CN107572498B - A kind of carbide doping porous charcoal and preparation method thereof - Google Patents
A kind of carbide doping porous charcoal and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of carbide doping porous charcoal and preparation method thereof, the carbide doping porous charcoal includes the metal carbides in porous charcoal and the insertion porous charcoal.The carbide that the present invention obtains adulterates porous charcoal, and the hole of porous charcoal focuses mostly in micropore and mesoporous, helps to improve the specific surface area of porous charcoal；And metal carbides are located inside porous charcoal, improve the essential conductivity of porous charcoal, avoid the conductivity that porous charcoal is reduced while increasing specific surface area.Embodiment the result shows that, carbide provided by the invention adulterates porous charcoal, and specific surface area reaches 400~1700m2/ g, and the porous carbon material obtained compared to conventional method, under the conditions of specific surface area is comparable, conductivity, which has, to be obviously improved, and avoids increasing specific surface area to reduce the drawbacks of conductivity is cost.
Description
Technical field
The present invention relates to porous carbon material technical field more particularly to a kind of carbide doping porous charcoal and its preparation sides
Method.
Background technique
Porous carbon material refers to that the carbon materials with different pore structures, pore-size have wider range.Porous charcoal
Material is with hole, high-specific surface area, the Gao Kongrong of possessed prosperity, and the spy that aperture size can be adjusted in a certain range
Point is mostly widely used in the fields such as purification of water quality, gas separation, solvent recovery, decoloration as adsorbent material, it may also be used for urge
Agent carrier and lithium ion battery, supercapacitor electrode material in.
Currently, the preparation method of porous carbon material mainly has activation method and template.
Activation method, which refers to, carries out activation pore-forming to raw material using gas medium or chemical reagent.Normal activated carbon micropore is flourishing,
Specific surface area is high, but haves the shortcomings that mesoporous is few, electric conductivity is low, and mesoporous and macropore, generally take the side of activation in order to obtain
Method needs to burn up a part of charcoal in this way.For example, Chinese patent CN1152546A, which discloses one kind, prepares mesoporous hair by raw material of coal
Anthracite, rich coal and sulfonated coal are mixed, are broken, milling by the method for the active carbon reached, mixed to be pressed into coal tar and pulp liquor
Type, carbonization, activation etc..But the electric conductivity of the porous charcoal obtained by activation method is not much different with common microporous activated carbon, one
As conductivity be lower than 0.1S/cm, and have decreasing trend with the increase conductivity of specific surface area.
Template, which refers to, is filled into carbon precursor in mould material, makes charcoal source charing, removal in the case where template has effect
Then template obtains template carbon (wherein hole is mainly replicated in outer surface or the inner surface of template in charcoal, usually outer surface).
Template has good aperture controllability, and the Carbon Materials of acquisition are with open cellular structure and duct is with similar to template
Structure feature.As CN1330566C discloses a kind of preparation method of the porous charcoal of regular texture and high-specific surface area: with boiling
Stone is template, and carbonization, demoulding after carbonaceous material are added in a template, obtains porous charcoal.Chinese patent CN101585527A is disclosed
The methods of the nano-scale particles as macropore porous charcoal in the preparation of template such as calcium carbonate, can prepare big Mesoporous Carbon Materials.
But the porous charcoal that above-mentioned template is prepared makes moderate progress still without to conductivity, substantially still with the conductivity of active carbon
Quite.
In order to further improve the low status of porous charcoal conductivity that above-mentioned activation method and template are prepared, phase at present
The preparation method, such as N doping etc. that Guan researcher provides doping charcoal make more using nitrogenous high molecular polymer as raw material
Hole charcoal can retain the part nitrogen-atoms in raw material mix during the preparation process.Except the N doping of charcoal, there are also oxygen dopings, phosphorus doping
Or boron doping.In these doping researchs, the elements such as nitrogen, oxygen, phosphorus, boron occupy the position of carbon atom in Carbon Materials, are equally difficult to change
The conductivity of kind gained charcoal, electric conductivity substantially still suitable with active carbon or even Carbon Materials become lower.
The preparation method of above-mentioned porous charcoal is unobvious to the improvement effect of the electric conductivity of porous carbon material.Now, it combines more
The method that high-temperature process improves active carbon conductivity, but high-temperature process will lead to specific surface area reduction, nitrogen, oxygen, phosphorus, boron etc. are mixed
Miscellaneous element removing, while hole overall shrinkage also being caused to become smaller, it is difficult to raising while taking into account specific surface area and conductivity.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of carbide doping porous charcoals and preparation method thereof.The present invention
The carbide of offer adulterates porous charcoal, not only conductivity with higher, specific surface area also with higher.
The present invention provides a kind of carbide to adulterate porous charcoal, including porous charcoal and the metal carbon being embedded in the porous charcoal
Compound；
The pore-size distribution of hole is in the range of 0.5~100nm in the porous charcoal；The hole of the porous charcoal includes hole
Diameter is distributed in that [0.5,2) micropore of nm, pore-size distribution are in [2,50) the macropore of the mesoporous of nm and pore-size distribution in [50,100] nm；
Wherein, Micropore volume >=0.20mL/g, macropore hole appearance≤0.05mL/g, 1.0mL/g >=total pore volume >=0.25mL/g.
It preferably, further include the metal carbides for being supported on the porous carbon surface.
Preferably, the metal carbides include titanium carbide, vanadium carbide, zirconium carbide, niobium carbide, molybdenum carbide, tantalum carbide, carbon
Change one of tungsten and hafnium carbide or a variety of；The quality of the metal carbides is the 1~25% of porous charcoal quality.
The present invention provides a kind of preparation methods of carbide doping porous charcoal, comprising the following steps:
(1) add water in the mixed solution for including organic carbon source, organic metal salt, curing agent and organic solvent, carry out water
Solution, obtains hydrolyzing composition；
(2) surface oxidation is carried out after solidifying the hydrolyzing composition that the step (1) obtains, obtains combined oxidation product；
(3) the combined oxidation product for obtaining the step (2) carries out pressurized treatments, obtains precast body；
The precast body that the step that is carbonized (3) obtains obtains carbide doping porous charcoal；
The carbide doping porous charcoal includes the metal carbides in porous charcoal and the insertion porous charcoal.
The present invention also provides a kind of preparation methods of carbide doping porous charcoal, comprising the following steps:
(a) surface oxidation will be carried out after the mixed solution solidification including organic carbon source, curing agent and organic solvent, obtains carbon
Source oxidation product；
(b) add water into organic metal salt organic solution, be hydrolyzed, obtain hydrolysis gel composite；
Pressurized treatments are carried out after carbon source oxidation product and hydrolysis gel composite that the step (a) obtains are mixed, are obtained
To precast body；
(c) precast body that the step (b) that is carbonized obtains obtains carbide doping porous charcoal；
Carbide doping porous charcoal include porous charcoal and the metal carbides being wrapped in inside the porous charcoal and
It is covered on the metal carbides of the porous carbon surface.
Preferably, the step (1) and the middle temperature hydrolyzed of step (a) independently are 0~70 DEG C, and the time of hydrolysis is independent
Ground is 0.5~12h；
Cured temperature independently is 80~150 DEG C in the step (2) and step (a), and the cured time independently is
0.5~12h；
The temperature aoxidized in the step (2) and step (a) independently is 180~260 DEG C, and the time of oxidation independently is
0.5~3h.
Preferably, the pressure of pressurized treatments independently is 1~50MPa in the step (3) and step (b).
Preferably, the step (4) and the middle carbonization of step (c) independently are: the precast body is warming up to carburizing temperature
0.5~6h is kept the temperature afterwards；The rate of the heating is 1~15 DEG C/min, and the carburizing temperature is 800~1600 DEG C.
Preferably, organic carbon in the mixed solution including organic carbon source, organic metal salt, curing agent and organic solvent
Source, organic metal salt, curing agent and organic solvent mass ratio be 100:(3~40): (5~20): (100~1000)；
Carbon source, the quality of curing agent and solvent in the mixed solution including organic carbon source, curing agent and organic solvent
Than for 100:(5~20): (50~500)；
The mass ratio of organic metal salt and organic solvent is (3~40) in the organic metal salt organic solution: (50~
500)；
Organic carbon source and the organic metal salt in the mixed solution including organic carbon source, curing agent and organic solvent
The mass ratio of organic metal salt is 100:(3~40 in organic solution).
Preferably, the organic carbon source includes phenolic resin, epoxy resin, polyvinylidene fluoride resin, furfural resin, poly- third
One of olefin(e) acid resin and polyurethane resin are a variety of；
The organic metal salt includes metal alkyl salt, metal alkoxides salt, alcohol radical metal salt, phenide salt and phenol
One of Base Metal salt is a variety of, and the metal is one of titanium, vanadium, zirconium, niobium, molybdenum, tantalum, tungsten and hafnium or a variety of；
The curing agent include one of hexamethylenetetramine, p-methyl benzenesulfonic acid, formaldehyde, benzene sulfonyl chloride and polyformaldehyde or
It is a variety of；
The organic solvent includes one of alcohol organic solvent, benzene class organic solvent and organic solvent of ketone or more
Kind.
The present invention provides a kind of carbide to adulterate porous charcoal, including porous charcoal and the metal carbon being embedded in the porous charcoal
Compound；Wherein, in the porous charcoal pore-size distribution of hole in the range of 0.5~100nm；The hole of the porous charcoal includes
Pore-size distribution is [0.5,2) micropore of nm, pore-size distribution are [2,50) mesoporous of nm and pore-size distribution are in the big of [50,100] nm
Hole；Wherein, Micropore volume >=0.20mL/g, macropore hole appearance≤0.05mL/g, 1.0mL/g >=total pore volume >=0.25mL/g.This hair
Bright obtained carbide doping porous charcoal, the hole of porous charcoal focus mostly in micropore and mesoporous, help to improve the ratio of porous charcoal
Surface area and carbide is located inside porous charcoal particle, improves the essential conductivity of porous charcoal, avoids the collection of micropore and mesoporous
The conductivity of porous charcoal is reduced while middle distribution increasing specific surface area.
The present invention also provides carbide doping porous charcoal preparation method, comprising the following steps: include organic carbon source,
Add water in the mixed solution of organic metal salt, curing agent and organic solvent, is hydrolyzed, obtains hydrolyzing composition；Will be described
To hydrolyzing composition solidification after aoxidized, carry out pressurized treatments after obtaining combined oxidation product, obtain precast body；It is carbonized again
The obtained precast body obtains carbide doping porous charcoal.
The present invention obtains the cross-linking products of carbon source and curing agent through a degree of crosslinking condensation occurs in hydrolytic process,
During subsequent cure, complete condensation is gradually completed, obtains high molecular weight solid cross-linking products；Organic metal salt is obtained through hydrolysis
Hydrolysate and the mixing of high molecular weight solid cross-linking products solidifying substance through oxidation process, high molecular weight solid cross-linking products
Oxidation reaction occurs for surface, and the cementitiousness of high molecular weight solid cross-linking products is effectively reduced, and then helps to improve final obtain
The specific surface area of the porous charcoal arrived；Partial particulate deformation can be made using pressurized treatments mode again, be crushed, with the shape of particle packing
Formula is further formed more tiny hole in turn, and then improves the specific surface area of subsequent porous charcoal；In subsequent carbonisation,
It decomposes and obtains charcoal and complicated gas component, wherein gas component provides reducing atmosphere for carbonisation；Hydrolyze obtained metal
Hydrolysate is reacted with the carbon in high molecular weight solid cross-linking products, generate metal carbides, and not with metal hydrolysate
The carbon of reaction is wrapped up in metal carbide surface, forms porous charcoal, and then the metal carbides are located at the interior of the porous charcoal
Porous charcoal essence electric conductivity is improved in portion.
Embodiment the result shows that, the present invention is prepared carbide doping porous charcoal, specific surface area reaches 400~
1700m2The specific surface area of/g, and the porous carbon material obtained compared to conventional method is led under the conditions of specific surface area is comparable
Electric rate, which has, to be obviously improved, and avoids increasing specific surface area to reduce the drawbacks of conductivity is cost.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the structural profile illustration that the carbide that the present invention is prepared adulterates porous charcoal particle；
Wherein, 1 is macropore, and 2 be mesoporous, and 3 be micropore, and 4 be metal carbides；
Fig. 2 is the XRD diagram that the carbide that embodiment 1 is prepared adulterates porous charcoal；
Fig. 3 is the TEM figure that the carbide that embodiment 1 is prepared adulterates porous charcoal；
Fig. 4 is the TEM figure for the porous charcoal that comparative example 1 is prepared.
Specific embodiment
The present invention provides a kind of carbide to adulterate porous charcoal, including porous charcoal and the metal carbon being embedded in the porous charcoal
Compound；
The pore-size distribution of hole is in the range of 0.5~100nm in the porous charcoal；The hole of the porous charcoal includes hole
Diameter is distributed in that [0.5,2) micropore of nm, pore-size distribution are in [2,50) the macropore of the mesoporous of nm and pore-size distribution in [50,100] nm；
Wherein, Micropore volume >=0.20mL/g, macropore hole appearance≤0.05mL/g, 1.0mL/g >=total pore volume >=0.25mL/g.
In the present invention, the carbide doping porous charcoal includes the metallic carbide in porous charcoal and the insertion porous charcoal
Object；The metal carbides preferably include titanium carbide, vanadium carbide, zirconium carbide, niobium carbide, molybdenum carbide, tantalum carbide, tungsten carbide and carbon
Change one of hafnium or a variety of.
Carbide doping porous charcoal provided by the invention includes the metal carbides in porous charcoal and the insertion porous charcoal.
The present invention does not have particular/special requirement, evenly dispersed or dispersion of reuniting to distribution mode of the carbide inside porous charcoal
With.Metal carbides are not preferably distributed in the hole of the porous charcoal in carbide doping porous charcoal provided by the invention.
In the present invention, it is also preferable to include the metal carbon for being supported on the porous carbon surface for the carbide doping porous charcoal
Compound.In the present invention, the metal carbides are preferably graininess.
In the present invention, the gross mass of the metal carbides is preferably the 1~25% of porous charcoal quality, further preferably
It is 2~20%, more preferably 5~15%, most preferably 10%.
In the present invention, in the porous charcoal pore-size distribution of hole within the scope of 0.5~100nm, preferably 1.0~
60nm, further preferably 2.0~20nm.In the present invention, the hole of the porous charcoal include aperture be [0.5,2) nm it is micro-
Hole, aperture are the [2,50) macropore that the mesoporous of nm and aperture are [50,100] nm.In the present invention, total pore volume in the porous charcoal
For 0.25~1.0mL/g, preferably 0.3~0.9mL/g, further preferably 0.4~0.8mL/g；The Kong Rong of the micropore >=
0.20mL/g, preferably 0.25~0.85mL/g, further preferably 0.35~0.75mL/g；The macropore hole appearance≤
0.05mL/g, preferably 0.01~0.04mL/g, further preferably 0.02~0.03mL/g.
In the present invention, the specific surface area of the carbide doping porous charcoal is preferably 400m2/ g~1700m2/ g, into one
Step is preferably 600m2/ g~1300m2/ g, more preferably 1000~1200m2/g。
In the present invention, the conductivity of the carbide doping porous charcoal is preferably 2~200S/cm, further preferably
40~50S/cm；In an embodiment of the present invention, the conductivity of the porous charcoal is specially 4S/cm, 10S/cm or 20S/cm.
Carbide inside porous charcoal doping porous charcoal is embedded in for metal carbides, the present invention provides above-mentioned technologies
The preparation method of the doping porous charcoal of carbide described in scheme, comprising the following steps:
(1) add water in the mixed solution for including organic carbon source, organic metal salt, curing agent and organic solvent, carry out water
Solution, obtains hydrolyzing composition；
(2) surface oxidation is carried out after solidifying the hydrolyzing composition that the step (1) obtains, obtains combined oxidation product；
(3) the combined oxidation product for obtaining the step (2) carries out pressurized treatments, obtains precast body；
(4) precast body that the step (3) that is carbonized obtains obtains carbide doping porous charcoal.
The present invention adds water into the mixed solution including organic carbon source, organic metal salt, curing agent and organic solvent, carries out
Hydrolysis, obtains hydrolyzing composition.In the present invention, described includes organic carbon source, organic metal salt, curing agent and organic solvent
Organic carbon source in mixed solution, organic metal salt, curing agent and organic solvent mass ratio be preferably 100:(3~40): (5~
20): (100~1000), further preferably 100:(5~30): (10~15): (200~500).
In the present invention, the organic carbon source preferably includes resinae carbon source, more preferably phenolic resin, epoxy resin,
One of polyvinylidene fluoride resin, furfural resin, polyacrylic resin and polyurethane resin are a variety of.In implementation of the invention
In example, the organic carbon source is specially the mixture or phenolic resin and epoxy resin of phenolic resin, polyurethane and epoxy resin
Mixture；The present invention does not have particular/special requirement to the mass ratio of each component in the mixture.
In the present invention, the organic metal salt preferably include metal alkyl salt, metal alkoxides salt, alcohol radical metal salt,
One of phenide salt and phenylol metal salt are a variety of；The metal alkyl salt further preferably includes methyl-metals
One of salt, ethyl metal salt, propyl metal salt, butyl metal salt and amyl metal salt are a variety of；The metal alkoxides
Salt further preferably includes methoxide salt, ethoxide salt, propanolato- salt, butylate salt and amoxy gold
Belong to one of salt or a variety of.The present invention is to the metal alkyl salt, metal alkoxides salt, alcohol radical metal salt, phenide salt
There is no particular/special requirement with the source of phenylol metal salt, using well-known to those skilled in the art.
In the present invention, the metal in the organic metal salt is preferably one in titanium, vanadium, zirconium, niobium, molybdenum, tantalum, tungsten and hafnium
Kind is a variety of.
In an embodiment of the present invention, the organic metal salt be preferably specially ethanol tantalum and ethanolato-titanium mixture or
The mixture or phenyl titanium of ethanol tantalum and ethanolato-titanium and mixture or methyltitanium, methoxyl group titanium, the methanol titanium, second of phenylol titanium
Alcohol titanium, ethyl titanium, ethanolato-titanium, propyl titanium, titanium propanolate, the mixture or methyl vanadium of butyl titanium and titanium butoxide, methylcyclopentadienyl zirconium,
The mixing of the mixture or amyl vanadium and amoxy vanadium of the mixture or butyl titanium and titanium butoxide of methoxyl group vanadium and methoxyl group zirconium
The mixture of object or phenyl zirconium and phenylol zirconium.The present invention does not have special want to the mass ratio different material in the mixture
It asks.
In the present invention, the curing agent preferably include hexamethylenetetramine, p-methyl benzenesulfonic acid, formaldehyde, benzene sulfonyl chloride and
One of polyformaldehyde is a variety of.The present invention is to the hexamethylenetetramine, p-methyl benzenesulfonic acid, formaldehyde, benzene sulfonyl chloride and poly- first
The source of aldehyde does not have particular/special requirement, using commercial goods well-known to those skilled in the art.
In the present invention, it is organic molten to preferably include alcohol organic solvent, benzene class organic solvent and ketone for the organic solvent
One of agent is a variety of；The alcohol organic solvent further preferably includes in methanol, ethyl alcohol, propyl alcohol, butanol and amylalcohol
It is one or more；The benzene class organic solvent preferably includes benzene and/or toluene；The organic solvent of ketone further preferably includes
One of ketone, ethyl ketone and acetone are a variety of.
The present invention does not have particular/special requirement to the manner of formulation of the mixed solution, and use is well-known to those skilled in the art
The dissolution mechanism of solute in the solution；In an embodiment of the present invention, the preparation temperature of the mixed solution be preferably 0~
70 DEG C, further preferably 20~50 DEG C.In the present invention, it is molten can effectively to slow down mixing for the configuration temperature of the mixed solution
Organic carbon source and curing agent reaction generate the rate of gel in liquid, avoid the reunion in mixed solution between substance, it is molten to improve mixing
The stability of liquid.
In the present invention, the quality of hydrolysis water be preferably organic solvent quality in the mixed solution 20~
100%, further preferably 50~80%, more preferably 60~70%.
In the adition process of the water hydrolysis occurs for the present invention；The present invention with water be initially added into for initial time and with
There is no the time points that hydrolyzing composition generates in mixed solution to calculate the time hydrolyzed, the time of the hydrolysis for the end time
Preferably 0.5~12h, further preferably 1~10h, more preferably 4~6h；In the present invention, the water adition process terminates
The time interval generated into mixed solution there is no hydrolyzing composition is preferably 30~120min, further preferably 50~
100min。
In the present invention, the temperature of the hydrolysis is preferably 0~70 DEG C, and further preferably 10~60 DEG C, more preferably
20~50 DEG C.In the present invention, the adding manner of the water is preferably added dropwise, the rate of the dropwise addition preferably≤2mL/min, into
One step is preferably 0.5~1.5mL/min.In the present invention, the adition process of the water preferably carries out under agitation；This hair
It is bright there is no particular/special requirement to the stirring condition, using solution agitating mode well-known to those skilled in the art.
In hydrolysis reaction of the present invention, organic metal salt is hydrolyzed to metal salt hydrolysate, the metal salt water
Solving product includes metal hydroxides, metal oxide, metal oxyhydroxide, metal hydroxides hydrate, metal oxygen
One of compound hydrate and metal oxyhydroxide hydrate are a variety of, while organic carbon source and curing agent are hydrolyzed
A degree of crosslinking condensation occurs in journey, obtains the carbon source of high molecular weight；Obtained hydrolyzing composition is organic metal salt
The compound of the cross-linking products of hydrolysate and organic carbon source and curing agent.
In the present invention, excellent in the mixed solution including organic carbon source, organic metal salt, curing agent and organic solvent
Choosing further includes pore creating material.In the present invention, the mass ratio of the organic carbon source and pore creating material is preferably 100:(10~50), into one
Step is preferably 100:(15~40), more preferably 100:(20~30).In the present invention, the pore creating material preferably includes polyethylene
One of alcohol, polyvinyl butyral, polyimide resin, citric acid and sodium citrate are a variety of.The present invention is to described poly-
Vinyl alcohol, polyvinyl butyral, polyimide resin, citric acid and sodium citrate source there is no particular/special requirement, using this
Known to the technical staff of field.In the present invention, the pore creating material, which is present in front of carbonization with inert fraction, prepared
In the mixture that journey different phase obtains, to occupy certain volume in precast body when pressurization obtains precast body；It is rising
During temperature to carburizing temperature, the pore creating material described in 450 DEG C or so first resolves into gas, to facilitate pre- in carbonized product
Stay certain hole；And since the pore creating material is and organic carbon source, organic metal salt, curing agent and organic molten when being added
Dosage form is to be mixed with molecular level, so that leaving in carbonisation is micropore or mesoporous at mixed solution.When in mixed solution
When further including pore creating material, hydrolyzing composition that the hydrolysis obtains is the hydrolysate of organic metal salt, organic carbon and solid
The cross-linking products of agent and the compound of pore creating material.
After the hydrolysis, the present invention solidifies the obtained hydrolyzing composition, obtains solidifying substance.In the present invention
In, the cured temperature is preferably 80~150 DEG C, further preferably 90~140 DEG C, more preferably 100~120 DEG C；Institute
Stating the cured time is preferably 0.5~12h, further preferably 1~10h, more preferably 5~8h.In the present invention, described solid
Change is being carried out in stirring condition, and the rate of the stirring is preferably 20~500rpm.Specific implementation of the present invention to the stirring
Mode does not have particular/special requirement, using material stirring mode well-known to those skilled in the art.
Through the cross-linking products of carbon source and curing agent that a degree of crosslinking condensation obtains occur in hydrolytic process, described
In solidification process, gradually condensation completely is completed in gelation, is obtained high molecular weight solid cross-linking products, is obtained with the hydrolysis
Hydrolysate mixing, as solidifying substance.In the present invention, in the gradually condensation course, carbon source and curing agent occurs not
Disconnected crosslinking condensation, is initially formed gelinite, with the continuous progress of crosslinking condensation, gelinite is changed into solid, facilitates material
Between be uniformly mixed, reach molecular level even level.In the present invention, the high molecular weight solid cross-linking products are still used as carbon
Source carries out subsequent reaction.
After completing the solidification, the present invention is preferably successively crushed and dries to the solidifying substance.In the present invention, institute
The partial size for stating broken solidifying substance is preferably 3~80 μm, further preferably 5~50 μm, more preferably 10~20 μm.This hair
It is bright there is no particular/special requirement to the crumbling method, using crumbling method well-known to those skilled in the art, target grain can be obtained
The solidifying substance of diameter.In an embodiment of the present invention, the crumbling method is specially airflow milling, ball milling, sand milling or high energy ball
Mill.The present invention using it is broken obtain the solidifying substance of target grain size after, help to improve solidifying substance Surface Oxygen in subsequent air
Change efficiency.In the present invention, surface oxidation is avoided that the formation of closed pore in the shattering process and air, and shattering process has
Help the accumulation again of particle, and then forms hole.
In the present invention, the drying is preferably dried in vacuo or dries drying；The temperature of the drying is preferably 80~
150℃；The time of the drying is preferably 1~5h.In the present invention, the drying can remove the residual moisture in solidifying substance
And solvent.The present invention does not have particular/special requirement to the specific embodiment of the drying, and use is well-known to those skilled in the art
Drying mode.For the present invention in aforementioned hydrolysis and solidification process, moisture and organic solvent are crosslinked the high score being condensed to yield
Son amount solid cross-linking products are taken and are wrapped up in, through the drying process, while realizing the removal of moisture and organic solvent script moisture and
Organic solvent plants oneself to form hole.
The present invention carries out surface oxidation to the solidifying substance, obtains combined oxidation product.In the present invention, the Surface Oxygen
The temperature of change is preferably 180~260 DEG C, further preferably 190~250 DEG C, more preferably 200~220 DEG C；The Surface Oxygen
The time of change is preferably 0.5~3h, further preferably 1~2.5h, more preferably 1.5~2h.In the present invention, the surface
Oxidation process carries out preferably in air atmosphere.In the present invention, the surface oxidation process keeps high molecular weight in solidifying substance solid
Oxidation reaction occurs for the surface of body cross-linking products, and the cementitiousness of high molecular weight solid cross-linking products in solidifying substance is effectively reduced,
And then help to improve the specific surface area of finally obtained porous charcoal.In the present invention, the surface oxidation only changes solid
The surface state of high molecular weight solid cross-linking products in material reduces cementitiousness, but does not change high inside solidifying substance particle
The cementability of molecular weight solid cross-linking products.
After completing the surface oxidation, the present invention carries out pressurized treatments to the combined oxidation product, obtains precast body.?
In the present invention, the pressure of the pressurized treatments is preferably 1~50MPa, further preferably 5~40MPa, more preferably 10~
20MPa.In the present invention, the pressure of the pressurized treatments is reached in a manner of constantly boosting；Speed of the present invention to the boosting
Rate does not have particular/special requirement, using rate of pressure rise well-known to those skilled in the art.In the present invention, the pressurized treatments
Time there is no particular/special requirement；In an embodiment of the present invention, it when carrying out pressurized treatments by the way of boosting, is limited when reaching
When pressure, stop pressurized treatments.The thickness for the precast body that the present invention is obtained through the pressurized treatments is preferably not less than
0.2mm, further preferably 0.5~2mm.The present invention expects intrinsic bonding force using oxidation, is promoted using pressurized treatments mode
The bonding of material is aoxidized, and pressurized treatments can make partial particulate deformation, be crushed, and then be further formed more tiny hole
Gap, and then improve the specific surface area of subsequent porous charcoal.The present invention does not have special want to the specific embodiment of the pressurized treatments
It asks, using pressurization embodiment well-known to those skilled in the art.
After the pressurized treatments, the present invention is carbonized to the obtained precast body, obtains carbide doping porous charcoal.
In the present invention, the carbonization is preferred are as follows: keeps the temperature 0.5~6h after the precast body is warming up to carburizing temperature.In the present invention,
The rate of the heating is preferably 1~15 DEG C/min, further preferably 2~12 DEG C/min, more preferably 5~10 DEG C/min；
The initial temperature of the heating is preferably room temperature, and further preferably 25~30 DEG C.The present invention does not have the mode of the heating
Particular/special requirement, using heating mode well-known to those skilled in the art.In the present invention, the carburizing temperature is preferably
800~1600 DEG C, further preferably 900~1500 DEG C, more preferably 1000~1400 DEG C；The time of the heat preservation is preferably
0.5~6h, further preferably 1~5h, more preferably 2~4h.
In the carbonisation, part polymeric solid cross-linking products gradually resolve into charcoal and complicated gas component,
The gas component provides reducing atmosphere for carbonisation；Under the conditions of the carburizing temperature and reducibility gas component, and
In the carbonisation, polymeric solid cross-linking products as carbon source, the metal salt hydrolysate that hydrolyzes be in contact
Undecomposed polymeric solid cross-linking products and carbon reaction, generate metal carbides；Not with metal salt hydrolyzed reaction product
Carbon source is carbonized, and cracking occurs and further generates crack, obtains porous charcoal, and then formation includes porous charcoal and is embedded in described porous
Metal carbides in charcoal improve porous charcoal essence electric conductivity.
In the present invention, the carbonization preferably carries out in the reaction chamber；The present invention does not have the concrete model of the reaction chamber
There is particular/special requirement, using reaction chamber well-known to those skilled in the art.
In the present invention, the carbonization preferably carries out under protective atmosphere；The protective atmosphere be preferably nitrogen, helium,
It is one or more in argon gas, hydrogen and ammonia.In the present invention, when having other gases for example oxygen entering reaction zone, the guarantor
Reacting for precast body and other gases can be avoided, generate and consume preferentially with other gas reactions by protecting atmosphere.In the present invention,
The line flow velocity that gas is passed through reaction chamber in the protective atmosphere is preferably not less than 5cm/min, further preferably 10~20cm/
min。
After the carbonization, present invention preferably employs active gases to be activated the carbonized product.In the present invention
In, the active gases be preferably carbon dioxide or carbon dioxide and carbon monoxide mixture or carbon dioxide and hydrogen it is mixed
Close the mixture of object or carbon dioxide and hydrogen and carbon monoxide.
In the present invention, the activation processing preferably mixes the carbonized product with active gases.In the present invention,
The mixing is preferably in the reaction chamber where the active gases to be passed into carbonized product；The active gases is passed through reaction
The line flow velocity of room is preferably not less than 5cm/min, further preferably 10~20cm/min；The active gases to be passed through the time excellent
It is selected as 3min~30min, further preferably 10~20min.In the present invention, the activation processing is preferably under protective atmosphere
It carries out；The protective atmosphere is consistent with protective atmosphere described in above-mentioned technical proposal, and details are not described herein.
In the present invention, the active gases is activated the carbonized product, gradually decomposes with carbonisation
Charcoal out reacts, and etches more holes on the surface of charcoal and pore interior to further increase the ratio table of porous charcoal
Area；Simultaneously because the corrasion of active gases makes metal carbides further increase electric conductivity to porous charcoal surface enrichment.
Carbonized product is preferably cooled to room temperature by the present invention, is further preferably cooled to 25~30 DEG C, is obtained carbide and is mixed
Miscellaneous porous charcoal.The present invention does not have particular/special requirement to the embodiment of the cooling, using well-known to those skilled in the art cold
But mode.
In the preparation method of above-mentioned carbide doping porous charcoal provided by the invention, organic metal salt and carbon source are in the solution
Molecular level mixing is carried out, guarantees that the admixture in subsequent processing is still uniformly to mix by sol-gel process, is prepared with this
Carbide adulterate porous charcoal, metal carbides ultimately form tiny crystal grains and are uniformly embedded in inside porous charcoal particle, as Fig. 1 is mentioned
Shown in the structural profile illustration of the carbide doping porous charcoal particle of confession, metal carbides are uniformly mixed in the porous charcoal
The inside of grain contains macropore, mesoporous and micropore in porous charcoal particle.
The application of carbide provided by the invention doping porous charcoal preferably include using the carbide adulterate porous charcoal as
The electrode material of supercapacitor is used in sea water desalination as the electrode material of battery or by carbide doping porous charcoal
Application.
In the present invention, the carbide doping porous charcoal application is preceding preferably crushes carbide doping porous charcoal；
The partial size of smashed carbide doping porous charcoal is preferably 5~8 μm；In the present invention, the crushing remains to retain carbide
Adulterate the structure of the carbide insertion porous charcoal of porous charcoal.
The present invention is to carbide doping porous charcoal as the electrode material of supercapacitor and the electrode material of battery
The mode of material does not have particular/special requirement, in such a way that active carbon well-known to those skilled in the art prepares electrode；This hair
It is bright there is no particular/special requirement to application mode of the carbide doping porous charcoal in sea water desalination, using those skilled in the art
Known sea water desalination mode.
It is also preferable to include the metallic carbides for being supported on the porous carbon surface for carbide doping porous charcoal provided by the invention
Object.
For the metal carbides doping porous charcoal that porous carbon surface is also loaded metal carbides, the present invention is also mentioned
A kind of method for having supplied carbide doping porous charcoal, comprising the following steps:
(a) surface oxidation will be carried out after the mixed solution solidification including organic carbon source, curing agent and organic solvent, obtains oxygen
Material；It to including adding water in organic metal salt organic solution, is hydrolyzed, obtains hydrolysis gel composite；
(b) after the oxidation material obtained the step (a) and hydrolysis gel composite mixing, pressurized treatments is carried out, are obtained
Precast body；
(c) precast body that the step (b) that is carbonized obtains obtains carbide doping porous charcoal.
The present invention will carry out surface oxidation after the mixed solution solidification including organic carbon source, curing agent and organic solvent, obtain
Expect to oxidation.In the present invention, organic carbon source in the mixed solution including organic carbon source, curing agent and organic solvent, solid
The mass ratio of agent and organic solvent is preferably 100:(5~20): (50~500), further preferably 100:(10~15):
(100~200), more preferably 100:12:150.In the present invention, the organic carbon source, curing agent and organic solvent is specific
Selection range is consistent with the selection range of organic carbon source, curing agent described in above-mentioned technical proposal and organic solvent, in above-mentioned skill
It is voluntarily selected in the corresponding selection range of organic carbon source described in art scheme, curing agent and organic solvent, details are not described herein.
The present invention obtains manner of formulation without spy to the mixed solution including organic carbon source, curing agent and organic solvent
It is different to require, using the manner of formulation of solution well-known to those skilled in the art.In the present invention, the mixed solution
Preparing temperature is preferably 0~70 DEG C, further preferably 25~60 DEG C, more preferably 30~50 DEG C.In the present invention, described mixed
The configuration temperature for closing solution can effectively slow down the rate that organic carbon source and curing agent reaction in mixed solution generate gel, avoid
Reunion in mixed solution between substance improves the stability of mixed solution.
The present invention solidifies the mixed solution, obtains solidifying substance.The present invention occurs organic in the solidification process
Crosslinking condensation reaction between carbon source and curing agent, gradually gelation is until become high molecular weight solid, as solidifying substance.At this
In invention, the cured temperature is preferably 80~150 DEG C, further preferably 95~130 DEG C, more preferably 105~110
℃；The cured time is preferably 0.5~12h, further preferably 2~10h, more preferably 6~7h.In the present invention,
The solidification temperature facilitates the very fast progress of crosslinking condensation reaction.In the present invention, the stirring condition that is solidificated in is carrying out, institute
The rate for stating stirring is preferably 20~500r/min.The present invention does not have particular/special requirement to the specific embodiment of the stirring, adopts
With material stirring mode well-known to those skilled in the art.In the present invention, the stirring facilitates in solidification process,
Organic carbon source and curing agent are formed by high molecular weight solid cross-linking products and wrap up in taking for organic solvent, and then combine subsequent solid
The drying process of material, convenient for reserving some holes.In the present invention, the high molecular weight solid cross-linking products are as carbon source.
In the present invention, it is also preferable to include make in the mixed solution including organic carbon source, curing agent and organic solvent
Hole agent.In the present invention, the mass ratio of the organic carbon source and pore creating material is preferably 100:(10~50), further preferably
100:(15~40), more preferably 100:(20~30).In the present invention, the pore creating material preferably includes polyvinyl alcohol, poly- second
One of enol butyral, polyimide resin, citric acid and sodium citrate are a variety of.The present invention to the polyvinyl alcohol,
Polyvinyl butyral, polyimide resin, citric acid and sodium citrate source there is no particular/special requirement, using art technology
Known to personnel.In the present invention, the pore creating material effect is it has been observed that details are not described herein.When the mixed solution
In when further including pore creating material, described solidify in obtained solidifying substance further includes pore creating material.
After completing the solidification, the present invention is preferably successively crushed and dries to the solidifying substance.In the present invention, institute
The partial size for stating broken solidifying substance is preferably 3~80 μm, further preferably 5~50 μm, more preferably 10~20 μm.This hair
It is bright there is no particular/special requirement to the crumbling method, using crumbling method well-known to those skilled in the art, target grain can be obtained
The solidifying substance of diameter.The present invention using it is broken obtain the solidifying substance of target grain size after, help to improve solidifying substance subsequent
Oxidation efficiency.In the present invention, the broken effect is consistent with the effect being crushed in preceding solution, no longer superfluous herein
It states.
In the present invention, the drying is preferably dried in vacuo or dries drying；The temperature of the drying is preferably 80~
150℃；The time of the drying is preferably 1~5h.In the present invention, it is molten can to remove the remnants in solidifying substance for the drying
Agent.The present invention does not have particular/special requirement to the specific embodiment of the drying, using drying well-known to those skilled in the art
Mode.
The present invention carries out surface oxidation to the solidifying substance, obtains carbon source oxidation product.In the present invention, the Surface Oxygen
The temperature of change is preferably 180~260 DEG C, further preferably 200~240 DEG C, more preferably 210~215 DEG C；The Surface Oxygen
The time of change is preferably 0.5~3h, further preferably 1.2~2.5h, more preferably 1.5~2h.In the present invention, the table
Face oxidation process carries out preferably in air atmosphere.In the present invention, the surface oxidation process makes the high score on solidifying substance surface
Oxidation reaction occurs for son amount solid cross-linking products, and the cementitiousness of high molecular weight solid cross-linking products in solidifying substance is effectively reduced,
Plug-hole phenomenon when fracture pore is pyrolyzed out when subsequent carbonization convenient for reducing, and then helps to improve finally obtained porous charcoal
Specific surface area.In the present invention, the surface oxidation process only changes high molecular weight solid cross-linking products in solidifying substance
Surface state does not change the cementability of carbon inside solidifying substance particle, and obtained carbon source oxidation product is still used as carbon source, carries out
Subsequent carbonisation.
The present invention adds water into the organic solution of organic metal salt, is hydrolyzed, and obtains hydrolysis gel composite.
In the present invention, in the organic metal salt organic solution mass ratio of organic metal salt and organic solvent be (3~
40): (50~500), further preferably (10~30): (100~300), more preferably (15~20): (150~200).?
In the present invention, organic metal salt described in the specific selection range and above-mentioned technical proposal of the organic metal salt and organic solvent
It is consistent with the selection range of organic solvent, the corresponding selection model of organic metal salt and organic solvent described in above-mentioned technical proposal
Interior any selection is enclosed, details are not described herein.In the present invention, the mixing including organic carbon source, curing agent and organic solvent
The mass ratio of organic carbon source and the organic metal salt is preferably 100:(3~40 in solution), further preferably 100:(10~
30), more preferably 100:(15~20).
In the present invention, the quality of hydrolysis water is preferably organic solvent matter in the organic metal salt organic solution
20~100%, further preferably 50~80%, more preferably the 60~70% of amount.
In the adition process of the water hydrolysis occurs for the present invention；The present invention with water be initially added into for initial time and with
There is no the time points that hydrolyzing composition generates in mixed solution to calculate the time hydrolyzed, the time of the hydrolysis for the end time
Preferably 0.5~12h, further preferably 1~10h, more preferably 4~6h；In the present invention, the water adition process terminates
The time interval generated into mixed solution there is no hydrolyzing composition is preferably 30~120min, further preferably 50~
100min。
In the present invention, the temperature of the hydrolysis is preferably 0~70 DEG C, and further preferably 20~60 DEG C, more preferably
30~50 DEG C.In the present invention, the adding manner of the water is preferably added dropwise, the rate of the dropwise addition preferably≤2mL/min, into
One step is preferably 0.5~1.5mL/min.In the present invention, the adition process of the water preferably carries out under agitation；This hair
It is bright there is no particular/special requirement to the stirring condition, using solution agitating mode well-known to those skilled in the art.
The present invention adds water to during the mixed solution, and reaction is hydrolyzed, and organic metal salt is hydrolyzed to metal
Salt hydrolysis product, while gel occurs in the presence of a solvent for metal salt hydrolysate, obtains hydrolysis gel composite.?
In the present invention, the metal salt hydrolysate preferably include metal hydroxides, metal oxide, metal oxyhydroxide,
One of metal hydroxides hydrate, metal oxide hydrate and metal oxyhydroxide hydrate are a variety of.?
In the present invention, in the hydrolysis gel composite, the partial size of metal salt hydrolysate is preferably 3~10nm.
In the present invention, the hydrolysis, which obtains hydrolysis gel composite, facilitates the reaction of metal and carbon, is had
Effect reduces the temperature of carburizing reagent；The nano-scale particle of metal salt hydrolysate is in subsequent and carbon in the hydrolysis gel composite
It can be more adequately blended in carbon source particle in the mixing of source.
The carbon source oxidation product that obtains with after hydrolysis gel composite mixing, is carried out pressurized treatments, obtained by the present invention
Precast body.In the present invention, the mixed mode is preferably ball milling or stirring；The ball milling is more preferably vacuum sphere
Mill；The stirring is further preferably stirred under vacuum.The present invention is to the vacuum degree of the vacuum ball milling and vacuum stirring without spy
It is different to require, using vacuum ball milling well-known to those skilled in the art or the vacuum degree of vacuum stirring.In the present invention, institute
Carbon source oxidation product is uniformly mixed with hydrolysis gel composite after stating ball milling or stirring.In the present invention, the pressurized treatments mistake
Cheng Zhong can make partial particulate deformation, be crushed, further refine hole.For the present invention in the mixed process, hydrolysis gel is multiple
Object is closed to be impregnated into the hole of carbon source oxidation product and on outer surface.
The present invention carries out pressurized treatments to the mixture of carbon source oxidation product and hydrolysis gel composite, obtains precast body.
In the present invention, the pressure of the pressurized treatments is preferably 1~50MPa, further preferably 10~45MPa, and more preferably 15
~30MPa.In the present invention, the pressure of the pressurized treatments is reached in a manner of constantly boosting；The present invention is to the boosting
Rate does not have particular/special requirement, using rate of pressure rise well-known to those skilled in the art.In the present invention, at the pressurization
The time of reason does not have particular/special requirement；In an embodiment of the present invention, it when carrying out pressurized treatments by the way of boosting, is limited when reaching
When constant-pressure, stop pressurized treatments.The thickness for the precast body that the present invention is obtained through the pressurized treatments is preferably not less than
0.2mm, further preferably 0.5~2mm.
The present invention is dried the carbon source product and hydrolysis gel composite preferably before the pressurized treatments, removes
Remove remaining moisture and solvent.In the present invention, the drying is preferably dried in vacuo or dries drying；The temperature of the drying
Preferably 80~150 DEG C；The time of the drying is preferably 1~5h.
The present invention bonding force intrinsic using carbon source oxidation product, promotes carbon source oxidation product using pressurized treatments mode
Bonding bonding, it is ensured that hole is reserved, and then improves the specific surface area of subsequent porous charcoal；And gel is hydrolyzed in pressure process
Metal salt hydrolysate, which has, in compound remixes generation.The present invention using dipping mixing method in the carbon source oxidation product and
Make metal ion and the relatively uniform mixing of carbon source in hydrolysis gel composite mixed process, hydrolysis gel composite with carbon source
When oxidation product mixes, it is impregnated into pore interior and the surface of carbon source oxidation product；Pressure process, granular carbon source oxidation produce
Object can be in contact the variation in face in pressurizing binding, so that hydrolysate touches the interface of new carbon source oxidation product, into
One step mixes metal ion and carbon source uniformly.The present invention does not have particular/special requirement to the specific embodiment of the pressurized treatments,
Using pressurization embodiment well-known to those skilled in the art.
After the pressurized treatments, the present invention is carbonized to the obtained precast body, obtains carbide doping porous charcoal.
In the present invention, the carbonization is preferred are as follows: keeps the temperature 0.5~6h after the precast body is warming up to carburizing temperature.In the present invention,
The rate of the heating is preferably 1~15 DEG C/min, further preferably 5~12 DEG C/min, more preferably 6~8 DEG C/min；Institute
The initial temperature for stating heating is preferably room temperature, and further preferably 25~30 DEG C.Specific embodiment party of the present invention to the heating
Formula does not have particular/special requirement, using heating mode well-known to those skilled in the art.In the present invention, the carburizing temperature
Preferably 800~1600 DEG C, further preferably 1000~1500 DEG C, more preferably 1100~1300 DEG C；The heat preservation when
Between preferably 0.5~6h, further preferably 1~5h, more preferably 2~4h.
In the present invention, the precast body is in carbonisation, because there are certain holes between particle, when convenient for carbonization
Volatilization gas spread discharge, and reduce carbonization when stress；Only surface is aoxidized polymeric solid in precast body, in carbon
Will occur partial melting during change to crack and shrink again, macroporosity and macropore will tail off, and primarily form micropore, mesoporous；
The partial melting process occurred in carbonisation makes the effects of primary granule in precast body is because of bonding, thawing, cracking, differentiation,
Form new particle.
In the carbonisation, carbon source high molecular weight solid gradually resolves into charcoal and complicated gas component, the gas
Body group is divided into carbonisation and provides reducing atmosphere；Under the conditions of the carburizing temperature and reducibility gas component, in the carbonization
In the process, the hydrolysis gel composite hydrolyzed is reacted with the carbon source oxidation product and carbon as carbon source, generates metallic carbide
Object；The carbon source oxide not reacted with hydrolysis gel composite is carbonized, and forms hole, and then being formed includes porous charcoal and insertion
Metal carbides in the porous charcoal and the metal carbides for being supported on the porous carbon surface improve porous charcoal essence and lead
Electrically.
In the present invention, the carbonization preferably carries out in the reaction chamber；The present invention does not have the concrete model of the reaction chamber
There is particular/special requirement, using reaction chamber well-known to those skilled in the art.
In the present invention, the carbonization preferably carries out under protective atmosphere；The protective atmosphere be preferably nitrogen, helium,
It is one or more in argon gas, hydrogen and ammonia.In the present invention, in the protective atmosphere gas be passed through reaction chamber line flow velocity it is excellent
Choosing is not less than 5cm/min, further preferably 10~20cm/min.
After the carbonization, the present invention preferably mixes carbonized product with active gases.In the present invention, the active gases
The preferably mixture or carbon dioxide of the mixture or carbon dioxide of carbon dioxide or carbon dioxide and carbon monoxide and hydrogen
With the mixture of hydrogen and carbon monoxide.In the present invention, the active gases is preferably passed into carbonization and produced by the mixing
In reaction chamber where object；The line flow velocity that the active gases is passed through reaction chamber is preferably not less than 5cm/min, further preferably
10~20cm/min；The time that is passed through of the active gases is preferably 3min~30min, further preferably 10~20min.?
In the present invention, the mixing of the carbonized product and active gases is preferably carried out under protective atmosphere；The protective atmosphere with it is above-mentioned
Protective atmosphere described in technical solution is consistent, and details are not described herein.
In the present invention, the active gases reacts with the charcoal that carbonisation gradually decomposites, charcoal surface and
More holes are etched in hole to further increase the specific surface area of porous charcoal；Simultaneously because the etching of active gases is made
With making metal carbides further increase electric conductivity to porous charcoal surface enrichment.
Carbonized product is preferably cooled to room temperature by the present invention, is further preferably cooled to 25~30 DEG C.The present invention is to described
Cooling embodiment does not have particular/special requirement, using the type of cooling well-known to those skilled in the art.
Carbonized product is preferably cooled to room temperature by the present invention, is further preferably cooled to 25~30 DEG C.The present invention is to described
Cooling embodiment does not have particular/special requirement, using the type of cooling well-known to those skilled in the art.
In the present invention, the application of the carbide doping porous charcoal is adulterated more with carbide described in preceding solution
The application of hole charcoal is consistent, and details are not described herein.
Carbide provided by the invention doping porous charcoal and preparation method thereof is carried out specifically below with reference to embodiment
It is bright, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
1. by phenolic resin, ethanolato-titanium, hexamethylenetetramine and ethyl alcohol by weight 100:3:5:100 in 25 DEG C of conditions
Simultaneously dissolution is sufficiently stirred in lower mixing, obtains mixed solution；
2. it is kept for 25 DEG C, water is added into mixed solution dropwise according to the rate of 1.7mL/min and continues to stir 0.5h, until
Completely, to obtain hydrolyzing composition, amount of water about 50mL is the 50% of etoh solvent quality for ethanolato-titanium hydrolysis；
3. hydrolyzing composition heating vacuum vaporation and solidifies under the conditions of 80 DEG C under persistently stirring and obtains solidifying substance, the time is
12h；
4. after solidifying substance is crushed, fluid bed process heated oxide 0.5h obtains oxidation material in 180 DEG C of air, wherein
The smashed granular size control of solidifying substance is 80 μm in D50；
5. oxidation material to be pressed into the thin slice of thick 0.5mm and diameter 10mm under 50MPa pressure；
6. precast body is put into carburizing reagent room, 800 are warming up to the rate control of 1 DEG C/min under the protection of argon gas
DEG C, and in 800 DEG C of heat preservation 6h, room temperature, which is cooled to, to get to carbide adulterates porous charcoal.Argon gas is protected always before being cooled to room temperature
It holds.
Ingredient and content analysis are carried out to the carbide doping porous charcoal being prepared using elemental analysis method, obtained
It is 1% or so of porous charcoal quality that the carbide, which adulterates carbide doping in porous charcoal, and carbide is titanium carbide；
It is measured, is used using pore-size and specific surface area of the nitrogen adsorption method to carbide doping porous charcoal
It is found that the total pore volume of the porous charcoal is 0.25mL/g, Micropore volume 0.20mL/g, hole is concentrated mainly on DFT mixed model
0.5nm~5nm, the peak value of distribution of pores is in 0.61nm；Single-point method is used to measure total pore volume as 0.28mL/g, i.e. macropore Kong Rongwei
0.03mL/g, BET method measurement the specific area is in 400m2/g；
Conductivity test is carried out to the carbide doping porous charcoal being prepared using four probe resistance test methods, can be obtained
The conductivity about 10S/cm of carbide doping porous charcoal.
The structural profile illustration for the carbide doping porous charcoal particle being prepared is as shown in Figure 1, wherein label 1 is big
Pore structure, 2 be microcellular structure, 3 be central hole structure, 4 be metal carbides, metal carbides are evenly distributed on porous charcoal particle
It is internal.
Structure observation is carried out to the carbide doping porous charcoal being prepared, as a result as Fig. 2 carbide adulterates porous charcoal
Shown in the TEM figure of XRD diagram and Fig. 3 carbide doping porous charcoal.As shown in Figure 2, occur in significantly broadened charcoal peak back end
The crystalline state spike of titanium carbide；From the figure 3, it may be seen that there is needle-shaped or bar shaped carbide grain to press from both sides in amorphous layer of charcoal deposit
It is miscellaneous to constitute entire carbide doping porous charcoal particle.
Comparative example 1
Porous charcoal is prepared according to the scheme of embodiment 1, difference is not add ethanolato-titanium in this comparative example.
Obtained porous charcoal specific surface area is 300m2/ g, conductivity are only 1S/cm.
Structure observation is carried out to the porous charcoal being prepared, as a result as shown in the TEM figure of the porous charcoal of Fig. 4, it is known that, amorphous
The layer of charcoal accumulation of state forms porous charcoal particle.
Embodiment 2
1. by phenolic resin, ethanolato-titanium, hexamethylenetetramine and ethyl alcohol by weight 100:40:20:1000, at 0 DEG C
Under the conditions of mix and be sufficiently stirred dissolution, obtain mixed solution；
2. to 70 DEG C, water hereafter is added simultaneously into mixed solution dropwise according to the rate of 1.7mL/min in heating said solution
5h is persistently stirred, until ethanolato-titanium hydrolysis is completely, to obtain hydrolyzing composition, amount of water about 500mL is etoh solvent quality
50%；
3. hydrolyzing composition persistently stir under in 100 DEG C of heating vacuum vaporations and solidify obtain solidifying substance, time 12h；
4. after solidifying substance is crushed, fluid bed process heated oxide 0.5h, is aoxidized and is answered in 260 DEG C of air
Oxidation product is closed, wherein the smashed granular size control of solidifying substance is 80 μm in D50；
5. combined oxidation product to be pressed into the thin slice of thick 0.2mm and diameter 10mm under 50MPa pressure；
6. precast body is put into carburizing reagent room, it is warming up under the protection of argon gas with the rate control of 5 DEG C/min
1600 DEG C, and in 1600 DEG C of heat preservation 6h, room temperature, which is cooled to, to get to carbide adulterates porous charcoal.It is cooled to argon gas one before room temperature
It is straight to keep.
Ingredient and content point are carried out to the carbide doping porous charcoal being prepared using the detection method of embodiment 1
Analysis, pore-size and specific area measuring and conductivity test can obtain carbide in carbide doping porous charcoal obtained and mix
Miscellaneous amount is 25% or so of porous charcoal quality；The structure of carbide doping porous charcoal are as follows: have in amorphous layer of charcoal deposit
Needle-shaped or bar shaped carbide grain, which is mingled with, constitutes entire carbide doping porous charcoal particle.Using nitrogen adsorption DFT hybrid guided mode
For type it is found that the total pore volume of the porous charcoal is 0.30mL/g, Micropore volume 0.23mL/g, hole concentrates on 0.5~5nm, hole
The peak value of distribution is in 0.8nm；Using single-point method to measure total pore volume, (it is 0.02mL/g or so that i.e. macropore hole, which holds, is for 0.32mL/g
The difference of single-point method total pore volume and DFT total pore volume), specific surface area is measured in 400m using BET method2/ g, conductivity about 200S/
Cm, the carbide are titanium carbide.
Comparative example 2
Porous charcoal is prepared according to the scheme of embodiment 2, difference is not add ethanolato-titanium in this comparative example.
Obtained porous charcoal specific surface area is 200m2/ g, conductivity are only 2S/cm.
Embodiment 3
1. by epoxy resin, ethanol tantalum, p-methyl benzenesulfonic acid and acetone by weight 100:10:10:200, in 20 DEG C of conditions
Simultaneously dissolution is sufficiently stirred in lower mixing, obtains mixed solution；
2. heating said solution to 70 DEG C, is hereafter added water into mixed solution dropwise and continues to stir, until organic metal
Salt hydrolysis is complete, to obtain hydrolyzing composition, the time is about 2h, amount of water about 200mL；
3. hydrolyzing composition in 100 DEG C of heating vacuum vaporations and solidifies under persistently stirring and obtains solidifying substance, the time is about
10h, wherein the smashed granular size control of solidifying substance is 50 μm in D50；
4. after solidifying substance is crushed, fluid bed process heated oxide 3h obtains combined oxidation product in 260 DEG C of air；
5. combined oxidation product to be pressed into the thin slice of thick 2mm and diameter 5mm under 1MPa pressure；
6. precast body is put into carburizing reagent room, it is warming up under the protection of argon gas with the rate control of 15 DEG C/min
1600 DEG C, and in 1600 DEG C of heat preservation 6h, room temperature, which is cooled to, to get to carbide adulterates porous charcoal.It is cooled to argon gas one before room temperature
It is straight to keep.
Ingredient and content point are carried out to the carbide doping porous charcoal being prepared using the detection method of embodiment 1
Analysis, pore-size and specific area measuring and conductivity test can obtain carbide in carbide doping porous charcoal obtained
Doping is 2% or so of porous charcoal quality；The structure of carbide doping porous charcoal are as follows: have in amorphous layer of charcoal deposit
Needle-shaped or bar shaped carbide grain, which is mingled with, constitutes entire carbide doping porous charcoal particle.Using nitrogen adsorption DFT hybrid guided mode
For type it is found that the total pore volume of the porous charcoal is 0.34mL/g, Micropore volume 0.27mL/g, hole concentrates on 0.5nm~5nm, hole
The peak value of gap distribution is in 0.82nm；Single-point method total pore volume is 0.36mL/g, measures specific surface area in 500m using BET method2/ g, electricity
Conductance about 20S/cm；The carbide is tantalum carbide.
Comparative example 3
Porous charcoal is prepared according to the scheme of embodiment 3, difference is not add ethanol tantalum in this comparative example.
Obtained porous charcoal specific surface area is 400m2/ g, conductivity are only 0.5S/cm.
Embodiment 4
1. by the mixture of phenolic resin and epoxy resin (mass ratio 1:1), hexamethylenetetramine and p-methyl benzenesulfonic acid (matter
Measure than 1:1) mixture and ethyl alcohol and acetone (mass ratio 1:1) mixture by weight 100:10:200, in 0 DEG C of condition
Simultaneously dissolution is sufficiently stirred in lower mixing, obtains mixed solution；
2. mixed solution is heating and curing to obtain solidifying substance in 80 DEG C under persistently stirring, the time is that (period keeps container close to 12h
It seals and solvent resides in solidifying substance)；
3. by solidifying substance ball mill grinding, in 80 DEG C of air dryings to remove remaining water and solvent, thereafter at 180 DEG C
Fluidized bed type heated oxide 0.5h in air, obtains carbon source oxidation product, and the wherein smashed granular size control of solidifying substance exists
D50 is 20 μm；
4. ethanol tantalum and ethyl alcohol obtain mixed solution by weight 3:50 mixed dissolution under the conditions of 0 DEG C, mixed to this dropwise
It closes and water is added in solution and continues to stir, until organic metal salt hydrolysis obtains hydrolysis gel composite completely, time 0.5h adds
Water is about 25mL；
5. oxidation material is uniformly mixed with hydrolysis gel composite ball mill, in 100 DEG C of dryings to remove remaining water and molten
Agent is pressed into the thick thin slice in 0.2mm, diameter 5mm under 50MPa pressure after broken；
6. precast body is put into carburizing reagent room, 1600 are warming up to the rate control of 15 DEG C/min under protection of argon gas
DEG C, and in 1600 DEG C of heat preservation 6h, room temperature, which is cooled to, to get to carbide adulterates porous charcoal.Argon gas is protected always before being cooled to room temperature
It holds.
Ingredient and content point are carried out to the carbide doping porous charcoal being prepared using the detection method of embodiment 1
Analysis, pore-size and specific area measuring and conductivity test can obtain carbide in carbide doping porous charcoal obtained and mix
Miscellaneous amount is 2% or so of porous charcoal quality；The structure of carbide doping porous charcoal are as follows: carbide exists in two forms, insertion
Into porous charcoal and it is supported on porous carbon surface.Use nitrogen adsorption DFT mixed model it is found that the total pore volume of the porous charcoal for
0.35mL/g, Micropore volume 0.27mL/g, hole concentrate on 0.5nm~5nm, distribution of pores peak value in 0.92nm；Single-point
Method total pore volume is 0.39mL/g, and then obtaining macropore to hold is 0.04mL/g, and specific surface area is in 500m2/ g or so, conductivity about 40S/
Cm, the carbide are tantalum carbide.
Comparative example 4
Porous charcoal is prepared according to the scheme of embodiment 4, difference is not add ethanol tantalum in this comparative example.
Obtained porous charcoal specific surface area is 400m2/ g, conductivity are only 0.5S/cm.
Embodiment 5
1. by the mixture of phenolic resin and epoxy resin (mass ratio 1:1), hexamethylenetetramine and p-methyl benzenesulfonic acid (matter
Measure than 1:1) mixture, polyvinyl alcohol and etoh solvent and acetone mixture by weight 100:10:10:200,0
Dissolution is mixed and be sufficiently stirred under the conditions of DEG C, obtains mixed solution；
2. mixed solution is heating and curing to obtain solidifying substance in 80 DEG C under persistently stirring, the time is that (period keeps container close to 12h
It seals and solvent resides in solidifying substance)；
3. by solidifying substance ball mill grinding, in 80 DEG C of air dryings to remove remaining water and solvent, thereafter at 260 DEG C
Fluidized bed type heated oxide 3h in air, obtains carbon source oxidation product, and wherein the smashed granular size control of solidifying substance is in D50
It is 20 μm；
4. the mixture and ethyl alcohol of ethanol tantalum and ethanolato-titanium (mass ratio 1:1) are obtained by weight 3:50 mixed dissolution
Mixed solution is added water into the mixed solution dropwise and continues to stir, and answers until ethanolato-titanium hydrolysis obtains hydrolysis gel completely
Object is closed, the temperature during solution mixing and the dropwise addition of water is 0 DEG C, and time 0.5h, amount of water is about 25mL；
5. oxidation material is uniformly mixed with hydrolysis gel composite ball mill, in 100 DEG C of dryings to remove remaining water and molten
Agent is pressed into the thick thin slice precast body in 0.2mm, diameter 5mm under 1MPa pressure after broken；
6. precast body is put into carburizing reagent room, 900 are warming up to the rate control of 15 DEG C/min under protection of argon gas
DEG C, and in 900 DEG C of heat preservation 6h, carbon dioxide 30min, the line stream of carbon dioxide in the reaction chamber are passed through at the end of 900 DEG C of heat preservations
Speed is not less than 5cm/min, naturally cools to room temperature thereafter to get to carbide and adulterates porous charcoal.It is cooled to argon gas one before room temperature
It is straight to keep.
Ingredient and content point are carried out to the carbide doping porous charcoal being prepared using the detection method of embodiment 1
Analysis, pore-size and specific area measuring and conductivity test can obtain carbide in carbide doping porous charcoal obtained and mix
Miscellaneous amount is 5% or so of porous charcoal quality；The structure of carbide doping porous charcoal are as follows: carbide exists in two forms, insertion
Into porous charcoal and it is supported on porous carbon surface.Use nitrogen adsorption DFT mixed model it is found that the total pore volume of the porous charcoal for
0.55mL/g, Micropore volume 0.36mL/g, hole concentrate on the peak value of 0.5nm~8.5nm, pore-size distribution in 0.6nm, 1.2
~1.8nm and 3.4~5.7nm；Single-point method total pore volume is 0.60mL/g, and then obtaining macropore to hold is 0.05mL/g, BET specific surface area
In 1000m2Carbide described in/g or so, conductivity about 50S/cm is tantalum carbide and titanium carbide.
Comparative example 5
Porous charcoal is prepared according to the scheme of embodiment 5, difference is not add ethanol tantalum and ethanolato-titanium in this comparative example.
Obtained porous charcoal specific surface area is 800m2/ g, conductivity are only 0.1S/cm.
Embodiment 6
1. by the mixture of phenolic resin and epoxy resin (mass ratio 1:1), hexamethylenetetramine and p-methyl benzenesulfonic acid (matter
Measure than 1:1) mixture, polyvinyl alcohol and ethyl alcohol and acetone (mass ratio 1:1) mixture by weight 100:20:50:
200, dissolution is mixed and be sufficiently stirred under the conditions of 0 DEG C, obtains mixed solution；
2. mixed solution is heating and curing to obtain solidifying substance in 150 DEG C under persistently stirring, the time is that (period keeps container to 12h
It seals and solvent resides in solidifying substance)；
3. by solidifying substance ball mill grinding, in 80 DEG C of air dryings to remove remaining water and solvent, thereafter at 180 DEG C
Fluidized bed type heated oxide 3h in air obtains oxidation material, and wherein the smashed granular size control of solidifying substance is 3 μm in D50；
4. by the mixture and etoh solvent of ethanol tantalum and ethanolato-titanium (mass ratio 1:1) by weight 3:50 mixed dissolution
Mixed solution is obtained, water is added into the mixed solution dropwise and continues to stir, until organic metal salt hydrolysis is hydrolyzed completely
Temperature during gel composite, control mixed dissolution and water droplet add is 0 DEG C, and time 0.5h, amount of water is about 25mL；
5. oxidation material is uniformly mixed with hydrolysis gel composite ball mill, in 100 DEG C of dryings to remove remaining water and molten
Agent is pressed into the thick thin slice precast body in 0.2mm, diameter 5mm under 1MPa pressure after broken；
6. precast body is put into carburizing reagent room, 1000 are warming up to the rate control of 15 DEG C/min under protection of argon gas
DEG C, and in 1000 DEG C of heat preservation 6h, carbon dioxide 30min, the line of carbon dioxide in the reaction chamber are passed through at the end of 1000 DEG C of heat preservations
Flow velocity is not less than 5cm/min, naturally cools to room temperature thereafter to get to carbide and adulterates porous charcoal.It is cooled to argon gas before room temperature
It is always maintained at.
Ingredient and content point are carried out to the carbide doping porous charcoal being prepared using the detection method of embodiment 1
Analysis, pore-size and specific area measuring and conductivity test can obtain carbide in carbide doping porous charcoal obtained and mix
Miscellaneous amount is 2% or so of porous charcoal quality；The structure of carbide doping porous charcoal are as follows: carbide exists in two forms, insertion
Into porous charcoal and it is supported on porous carbon surface.Use nitrogen adsorption DFT mixed model it is found that the total pore volume of the porous charcoal for
0.63mL/g, Micropore volume 0.48mL/g, hole concentrate on the peak value of 0.5~8.5nm, pore-size distribution in 0.5~1.4nm and
1.7~2.8nm and 4.7~5.7nm；Single-point method total pore volume is 0.67mL/g, and then obtaining macropore to hold is 0.04mL/g, and BET compares table
Area is in 1300m2/ g or so, conductivity about 4S/cm, the carbide are tantalum carbide and titanium carbide, and the carbide is carbonization
The conductivity about 4S/cm of tantalum carbide doping porous charcoal.
Comparative example 6
Porous charcoal is prepared according to the scheme of embodiment 6, difference is not add ethanol tantalum and ethanolato-titanium in this comparative example.
Obtained porous charcoal specific surface area is 1000m2/ g, conductivity are only 0.1S/cm.
Embodiment 7
1. at 20 °C, with phenolic resin, polyurethane and epoxy resin (mass ratio 1:1:1) for organic carbon source, second
Oxygroup titanium is that organic metal salt, hexamethylenetetramine and p-methyl benzenesulfonic acid (mass ratio 1:1) are curing agent, polyvinyl alcohol and poly- second
Enol butyral as pore creating material (mass ratio 1:1), using ethyl alcohol and acetone (mass ratio 1:1) as solvent, by organic carbon source, have
Machine metal salt, curing agent, pore creating material and solvent mix by weight 100:1:20:50:1000 and are sufficiently stirred dissolution, are mixed
Solution is closed, temperature is about 20 DEG C；
2. heating said solution to 70 DEG C, is hereafter added water into mixed solution dropwise and continues to stir, until organic metal
Salt hydrolysis is complete, to obtain hydrolyzing composition, the time is about 2h, amount of water about 500mL；
3. hydrolyzing composition in 100 DEG C of heating vacuum vaporations and solidifies under persistently stirring and obtains solidifying substance, the time is about
10h, wherein the smashed granular size control of solidifying substance is 3 μm in D50；
4. after solidifying substance is crushed, fluid bed process heating 0.5h obtains oxidation material in 180 DEG C of air；
5. oxidation material to be pressed into the thin slice precast body of thick 2mm, diameter 5mm under 1MPa pressure；
6. precast body is put into carburizing reagent room, 850 are warming up to the rate control of 15 DEG C/min under protection of argon gas
DEG C, and in 850 DEG C of heat preservation 6h, carbon dioxide 30min, the line stream of carbon dioxide in the reaction chamber are passed through at the end of 850 DEG C of heat preservations
Speed is not less than 5cm/min, naturally cools to room temperature thereafter to get to carbide and adulterates porous charcoal.It is cooled to argon gas one before room temperature
It is straight to keep.
Ingredient and content point are carried out to the carbide doping porous charcoal being prepared using the detection method of embodiment 1
Analysis, pore-size and specific area measuring and conductivity test can obtain carbide in carbide doping porous charcoal obtained and mix
Miscellaneous amount is 1% or so of porous charcoal quality；The structure of carbide doping porous charcoal are as follows: carbide is embedded into porous charcoal.Using
Nitrogen adsorption DFT mixed model is it is found that the total pore volume of the porous charcoal is 0.85mL/g, Micropore volume 0.61mL/g, hole collection
In 0.5~8.4nm, pore-size distribution peak value in 0.6nm and 1.0~2.0nm and 3.0~5.7nm；Single-point method total pore volume is
0.90mL/g, and then obtaining macropore to hold is 0.05mL/g, BET specific surface area is in 1700m2/ g or so, conductivity about 2S/cm, it is described
Carbide is tantalum carbide and titanium carbide.
Comparative example 7
Porous charcoal is prepared according to the scheme of embodiment 7, difference is not add ethanolato-titanium in this comparative example.
Obtained porous charcoal specific surface area is 1200m2/ g, conductivity are only 0.07S/cm.
Embodiment 8
1. with phenolic resin, polyurethane and epoxy resin (mass ratio 1:1:1) for organic carbon source, ethanol tantalum and ethanolato-titanium
(mass ratio 1:1) is that organic metal salt, hexamethylenetetramine and p-methyl benzenesulfonic acid (mass ratio 1:1) are curing agent, polyvinyl alcohol
It is used as solvent as pore creating material (mass ratio 1:1) and ethyl alcohol and acetone (mass ratio 1:1) with polyvinyl butyral, it will be organic
Carbon source, organic metal salt, curing agent, pore creating material and solvent are mixed by weight 100:30:20:50:1000 and are sufficiently stirred molten
Solution, obtains mixed solution, temperature is about 20 DEG C；
2. heating said solution to 70 DEG C, is hereafter added water into mixed solution dropwise and continues to stir, until organic metal
Salt hydrolysis is complete, to obtain hydrolyzing composition, the time is about 2h, amount of water about 500mL；
3. hydrolyzing composition in 100 DEG C of heating vacuum vaporations and solidifies under persistently stirring and obtains solidifying substance, the time is about
10h, wherein the smashed granular size control of solidifying substance is 3 μm in D50；
4. after solidifying substance is crushed, fluid bed process heating 0.5h obtains oxidation material in 180 DEG C of air；
5. oxidation material to be pressed into the thin slice precast body of thick 2mm, diameter 5mm under 1MPa pressure；
6. precast body is put into carburizing reagent room, 850 are warming up to the rate control of 15 DEG C/min under protection of argon gas
DEG C, and carbon dioxide and hydrogen mixed gas (volume ratio 4:1) 30min are passed through at the end of 850 DEG C of heat preservation 6h, 850 DEG C of heat preservations, two
The line flow velocity of carbonoxide and hydrogen mixed gas in the reaction chamber is not less than 5cm/min, naturally cools to room temperature thereafter to get carbon is arrived
Compound adulterates porous charcoal.Argon gas is always maintained at before being cooled to room temperature.
Ingredient and content point are carried out to the carbide doping porous charcoal being prepared using the detection method of embodiment 1
Analysis, pore-size and specific area measuring and conductivity test can obtain carbide in carbide doping porous charcoal obtained and mix
Miscellaneous amount is 25% or so of porous charcoal quality；The structure of carbide doping porous charcoal are as follows: carbide is embedded into porous charcoal.Using
Nitrogen adsorption DFT mixed model is it is found that the total pore volume of the porous charcoal is 0.95mL/g, Micropore volume 0.67mL/g, hole collection
In 0.5nm~55nm, pore-size distribution peak value in 0.61nm and 0.69~0.85nm and 1.0~2.2nm and 10~17nm；It is single
Point method total pore volume is 1.00mL/g, and then obtaining macropore to hold is 0.05mL/g, and BET specific surface area is in 1700m2/ g or so, conductivity
About 20S/cm, the carbide are tantalum carbide and titanium carbide.
Comparative example 8
Porous charcoal is prepared according to the scheme of embodiment 8, difference is not add ethanolato-titanium in this comparative example.
Obtained porous charcoal specific surface area is 1350m2/ g, conductivity are only 0.05S/cm.
The carbide doping porous charcoal that the present invention is prepared it can be seen from the result of above embodiments and comparative example,
Specific surface area reaches 400~1700m2/ g, and the porous carbon material obtained compared to conventional method, in the comparable item of specific surface area
Under part, conductivity, which has, to be obviously improved, and avoids increasing specific surface area to reduce the drawbacks of conductivity is cost.
The above is only a preferred embodiment of the present invention, it is not intended to limit the present invention in any form.It should
It points out, for those skilled in the art, without departing from the principle of the present invention, if can also make
Dry improvements and modifications, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (9)
1. a kind of carbide adulterates porous charcoal, including porous charcoal and the metal carbides being embedded in the porous charcoal；
The pore-size distribution of hole is in the range of 0.5~100nm in the porous charcoal；The hole of the porous charcoal includes aperture point
Cloth is [0.5,2) micropore of nm, pore-size distribution are in [2,50) the macropore of the mesoporous of nm and pore-size distribution in [50,100] nm；Its
In, Micropore volume >=0.20mL/g, macropore hole appearance≤0.05mL/g, 1.0mL/g >=total pore volume >=0.25mL/g；
The metal carbides include titanium carbide, vanadium carbide, zirconium carbide, niobium carbide, molybdenum carbide, tantalum carbide, tungsten carbide and carbonization
One of hafnium is a variety of；The quality of the metal carbides is the 1~25% of porous charcoal quality；
The preparation method of the carbide doping porous charcoal, comprising the following steps:
(1) add water in the mixed solution for including organic carbon source, organic metal salt, curing agent and organic solvent, be hydrolyzed, obtain
To hydrolyzing composition；
(2) surface oxidation is carried out after solidifying the hydrolyzing composition that the step (1) obtains, obtains combined oxidation product；
(3) the combined oxidation product for obtaining the step (2) carries out pressurized treatments, obtains precast body；
(4) precast body that the step (3) that is carbonized obtains obtains carbide doping porous charcoal；
The organic carbon source is phenolic resin, epoxy resin, polyvinylidene fluoride resin, furfural resin, polyacrylic resin and gathers
One of urethane resin is a variety of；
The organic metal salt is metal alkyl salt, metal alkoxides salt, alcohol radical metal salt, phenide salt and phenol Base Metal
One of salt is a variety of, and the metal is one of titanium, vanadium, zirconium, niobium, molybdenum, tantalum, tungsten and hafnium or a variety of；
The curing agent is one of hexamethylenetetramine, p-methyl benzenesulfonic acid, formaldehyde, benzene sulfonyl chloride and polyformaldehyde or a variety of.
2. a kind of carbide adulterates porous charcoal, including porous charcoal and the metal carbides being embedded in the porous charcoal；
The pore-size distribution of hole is in the range of 0.5~100nm in the porous charcoal；The hole of the porous charcoal includes aperture point
Cloth is [0.5,2) micropore of nm, pore-size distribution are in [2,50) the macropore of the mesoporous of nm and pore-size distribution in [50,100] nm；Its
In, Micropore volume >=0.20mL/g, macropore hole appearance≤0.05mL/g, 1.0mL/g >=total pore volume >=0.25mL/g；
The metal carbides include titanium carbide, vanadium carbide, zirconium carbide, niobium carbide, molybdenum carbide, tantalum carbide, tungsten carbide and carbonization
One of hafnium is a variety of；The quality of the metal carbides is the 1~25% of porous charcoal quality；
Further include the metal carbides for being supported on the porous carbon surface, preparation method includes the following steps:
(a) surface oxidation will be carried out after the mixed solution solidification including organic carbon source, curing agent and organic solvent, obtains carbon source oxygen
Change product；
Add water into organic metal salt organic solution, be hydrolyzed, obtains hydrolysis gel composite；
(b) after the carbon source oxidation product for obtaining the step (a) and hydrolysis gel composite mix, pressurized treatments is carried out, are obtained
To precast body；
(c) precast body that the step (b) that is carbonized obtains obtains carbide doping porous charcoal；
The organic carbon source is phenolic resin, epoxy resin, polyvinylidene fluoride resin, furfural resin, polyacrylic resin and gathers
One of urethane resin is a variety of；
The organic metal salt is metal alkyl salt, metal alkoxides salt, alcohol radical metal salt, phenide salt and phenol Base Metal
One of salt is a variety of, and the metal is one of titanium, vanadium, zirconium, niobium, molybdenum, tantalum, tungsten and hafnium or a variety of；
The curing agent is one of hexamethylenetetramine, p-methyl benzenesulfonic acid, formaldehyde, benzene sulfonyl chloride and polyformaldehyde or a variety of.
3. a kind of preparation method of carbide doping porous charcoal, comprising the following steps:
(1) add water in the mixed solution for including organic carbon source, organic metal salt, curing agent and organic solvent, be hydrolyzed, obtain
To hydrolyzing composition；
(2) surface oxidation is carried out after solidifying the hydrolyzing composition that the step (1) obtains, obtains combined oxidation product；
(3) the combined oxidation product for obtaining the step (2) carries out pressurized treatments, obtains precast body；
(4) precast body that the step (3) that is carbonized obtains obtains carbide doping porous charcoal；
The carbide doping porous charcoal includes the metal carbides in porous charcoal and the insertion porous charcoal；
The organic carbon source is phenolic resin, epoxy resin, polyvinylidene fluoride resin, furfural resin, polyacrylic resin and gathers
One of urethane resin is a variety of；
The organic metal salt is metal alkyl salt, metal alkoxides salt, alcohol radical metal salt, phenide salt and phenol Base Metal
One of salt is a variety of, and the metal is one of titanium, vanadium, zirconium, niobium, molybdenum, tantalum, tungsten and hafnium or a variety of；
The curing agent is one of hexamethylenetetramine, p-methyl benzenesulfonic acid, formaldehyde, benzene sulfonyl chloride and polyformaldehyde or a variety of.
4. a kind of preparation method of carbide doping porous charcoal, comprising the following steps:
(a) surface oxidation will be carried out after the mixed solution solidification including organic carbon source, curing agent and organic solvent, obtains carbon source oxygen
Change product；
Add water into organic metal salt organic solution, be hydrolyzed, obtains hydrolysis gel composite；
(b) after the carbon source oxidation product for obtaining the step (a) and hydrolysis gel composite mix, pressurized treatments is carried out, are obtained
To precast body；
(c) precast body that the step (b) that is carbonized obtains obtains carbide doping porous charcoal；
The carbide doping porous charcoal includes porous charcoal and the metal carbides being embedded in the porous charcoal and is supported on institute
State the metal carbides of porous carbon surface；
The organic carbon source is phenolic resin, epoxy resin, polyvinylidene fluoride resin, furfural resin, polyacrylic resin and gathers
One of urethane resin is a variety of；
The organic metal salt is metal alkyl salt, metal alkoxides salt, alcohol radical metal salt, phenide salt and phenol Base Metal
One of salt is a variety of, and the metal is one of titanium, vanadium, zirconium, niobium, molybdenum, tantalum, tungsten and hafnium or a variety of；
The curing agent is one of hexamethylenetetramine, p-methyl benzenesulfonic acid, formaldehyde, benzene sulfonyl chloride and polyformaldehyde or a variety of.
5. preparation method according to claim 3 or 4, which is characterized in that hydrolyzed in the step (1) and step (a)
Temperature independently is 0~70 DEG C, and the time of hydrolysis independently is 0.5~12h；
Cured temperature independently is 80~150 DEG C in the step (2) and step (a), and the cured time independently is 0.5~
12h；
The temperature aoxidized in the step (2) and step (a) independently is 180~260 DEG C, and the time of oxidation independently is 0.5
~3h.
6. preparation method according to claim 3 or 4, which is characterized in that in the step (3) and step (b) at pressurization
The pressure of reason independently is 1~50MPa.
7. preparation method according to claim 3 or 4, which is characterized in that carbonization is only in the step (4) and step (c)
On the spot are as follows: keep the temperature 0.5~6h after the precast body is warming up to carburizing temperature；The rate of the heating is 1~15 DEG C/min, institute
Stating carburizing temperature is 800~1600 DEG C.
8. preparation method according to claim 3 or 4, which is characterized in that it is described include organic carbon source, organic metal salt,
Organic carbon source in the mixed solution of curing agent and organic solvent, organic metal salt, curing agent and organic solvent mass ratio be
100:(3~40): (5~20): (100~1000)；
The quality of organic carbon source, curing agent and solvent in the mixed solution including organic carbon source, curing agent and organic solvent
Than for 100:(5~20): (50~500)；
The mass ratio of organic metal salt and organic solvent is (3~40): (50~500) in the organic metal salt organic solution；
Organic carbon source and the organic metal salt are organic in the mixed solution including organic carbon source, curing agent and organic solvent
The mass ratio of organic metal salt is 100:(3~40 in solution).
9. preparation method according to claim 3 or 4, which is characterized in that the organic solvent include alcohol organic solvent,
One of benzene class organic solvent and organic solvent of ketone are a variety of.
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