CN105800600B - The method that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp - Google Patents
The method that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp Download PDFInfo
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Abstract
It the present invention relates to the use of the method that pericarp prepares nitrogen auto-dope three-dimensional grapheme.It is using pericarp as carbon source and nitrogen source, and after hydrothermal carbonization, by the activation process of activator, then pickling is dried and obtained.Present invention selection pericarp prepares nitrogen auto-dope three-dimensional grapheme for raw material, not only meets the needs of sustainable development and environmental protection, also effectively reduces the cost of raw material.Product specific surface area produced by the present invention is up to 1700m2g‑1More than, the ion that larger specific surface area and three-dimensional grapheme loose structure are conducive to electrolyte is transmitted and transported inside it, and has extraordinary electric conductivity.The doping of nitrogen allows it to form catalysis and stores up the avtive spot needed for lithium reaction, energy storage and conversion art is can be widely applied to, such as fuel cell and lithium ion battery etc..In addition, grapheme material has extraordinary electric conductivity in itself, and nitrogen-doping can make carbon material have higher activity.
Description
Technical field
The present invention relates to a kind of method that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp, belongs to grapheme material preparation
Field.
Background technology
Graphene is that a kind of carbon atom forms hexangle type, and the two dimension of only one carbon atom thickness with sp2 hybridized orbits
Material；Compared with other carbon materials, graphene have more preferable electric conductivity, the specific surface area of bigger, the Young's modulus of higher with
And thermal conductivity；The structure and a series of remarkable performances for going uniqueness become one of forward position of current material science research,
Catalysis, electronics, biology and energy storage field are with a wide range of applications；In recent years, it has been found that by two-dimensional graphene lamella into
Row assembling is prepared into a kind of three-dimensional structure material, can effectively prevent the reunion of graphene sheet layer, this three-dimensional structure graphite
Alkene is being kept outside the excellent electricity of original two-dimensional graphene, mechanics and thermal property, more for the distinctive low-density of three-dimensional system, height
The features such as specific surface area and high porosity, three-dimensional structure graphene extend the application space of grapheme material, have broader
Application prospect.
At present, the preparation method of the three-dimensional structure graphene of document report mainly has two kinds of self-assembly method and template.
In self-assembling method, lyogel is obtained with organic reagent or DNA modification graphene oxide first, such as Zhu l are dilute with N- isopropyls
Acid amides modification and crosslinking-oxidization graphene obtain lyogel [Adv.Funct.Mater., 2012,22,4017-4022], and Xu etc. is used
Graphene oxide lyogel [ACS Nano, 2010,4,7358-7362] is obtained after the assembling of DNA modification graphene oxide；Again will system
Standby lyogel be freeze-dried or supercritical drying after obtain three-dimensional graphene oxide.In template, CVD method is common
Method, three-dimensional grapheme can be obtained by three-dimensional template carrying out deposition.Using nickel foam as template, ethanol is such as Cao
Carbon source, three-dimensional grapheme material [Small, 2011,22,3163-3168] is prepared by CVD method.Above-mentioned synthetic method is not only
It is complex process, of high cost, and be mostly transformed by raw mineral materials.Because the limited reserves of fossil resource and preparation
During environmental pollution it is serious, prepare graphene using reproducible agricultural product castoff and protected for sustainable development and environment
Shield is vital.
Biomass material have abundance, without toxicity, without pollution, it is cheap many advantages, such as.Pericarp belongs to
A kind of expendable house refuse, the pericarp largely abandoned add the burden of environment.Pericarp industrialized utilization is both variable
Waste be changed into values, environmental protection, and can be that enterprise brings economic benefit, and tool is of great significance.
At present, there is not yet preparing the relevant report of nitrogen auto-dope three-dimensional grapheme using pericarp.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art and shortcoming, there is provided one kind using pericarp prepares nitrogen auto-dope
The method of three-dimensional grapheme.
To achieve the above object, the technical solution adopted by the present invention is：
The method that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp, is the hydrothermal carbonization using pericarp as carbon source and nitrogen source
Afterwards, dry and obtain, comprise the following steps by the activation process of activator, then pickling：
1) pericarp is cleaned into simultaneously stripping and slicing, adds water, 180~200 DEG C of hydro-thermal 12~24h of insulation reaction, post processing obtains black
Gelatinous carbide；
2) 12~48h of gelatinous carbide vacuum freeze drying in step 1) is obtained into preliminary carbonized product；
3) it is the preliminary carbonized product in step 2) and activator mixing and ball milling is uniform；
4) by after ball milling in step 3) product drying until ethanol volatilize completely, be then warming up under Ar gas shieldeds
600~1000 DEG C of 1~5h of insulation carry out high-temperature activation；
5) step 4) products therefrom is removed into unreacted activator and other impurities through pickling, be washed with water to neutrality, so
Vacuum drying obtains nitrogen auto-dope three-dimensional grapheme afterwards.
By such scheme, the step 1) post processing is：Product after hydro-thermal reaction is rinsed repeatedly with water, is filtered.
By such scheme, in step 2) vacuum freeze drying be under the conditions of -60~0 DEG C, 10~50Pa of absolute pressure into
OK.
By such scheme, the activator in step 3) is KOH, NaOH, K2CO3、Na2CO3、ZnCl2In one or more.
By such scheme, when activator is KOH in step 3), the mass ratio of preliminary carbonized product and KOH is 1:1~1:5,
When activator is NaOH, the mass ratio of preliminary carbonized product and NaOH is 1:1~1:5, activator K2CO3When, preliminary carbonization production
Thing and K2CO3Mass ratio be 1:1~1:7, activator Na2CO3When, preliminary carbonized product and Na2CO3Mass ratio be 1:1
~1:7, activator ZnCl2When, preliminary carbonized product and ZnCl2Mass ratio be 1:1~1:4.
By such scheme, ball milling will treat that ball milling raw material is put into ball grinder in step 3), add ethanol to ball grinder 3/4
Place is put, with 5~8h of speed ball milling of 500rpm on ball mill.
By such scheme, the drying temperature in step 4) is 100~120 DEG C.
By such scheme, the heating rate in step 4) high temperature activation process is 5~10 DEG C of min-1。
By such scheme, the pickling in step 5) is 30~100 DEG C of 5~20h of pickling in acid solution.
By such scheme, acid solution can be in acetum, hydrochloric acid solution, sulfuric acid solution or salpeter solution in step 5)
One kind.
By such scheme, acid solutions are 0.1~0.5molL in step 5)-1。
Research finds, in the pericarp of most fruits all containing substantial amounts of cellulose, hemicellulose, lignin, protein,
The materials such as amino acid.Pericarp is carbonized by preliminary, after freeze-drying, a large amount of cellulosic structures in pericarp is preserved,
Then again under the activation of activator, you can using the cellulose in pericarp as native template, generate graphene；Live in high temperature
Change processing stage, curling generation three-dimensional grapheme can occur for these graphenes.In activation process, activator can be reacted with carbon to be stayed
Lower hole, so as to form porous graphene structure.In addition, the protein and amino acid in pericarp are decomposed at high temperature, can
Nitrogen auto-dope three-dimensional grapheme is generated as nitrogen source.Present invention process is relatively simple, and cost is relatively low, suitable for large-scale production.
Compared with background technology, the present invention has the following advantages：
1) pericarp that the present invention have selected natural reproducible is that raw material prepares nitrogen auto-dope three-dimensional grapheme, and not only meeting can
Sustainable development and the demand of environmental protection, and its abundance, it is cheap, effectively reduce the cost of raw material.
2) protein and amino acid are contained in the pericarp raw material that the present invention selects, these nitrogen sources are decomposed at high temperature makes system
Nitrogen element content is high in the three-dimensional grapheme obtained, and nitrogen is uniformly distributed on three-dimensional grapheme surface, forms avtive spot,
Favorably improve its oxygen reduction catalytic activity.
3) three-dimensional grapheme product of the invention is obtained by simple hydrothermal carbonization and activating process.Hydrothermal carbonization and cold
Lyophilized dry processing, enables a large amount of cellulosic structures in pericarp to preserve.Pericarp is after preliminary carbonization, with pericarp
Cellulose is native template, and graphene is generated under the activation of activator；In the high-temperature process stage, these graphenes can be sent out
Raw curling generation three-dimensional grapheme.In activation process, activator can be reacted with carbon leaves hole, so as to form porous graphene
Structure.In addition, the protein and amino acid in pericarp are decomposed at high temperature, nitrogen source generation nitrogen auto-dope three-dimensional stone can be used as
Black alkene.Present invention process is relatively simple, and cost is relatively low, suitable for large-scale production.
4) three-dimensional grapheme produced by the present invention has loose structure, and aperture is mainly distributed between 2~3nm, belongs to Jie
Hole, and this some holes is evenly distributed on three-dimensional grapheme surface, loose structure is conducive to electrolyte and enters material internal and active sites
Point contact, there is provided the catalytic activity of material.
5) product specific surface area produced by the present invention is up to 1700m2g-1More than, larger specific surface area and three-dimensional grapheme
The ion that structure not only contributes to electrolyte is transmitted and transported inside it, and has extraordinary electric conductivity.Nitrogen
Doping allows it to form catalysis and stores up the avtive spot needed for lithium reaction, can be widely applied to energy storage and conversion art,
Such as fuel cell and lithium ion battery etc..
Brief description of the drawings
Fig. 1 is the SEM figures of 1 gained nitrogen auto-dope three-dimensional grapheme of embodiment.
Fig. 2 is the TEM figures of 1 gained nitrogen auto-dope three-dimensional grapheme of embodiment.
Fig. 3 is the Raman figures of 1 gained nitrogen auto-dope three-dimensional grapheme of embodiment.
Fig. 4 is the nitrogen adsorption desorption isothermal curve figure of 1 gained nitrogen auto-dope three-dimensional grapheme of embodiment.
Fig. 5 is the aperture component curve figure of 1 gained nitrogen auto-dope three-dimensional grapheme of embodiment.
Fig. 6 is the XPS figures of 1 gained nitrogen auto-dope three-dimensional grapheme of embodiment.
Fig. 7 is the EDS mapping figures of 1 gained nitrogen auto-dope three-dimensional grapheme of embodiment.
Fig. 8 is the hydrogen reduction electro-chemical test figure of 1 gained nitrogen auto-dope three-dimensional grapheme of embodiment.
Embodiment
The method for being prepared nitrogen auto-dope three-dimensional grapheme using pericarp to the present invention below by specific embodiment is made into one
Walk explanation.
Embodiment 1
1) banana skin is cleaned into simultaneously stripping and slicing, adds water, 180 DEG C of hydro-thermal insulation reaction 12h.Product is rinsed repeatedly with water, mistake
Filter, obtains black gelatinous carbide；
2) the gelatinous carbide in step 1) is freeze-dried to 24h under the conditions of -60 DEG C, absolute pressure 20Pa to obtain just
Walk carbonized product；
3) by the preliminary carbonized product in step 2) and KOH solids in mass ratio 1：2 mix and are put into ball grinder, add
At ethanol to 3/4 position of ball grinder, with the speed ball milling 5h of 500rpm on ball mill；
4) by 120 DEG C of dryings of product after ball milling in step 3) until ethanol volatilize completely, then pressed under Ar gas shieldeds
According to 5 DEG C of min-1Speed be warming up to 800 DEG C insulation 1h carry out high-temperature activations；
5) by step 4) products therefrom in 0.5mol.L-1In sulfuric acid solution 80 DEG C of pickling 5h remove unreacted activators and
Other impurities, are washed with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
Fig. 1 is scanning electron microscope (SEM) picture of the product, it can be seen that graphene is curled into porous, accordion, is typical case
Three-dimensional grapheme structure.
Fig. 2 is transmission electron microscope (TEM) picture of the product, it can be seen that the lattice fringe of graphene.
Fig. 3 is Raman spectrum (Raman) figure of the product, in 2700cm-1There are the 2D peaks of graphene in place, shows there is graphite
The presence of alkene structure.
Fig. 4 is the nitrogen adsorption desorption isothermal curve of the product, and the ratio table of this product is obtained by nitrogen adsorption desorption isothermal curve
Area (BET) is 1705m2g-1。
Fig. 5 is the aperture component curve figure of the product, and aperture is mainly distributed between 2~3nm as seen from the figure, belongs to Jie
Hole.
Fig. 6 is x-ray photoelectron spectroscopy (XPS) figure of the product, and as can be seen from the figure the product mainly contains C, N, O
Three kinds of elements, wherein N element content are 2.11At.%.
Fig. 7 is that the EDS mapping of the product scheme, and graphite is evenly distributed in from mapping it can be seen from the figure that N elements
Alkene surface.
Fig. 8 is the hydrogen reduction electro-chemical test figure of the product, and reference electrode is saturated calomel electrode, electrolyte 0.1M
KOH solution.The spike potential that rises of the product is -0.03V, carrying current 5.47mA/cm2, business platinum carbon is superior to, is had excellent
Oxygen reduction catalytic activity.
Embodiment 2
1) orange peel is cleaned into simultaneously stripping and slicing, adds water, 180 DEG C of hydro-thermal insulation reaction 18h.Product is rinsed repeatedly with water, mistake
Filter, obtains black gelatinous carbide；
2) the gelatinous carbide in step 1) is freeze-dried 48h under the conditions of 0 DEG C, absolute pressure 10Pa to obtain tentatively
Carbonized product；
3) by the preliminary carbonized product and K in step 2)2CO3Solid in mass ratio 1：1 mixes and is put into ball grinder, adds
Enter at ethanol to 3/4 position of ball grinder, with the speed ball milling 5h of 500rpm on ball mill；
4) by 100 DEG C of dryings of product after ball milling in step 3) until ethanol volatilize completely, then pressed under Ar gas shieldeds
According to 5 DEG C of min-1Speed be warming up to 600 DEG C insulation 1h carry out high-temperature activations；
5) by step 4) products therefrom in 0.1mol.L-1In sulfuric acid solution 80 DEG C of pickling 5h remove unreacted activators and
Other impurities, are washed with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area for testing to obtain this product by nitrogen adsorption desorption is 1712m2g-1。
Must being mainly distributed on 2~4nm to aperture by aperture component curve figure, belong to mesoporous.
It is 2.09At.% to test to obtain N element content in this product by XPS.
Spike potential is -0.03V, carrying current 5.47mA/cm obtaining this product by electro-chemical test figure2。
Embodiment 3
1) banana skin is cleaned into simultaneously stripping and slicing, adds water, 190 DEG C of hydro-thermal insulation reaction 14h.Product is rinsed repeatedly with water, mistake
Filter, obtains black gelatinous carbide；
2) the gelatinous carbide in step 1) is freeze-dried to 12h under the conditions of -50 DEG C, absolute pressure 50Pa to obtain just
Walk carbonized product；
3) by the preliminary carbonized product in step 2) and NaOH solids in mass ratio 1：3 mix and are put into ball grinder, add
Enter at ethanol to 3/4 position of ball grinder, with the speed ball milling 6h of 500rpm on ball mill；
4) by 120 DEG C of dryings of product after ball milling in step 3) until ethanol volatilize completely, then pressed under Ar gas shieldeds
According to 6 DEG C of min-1Speed be warming up to 700 DEG C insulation 2h carry out high-temperature activations；
5) by step 4) products therefrom in 0.2mol.L-130 DEG C of pickling 10h remove unreacted activator in sulfuric acid solution
And other impurities, it is washed with water to neutrality, then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) for testing to obtain this product by nitrogen adsorption desorption is 1693m2g-1。
Must being mainly distributed on 2~5nm to aperture by aperture component curve figure, belong to mesoporous.
It is 1.76At.% to test to obtain N element content in this product by XPS.
Spike potential is -0.02V, carrying current 5.40mA/cm obtaining this product by electro-chemical test figure2。
Embodiment 4
1) granatum is cleaned into simultaneously stripping and slicing, adds water, 200 DEG C of hydro-thermal insulation reaction 24h.Product is rinsed repeatedly with water, mistake
Filter, obtains black gelatinous carbide；
2) the gelatinous carbide in step 1) is freeze-dried to 12h under the conditions of -40 DEG C, absolute pressure 20Pa to obtain just
Walk carbonized product；
3) by the preliminary carbonized product and Na in step 2)2CO3Solid in mass ratio 1：4 mix and are put into ball grinder, add
Enter at ethanol to 3/4 position of ball grinder, with the speed ball milling 7h of 500rpm on ball mill；
4) by 100 DEG C of dryings of product after ball milling in step 3) until ethanol volatilize completely, then pressed under Ar gas shieldeds
According to 7 DEG C of min-1Speed be warming up to 800 DEG C insulation 3h carry out high-temperature activations；
5) by step 4) products therefrom in 0.3mol.L-1100 DEG C of pickling 15h remove unreacted activator in sulfuric acid solution
And other impurities, it is washed with water to neutrality, then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) for testing to obtain this product by nitrogen adsorption desorption is 1703m2g-1。
Must being mainly distributed on 3~4nm to aperture by aperture component curve figure, belong to mesoporous.
It is 1.89At.% to test to obtain N element content in this product by XPS.
Spike potential is -0.025V, carrying current 5.32mA/cm obtaining this product by electro-chemical test figure2。
Embodiment 5
1) sugarcane skin is cleaned into simultaneously stripping and slicing, adds water, 180 DEG C of hydro-thermal insulation reaction 16h.Product is rinsed repeatedly with water, mistake
Filter, obtains black gelatinous carbide；
2) the gelatinous carbide in step 1) is freeze-dried to 48h under the conditions of -40 DEG C, absolute pressure 40Pa to obtain just
Walk carbonized product；
3) by the preliminary carbonized product and ZnCl in step 2)2Solid in mass ratio 1：4 mix and are put into ball grinder, add
Enter at ethanol to 3/4 position of ball grinder, with the speed ball milling 8h of 500rpm on ball mill；
4) by 90 DEG C of dryings of product after ball milling in step 3) until ethanol volatilize completely, then under Ar gas shieldeds according to
8℃min-1Speed be warming up to 900 DEG C insulation 4h carry out high-temperature activations；
5) by step 4) products therefrom in 0.4mol.L-1100 DEG C of pickling 20h remove unreacted activator in sulfuric acid solution
And other impurities, it is washed with water to neutrality, then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) for testing to obtain this product by nitrogen adsorption desorption is 1710m2g-1。
Must being mainly distributed on 2~4nm to aperture by aperture component curve figure, belong to mesoporous.
It is 1.97At.% to test to obtain N element content in this product by XPS.
Spike potential is -0.03V, carrying current 5.50mA/cm obtaining this product by electro-chemical test figure2。
Embodiment 6
1) watermelon peel is cleaned into simultaneously stripping and slicing, adds water, 190 DEG C of hydro-thermal insulation reaction 12h.Product is rinsed repeatedly with water, mistake
Filter, obtains black gelatinous carbide；
2) the gelatinous carbide in step 1) is freeze-dried to 12h under the conditions of -30 DEG C, absolute pressure 30Pa to obtain just
Walk carbonized product；
3) by the preliminary carbonized product in step 2) and KOH solids in mass ratio 1：2 mix and are put into ball grinder, add
At ethanol to 3/4 position of ball grinder, with the speed ball milling 5h of 500rpm on ball mill；
4) by 110 DEG C of dryings of product after ball milling in step 3) until ethanol volatilize completely, then pressed under Ar gas shieldeds
According to 9 DEG C of min-1Speed be warming up to 1000 DEG C insulation 5h carry out high-temperature activations；
5) by step 4) products therefrom in 0.5mol.L-1In sulfuric acid solution 40 DEG C of pickling 5h remove unreacted activators and
Other impurities, are washed with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) for testing to obtain this product by nitrogen adsorption desorption is 1685m2g-1。
Must being mainly distributed on 2~7nm to aperture by aperture component curve figure, belong to mesoporous.
It is 1.93At.% to test to obtain N element content in this product by XPS.
Spike potential is -0.01V, carrying current 5.37mA/cm obtaining this product by electro-chemical test figure2。
Embodiment 7
1) orange peel is cleaned into simultaneously stripping and slicing, adds water, 200 DEG C of hydro-thermal insulation reaction 20h.Product is rinsed repeatedly with water, mistake
Filter, obtains black gelatinous carbide；
2) the gelatinous carbide in step 1) is freeze-dried to 36h under the conditions of -20 DEG C, absolute pressure 10Pa to obtain just
Walk carbonized product；
3) by the preliminary carbonized product in step 2) and NaOH solids in mass ratio 1：2 mix and are put into ball grinder, add
Enter at ethanol to 3/4 position of ball grinder, with the speed ball milling 8h of 500rpm on ball mill；
4) by 120 DEG C of dryings of product after ball milling in step 3) until ethanol volatilize completely, then pressed under Ar gas shieldeds
According to 10 DEG C of min-1Speed be warming up to 1000 DEG C insulation 5h carry out high-temperature activations；
5) by step 4) products therefrom in 0.5mol.L-150 DEG C of pickling 20h remove unreacted activator in sulfuric acid solution
And other impurities, it is washed with water to neutrality, then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) for testing to obtain this product by nitrogen adsorption desorption is 1695m2g-1。
Must being mainly distributed on 2~4nm to aperture by aperture component curve figure, belong to mesoporous.
It is 2.12At.% to test to obtain N element content in this product by XPS.
Spike potential is -0.03V, carrying current 5.67mA/cm obtaining this product by electro-chemical test figure2。
Embodiment 8
1) sugarcane skin is cleaned into simultaneously stripping and slicing, adds water, 180 DEG C of hydro-thermal insulation reaction 22h.Product is rinsed repeatedly with water, mistake
Filter, obtains black gelatinous carbide；
2) the gelatinous carbide in step 1) is freeze-dried to 24h under the conditions of -60 DEG C, absolute pressure 20Pa to obtain just
Walk carbonized product；
3) by the preliminary carbonized product and Na in step 2)2CO3Solid in mass ratio 1：3 mix and are put into ball grinder, add
Enter at ethanol to 3/4 position of ball grinder, with the speed ball milling 5h of 500rpm on ball mill；
4) by 100 DEG C of dryings of product after ball milling in step 3) until ethanol volatilize completely, then pressed under Ar gas shieldeds
According to 5 DEG C of min-1Speed be warming up to 800 DEG C insulation 1h carry out high-temperature activations；
5) by step 4) products therefrom in 0.5mol.L-160 DEG C of pickling 10h remove unreacted activator in sulfuric acid solution
And other impurities, it is washed with water to neutrality, then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) for testing to obtain this product by nitrogen adsorption desorption is 1690m2g-1。
Must being mainly distributed on 2~6nm to aperture by aperture component curve figure, belong to mesoporous.
It is 2.31At.% to test to obtain N element content in this product by XPS.
Spike potential is -0.04V, carrying current 5.14mA/cm obtaining this product by electro-chemical test figure2。
Embodiment 9
1) banana skin is cleaned into simultaneously stripping and slicing, adds water, 200 DEG C of hydro-thermal insulation reaction 12h.Product is rinsed repeatedly with water, mistake
Filter, obtains black gelatinous carbide；
2) the gelatinous carbide in step 1) is freeze-dried 36h under the conditions of 0 DEG C, absolute pressure 20Pa to obtain tentatively
Carbonized product；
3) by the preliminary carbonized product and ZnCl in step 2)2Solid in mass ratio 1：4 mix and are put into ball grinder, add
Enter at ethanol to 3/4 position of ball grinder, with the speed ball milling 5h of 500rpm on ball mill；
4) by 120 DEG C of dryings of product after ball milling in step 3) until ethanol volatilize completely, then pressed under Ar gas shieldeds
According to 5 DEG C of min-1Speed be warming up to 800 DEG C insulation 1h carry out high-temperature activations；
5) by step 4) products therefrom in 0.2mol.L-1In sulfuric acid solution 70 DEG C of pickling 5h remove unreacted activators and
Other impurities, are washed with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) for testing to obtain this product by nitrogen adsorption desorption is 1700m2g-1。
Must being mainly distributed on 2~4nm to aperture by aperture component curve figure, belong to mesoporous.
It is 2.20At.% to test to obtain N element content in this product by XPS.
Spike potential is -0.03V, carrying current 5.07mA/cm obtaining this product by electro-chemical test figure2。
Embodiment 10
1) watermelon peel is cleaned into simultaneously stripping and slicing, adds water, 180 DEG C of hydro-thermal insulation reaction 22h.Product is rinsed repeatedly with water, mistake
Filter, obtains black gelatinous carbide；
2) the gelatinous carbide in step 1) is freeze-dried to 24h under the conditions of -60 DEG C, absolute pressure 10Pa to obtain just
Walk carbonized product；
3) by the preliminary carbonized product and ZnCl in step 2)2Solid in mass ratio 1：3 mix and are put into ball grinder, add
Enter at ethanol to 3/4 position of ball grinder, with the speed ball milling 5h of 500rpm on ball mill；
4) by 110 DEG C of dryings of product after ball milling in step 3) until ethanol volatilize completely, then pressed under Ar gas shieldeds
According to 5 DEG C of min-1Speed be warming up to 600 DEG C insulation 1h carry out high-temperature activations；
5) by step 4) products therefrom in 0.3mol.L-180 DEG C of pickling 15h remove unreacted activator in sulfuric acid solution
And other impurities, it is washed with water to neutrality, then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) for testing to obtain this product by nitrogen adsorption desorption is 1725m2g-1。
Must being mainly distributed on 4~6nm to aperture by aperture component curve figure, belong to mesoporous.
It is 2.06At.% to test to obtain N element content in this product by XPS.
Spike potential is -0.03V, carrying current 5.57mA/cm obtaining this product by electro-chemical test figure2。
Embodiment 11
1) granatum is cleaned into simultaneously stripping and slicing, adds water, 180 DEG C of hydro-thermal insulation reaction 14h.Product is rinsed repeatedly with water, mistake
Filter, obtains black gelatinous carbide；
2) the gelatinous carbide in step 1) is freeze-dried to 24h under the conditions of -20 DEG C, absolute pressure 50Pa to obtain just
Walk carbonized product；
3) by the preliminary carbonized product and ZnCl in step 2)2Solid in mass ratio 1：2 mix and are put into ball grinder, add
Enter at ethanol to 3/4 position of ball grinder, with the speed ball milling 5h of 500rpm on ball mill；
4) by 100 DEG C of dryings of product after ball milling in step 3) until ethanol volatilize completely, then pressed under Ar gas shieldeds
According to 9 DEG C of min-1Speed be warming up to 800 DEG C insulation 1h carry out high-temperature activations；
5) by step 4) products therefrom in 0.1mol.L-1In sulfuric acid solution 90 DEG C of pickling 5h remove unreacted activators and
Other impurities, are washed with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) for testing to obtain this product by nitrogen adsorption desorption is 1680m2g-1。
Must being mainly distributed on 2~4nm to aperture by aperture component curve figure, belong to mesoporous.
It is 2.21At.% to test to obtain N element content in this product by XPS.
Spike potential is -0.03V, carrying current 5.07mA/cm obtaining this product by electro-chemical test figure2。
Claims (9)
1. the method for nitrogen auto-dope three-dimensional grapheme is prepared using pericarp, it is characterised in that：It is to be used as carbon source and nitrogen using pericarp
Source, after hydrothermal carbonization, by the activation process of activator, then pickling is dried and obtained, comprises the following steps：
1）Pericarp is cleaned into simultaneously stripping and slicing, adds water, 180~200 DEG C of hydro-thermal 12~24h of insulation reaction, post processing obtains black gel
Shape carbide；
2）By step 1）In 12~48h of gelatinous carbide vacuum freeze drying obtain preliminary carbonized product；
3）By step 2）In preliminary carbonized product and activator mixing and ball milling it is uniform；Step 3）In activator for KOH,
NaOH、K2CO3、Na2CO3、ZnCl2In one or more；
4）By step 3）Product drying after middle ball milling until ethanol volatilizees completely, be then warming up to 600 under Ar gas shieldeds~
1000 DEG C of 1~5h of insulation carry out high-temperature activation；
5）By step 4）Products therefrom removes unreacted activator and other impurities through pickling, is washed with water to neutrality, Ran Houzhen
Sky drying obtains nitrogen auto-dope three-dimensional grapheme.
2. the method according to claim 1 that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp, it is characterised in that：Step
2）Middle vacuum freeze drying is carried out under the conditions of -60~0 DEG C, 10~50Pa of absolute pressure.
3. the method according to claim 2 that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp, it is characterised in that：Step
3）When middle activator is KOH, the mass ratio of preliminary carbonized product and KOH is 1:1~1:5, when activator is NaOH, preliminary carbonization
The mass ratio of product and NaOH are 1:1~1:5, activator K2CO3When, preliminary carbonized product and K2CO3Mass ratio be 1:1
~1:7, activator Na2CO3When, preliminary carbonized product and Na2CO3Mass ratio be 1:1~1:7, activator ZnCl2When,
Preliminary carbonized product and ZnCl2Mass ratio be 1:1~1:4.
4. the method according to claim 1 that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp, it is characterised in that：Step
3）Middle ball milling will treat that ball milling raw material is put into ball grinder, add at ethanol to 3/4 position of ball grinder, with 500rpm on ball mill
5~8h of speed ball milling.
5. the method according to claim 1 that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp, it is characterised in that：Step
4）In drying temperature be 100~120 DEG C.
6. the method according to claim 1 that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp, it is characterised in that：Step
4）Heating rate in high temperature activation process is 5~10 DEG C of min-1。
7. the method according to claim 1 that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp, it is characterised in that：Step
5）In pickling be in acid solution 30~100 DEG C of 5~20h of pickling.
8. the method according to claim 7 that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp, it is characterised in that：Step
5）Middle acid solution is one kind in acetum, hydrochloric acid solution, sulfuric acid solution or salpeter solution.
9. the method according to claim 1 that nitrogen auto-dope three-dimensional grapheme is prepared using pericarp, it is characterised in that：Step
5）Middle acid solutions are 0.1~0.5mol.L-1。
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