materials, have been developed. Although the electrochemical performance of plant-based porous carbon has been significantly improved using the aforementioned methods, yet issues such as the lack of green methods and low-cost activation methods to prepare large surface area porous carbon, the design and controlled modulation of carbon micro-structures, the influence of heteroatom doping on pseudocapacitance, and weak interaction between pseudocapacitive components and plant-based porous carbon still need to be resolved. We hope that this review may provide the necessary background and ideas to develop more effective preparation methods for high-performance plant-based porous carbon.

Key words: Supercapacitor, Electrode material, Plant, Porous carbon, Electrochemical performance

Nannan Guo,Su Zhang,Luxiang Wang,Dianzeng Jia. Application of Plant-Based Porous Carbon for Supercapacitors[J].Acta Physico-Chimica Sinica, 2020, 36(2): 1903055.

Figures/Tables 15

Fig 1

Table 1

Fig 2

Table 2

Comparison of electrochemical performance of plants-based porous carbon materials with different porous structure."

Precursor	Specific surface area/ (m²∙g⁻¹)	Pore Volume/ (cm³∙g⁻¹)	Specific capacitance/ (F∙g⁻¹)	Scan rate	Specific capacitance / (F∙g⁻¹)	Scan rate	Unit surface area capacitance /(F∙m⁻²)	Rate performance	Electrolyte	Testing system	Reference
Tremella	3760	2.15	284	1 A∙g⁻¹	214	30 A∙g⁻¹	0.076	0.75	6 mol∙L⁻¹ KOH	Two electrode	94
Celtuce leave	3404	1.88	421	0.5 A∙g⁻¹	293	10 A∙g^-1	0.124	0.70	2 mol∙L^-1 KOH	Three electrode	95
			271	0.5 A∙g⁻¹	156	10 A∙g^-1	0.08	0.58	2 mol∙L^-1 KOH	Two electrode
Corn gluten meal	3353	2.07	488	0.5 A∙g⁻¹	220	20 A∙g⁻¹	0.146	0.45	6 mol∙L⁻¹ KOH	Three electrode	96
			298	0.5 A∙g⁻¹	165	20 A∙g⁻¹	0.089	0.55	6 mol∙L⁻¹ KOH	Two electrode
Liquefied wood	3223	1.686	247	0.5 A∙g⁻¹	227	10 A∙g⁻¹	0.077	0.92	1 mol∙L⁻¹ H₂SO₄	Two electrode	97
Cabbage leaves	3102	1.41	336	1 A∙g⁻¹	271	10 A∙g⁻¹	0.108	0.80	2 mol∙L⁻¹ KOH	Three electrode	98
Hemp stem	3062	1.44	318	0.1 A∙g⁻¹	193	50 A∙g⁻¹	0.104	0.61	6 mol∙L⁻¹ KOH	Three electrode	55
			230	1 A∙g⁻¹	170	50 A∙g⁻¹	0.075	0.74	6 mol∙L⁻¹ KOH	Two electrode
Bamboo	3061	1.46	258	0.1 A∙g⁻¹	93	5 A∙g⁻¹	0.084	0.36	6 mol∙L⁻¹ KOH	Three electrode	99
Glucose	2760	1.3	~240	1 A∙g⁻¹	138	90 A∙g⁻¹	0.087	0.58	1 mol∙L⁻¹ H₂SO₄	Two electrode	54
			3050	2.4	138	0.2 A∙g⁻¹	113	30 A∙g⁻¹	0.041	0.82	EMIM BF₄
Various pollen	3037	2.27	185	1 A∙g⁻¹	–	–	0.061	–	TEABF₄	Two electrode	100
			207	1 A∙g⁻¹	–	–	0.068	–	EMIMBF₄	Two electrode
Eucalyptus sawdust	2950	1.46	268	0.2 A∙g⁻¹	132	100 A∙g⁻¹	0.091	0.49	1 mol∙L⁻¹ H₂SO₄	Two electrode	53
			168	1 A∙g⁻¹	128	60 A∙g⁻¹	0.057	0.76	EMIM TFSI
Garlic skin	2818	1.33	427	0.5 A∙g⁻¹	315	50 A∙g⁻¹	0.152	0.74	6 mol∙L⁻¹ KOH	Two electrode	101
Pomelo peel	2725	1.28	~245	1 A∙g⁻¹	163.2	20 A∙g⁻¹	0.09	0.67	6 mol∙L⁻¹ KOH	Two electrode	57
Corn straw	2790	2.04	~282	1 A∙g⁻¹	205	100 A∙g⁻¹	0.101	0.73	6 mol∙L⁻¹ KOH	Two electrode	16
			~210	1 A∙g⁻¹	68	60 A∙g⁻¹	0.075	0.32	1 mol∙L⁻¹ Na₂SO₄	Two electrode
Spruce bark	2385	1.68	~280	1 A∙g⁻¹	249	10 A∙g⁻¹	0.117	0.89	6 mol∙L⁻¹ KOH	Two electrode	56
Sugarcane bagasse	2341	1.07	320	1 A∙g⁻¹	264	100 A∙g⁻¹	0.137	0.83	6 mol∙L⁻¹ KOH	Two electrode	102
Shaddock skin	2327	1.56	152	1 A∙g⁻¹	132	100 A∙g⁻¹	0.065	0.87	EMIMTFSI	Two electrode	45
shaddock skin	2300	1	180	1 A∙g⁻¹	–	–	0.078	–	0.5 mol∙L⁻¹ H₂SO₄	Three electrode	103
Moringa oleifera stem	2250	2.5	~220	0.2 A∙g⁻¹	195	5 A∙g⁻¹	0.097	0.87	1 mol∙L⁻¹ H₂SO₄	Two electrode	44
Clover	2244	1.44	436	1 A∙g⁻¹	298	50 A∙g⁻¹	0.194	0.68	1 mol∙L⁻¹ H₂SO₄	Three electrode	104
Soybean root	2143	0.94	260	1 A∙g⁻¹	225	20 A∙g⁻¹	0.121	0.87	6 mol∙L⁻¹ KOH	Two electrode	15
Soybean residue	2130	0.92	258	0.2 A∙g⁻¹	159	80 A∙g⁻¹	0.121	0.62	1 mol∙L⁻¹ H₂SO₄	Two electrode	105
Tobacco rod	2115	1.22	~224	1 A∙g⁻¹	~148	15 A∙g⁻¹	0.117	0.66	6 mol∙L⁻¹ KOH	Two electrode	106
Elm samara	1947	1.33	310	1 A∙g⁻¹	198	20 A∙g⁻¹	0.159	0.64	6 mol∙L⁻¹ KOH	Two electrode	9
Apricot shell	1790	0.96	268	0.5 A∙g⁻¹	212	20 A∙g⁻¹	0.15	0.79	1 mol∙L⁻¹ H₂SO4	Two electrode	42
Lignin	1690	0.78	240	1 A∙g⁻¹	209	30 A∙g⁻¹	0.142	0.87	6 mol∙L⁻¹ KOH	Two electrode	107
Cherry calyce	1612	1.2	303	1 A∙g⁻¹	259	20 A∙g⁻¹	0.188	0.85	6 mol∙L⁻¹ KOH	Two electrode	108
Auricularia	1607	1.57	347	1 A∙g⁻¹	278	50 A∙g⁻¹	0.216	0.8	6 mol∙L⁻¹ KOH	Three electrode	109
Cellulose	1535	0.87	198	1 A∙g⁻¹	133	10 A∙g⁻¹	0.129	0.67	6 mol∙L⁻¹ KOH	Three electrode	110
Algae	1338	0.59	143	1 A∙g⁻¹	79	20 A∙g⁻¹	0.107	0.55	6 mol∙L⁻¹ KOH	Two electrode	111
Cellulose	1326	–	296	2 mV∙s⁻¹	221	500mV∙s⁻¹	0.223	0.75	6 mol∙L⁻¹ KOH	Three electrode	112
Banana fiber	1097	–	86	5 mV∙s⁻¹	83	100 mV∙s⁻¹	0.078	0.97	1 mol∙L⁻¹ Na₂SO₄	Two electrode	113
Lotus	1015	0.824	340	0.5 A∙g⁻¹	240	20 A∙g⁻¹	0.335	0.71	2 mol∙L⁻¹ KOH	Three electrode	114
Coffee bean	1019	0.48	368	0.05 A∙g⁻¹	–	–	0.361	–	1 mol∙L⁻¹ H₂SO₄	Three electrode	115
Lignin	903	0.53	247	1 A∙g⁻¹	110	20 A∙g⁻¹	0.274	0.45	7 mol∙L⁻¹ KOH	Two electrode	116
Cork	689	0.75	242	0.1 A∙g⁻¹	199	50 A∙g⁻¹	0.351	0.82	6 mol∙L⁻¹ KOH	Two electrode	17
Comparison of electrochemical performance of other porous carbon materials with different porous structure
Activated graphene	3290	–	174	2.1 A∙g⁻¹	–	–	0.053	–	EMIM TFSI/ EMIM BF₄	Two electrode	117
Hierarchical carbon	2582	–	410	5 A∙g⁻¹	349	100 A∙g⁻¹	0.159	0.85	1 mol∙L⁻¹ H₂SO₄	Three electrode	118
Carbon nanocage	2561	--	205	1 A∙g⁻¹	179	200 A∙g⁻¹	0.008	0.87	6 mol∙L⁻¹ KOH	Two electrode	119
Porous carbon	2000	0.58	202	0.2 A∙g⁻¹	–	–	0.101	–	1 mol∙L⁻¹ H₂SO₄	Two electrode	120
Graphene	1435	4.11	236.8	1 A∙g⁻¹	171	30 A∙g⁻¹	0.217	0.72	6 mol∙L⁻¹ KOH	Two electrode	121
Carbon xerogel microspheres	1133	0.46	251	0.125 A∙g⁻¹	141	4 A∙g⁻¹	0.222	0.56	1 mol∙L⁻¹ H₂SO₄	Three electrode	122
Graphene	890	--	200	0.5 A∙g⁻¹	166	10 A∙g⁻¹	0.224	0.83	2 mol∙L⁻¹ KOH	Two electrode	123
Graphene/Carbon nanotube	652	--	199	0.5 A∙g⁻¹	99	20 A∙g⁻¹	0.305	0.50	EMIM BF₄	Two electrode	124
Graphene	630	0.42	255	0.5 A∙g⁻¹	100	30 A∙g⁻¹	0.403	0.39	6 mol∙L⁻¹ KOH	Three electrode	125
Activated carbon	511	0.25	164	0.1 mA∙cm⁻²	134	20 mA∙cm^-2	0.320	0.82	30% (w) KOH	Two electrode	126

Table 2

Fig 3

Fig 4

Fig 5

Fig 6

Fig 7

Fig 8

Fig 9

Table 3

Table 4

Comparison of electrochemical performance of plant-based porous carbon materials with different pore structures."

Precursor	Specific surface area/(m²∙g⁻¹)	Pore volume/ (cm³∙g⁻¹)	Gravimetric capacitance/(F∙g⁻¹)	Density/ (g∙cm⁻³)	Volumetric capacitance/(F∙cm⁻³)	Scan rate	Electrolyte	Testing system	Reference
Elm samara	1947	1.33	470	0.57	267	1 A∙g⁻¹	6 mol∙L⁻¹ KOH	Two electrode	9
Hemp stem	3062	1.72	318	0.23	73	0.1 A∙g⁻¹	6 mol∙L⁻¹ KOH	Two electrode	55
Pomelo peel	2725	1.28	342	0.5	171	0.2 A∙g⁻¹	6 mol∙L⁻¹ KOH	Three electrode	57
Celtuce leave	3290	1.71	421	0.45	190	0.5 A∙g⁻¹	2 mol∙L⁻¹ KOH	Three electrode	95
Garlic skin	2818	1.32	427	0.38	162	0.5 A∙g⁻¹	6 mol∙L⁻¹ KOH	Two electrode	101
Sodium lignosulfonate	905	0.53	247	0.97	240	0.05 A∙g⁻¹	7 mol∙L⁻¹ KOH	Three electrode	116
Soybean	580	0.41	425	1.1	468	0.5 A∙g⁻¹	6 mol∙L⁻¹ KOH	Three electrode	14
Perilla frutescens	655	0.44	270	1.06	287	0.5 A∙g⁻¹	6 mol∙L⁻¹ KOH	Three electrode	140
Pomelo peel	832	0.57	374	0.93	349	0.1 A∙g⁻¹	6 mol∙L⁻¹ KOH	Three electrode	145
Willow catkin	997	0.51	306	0.99	303	0.1 A∙g⁻¹	6 mol∙L⁻¹ KOH	Three electrode	146
Auricularia	1103	0.54	374	0.96	360	0.5 A∙g⁻¹	6 mol∙L⁻¹ KOH	Three electrode	147
Kelp	1002	0.62	440	0.82	360	0.5 A∙g⁻¹	6 mol∙L⁻¹ KOH	Three electrode	148
Waxberry	658.5	0.38	--	--	1320.4	0.1 A∙g⁻¹	6 mol∙L⁻¹ KOH	Three electrode	149
Jujube	829	0.45	449	1.06	476	1 mV∙s⁻¹	1 mol∙L⁻¹ H₂SO₄	Three electrode	150
Bacterial cellulose	1037	1.04	261	0.65	170	2 mV∙s⁻¹	6 mol∙L⁻¹ KOH	Three electrode	151
Corn straw	1413	0.68	378.9	0.85	321.1	0.05 A∙g⁻¹	6 mol∙L⁻¹ KOH	Three electrode	152
Comparison of electrochemical performance of other porous carbon materials with different pore structures
Activated graphene	3290	–	174	0.59	100	1 A∙g⁻¹	EMIMTFSI	Two electrode	117
Hierarchical carbon	2582	–	207	0.72	149	0.5 A∙g⁻¹	BMIMPF6/AN	Two electrode	118
Carbon nanocage	2561	–	205	0.46	94	1 A∙g⁻¹	KOH	Two electrode	119
Graphene/Carbon nanotube	652	–	199	1.06	211	0.5 A∙g⁻¹	EMIM BF₄	Two electrode	124
Graphene	630	0.42	255	0.77	196	0.5 A∙g⁻¹	6 mol∙L⁻¹ KOH	Three electrode	125
Activated carbon	511	0.25	164	1.04	170	1 mA∙cm⁻²	30% KOH (w)	Two electrode	126
Carbon nanotube	–	–	159	0.83	132	50 mV∙s⁻¹	1 mol∙L⁻¹ H₂SO₄	Three electrode	153
Carbon nanotube	–	–	260	0.5	130	0.1 A∙g⁻¹	EMIM BF₄	Two electrode	154
Porous graphene	–	–	298	0.70	212	1 A∙g⁻¹	EMIM BF₄	Two electrode	155

Table 4

Fig 10

Fig 11

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Precursor	Activator	Reagent	O (mole fraction)	N (mole fraction)	Reference
Hemp stem	KOH	NH₃	17.9%	4.4%	82
Clover	KCl	–	6.9%	2.6%	104
Soybean residue	KOH	–	13.9% (w)	1.6 %(w)	105
Tobacco rod	KOH	–	9.8%	1.3%	106
Wheat gluten	KOH	–	8.5%	1.3%	130
Algae	KOH	–	11.8%	0.9%	132
Soybean dreg	KOH		12.5%	1.9%	133
Mushroom	KOH	–	8.4%	1.7%	134
Flour	KOH	–	11.2%	1.1%	135
Loofa sponge	KOH	–	4.8%	0.7%	136
Pine needle	KOH	–	–	1.5%	137
Potato residue	ZnCl₂	–	–	0.4% (w)	138
Honeysuckles	Pyrolysis	–	14.4%	2%	139
Perilla frutescens	Pyrolysis	–	18.8%	1.7%	140
Sugar bagasse	CaCl₂	Urea	7.0%	5.6%	141
Cotton fabric	Air	Melamine	7.1%	6.9%	142

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Application of Plant-Based Porous Carbon for Supercapacitors

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