CN107610945B - A kind of preparation method of nitrogen-phosphor codoping charcoal based super capacitor electrode material - Google Patents
A kind of preparation method of nitrogen-phosphor codoping charcoal based super capacitor electrode material Download PDFInfo
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Abstract
A kind of preparation method of nitrogen-phosphor codoping charcoal based super capacitor electrode material, belongs to field of charcoal material.By raw material powder pyrolysis charring, it is put into melamine water-bath dipping, sodium phosphite heat together is adulterated, and mixes heat together after filtering drying with a certain amount of alkali, and gained Carbon Materials distilled water clean dry obtains charcoal based super capacitor electrode material.The material has preferable capacitive property, and in the KOH electrolyte of 6mol/L, when current density is 1A/g, specific capacitance reaches as high as 202.8F/g.The raw materials used in the present invention is biological material, cheap and easy to get, and preparation is simple, and biomass economy value both can be improved, reduced the wasting of resources, and can reduce supercapacitor cost.
Description
Technical field
The present invention relates to the preparations of biological carbon based material, belong to field of charcoal material, are related to a kind of nonmetalloid N, P and are co-doped with
The method of miscellaneous biology carbon based material, it is particularly applicable to have higher capacitance performance using coconut husk, cotton, niblet as raw material preparation
Biological carbon based material.
Background technique
Porous carbon material has flourishing gap structure, huge specific surface area, preferable hydrothermal stability and higher
The features such as conductivity and be widely used as electrode material, elctro-catalyst and catalyst carrier, played very in new energy technology
Important role.The porous carbon material of novel doping nonmetalloid, unique gap are constructed by simple effective method
Structure provides the channel of mass transfer, and conducive to the raising of material property, electrode material, the electrochemistry that can be used as supercapacitor are anti-
Answer catalyst or catalyst carrier.
In recent years, biological carbon based material is concerned as a kind of efficient, green, multi-functional electrode material.People's benefit
Charcoal is prepared with biomass pyrolytic, nonmetalloids, the capacitive effects such as doping N, P are preferable.Biomass is many kinds of, price
Cheap, substantial amounts and widely distributed, and flourishing microcellular structure is advantageously formed, it is the quality material for preparing charcoal.Institute
The advantages that Carbon Materials obtained are in broken shape, and compact structure, ash content is lower, strong adsorption, low in cost, is mainly used in and drinks
The food service industrys such as water, alcoholic, the numerous areas such as the chemical fields such as purification, the decoloration of trade effluent and medicine, catalysis, national defence.
Therefore the present invention proposes a kind of preparation direction of charcoal based super capacitor electrode material, it is desirable to provide to biology
Matter Carbon Materials adulterate the rational method of nonmetalloid, obtain a kind of charcoal base electrode material for having higher capacitance performance, together
When the utilization rate of biomass energy can be improved, and reduce elctro-catalyst cost, biomass raw material used are coconut husk, cotton and jade
Rice seed, doped chemical are nitrogen and phosphorus.Using biomass as the charcoal of raw material pyrolysis preparation except traditional Carbon Materials the advantages of in addition to,
Surface has functional group abundant, and metal and hetero atom can be preferably entrained in Carbon Materials, thus has in electro-catalysis field
There is good application prospect.
Summary of the invention
The object of the present invention is to provide a kind of doping nitrogen P elements charcoal base electrode materials applied to supercapacitor
Preparation method, charcoal base electrode material has higher capacitance performance, while the utilization rate of biomass energy can be improved, and reduce
Elctro-catalyst cost.
To achieve the above object, the method that the present invention uses is as follows:
(1) vacuum drying after crushing biological material obtains biological material powder；
(2) under the protection of nitrogen, by biological material powder pyrolysis charring at 480-580 DEG C obtained by step (1)
0.5-3h, pyrolysis charring 1-2h at preferably 500-520 DEG C；
(3) by KOH, K2CO3With pyrolytic carbon compound 1.8-2.3:0.8-1.2:0.8-1.2 in mass ratio obtained by step (2)
(preferably 2:1:1) mixing, and N element is adulterated, deionized water is added after mixing, is impregnated；Deionized water need to only submerge material
.
(4) step (3) dipping solution is placed in a vacuum drying oven, is dried in vacuo, the dry 12h such as at 80 DEG C；
(5) under nitrogen protection, step (4) desciccate is activated into 2-3h at 700-800 DEG C；
(6) under the protection of nitrogen, P element is adulterated to step (5) product；
(7) it is impregnated for 24 hours after impregnating step (6) products therefrom 24 hours with deionized water with 0.5mol/L hydrochloric acid solution,
Filtering drying after being washed with deionized water to neutrality obtains the biomass active carbon electrode material of doping nonmetalloid.
Preferably, the biomass is coconut husk, niblet (preferably Corn Seed) and cotton (preferably medical high quality cotton).
Preferably, N element doping is doped using melamine, and N element doping is step (1) institute in melamine
Obtain the 0-5% of biological material powder quality.
Preferably, the doping reagent using sodium phosphite as P element, P element are doped by mass percentage, P element
Doping is the 0-5% of biological material powder quality obtained by step (1), and sodium phosphite is placed in porcelain boat upstream, step (5) product
It is placed in downstream, 1.5-3h is reacted at 280-320 DEG C, preferably 300 DEG C reaction 2h take out and grind after being cooled to room temperature.
Further preferably, when biomass is coconut husk, N element doping is 1%, and P element doping is 0；Biomass is jade
When the grain of rice, N element doping is 3%, and P element doping is 3%；When biomass is cotton, N element doping is 1%, P member
Plain doping is 1%.
Advantages of the present invention: the material has preferable capacitive property, in the KOH electrolyte of 6mol/L, current density
When for 1A/g, specific capacitance is not less than 162F/g, even up to 202.8F/g.The raw materials used in the present invention is biological material, inexpensively
It is easy to get, preparation is simple, and biomass economy value both can be improved, reduced the wasting of resources, and can reduce supercapacitor
Cost.
Detailed description of the invention
Fig. 1 is the constant current charge-discharge test image under 1A/g of embodiment of the present invention current density；
1-5 respectively corresponds embodiment 1-5；
Fig. 2 is cyclic voltammetry image under 0.025V/s of embodiment of the present invention rate；
1-5 respectively corresponds embodiment 1-5
Fig. 3 is constant current charge-discharge image under the different current densities of embodiment 1；
Specific implementation method
Technical solution of the present invention is further illustrated below by section Example, but the present invention is not limited to following realities
Apply example.
Embodiment 1
A kind of coconut shell based activated carbon preparation method of the doping N element applied to supercapacitor, belongs to chemical activation method,
It includes the next steps:
(1) vacuum drying after crushing coconut husk obtains coconut shell powder；
(2) under the protection of nitrogen, by step (1) product at 500 DEG C pyrolysis charring 1h, taken out simultaneously after being cooled to room temperature
Grinding；
(3) by KOH, K2CO3It is mixed with step (2) product 2:1:1 in mass ratio, and mixes three by 1% N element doping
Deionized water is added after mixing in poly cyanamid, and water-bath impregnates for 24 hours at 80 DEG C；
(4) dipping solution is placed in a vacuum drying oven, the dry 12h at 80 DEG C；
It (5) under nitrogen protection, will activation after being cooled to room temperature by step (4) product to activate 2.67h at 700 DEG C
Charcoal takes out and grinds；
(6) step (5) product is impregnated with deionized water and is impregnated 24 hours with 0.5mol/L hydrochloric acid solution afterwards for 24 hours, then used
Deionized water is washed till filtering drying after neutrality, obtains doping N element coconut shell based activated carbon.
The material is in 6mol/L KOH electrolyte, when current density is 1A/g, specific capacitance 202.8F/g.
Embodiment 2
A kind of coconut shell based activated carbon preparation method for adulterating N, P element applied to supercapacitor, belongs to chemical activation
Method includes the next steps:
(1) vacuum drying after crushing coconut husk obtains coconut shell powder；
(2) under the protection of nitrogen, by step (1) product at 500 DEG C pyrolysis charring 1h, taken out simultaneously after being cooled to room temperature
Grinding；
(3) by KOH, K2CO3It mixes with step (2) product 2:1:1 in mass ratio, and is adulterated by 5% N element doping
The deionized water of 40ml is added in melamine after mixing, water-bath impregnates for 24 hours at 80 DEG C；
(4) dipping solution is placed in a vacuum drying oven, the dry 12h at 80 DEG C；
(5) under nitrogen protection, in high temperature process furnances by step (4) product to activate 2.67h at 800 DEG C, it is cooling
Activated carbon is taken out and ground after to room temperature.
(6) under the protection of nitrogen, the doping reagent using sodium phosphite as P element 5% adulterates by mass percentage, will
Sodium phosphite is placed in porcelain boat upstream, and step (5) product is placed in downstream, in 300 DEG C of reaction 2h, is cooled to room temperature and takes out and grind
Mill；
(7) step (6) product is impregnated with deionized water and is impregnated for 24 hours with 0.5mol/L hydrochloric acid solution afterwards for 24 hours, deionized water
It is washed till filtering drying after neutrality, obtains codope N, P element coconut shell based activated carbon.
The material is in 6mol/L KOH electrolyte, when current density is 1A/g, specific capacitance 168F/g.
Embodiment 3
A kind of cotton matrix activated carbon preparation method of the doping P element applied to supercapacitor, belongs to chemical activation method,
It includes the next steps:
(1) medical absorbent cotton is shredded, obtains medical absorbent cotton fragment；
(2) under the protection of nitrogen, by step (1) product at 500 DEG C pyrolysis charring 1h, taken out simultaneously after being cooled to room temperature
Grinding；
(3) by KOH, K2CO3The deionized water of 40ml is added after mixing with step (2) product 2:1:1 in mass ratio, 80
Water-bath impregnates for 24 hours at DEG C；
(4) dipping solution is placed in a vacuum drying oven, the dry 12h at 80 DEG C；
(5) under nitrogen protection, step (4) product is activated into 2.67h at 700 DEG C in high temperature process furnances, be cooled to
It takes out and grinds after room temperature；
(6) under the protection of nitrogen, the doping reagent using sodium phosphite as P element 5% adulterates by mass percentage, will
Sodium phosphite is placed in porcelain boat upstream, and step (5) product is placed in downstream, rises to 300 DEG C with 2 DEG C/min heating rate, keeps the temperature 2h, cold
But it takes out and grinds to room temperature；
(7) it is impregnated with deionized water and is impregnated for 24 hours with 0.5mol/L hydrochloric acid solution afterwards for 24 hours, deionized water is washed till mistake after neutrality
Filter drying obtains doping P element cotton matrix activated carbon.
The material is in 6mol/L KOH electrolyte, when current density is 1A/g, specific capacitance 162F/g
Embodiment 4
A kind of cotton matrix activated carbon preparation method for adulterating N, P element applied to supercapacitor, belongs to chemical activation
Method includes the next steps:
(1) medical absorbent cotton is shredded, obtains medical absorbent cotton fragment；
(2) under the protection of nitrogen, by step (1) product at 500 DEG C pyrolysis charring 1h, taken out simultaneously after being cooled to room temperature
Grinding；
(3) by KOH, K2CO3It mixes with pyrolysis charring product 2:1:1 in mass ratio, and is adulterated by 1% N element doping
The deionized water of 40ml is added in melamine after mixing, water-bath impregnates for 24 hours at 80 DEG C；
(4) dipping solution is placed in a vacuum drying oven, the dry 12h at 80 DEG C；
(5) under nitrogen protection, step (4) product is activated into 2.67h at 750 DEG C in high temperature process furnances, be cooled to
Activated carbon is taken out and ground after room temperature.
(6) under the protection of nitrogen, the doping reagent using sodium phosphite as P element 1% adulterates by mass percentage, will
Sodium phosphite is placed in porcelain boat upstream, and step (5) product is placed in downstream, keeps the temperature 2h under 300 °, be cooled to room temperature taking-up and grind；
(7) it is impregnated 24 hours, is gone with 0.5mol/L hydrochloric acid solution after impregnating step (6) product 24 hours with deionized water
Ion is washed to filtering drying after neutrality, obtains codope N, P element cotton matrix activated carbon.
The material is in 6mol/L KOH electrolyte, when current density is 1A/g, specific capacitance 185F/g.
Embodiment 5
The corn seed method for preparation of active carbon of a kind of codope N, P element, belong to chemical activation method, including once walk
It is rapid:
(1) vacuum drying after crushing corn seed obtains corn seed powder；
(2) it under the protection of nitrogen, by step (1) product with the pyrolysis charring 1h at 500 DEG C, is taken out after being cooled to room temperature
And it grinds；
(3) by KOH, K2CO3It mixes with step (2) product 2:1:1 in mass ratio, and is adulterated by 3% N element doping
The deionized water of 40ml is added in melamine after mixing, water-bath impregnates for 24 hours at 80 DEG C；
(4) dipping solution is placed in a vacuum drying oven, the dry 12h at 80 DEG C；
(5) under nitrogen protection, step (4) product is warming up to 800 with the speed of 10 DEG C/min in high temperature process furnances
After DEG C, 2.67h is activated, activated carbon is taken out and ground after being cooled to room temperature.
(6) under the protection of nitrogen, the doping reagent using sodium phosphite as P element 3% adulterates by mass percentage, will
Sodium phosphite is placed in porcelain boat upstream, and step (5) product is placed in downstream, reacts 2h at 300 DEG C, is cooled to room temperature and takes out and grind
Mill；
(7) step (6) product is impregnated with deionized water and is impregnated for 24 hours with 0.5mol/L hydrochloric acid solution afterwards for 24 hours, deionized water
It is washed till filtering drying after neutrality, obtains codope N, P element corn seed active carbon.
The material is in 6mol/L KOH electrolyte, when current density is 1A/g, specific capacitance 194F/g.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although referring to before
Stating embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be to preceding
Technical solution documented by each embodiment is stated to modify or equivalent replacement of some of the technical features；And these
It modifies or replaces, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (1)
1. the corn seed method for preparation of active carbon of a kind of codope N, P element, which is characterized in that belong to chemical activation method, wrap
Include following steps:
(1) vacuum drying after crushing corn seed obtains corn seed powder；
(2) under the protection of nitrogen, by step (1) product to take out and grind after being cooled to room temperature in 500 °C of lower pyrolysis charring 1h
Mill；
(3) by KOH, K2CO3It is mixed with step (2) product 2:1:1 in mass ratio, and adulterates melamine by 3% N element doping
The deionized water of 40ml is added in amine after mixing, impregnate for 24 hours in 80 °C of lower water-baths；
(4) dipping solution is placed in a vacuum drying oven, the dry 12h at 80 DEG C；
(5) under nitrogen protection, step (4) product is warming up to 800 DEG C with the speed of 10 DEG C/min in high temperature process furnances
Afterwards, 2.67h is activated, activated carbon is taken out and ground after being cooled to room temperature；
(6) under the protection of nitrogen, the doping reagent using sodium phosphite as P element 3% adulterates by mass percentage, by phosphorous
Sour sodium is placed in porcelain boat upstream, and step (5) product is placed in downstream, reacts 2h under 300 °C, be cooled to room temperature taking-up and grind；
(7) step (6) product is impregnated with deionized water and is impregnated for 24 hours with 0.5mol/L hydrochloric acid solution afterwards for 24 hours, deionized water is washed till
Filtering drying after neutrality obtains codope N, P element corn seed active carbon；
The material is in 6mol/L KOH electrolyte, when current density is 1A/g, specific capacitance 194F/g.
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| CN109019554B (en) * | 2018-07-31 | 2020-10-27 | 湖南理工学院 | Nitrogen-phosphorus co-doped porous biomass carbon material, preparation method thereof and application thereof in supercapacitor |
| CN111498845B (en) * | 2020-04-14 | 2021-12-21 | 浙江科技学院 | Preparation method and application of nitrogen-sulfur double-doped biochar |
| CN111821949B (en) * | 2020-07-21 | 2021-08-27 | 南京农业大学 | Nitrogen-phosphorus co-doped peanut shell carbon and preparation method and application thereof |
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| CN104445141A (en) * | 2014-11-07 | 2015-03-25 | 同济大学 | Nitrogen-doped modified porous carbon with high specific surface area and preparation method thereof |
| CN105469999A (en) * | 2015-11-20 | 2016-04-06 | 浙江农林大学 | Method of preparing electrode material for carbon-based supercapacitor by taking bamboo powder as raw material |
| CN106000438A (en) * | 2016-06-03 | 2016-10-12 | 兰州交通大学 | Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials |
| CN106115652A (en) * | 2016-04-14 | 2016-11-16 | 湘潭大学 | A kind of B (or P), N codope Folium Perillae porous carbon and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445141A (en) * | 2014-11-07 | 2015-03-25 | 同济大学 | Nitrogen-doped modified porous carbon with high specific surface area and preparation method thereof |
| CN105469999A (en) * | 2015-11-20 | 2016-04-06 | 浙江农林大学 | Method of preparing electrode material for carbon-based supercapacitor by taking bamboo powder as raw material |
| CN106115652A (en) * | 2016-04-14 | 2016-11-16 | 湘潭大学 | A kind of B (or P), N codope Folium Perillae porous carbon and preparation method thereof |
| CN106000438A (en) * | 2016-06-03 | 2016-10-12 | 兰州交通大学 | Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials |
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