CN101837969B - Method for preparing nitrogenous porous carbon material for electrode material of super-capacitor - Google Patents
Method for preparing nitrogenous porous carbon material for electrode material of super-capacitor Download PDFInfo
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Abstract
The invention discloses a method for preparing a nitrogenous porous carbon material for an electrode material of a super-capacitor, which belongs to the field of electrochemistry and new energy materials. The method comprises the following steps of: using amino-glucose hydrochloride or amino-glucose sulfate as a raw material; preparing a nitrogenous porous carbon precursor by using a hydro-thermal method; mixing the precursor with potassium hydroxide; and realizing one-step carbonization and activation under the protection of an inert gas. The prepared nitrogenous porous carbon material has an appropriate specific area, and appropriate nitrogen content, the specific capacitance of the nitrogenous porous carbon material in aqueous electrolyte can be up to 270 F/g, the specific capacity of the nitrogenous porous carbon material in an organic system can be 160 F/g, and the nitrogenous porous carbon material is an ideal electrode material of the super-capacitor.
Description
Technical field
The invention discloses a kind of method for preparing nitrogenous porous carbon material for electrode material of super-capacitor, belong to electrochemistry and new energy materials field.
Background technology
Climate warming, environmental pollution and energy shortage are the significant challenge that current mankind faces, and development is green, reproducible energy storage device is the important topic of pendulum in face of the mankind.Ultracapacitor is as a kind of new green power memory device, have than much bigger energy density of traditional capacitor and the power density more much higher, have extremely wide application prospect in fields such as traffic, mobile communication, information technology, aerospace and science and techniques of defence than battery.For example, aspect the high-performance electromobile, with ultracapacitor and battery, fuel cell parallel connection, normal operating conditions provides energy by battery, when the needs pulse energy, supply with by ultracapacitor, thereby can prolong the work-ing life of battery, the excess energy in the simultaneously all right stocking system is improved the power source integral performance.According to the difference of energy storage mechanism, ultracapacitor can be divided into double layer capacitor and fake capacitance device or redox electrical condenser [2].Double layer capacitor comes stored charge by the electrostatic double layer of electrode and electrolyte interface, and its electrode materials is mainly the raw material of wood-charcoal material of high-specific surface area.Quick reversible redox reaction takes place by electrode active material and comes stored charge in the fake capacitance device, and corresponding electrode materials has transition metal oxide and conductive polymers.The fake capacitance utensil has high ratio capacitance, for example for ruthenium oxide hydrate (RuO
2NH
2O) [O.Barbieri, et al, J.Electrochem.Soc., 2006,153:A2049.], it can reach 920F/g than electric capacity, but the precious metal fancy price has limited its application in commerce.Cheap transition metal oxide, for example MnOx.nH of electrochemical deposition
2O nano material [T.Shinomiya, et al, Electrochim.Acta, 2006,51:4412.], specific storage can reach～400F/g at present.The advantage that conductive polymers has is cheap, specific conductivity is high, but electrode materials cycle life prepared therefrom is low.
For double layer capacitor, its capacitance is proportional to the interface of electrode/electrolyte, therefore the performance of electrode is subjected to the long-pending restriction of charcoal material surface, and not all hole all contrasts electric capacity effect is arranged, have only the accessibility surface of electrolytic solution that the raising of electric capacity is had effect [J.Chmiola, et al, Science, 2006,313:1760.].In general, the contrast table area is 1000m
2The absorbent charcoal material of/g, it can reach 150F/g[C.Vix-Guterl than electric capacity, et al, Carbon, 2005,43:1293].Owing to be subjected to the restriction of specific surface area, the ratio capacitance of raw material of wood-charcoal material is still relatively low but generally speaking.Except the means of further increasing specific surface area, the raw material of wood-charcoal material is carried out out-phase mix, introduce nitrogen or oxygen functional group, the feature that can give acid of raw material of wood-charcoal material or alkali can make its performance that has fake capacitance concurrently, also is one of present researchdevelopment trend.Oxygen functional group introduces in reactivation process, makes the raw material of wood-charcoal material have the tart feature, has promptly introduced electron acceptor(EA) at carbon surface.For example, be 273m at specific surface
2A large amount of Sauerstoffatom that mixes in the raw material of wood-charcoal material of/g can obtain the ratio capacitance [E.Raymundo-of 220F/g
Et al, Adv.Mater., 2006,18:1877].The nitrogen functional group has the feature of alkali, has promptly introduced electron donor(ED).Porous charcoal not only can improve electronic conductivity through nitrogenize, but also can improve it than electric capacity, because charcoal has electric double layer capacitance, the nitrogen functional group can also bring pseudo-capacitance.The method for preparing nitrogenous porous charcoal has: prepare porous charcoal under the atmosphere of nitrogenous elemental gas, as ammonia [J.Phys.Chem.Solids 2004,65:269 for K.Jurewicz, et al]; Perhaps adopt nitrogenous carbon matrix precursor to prepare porous charcoal, as trimeric cyanamide [D.Hulicova, et al, Chem.Mater.2005,17:1241], fine [the F.Beguin et al Adv.Mater.2005 of polypropylene, 17:1241], polyvinyl pyridine [E.Frackowiak, et al.Electrochim.Acta 2006,51:2209; F.Beguin, et al.Adv.Mater.2005,17,2380] etc.
Adopt green nitrogenous carbon matrix precursor one glucosamine salt, through hydro-thermal charing and activation, can obtain having the suitable specific surface area and the porous carbon material of nitrogen-containing functional group, be the ideal electrode material for super capacitor, and this kind preparation method does not see document and patent report as yet.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing nitrogenous porous carbon material for electrode material of super-capacitor.The present invention is a raw material with glucosamine hydrochloride or glucosamine sulphate, by the nitrogenous porous charcoal precursor of Hydrothermal Preparation, then this presoma is mixed with potassium hydroxide, realizes a step charing and an activation under the protection of rare gas element.Prepared nitrogenous porous charcoal has both suitable specific surface area and nitrogen content.Electrochemical property test shows that the nitrogenous porous charcoal of preparation has higher ratio electric capacity, good multiplying power and cyclical stability, is the ideal electrode material as ultracapacitor.
A kind of method for preparing nitrogenous porous carbon material for electrode material of super-capacitor, its processing step is:
Glucosamine hydrochloride or glucosamine sulphate and deionized water are even with 1: 4～1: 10 mixed, be 120～180 ℃ in temperature and handled 3-24 hour in autoclave, obtain nitrogenous porous charcoal presoma; Then this presoma was mixed by mass ratio with potassium hydroxide in 1: 1～1: 8, under inert atmosphere, be 500～1000 ℃ of further charings and activate 1～4 hour in temperature; At last that the product washing that obtains is extremely neutral, obtain nitrogenous porous carbon material.
Advantage or positively effect
The nitrogenous porous charcoal that adopts the preparation of this method has the following advantages as the electrode materials of ultracapacitor: (i) selected raw material economics environmental protection; (ii) this nitrogenous porous charcoal has moderate specific surface area and nitrogen content; (iii) this nitrogenous porous charcoal has high specific conductivity, thereby makes device can have good high rate performance; (iv) preparation technology is simple, and cost is low, is suitable for suitability for industrialized production.
Description of drawings
The typical scan electromicroscopic photograph of the nitrogenous porous charcoal presoma of Fig. 1.
The typical scan electromicroscopic photograph of the nitrogenous porous charcoal I of Fig. 2.
Absorption/analytic curve of the nitrogenous porous charcoal I of Fig. 3.
The nitrogenous porous charcoal I of Fig. 4 cyclic voltammetry curve when sweep velocity is 1mV/s in 1M sulfuric acid.
The nitrogenous porous charcoal I of Fig. 5 is the charging and discharging curve during different electric current in 1M sulfuric acid.
The nitrogenous porous charcoal I of Fig. 6 in 1M sulfuric acid ratio electric capacity and the graph of a relation of current density.
The nitrogenous porous charcoal I of Fig. 7 in 6M potassium hydroxide ratio electric capacity and the graph of a relation of current density.
Embodiment
The present invention will be further described below in conjunction with embodiment, but do not limit protection scope of the present invention:
Embodiment 1: the nitrogenous porous charcoal I of electrode material for super capacitor.
Amino Portugal's glucosamine salt hydrochlorate and deionized water were with 1: 9 uniform mixing, in the autoclave of tetrafluoroethylene, 180 ℃ of hydrothermal treatment consists 12 hours, obtain the nitrogenous porous charcoal presoma of hydro-thermal, Fig. 1 is the typical scan electromicroscopic photograph of hydro-thermal synthetic porous charcoal presoma, the nitrogen content of this presoma is 7.1%, and carbon content is 67.22%, and specific surface area is 18m
2/ g; Then this presoma is mixed by mass ratio with potassium hydroxide at 1: 2, under nitrogen protection,, obtain product and be washed with water to neutrality, obtain nitrogenous porous charcoal I 600 ℃ of insulations 4 hours.Typical scan electromicroscopic photograph such as Fig. 2 of nitrogenous porous charcoal.The nitrogen content of this nitrogenous porous charcoal is 4%, and carbon content is 57%.Absorption/the analytic curve that obtains by the test of nitrogen adsorption/parsing as shown in Figure 3, its specific surface area is 570m
2/ g.This electrode materials in the 1M sulfuric acid electrolyte, with the typical recycling volt-ampere curve of three-electrode method test as shown in Figure 4, the redox current peak that has tangible nitrogen functional group to bring.By test electrode material discharging and recharging (as shown in Figure 5) when the different current density, the ratio electric capacity that calculates nitrogenous porous charcoal with than the relation curve of electric current as shown in Figure 6, the high specific capacitance of this electrode materials can be up to 270F/g.The ratio electric capacity of this electrode materials in 6M potassium hydroxide with than the relation curve of electric current as shown in Figure 7, the high specific capacitance of this electrode materials can be up to 210F/g.The high specific capacitance of this electrode materials in the carbonic allyl ester solution of 1M tetraethyl-Tetrafluoroboric acid ammonia can reach 160F/g.
Embodiment 2: the nitrogenous porous charcoal II of electrode material for super capacitor.
Amino Portugal's glucosamine salt hydrochlorate and deionized water be with 1: 9 uniform mixing, and in the autoclave of tetrafluoroethylene, 180 ℃ of hydrothermal treatment consists 12 hours obtain the nitrogenous porous charcoal presoma of hydro-thermal; Then this presoma is mixed by mass ratio with potassium hydroxide at 1: 8, under nitrogen protection,, obtain product and be washed with water to neutrality, obtain nitrogenous porous charcoal II 600 ℃ of insulations 4 hours.The nitrogen content of this nitrogenous porous charcoal is 1.3%, and carbon content is 18.22%.Its specific surface area is 330m
2/ g.This electrode materials is in the 1M sulfuric acid electrolyte, and high specific capacitance can be up to 86F/g.The ratio electric capacity of this electrode materials in 6M potassium hydroxide can be up to 61F/g.The high specific capacitance of this electrode materials in the carbonic allyl ester solution of 1M tetraethyl-Tetrafluoroboric acid ammonia can reach 58F/g.
Embodiment 3: the nitrogenous porous charcoal III of electrode material for super capacitor.
Amino Portugal's glucosamine salt hydrochlorate and deionized water be with 1: 9 uniform mixing, and in the autoclave of tetrafluoroethylene, 180 ℃ of hydrothermal treatment consists 12 hours obtain the nitrogenous porous charcoal presoma of hydro-thermal; Then this presoma is mixed by mass ratio with potassium hydroxide at 1: 4, under nitrogen protection,, obtain product and be washed with water to neutrality, obtain nitrogenous porous charcoal III 600 ℃ of insulations 4 hours.The nitrogen content of this nitrogenous porous charcoal is 2.8%, and carbon content is 40.8%.Its specific surface area is 600m
2/ g.This electrode materials is in the 1M sulfuric acid electrolyte, and high specific capacitance can be up to 269F/g.The ratio electric capacity of this electrode materials in 6M potassium hydroxide can be up to 175F/g.The high specific capacitance of this electrode materials in the carbonic allyl ester solution of 1M tetraethyl-Tetrafluoroboric acid ammonia can reach 143F/g.
Embodiment 4: the nitrogenous porous charcoal IV of electrode material for super capacitor.
Amino Portugal's glucosamine salt hydrochlorate and deionized water be with 1: 9 uniform mixing, and in the autoclave of tetrafluoroethylene, 180 ℃ of hydrothermal treatment consists 12 hours obtain the nitrogenous porous charcoal presoma of hydro-thermal; Then this presoma is mixed by mass ratio with potassium hydroxide at 1: 2, under nitrogen protection,, obtain product and be washed with water to neutrality, obtain nitrogenous porous charcoal IV 500 ℃ of insulations 4 hours.The nitrogen content of this nitrogenous porous charcoal is 4.2%, and carbon content is 54.55%.Its specific surface area is 560m
2/ g.This electrode materials is in the 1M sulfuric acid electrolyte, and high specific capacitance can be up to 300F/g.The ratio electric capacity of this electrode materials in 6M potassium hydroxide can be up to 231F/g.The high specific capacitance of this electrode materials in the carbonic allyl ester solution of 1M tetraethyl-Tetrafluoroboric acid ammonia can reach 158F/g.
Embodiment 5: the nitrogenous porous charcoal V of electrode material for super capacitor.
Amino Portugal's glucosamine salt hydrochlorate and deionized water be with 1: 9 uniform mixing, and in the autoclave of tetrafluoroethylene, 180 ℃ of hydrothermal treatment consists 12 hours obtain the nitrogenous porous charcoal presoma of hydro-thermal; Then this presoma is mixed by mass ratio with potassium hydroxide at 1: 1, under nitrogen protection,, obtain product and be washed with water to neutrality, obtain nitrogenous porous charcoal V 600 ℃ of insulations 4 hours.The nitrogen content of this nitrogenous porous charcoal is 5.3%, and carbon content is 62.33%.Its specific surface area is 100.5m
2/ g.This electrode materials is in the 1M sulfuric acid electrolyte, and high specific capacitance can be up to 211F/g.The ratio electric capacity of this electrode materials in 6M potassium hydroxide can be up to 270F/g.The high specific capacitance of this electrode materials in the carbonic allyl ester solution of 1M tetraethyl-Tetrafluoroboric acid ammonia can reach 129F/g.
Embodiment 6: the nitrogenous porous charcoal VI of electrode material for super capacitor.
Amino Portugal's glucosamine salt hydrochlorate and deionized water be with 1: 9 uniform mixing, and in the autoclave of tetrafluoroethylene, 180 ℃ of hydrothermal treatment consists 12 hours obtain the nitrogenous porous charcoal presoma of hydro-thermal; Then this presoma is mixed by mass ratio with potassium hydroxide at 1: 4, under nitrogen protection,, obtain product and be washed with water to neutrality, obtain nitrogenous porous charcoal VI 600 ℃ of insulations 2 hours.The nitrogen content of this nitrogenous porous charcoal is 4.4%, and carbon content is 50.2%.Its specific surface area is 579m
2/ g.This electrode materials is in the 1M sulfuric acid electrolyte, and high specific capacitance can be up to 272F/g.The ratio electric capacity of this electrode materials in 6M potassium hydroxide can be up to 212F/g.The high specific capacitance of this electrode materials in the carbonic allyl ester solution of 1M tetraethyl-Tetrafluoroboric acid ammonia can reach 143F/g.
Glucosamine hydrochloride described in above-mentioned 6 embodiment can replace with glucosamine sulphate, and effect is identical with the employing glucosamine hydrochloride.
Claims (1)
1. method for preparing nitrogenous porous carbon material for electrode material of super-capacitor, it is characterized in that: processing step is:
(1) glucosamine hydrochloride and deionized water mix, and carry out hydrothermal treatment consists in autoclave, obtain nitrogenous porous charcoal presoma; Glucosamine hydrochloride and deionized water quality ratio are 1: 4～1: 10, and the hydrothermal treatment consists temperature is 120-180 ℃, and the hydrothermal treatment consists time is 3-24 hour;
(2) nitrogenous porous charcoal presoma and the potassium hydroxide that step (1) is obtained mixes, and carries out a step charing and an activation under inert atmosphere; The scope of nitrogenous porous charcoal presoma and potassium hydroxide blended mass ratio is 1: 1～1: 8, and the carbonization temperature scope is 500～1000 ℃, and carbonization time is 1～4 hour;
(3) product that step (2) is obtained washs to pH=7, obtains nitrogenous porous carbon material.
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| CN103663448B (en) * | 2012-09-19 | 2017-08-01 | 天津普兰纳米科技有限公司 | Preparation method, gained carbon material and its application of carbon material |
| CN105692611B (en) * | 2016-03-21 | 2018-03-23 | 中国科学院理化技术研究所 | A kind of preparation method of the activated carbon from activated sludge rich in nitrogen and oxygen |
| CN106564868B (en) * | 2016-10-09 | 2018-07-20 | 上海应用技术大学 | A kind of preparation method of nitrogen-doped porous carbon material |
| CN106744797A (en) * | 2016-12-08 | 2017-05-31 | 浙江工业大学 | Controllable porous carbon material of a kind of nitrogen content and preparation method thereof |
| CN106865540A (en) * | 2017-03-24 | 2017-06-20 | 桂林电子科技大学 | A kind of N doping loose structure carbon material and its preparation method and application |
| CN108275681A (en) * | 2018-01-16 | 2018-07-13 | 上海理工大学 | A kind of preparation method of cellular porous carbon ball |
| CN109052367B (en) * | 2018-09-30 | 2020-02-14 | 华中科技大学 | Preparation method of pyridine nitrogen-enriched ultrathin carbon nanosheet material and metal composite material thereof |
| CN110182781A (en) * | 2019-05-24 | 2019-08-30 | 宿州学院 | A kind of preparation method of supercapacitor three-dimensional framework charcoal nanometer sheet |
| CN112007680B (en) * | 2020-08-20 | 2021-10-15 | 大连理工大学 | Preparation method of two-dimensional nanosheet structure transition metal-N-C material and application of material in lithium-sulfur battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042481A (en) * | 1988-11-05 | 1990-05-30 | 汪秀英 | Remove the special-purpose activated charcoal of bitter taste and peculiar smell in the wine |
| WO2007044614A2 (en) * | 2005-10-06 | 2007-04-19 | Headwaters Technology Innovation Llc | Carbon nanostructures manufactured from catalytic templating nanoparticles |
| CN101004977A (en) * | 2006-01-18 | 2007-07-25 | 中国科学院化学研究所 | Active carbon electrode material for super capacitor and its preparing method |
| JP2009201405A (en) * | 2008-02-27 | 2009-09-10 | Kochi Univ | Method for producing glucose, and method for producing sulfonated active carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042481A (en) * | 1988-11-05 | 1990-05-30 | 汪秀英 | Remove the special-purpose activated charcoal of bitter taste and peculiar smell in the wine |
| WO2007044614A2 (en) * | 2005-10-06 | 2007-04-19 | Headwaters Technology Innovation Llc | Carbon nanostructures manufactured from catalytic templating nanoparticles |
| CN101004977A (en) * | 2006-01-18 | 2007-07-25 | 中国科学院化学研究所 | Active carbon electrode material for super capacitor and its preparing method |
| JP2009201405A (en) * | 2008-02-27 | 2009-09-10 | Kochi Univ | Method for producing glucose, and method for producing sulfonated active carbon |
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