CN105800600A - Method for preparing nitrogen self-doped three-dimensional graphene from peels - Google Patents
Method for preparing nitrogen self-doped three-dimensional graphene from peels Download PDFInfo
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Abstract
The invention relates to a method for preparing nitrogen self-doped three-dimensional graphene from peels. With peels as a carbon source and a nitrogen source, the method comprises the following steps: performing hydrothermal carbonization; performing activation treatment using an activator; and performing acid washing and drying to obtain the nitrogen self-doped three-dimensional graphene. In the invention, since the peels are selected as a raw material for preparing the nitrogen self-doped three-dimensional graphene, the needs for sustainable development and environmental protection can be met, and the raw material cost is effectively reduced. The specific surface area of the prepared product exceeds 1700m<2>g<-1>; the relatively large specific surface area and three-dimensional graphene porous structure are beneficial to the transfer and transport of ions in the electrolyte; and the electrical conductivity is very good. Due to the doping of nitrogen element, active sites for catalysis and lithium storage reactions can be formed, and the nitrogen self-doped three-dimensional graphene can be widely applied to the fields of energy storage and transformation such as fuel cells and lithium ion batteries. Moreover, the graphene material has excellent electrical conductivity, and the carbon material has relatively high activity due to the doping of nitrogen element.
Description
Technical field
The present invention relates to a kind of method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme, belong to grapheme material preparation field.
Background technology
Graphene is that a kind of carbon atom forms hexangle type, and the two-dimensional material of only one of which carbon atom thickness with sp2 hybrid orbital；
Compared with other material with carbon elements, Graphene has more preferable electric conductivity, bigger specific surface area, higher Young's modulus and thermal conductance
Rate；Go one of the structure of uniqueness and the performance forward position becoming current material science research of a series of brilliance, at catalysis, electricity
Son, biology and energy storage field are with a wide range of applications；In recent years, it has been found that carry out two-dimensional graphene lamella assembling system
A kind of three dimensional structure material of standby one-tenth, can effectively stop the reunion of graphene sheet layer, and this three dimensional structure Graphene is keeping former
Have outside two-dimensional graphene excellence electricity, mechanics and thermal property, more for the distinctive low-density of three-dimensional system, high-specific surface area and
The features such as high porosity, three dimensional structure Graphene extends the application space of grapheme material, has broader practice prospect.
At present, the preparation method of the three dimensional structure Graphene of document report mainly has self-assembly method and template two kinds.In self assembly
In method, first obtain lyogel, such as l dilute acyls of N-isopropyl such as Zhu with organic reagent or DNA modification graphene oxide
Amine-modified and crosslinking-oxidization Graphene obtains lyogel [Adv.Funct.Mater., 2012,22,4017-4022], and Xu etc. uses
DNA modification graphene oxide obtains graphene oxide lyogel [ACS Nano, 2010,4,7358-7362] after assembling；Again will system
Standby lyogel obtains three-dimensional graphene oxide after carrying out lyophilization or supercritical drying.In template, CVD is normal
Method, three-dimensional template carries out deposition and can obtain three-dimensional grapheme.If Cao etc. is with nickel foam as template, ethanol
For carbon source, prepare three-dimensional grapheme material [Small, 2011,22,3163-3168] by CVD.Above-mentioned synthetic method is not
Only complex process, cost height, and be mostly transformed by raw mineral materials.Because the limited reserves of fossil resource and system
During Bei, environmental pollution is serious, uses reproducible agricultural product castoff to prepare Graphene and protects for sustainable development and environment
Protect it is critical that.
Biomass material has abundance, does not has the plurality of advantages such as toxicity, not pollution, low price.Peel belongs to a kind of
Expendable house refuse, the peel abandoned in a large number adds the burden of environment.Peel industrialized utilization both can be turned waste into wealth,
Protection environment, can be again that enterprise brings economic benefit, tool to be of great significance.
At present, there is not yet the relevant report utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme.
Summary of the invention
Present invention aims to the deficiencies in the prior art and shortcoming, it is provided that one utilizes peel to prepare nitrogen auto-dope three-dimensional stone
The method of ink alkene.
For achieving the above object, the technical solution used in the present invention is:
The method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme, is using peel as carbon source and nitrogen source, after hydrothermal carbonization, warp
The activation processing of agent of making a living, then pickling is dried and is obtained, and comprises the following steps:
1) being cleaned and stripping and slicing by peel, add water, 180～200 DEG C of hydro-thermal insulation reaction 12～24h, post processing obtains black and coagulates
Gluey carbide；
2) by step 1) in gel carbide vacuum lyophilization 12～48h obtain preliminary carbonized product；
3) by step 2) in preliminary carbonized product uniform with activator mixing and ball milling；
4) by step 3) in product after ball milling be dried until ethanol volatilizees completely, be then warmed up under Ar gas shielded
600～1000 DEG C of insulations 1～5h carry out high-temperature activation；
5) by step 4) products therefrom removes unreacted activator and other impurity through pickling, washes with water to neutrality, then
Vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
By such scheme, step 1) described post processing is: hydro-thermal reaction afterproduct water rinsed repeatedly, filters.
By such scheme, step 2) in vacuum lyophilization be-60～0 DEG C, carry out under the conditions of absolute pressure 10～50Pa.
By such scheme, step 3) in activator be KOH, NaOH, K2CO3、Na2CO3、ZnCl2In one
Or it is several.
By such scheme, step 3) in activator when being KOH, preliminary carbonized product is 1:1～1:5 with the mass ratio of KOH,
When activator is NaOH, preliminary carbonized product is 1:1～1:5 with the mass ratio of NaOH, and activator is K2CO3Time, just
Step carbonized product and K2CO3Mass ratio be 1:1～1:7, activator is Na2CO3Time, preliminary carbonized product and Na2CO3
Mass ratio be 1:1～1:7, activator is ZnCl2Time, preliminary carbonized product and ZnCl2Mass ratio be 1:1～1:4.
By such scheme, step 3) in ball milling will treat that ball milling raw material is put in ball grinder, add ethanol to ball grinder 3/4 position
Place, with the speed ball milling 5～8h of 500rpm on ball mill.
By such scheme, step 4) in baking temperature be 100～120 DEG C.
By such scheme, step 4) in heating rate during high-temperature activation be 5～10 DEG C of min-1。
By such scheme, step 5) in pickling be 30～100 DEG C of pickling 5～20h in acid solution.
By such scheme, step 5) in acid solution can be in acetum, hydrochloric acid solution, sulfuric acid solution or salpeter solution
A kind of.
By such scheme, step 5) in acid solutions be 0.1～0.5molL-1。
Research finds, all contains substantial amounts of cellulose, hemicellulose, lignin, protein, ammonia in the peel of most fruits
The materials such as base acid.Peel is through preliminary carbonization, after lyophilization, makes a large amount of cellulosic structures in peel be preserved, so
After again under the activation of activator, i.e. can with the cellulose in peel as native template, generate Graphene；At high-temperature activation
Processing stage, these Graphenes can occur curling to generate three-dimensional grapheme.In activation process, activator can react with carbon and stay
Hole, thus form porous graphene structure.Additionally, protein and aminoacid in peel are at high temperature decomposed, can make
Nitrogen auto-dope three-dimensional grapheme is generated for nitrogen source.Present invention process is relatively simple, and cost is relatively low, is suitable to large-scale production.
Compared with background technology, the invention have the advantages that
1) present invention have selected the peel of natural reproducible is that nitrogen auto-dope three-dimensional grapheme prepared by raw material, not only meets sustainable
Development and the demand of environmental conservation, and its abundance, cheap, effectively reduce raw-material cost.
2) containing protein and aminoacid in the peel raw material that the present invention selects, these nitrogen sources are at high temperature decomposed to be made to prepare
In three-dimensional grapheme, nitrogen element content is high, and nitrogen element is uniformly distributed on three-dimensional grapheme surface, forms avtive spot, favorably
Improve its oxygen reduction catalytic activity.
3) the three-dimensional grapheme product of the present invention is obtained by simple hydrothermal carbonization and activating process.Hydrothermal carbonization and freezing are done
Dry process, makes a large amount of cellulosic structures in peel be preserved.Peel is after preliminary carbonization, with the fiber in peel
Element is native template, generates Graphene under the activation of activator；In the high-temperature process stage, these Graphenes can be rolled up
Qu Shengcheng three-dimensional grapheme.In activation process, activator can react with carbon and leave hole, thus forms porous graphene structure.
Additionally, protein and aminoacid in peel are at high temperature decomposed, nitrogen auto-dope three-dimensional grapheme can be generated as nitrogen source.
Present invention process is relatively simple, and cost is relatively low, is suitable to large-scale production.
4) three-dimensional grapheme that the present invention prepares has loose structure, and aperture is mainly distributed between 2～3nm, belongs to mesoporous,
And this some holes is uniform in three-dimensional grapheme surface distributed, loose structure is conducive to electrolyte entrance material internal to contact with avtive spot,
Provide the catalysis activity of material.
5) the product specific surface area that the present invention prepares is up to 1700m2g-1Above, bigger specific surface area and three-dimensional grapheme structure
The ion not only contributing to electrolyte transmits therein and transports, and has extraordinary electric conductivity.The doping of nitrogen element makes
Its avtive spot that can be formed needed for catalysis and storage lithium reaction, can be widely applied to energy storage and conversion art, such as fuel electricity
The aspect such as pond and lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the SEM figure of embodiment 1 gained nitrogen auto-dope three-dimensional grapheme.
Fig. 2 is the TEM figure of embodiment 1 gained nitrogen auto-dope three-dimensional grapheme.
Fig. 3 is the Raman figure of embodiment 1 gained nitrogen auto-dope three-dimensional grapheme.
Fig. 4 is the nitrogen adsorption desorption isothermal curve figure of embodiment 1 gained nitrogen auto-dope three-dimensional grapheme.
Fig. 5 is the aperture component curve figure of embodiment 1 gained nitrogen auto-dope three-dimensional grapheme.
Fig. 6 is the XPS figure of embodiment 1 gained nitrogen auto-dope three-dimensional grapheme.
Fig. 7 is the EDS mapping figure of embodiment 1 gained nitrogen auto-dope three-dimensional grapheme.
Fig. 8 is the hydrogen reduction electro-chemical test figure of embodiment 1 gained nitrogen auto-dope three-dimensional grapheme.
Detailed description of the invention
The method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme the present invention below by specific embodiment is described further.
Embodiment 1
1) Pericarpium Musae is cleaned and stripping and slicing, add water, 180 DEG C of hydro-thermal insulation reaction 12h.Products in water is rinsed repeatedly, filters,
Obtain black gel carbide；
2) by step 1) in gel carbide-60 DEG C, lyophilization 24h obtains tentatively under the conditions of absolute pressure 20Pa
Carbonized product；
3) by step 2) in preliminary carbonized product mix with KOH solid 1:2 in mass ratio and put in ball grinder, add
Enter ethanol to ball grinder 3/4 position, with the speed ball milling 5h of 500rpm on ball mill；
4) by step 3) in product 120 DEG C after ball milling be dried until ethanol volatilizees completely, then under Ar gas shielded according to
5℃min-1Ramp to 800 DEG C insulation 1h carry out high-temperature activation；
5) by step 4) products therefrom is at 0.5mol.L-1In sulfuric acid solution 80 DEG C of pickling 5h remove unreacted activators and its
His impurity, washes with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
Fig. 1 is scanning electron microscope (SEM) picture of this 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 this product, it can be seen that the lattice fringe of Graphene.
Fig. 3 is Raman spectrum (Raman) figure of this product, at 2700cm-1There is the 2D peak of Graphene in place, shows there is stone
The existence of ink alkene structure.
Fig. 4 is the nitrogen adsorption desorption isothermal curve of this product, nitrogen adsorption desorption isothermal curve obtain the specific surface area of this product
(BET) it is 1705m2g-1。
Fig. 5 is the aperture component curve figure of this product, and aperture is mainly distributed between 2～3nm as seen from the figure, belongs to mesoporous.
Fig. 6 is x-ray photoelectron power spectrum (XPS) figure of this product, and as can be seen from the figure this product mainly contains C, N, O
Three kinds of elements, wherein N element content is 2.11At.%.
Fig. 7 is the EDS mapping figure of this product, can be seen that N element is evenly distributed in graphite from mapping figure
Alkene surface.
Fig. 8 is the hydrogen reduction electro-chemical test figure of this product, and reference electrode is saturated calomel electrode, and electrolyte is 0.1M KOH
Solution.The spike potential that rises of this product is-0.03V, and carrying current is 5.47mA/cm2, it is superior to business platinum carbon, there is excellence
Oxygen reduction catalytic activity.
Embodiment 2
1) orange peel is cleaned and stripping and slicing, add water, 180 DEG C of hydro-thermal insulation reaction 18h.Products in water is rinsed repeatedly, filters,
Obtain black gel carbide；
2) by step 1) in gel carbide 0 DEG C, lyophilization 48h obtains tentatively under the conditions of absolute pressure 10Pa
Carbonized product；
3) by step 2) in preliminary carbonized product and K2CO3Solid 1:1 in mass ratio mixes and puts in ball grinder, adds
Enter ethanol to ball grinder 3/4 position, with the speed ball milling 5h of 500rpm on ball mill；
4) by step 3) in product 100 DEG C after ball milling be dried until ethanol volatilizees completely, then under Ar gas shielded according to
5℃min-1Ramp to 600 DEG C insulation 1h carry out high-temperature activation；
5) by step 4) products therefrom is at 0.1mol.L-1In sulfuric acid solution 80 DEG C of pickling 5h remove unreacted activators and its
His impurity, washes with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area being obtained this product by the test of nitrogen adsorption desorption is 1712m2g-1。
Must be mainly distributed on 2～4nm to aperture by aperture component curve figure, belong to mesoporous.
Being obtained N element content in this product by XPS test is 2.09At.%.
Being obtained this product by electro-chemical test figure, spike potential is-0.03V, and carrying current is 5.47mA/cm2。
Embodiment 3
1) Pericarpium Musae is cleaned and stripping and slicing, add water, 190 DEG C of hydro-thermal insulation reaction 14h.Products in water is rinsed repeatedly, filters,
Obtain black gel carbide；
2) by step 1) in gel carbide-50 DEG C, lyophilization 12h obtains tentatively under the conditions of absolute pressure 50Pa
Carbonized product；
3) by step 2) in preliminary carbonized product mix with NaOH solid 1:3 in mass ratio and put in ball grinder, add
Enter ethanol to ball grinder 3/4 position, with the speed ball milling 6h of 500rpm on ball mill；
4) by step 3) in product 120 DEG C after ball milling be dried until ethanol volatilizees completely, then under Ar gas shielded according to
6℃min-1Ramp to 700 DEG C insulation 2h carry out high-temperature activation；
5) by step 4) products therefrom is at 0.2mol.L-1In sulfuric acid solution 30 DEG C of pickling 10h remove unreacted activators and
Other impurity, wash with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) being obtained this product by the test of nitrogen adsorption desorption is 1693m2g-1。
Must be mainly distributed on 2～5nm to aperture by aperture component curve figure, belong to mesoporous.
Being obtained N element content in this product by XPS test is 1.76At.%.
Being obtained this product by electro-chemical test figure, spike potential is-0.02V, and carrying current is 5.40mA/cm2。
Embodiment 4
1) Pericarpium Granati is cleaned and stripping and slicing, add water, 200 DEG C of hydro-thermal insulation reaction 24h.Products in water is rinsed repeatedly, filters,
Obtain black gel carbide；
2) by step 1) in gel carbide-40 DEG C, lyophilization 12h obtains tentatively under the conditions of absolute pressure 20Pa
Carbonized product；
3) by step 2) in preliminary carbonized product and Na2CO3Solid 1:4 in mass ratio mixes and puts in ball grinder,
Addition ethanol is to ball grinder 3/4 position, with the speed ball milling 7h of 500rpm on ball mill；
4) by step 3) in product 100 DEG C after ball milling be dried until ethanol volatilizees completely, then under Ar gas shielded according to
7℃min-1Ramp to 800 DEG C insulation 3h carry out high-temperature activation；
5) by step 4) products therefrom is at 0.3mol.L-1In sulfuric acid solution 100 DEG C of pickling 15h remove unreacted activators and
Other impurity, wash with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) being obtained this product by the test of nitrogen adsorption desorption is 1703m2g-1。
Must be mainly distributed on 3～4nm to aperture by aperture component curve figure, belong to mesoporous.
Being obtained N element content in this product by XPS test is 1.89At.%.
Being obtained this product by electro-chemical test figure, spike potential is-0.025V, and carrying current is 5.32mA/cm2。
Embodiment 5
1) Cortex Sacchari sinensis is cleaned and stripping and slicing, add water, 180 DEG C of hydro-thermal insulation reaction 16h.Products in water is rinsed repeatedly, filters,
Obtain black gel carbide；
2) by step 1) in gel carbide-40 DEG C, lyophilization 48h obtains tentatively under the conditions of absolute pressure 40Pa
Carbonized product；
3) by step 2) in preliminary carbonized product and ZnCl2Solid 1:4 in mass ratio mixes and puts in ball grinder, adds
Enter ethanol to ball grinder 3/4 position, with the speed ball milling 8h of 500rpm on ball mill；
4) by step 3) in product 90 DEG C after ball milling be dried until ethanol volatilizees completely, then according to 8 DEG C under Ar gas shielded
min-1Ramp to 900 DEG C insulation 4h carry out high-temperature activation；
5) by step 4) products therefrom is at 0.4mol.L-1In sulfuric acid solution 100 DEG C of pickling 20h remove unreacted activators and
Other impurity, wash with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) being obtained this product by the test of nitrogen adsorption desorption is 1710m2g-1。
Must be mainly distributed on 2～4nm to aperture by aperture component curve figure, belong to mesoporous.
Being obtained N element content in this product by XPS test is 1.97At.%.
Being obtained this product by electro-chemical test figure, spike potential is-0.03V, and carrying current is 5.50mA/cm2。
Embodiment 6
1) Exocarpium Citrulli is cleaned and stripping and slicing, add water, 190 DEG C of hydro-thermal insulation reaction 12h.Products in water is rinsed repeatedly, filters,
Obtain black gel carbide；
2) by step 1) in gel carbide-30 DEG C, lyophilization 12h obtains tentatively under the conditions of absolute pressure 30Pa
Carbonized product；
3) by step 2) in preliminary carbonized product mix with KOH solid 1:2 in mass ratio and put in ball grinder, add
Enter ethanol to ball grinder 3/4 position, with the speed ball milling 5h of 500rpm on ball mill；
4) by step 3) in product 110 DEG C after ball milling be dried until ethanol volatilizees completely, then under Ar gas shielded according to
9℃min-1Ramp to 1000 DEG C insulation 5h carry out high-temperature activation；
5) by step 4) products therefrom is at 0.5mol.L-1In sulfuric acid solution 40 DEG C of pickling 5h remove unreacted activators and its
His impurity, washes with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) being obtained this product by the test of nitrogen adsorption desorption is 1685m2g-1。
Must be mainly distributed on 2～7nm to aperture by aperture component curve figure, belong to mesoporous.
Being obtained N element content in this product by XPS test is 1.93At.%.
Being obtained this product by electro-chemical test figure, spike potential is-0.01V, and carrying current is 5.37mA/cm2。
Embodiment 7
1) orange peel is cleaned and stripping and slicing, add water, 200 DEG C of hydro-thermal insulation reaction 20h.Products in water is rinsed repeatedly, filters,
Obtain black gel carbide；
2) by step 1) in gel carbide-20 DEG C, lyophilization 36h obtains tentatively under the conditions of absolute pressure 10Pa
Carbonized product；
3) by step 2) in preliminary carbonized product mix with NaOH solid 1:2 in mass ratio and put in ball grinder, add
Enter ethanol to ball grinder 3/4 position, with the speed ball milling 8h of 500rpm on ball mill；
4) by step 3) in product 120 DEG C after ball milling be dried until ethanol volatilizees completely, then under Ar gas shielded according to
10℃min-1Ramp to 1000 DEG C insulation 5h carry out high-temperature activation；
5) by step 4) products therefrom is at 0.5mol.L-1In sulfuric acid solution 50 DEG C of pickling 20h remove unreacted activators and
Other impurity, wash with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) being obtained this product by the test of nitrogen adsorption desorption is 1695m2g-1。
Must be mainly distributed on 2～4nm to aperture by aperture component curve figure, belong to mesoporous.
Being obtained N element content in this product by XPS test is 2.12At.%.
Being obtained this product by electro-chemical test figure, spike potential is-0.03V, and carrying current is 5.67mA/cm2。
Embodiment 8
1) Cortex Sacchari sinensis is cleaned and stripping and slicing, add water, 180 DEG C of hydro-thermal insulation reaction 22h.Products in water is rinsed repeatedly, filters,
Obtain black gel carbide；
2) by step 1) in gel carbide-60 DEG C, lyophilization 24h obtains tentatively under the conditions of absolute pressure 20Pa
Carbonized product；
3) by step 2) in preliminary carbonized product and Na2CO3Solid 1:3 in mass ratio mixes and puts in ball grinder,
Addition ethanol is to ball grinder 3/4 position, with the speed ball milling 5h of 500rpm on ball mill；
4) by step 3) in product 100 DEG C after ball milling be dried until ethanol volatilizees completely, then under Ar gas shielded according to
5℃min-1Ramp to 800 DEG C insulation 1h carry out high-temperature activation；
5) by step 4) products therefrom is at 0.5mol.L-1In sulfuric acid solution 60 DEG C of pickling 10h remove unreacted activators and
Other impurity, wash with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) being obtained this product by the test of nitrogen adsorption desorption is 1690m2g-1。
Must be mainly distributed on 2～6nm to aperture by aperture component curve figure, belong to mesoporous.
Being obtained N element content in this product by XPS test is 2.31At.%.
Being obtained this product by electro-chemical test figure, spike potential is-0.04V, and carrying current is 5.14mA/cm2。
Embodiment 9
1) Pericarpium Musae is cleaned and stripping and slicing, add water, 200 DEG C of hydro-thermal insulation reaction 12h.Products in water is rinsed repeatedly, filters,
Obtain black gel carbide；
2) by step 1) in gel carbide 0 DEG C, lyophilization 36h obtains tentatively under the conditions of absolute pressure 20Pa
Carbonized product；
3) by step 2) in preliminary carbonized product and ZnCl2Solid 1:4 in mass ratio mixes and puts in ball grinder, adds
Enter ethanol to ball grinder 3/4 position, with the speed ball milling 5h of 500rpm on ball mill；
4) by step 3) in product 120 DEG C after ball milling be dried until ethanol volatilizees completely, then under Ar gas shielded according to
5℃min-1Ramp to 800 DEG C insulation 1h carry out high-temperature activation；
5) by step 4) products therefrom is at 0.2mol.L-1In sulfuric acid solution 70 DEG C of pickling 5h remove unreacted activators and its
His impurity, washes with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) being obtained this product by the test of nitrogen adsorption desorption is 1700m2g-1。
Must be mainly distributed on 2～4nm to aperture by aperture component curve figure, belong to mesoporous.
Being obtained N element content in this product by XPS test is 2.20At.%.
Being obtained this product by electro-chemical test figure, spike potential is-0.03V, and carrying current is 5.07mA/cm2。
Embodiment 10
1) Exocarpium Citrulli is cleaned and stripping and slicing, add water, 180 DEG C of hydro-thermal insulation reaction 22h.Products in water is rinsed repeatedly, filters,
Obtain black gel carbide；
2) by step 1) in gel carbide-60 DEG C, lyophilization 24h obtains tentatively under the conditions of absolute pressure 10Pa
Carbonized product；
3) by step 2) in preliminary carbonized product and ZnCl2Solid 1:3 in mass ratio mixes and puts in ball grinder, adds
Enter ethanol to ball grinder 3/4 position, with the speed ball milling 5h of 500rpm on ball mill；
4) by step 3) in product 110 DEG C after ball milling be dried until ethanol volatilizees completely, then under Ar gas shielded according to
5℃min-1Ramp to 600 DEG C insulation 1h carry out high-temperature activation；
5) by step 4) products therefrom is at 0.3mol.L-1In sulfuric acid solution 80 DEG C of pickling 15h remove unreacted activators and
Other impurity, wash with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) being obtained this product by the test of nitrogen adsorption desorption is 1725m2g-1。
Must be mainly distributed on 4～6nm to aperture by aperture component curve figure, belong to mesoporous.
Being obtained N element content in this product by XPS test is 2.06At.%.
Being obtained this product by electro-chemical test figure, spike potential is-0.03V, and carrying current is 5.57mA/cm2。
Embodiment 11
1) Pericarpium Granati is cleaned and stripping and slicing, add water, 180 DEG C of hydro-thermal insulation reaction 14h.Products in water is rinsed repeatedly, filters,
Obtain black gel carbide；
2) by step 1) in gel carbide-20 DEG C, lyophilization 24h obtains tentatively under the conditions of absolute pressure 50Pa
Carbonized product；
3) by step 2) in preliminary carbonized product and ZnCl2Solid 1:2 in mass ratio mixes and puts in ball grinder, adds
Enter ethanol to ball grinder 3/4 position, with the speed ball milling 5h of 500rpm on ball mill；
4) by step 3) in product 100 DEG C after ball milling be dried until ethanol volatilizees completely, then under Ar gas shielded according to
9℃min-1Ramp to 800 DEG C insulation 1h carry out high-temperature activation；
5) by step 4) products therefrom is at 0.1mol.L-1In sulfuric acid solution 90 DEG C of pickling 5h remove unreacted activators and its
His impurity, washes with water to neutrality, and then vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The specific surface area (BET) being obtained this product by the test of nitrogen adsorption desorption is 1680m2g-1。
Must be mainly distributed on 2～4nm to aperture by aperture component curve figure, belong to mesoporous.
Being obtained N element content in this product by XPS test is 2.21At.%.
Being obtained this product by electro-chemical test figure, spike potential is-0.03V, and carrying current is 5.07mA/cm2。
Claims (10)
1. utilize the method that peel prepares nitrogen auto-dope three-dimensional grapheme, it is characterised in that: it is using peel as carbon source and nitrogen source,
After hydrothermal carbonization, through the activation processing of activator, then pickling is dried and is obtained, and comprises the following steps:
1) being cleaned and stripping and slicing by peel, add water, 180～200 DEG C of hydro-thermal insulation reaction 12～24h, post processing obtains black and coagulates
Gluey carbide；
2) by step 1) in gel carbide vacuum lyophilization 12～48h obtain preliminary carbonized product；
3) by step 2) in preliminary carbonized product uniform with activator mixing and ball milling；
4) by step 3) in product after ball milling be dried until ethanol volatilizees completely, be then warmed up under Ar gas shielded
600～1000 DEG C of insulations 1～5h carry out high-temperature activation；
5) by step 4) products therefrom removes unreacted activator and other impurity through pickling, washes with water to neutrality, then
Vacuum drying obtains nitrogen auto-dope three-dimensional grapheme.
The method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme the most according to claim 1, it is characterised in that: step
Rapid 2) in vacuum lyophilization be-60～0 DEG C, carry out under the conditions of absolute pressure 10～50Pa.
The method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme the most according to claim 1, it is characterised in that: step
Rapid 3) activator in is KOH, NaOH, K2CO3、Na2CO3、ZnCl2In one or more.
The method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme the most according to claim 3, it is characterised in that: step
Rapid 3), when in, activator is KOH, preliminary carbonized product is 1:1～1:5 with the mass ratio of KOH, when activator is NaOH,
Preliminary carbonized product is 1:1～1:5 with the mass ratio of NaOH, and activator is K2CO3Time, preliminary carbonized product and K2CO3
Mass ratio be 1:1～1:7, activator is Na2CO3Time, preliminary carbonized product and Na2CO3Mass ratio be 1:1～1:7,
Activator is ZnCl2Time, preliminary carbonized product and ZnCl2Mass ratio be 1:1～1:4.
The method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme the most according to claim 1, it is characterised in that: step
Rapid 3) in, ball milling will treat that ball milling raw material is put in ball grinder, add ethanol to ball grinder 3/4 position, on ball mill with
The speed ball milling 5～8h of 500rpm.
The method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme the most according to claim 1, it is characterised in that: step
Rapid 4) baking temperature in is 100～120 DEG C.
The method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme the most according to claim 1, it is characterised in that: step
Rapid 4) in, the heating rate during high-temperature activation is 5～10 DEG C of min-1。
The method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme the most according to claim 1, it is characterised in that: step
Rapid 5) pickling in is 30～100 DEG C of pickling 5～20h in acid solution.
The method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme the most according to claim 8, it is characterised in that: step
Rapid 5) one during acid solution is acetum, hydrochloric acid solution, sulfuric acid solution or salpeter solution in.
The method utilizing peel to prepare nitrogen auto-dope three-dimensional grapheme the most according to claim 1, it is characterised in that: step
Rapid 5) in, acid solutions is 0.1～0.5molL-1。
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