CN109742400A - Preparation method, porous carbon materials, self-supporting secondary battery negative pole and the secondary cell of porous carbon materials - Google Patents
Preparation method, porous carbon materials, self-supporting secondary battery negative pole and the secondary cell of porous carbon materials Download PDFInfo
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- CN109742400A CN109742400A CN201910010476.6A CN201910010476A CN109742400A CN 109742400 A CN109742400 A CN 109742400A CN 201910010476 A CN201910010476 A CN 201910010476A CN 109742400 A CN109742400 A CN 109742400A
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Abstract
The invention belongs to technical field of secondary batteriess, in particular to a kind of preparation method of porous carbon materials, porous carbon materials, self-supporting secondary battery negative pole and secondary cell.The preparation method of porous carbon materials provided by the invention includes the following steps: to mix organic monomer, foam metal with optionally catalyst, makes that home position polymerization reaction occurs, obtains the foam metal of polymer overmold, calcines, obtain porous carbon materials.This method utilizes foam metal transpirable feature at high temperature, synchronizes the removal of the synthesis and template that realize material, achievees the effect that get twice the result with half the effort.In addition, this method repeatability is high, controllability is strong, and simple process has great prospects for commercial application, it can be achieved that large-scale production.Porous carbon materials made from preparation method according to the present invention have good homogeneity, while the porous carbon materials have good ionic conductivity, can be used as self-supporting secondary battery negative pole, are conducive to the chemical property for improving secondary cell.
Description
Technical field
The invention belongs to technical field of secondary batteries, in particular to a kind of preparation method, porous of porous carbon materials
Carbon material, self-supporting secondary battery negative pole and secondary cell.
Background technique
The continuous consumption of the non-renewable resources such as fossil fuel and thus bring environmental problem, force people's exploitation new
Type, renewable, environmentally friendly energy storage device.Representative one of of the secondary cell as numerous energy storage devices, because energy density is high, follows
Ring performance is good, the advantages that having extended cycle life is by favor, has been widely used in daily life.However, electronics city
More stringent requirements are proposed for performance of the continuous development in field and electric vehicle market to secondary cell.As secondary cell important composition
Partial negative electrode material is also research emphasis at this stage.
Although lithium metal capacity is high, the fusing point of lithium is low, to air-sensitive, is easily oxidized, and cathode of lithium is easily grown
Li dendrite forms " dead lithium " or causes internal short-circuit of battery, and safety issue is prominent, in addition, lithium resource reserves are very limited, at
This height.These problems limit the application of cathode of lithium.
Commercialized secondary battery cathode material is mainly graphite, although its compacted density is high, price also compares just
Preferably, but since its granular size is different, surface defect is more, poor with the compatibility of electrolyte, side reaction is relatively more, because
This capacity is not stable in performance.In addition, needing additional addition bonding agent during graphite is prepared into cathode pole piece and leading
Electric agent, this can be such that the energy density of secondary cell reduces again.
In consideration of it, at least one of the present invention is specifically proposed to solve the above problems.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of porous carbon materials, by organic monomer, foam metal
It is mixed with optionally catalyst, makes that home position polymerization reaction occurs, obtain the foam metal of polymer overmold, calcine, obtain porous
Carbon material.This method repeatability is high, and controllability is strong, and simple process is, it can be achieved that be mass produced, before having great industrial application
Scape.
The second object of the present invention is to provide a kind of porous carbon materials, the porous carbon materials have good homogeneity and
Ionic conductivity is conducive to the cyclical stability for improving secondary cell using the porous carbon materials as the cathode of secondary cell.
The third object of the present invention is to provide a kind of self-supporting secondary battery negative pole, which is above-mentioned porous carbon
Material, does not need metal collector, does not need to add additional binder and conductive agent yet, be conducive to further increase secondary cell
Energy density.
The fourth object of the present invention is to provide a kind of secondary cell, which includes above-mentioned self-supporting secondary cell
Cathode.
The fifth object of the present invention is to provide a kind of electronic device comprising above-mentioned secondary cell, electric tool, electronic
Vehicle or electric power storage system.
To achieve the above object, the technical solution adopted by the present invention are as follows:
According to an aspect of the present invention, a kind of preparation method of porous carbon materials is provided, is included the following steps:
Organic monomer, foam metal are mixed with optionally catalyst, makes that home position polymerization reaction occurs, obtains polymer packet
The foam metal covered, calcining, obtains porous carbon materials.
As further preferred technical solution, in the foam metal of the polymer overmold, polymer and foam metal
Volume ratio be (5-10): 1, preferably (8-10): 1.
As further preferred technical solution, the polymer include: phenolic resin, polyaniline, polypyrrole, polythiophene or
In poly-dopamine any one or at least two combination；
Preferably, the foam metal includes foam zinc；
Preferably, the catalyst includes inorganic acid, and the inorganic acid includes concentrated hydrochloric acid and/or dilute sulfuric acid.
As further preferred technical solution, the mixed temperature is 10-50 DEG C, preferably 20-40 DEG C；
Preferably, the mixed time is 30-120min, preferably 60-100min；
Preferably, the calcining includes the steps that once being carbonized and secondary carbonization；
Preferably, the temperature being once carbonized is 400-700 DEG C, preferably 400-600 DEG C；
Preferably, the time being once carbonized is 3-7h, preferably 4-6h；
Preferably, the temperature of the secondary carbonization is 900-1500 DEG C, preferably 900-1000 DEG C；
Preferably, the time of the secondary carbonization is 2-5h, preferably 3-5h.
As further preferred technical solution, the preparation method of the porous carbon materials includes the following steps:
Phenol, low-carbon aldehyde, concentrated hydrochloric acid are mixed at 80-100 DEG C with foam zinc, makes that home position polymerization reaction occurs, obtains
The foam zinc of phenolic resin cladding, the foam zinc that phenolic resin coats once is carbonized at 400-600 DEG C, in 900-1000
DEG C secondary carbonization is carried out, porous carbon materials are made.
As further preferred technical solution, the low-carbon aldehyde include in formaldehyde, acetaldehyde or propionic aldehyde any one or extremely
Few two kinds of combination；
Preferably, the low-carbon aldehyde is formaldehyde and/or acetaldehyde.
According to another aspect of the present invention, a kind of porous carbon materials are also provided, using the system of the porous carbon materials
Preparation Method is made；
The aperture of the porous carbon materials is 100-400 μm, and the porous carbon materials have three dimensional skeletal structure, the bone
Frame with a thickness of 50-150 μm.
According to another aspect of the present invention, a kind of self-supporting secondary battery negative pole, the secondary electricity of self-supporting are also provided
Pond cathode is porous carbon materials or the porous carbon materials made from the preparation method of the porous carbon materials.
According to another aspect of the present invention, a kind of secondary cell is also provided, including anode, cathode, between anode and negative
Diaphragm and electrolyte between pole；
Wherein, the cathode is the self-supporting secondary battery negative pole.
According to another aspect of the present invention, a kind of electronic device comprising the secondary cell, electronic work are also provided
Tool, electric vehicle or electric power storage system.
Compared with prior art, the beneficial effects of the present invention are:
1, the preparation method of porous carbon materials provided by the invention, it is raw in situ with organic monomer using foam metal as template
At polymer be carbon source, the foam metal of obtained polymer overmold is calcined, porous carbon materials are obtained.Wherein, exist
During calcining, melt structure is first generated, rear pattern plate evaporates, and the porous carbon materials made are more uniform.
2, the present invention utilizes foam metal transpirable feature at high temperature, the synchronous synthesis for realizing porous carbon materials and mould
The removal of plate achievees the effect that get twice the result with half the effort.In addition, this method repeatability is high, controllability is strong, and simple process is, it can be achieved that big rule
Mould production, has great prospects for commercial application.
3, porous carbon materials made from the preparation method of the porous carbon materials provided according to the present invention have good uniform
Property, while the porous carbon materials have good ionic conductivity, can be used as secondary battery negative pole, are conducive to improve secondary cell
Cyclical stability.
4, porous carbon materials provided by the invention are at low cost, environmental-friendly and can realize self-supporting, do not need metal afflux
Body does not need to add additional binder and conductive agent, by the porous carbon materials directly as the cathode of secondary cell, favorably yet
In the energy density for further increasing secondary cell, had broad application prospects in secondary cell field.Simultaneously comprising this two
Electronic device, electric tool, electric vehicle or the electric power storage system of primary cell, it is at least having the same excellent with the secondary cell
Gesture.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the SEM figure in the embodiment of the present invention 1 using porous carbon materials made from preparation method provided by the invention
Piece；
Fig. 2 is to be used as using porous carbon materials made from preparation method provided by the invention from branch in the embodiment of the present invention 1
Support the cycle performance figure of the lithium ion battery of cathode assembling.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and are not construed as limiting model of the invention
It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
It should be understood that
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and preferred implementation method
It can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be with
Intercombination forms new technical solution.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit
A or multiple upper limits.
In the present invention, unless otherwise indicated, each reaction or operating procedure can be carried out sequentially, can not also be in sequence
It carries out.Preferably, method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art
Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
In a first aspect, providing a kind of preparation method of porous carbon materials at least one embodiment, include the following steps:
Organic monomer, foam metal are mixed with optionally catalyst, makes that home position polymerization reaction occurs, obtains polymer packet
The foam metal covered, calcining, obtains porous carbon materials.
The present invention in view of the defects existing in the prior art, proposes a kind of preparation method of porous carbon materials, this method with
Foam metal is template, using the generated in-situ polymer of organic monomer as carbon source, by the foam metal of obtained polymer overmold
It is calcined, obtains porous carbon materials.Wherein, during calcining, melt structure is first generated, rear pattern plate evaporation generates hole,
So that porous carbon materials obtained are more uniform, the cathode of self-supporting secondary cell can be used as, be conducive to improve secondary cell
Cyclical stability and energy density.
Meanwhile the present invention utilizes foam metal transpirable feature at high temperature, the synchronous synthesis and template for realizing material
Removal, overcome conventional method and be unable to control the long disadvantage of structure, preparation flow, achieve the effect that get twice the result with half the effort.In addition, should
Method repeatability is high, and controllability is strong, and simple process has great prospects for commercial application, it can be achieved that large-scale production.
It should be noted that present invention particular/special requirement no for the selection of organic monomer, as long as being immersed in foam metal
After organic monomer solution can in-situ preparation polymer, such as: organic monomer can be a kind of monomer, such as pyrroles or benzene
Amine, pyrroles, which polymerize, generates polypyrrole, and aniline polymerization generates polyaniline；It is also possible to two kinds of monomers, such as phenol and formaldehyde, the two
Polymerization generates phenolic resin etc..
Foam metal refers to the metal with three-dimensional structure.The three-dimensional structure of foam metal can guarantee subsequent
The porous carbon materials of generation can realize self-supporting.Foam metal need to form the melt environment of metal in certain temperature range,
It evaporation can be achieved in another temperature range removes template to generate hole, while realizing the uniform synthesis and template of porous carbon materials
Removal, achievees the effect that get twice the result with half the effort.
The meaning of above-mentioned " self-supporting " are as follows: porous carbon materials prepared by the present invention can directly as the cathode of secondary cell,
Without metal collector, do not need to add additional binder and conductive agent yet.
The meaning of " the optionally catalyst " are as follows: according to practical different selecting response addition or do not add catalyst.
Some more home position polymerization reactions of progress without adding catalyst can carry out that completely, catalyst can not be added at this time.
And some home position polymerization reactions must be completed under the catalytic action of catalyst, need to add catalyst at this time.
With after optionally catalyst mixes, foam metal is completely immersed into organic monomer solution for organic monomer, foam metal
In, polymerization reaction occurs in situ for organic monomer, and the polymer overmold of generation is in the hole of foam metal and surface, realization are wrapped completely
It covers, the foam metal of polymer overmold is calcined, porous carbon materials have been obtained.
In a preferred embodiment, in the foam metal of polymer overmold, the body of polymer and foam metal
Product is than being (5-10): 1, preferably (8-10): 1.
It should be noted that the volume example of polymer and foam metal is important the realization present invention, suitable body
Product facilitates processability more preferably porous carbon materials than that can make foam metal cladding completely.It is typical but unrestricted, polymer
Volume ratio with foam metal can be 5:1,6:1,7:1,7.5:1,8:1,9:1 or 10:1.
In a preferred embodiment, polymer includes: phenolic resin, polyaniline, polypyrrole, polythiophene or poly- more
In bar amine any one or at least two combination；
Preferably, foam metal includes foam zinc；
Preferably, catalyst includes inorganic acid, and the inorganic acid includes concentrated hydrochloric acid and/or dilute sulfuric acid.
It should be noted that the generated in-situ polymer of organic monomer is to realize weight of the invention as carbon source of the invention
Guarantee, according to inorganic carbon source, such as glucose etc. cannot achieve cladding bubble since the requirement of reaction is not achieved in its concentration
Foam metal, and then can not achieve the preparation of the porous carbon materials with self-support functions.Typical but unrestricted, polymer can be with
For in phenolic resin, polyaniline, polypyrrole, polythiophene or poly-dopamine any one or at least two combination；
The monomer of phenolic resin be phenols and aldehydes, the two polycondensation be phenolic resin, polyaniline, polypyrrole, polythiophene and
The monomer of poly-dopamine is respectively aniline, pyrroles, thiophene and dopamine, and aniline addition polymerization is polyaniline, and pyrroles's addition polymerization is polypyrrole,
Thiophene addition polymerization is polythiophene, and dopamine addition polymerization is poly-dopamine.
Foam metal of the present invention can form melt structure as template under certain calcination temperature, guarantee product
The homogeneity of porous carbon materials.In addition, foam metal has three-dimensional structure, which has to the porous carbon materials of preparation props up certainly
Support function provides the foundation.Typical but unrestricted, foam metal for example can be foam zinc.
In a preferred embodiment, mixed temperature is 10-50 DEG C, preferably 20-40 DEG C；
Preferably, the mixed time is 30-120min, preferably 60-100min；
Preferably, calcining includes the steps that once being carbonized and secondary carbonization；
Preferably, the temperature being once carbonized is 400-700 DEG C, preferably 400-600 DEG C；
Preferably, the time being once carbonized is 3-7h, preferably 4-6h；
Preferably, the temperature of secondary carbonization is 900-1500 DEG C, preferably 900-1000 DEG C；
Preferably, the time of secondary carbonization is 2-5h, preferably 3-5h.
The present invention does not have particular/special requirement for mixed temperature and time, as long as guaranteeing going on smoothly for home position polymerization reaction
Can (if the mixed time is too short, temperature is too low, home position polymerization reaction carry out not exclusively, product is very few；If mixed time mistake
Long, temperature is excessively high, and the degree of home position polymerization reaction is excessive, and reaction product is caused to be difficult to handle).It is typical but unrestricted, mixing
Time can be 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min；
Mixed temperature can be 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 45 DEG C or 50 DEG C.
It is to be appreciated that the selection for the temperature and time being once carbonized is to provide a melt ring to foam metal
Border, while the preliminary carbonisation for completing polymer.If temperature is excessively high, overlong time, foam metal starts evaporation loss occur,
Melt environment is not can guarantee；If temperature is too low, the time is too short, and carbonisation is incomplete, produces in subsequent secondary carbonisation
Raw bulk gas, destroys the complete structure of porous carbon materials, if the temperature being once carbonized is lower than the melting temperature of foam metal,
Melt environment can not be formed.It is typical but it is non-first limit, the temperature being once carbonized can be 400 DEG C, 500 DEG C, 600 DEG C or 700
℃；The time being once carbonized can be 3h, 4h, 5h, 6h or 7h.
Secondary carbonisation first is that guarantee porous carbon materials graphitization, make product have good electric conductivity；Second is that complete
At the evaporation of foam metal, removing template is removed.If temperature is excessively high, overlong time will cause the immediate loss of foam metal, destroy more
The continuous structure of hole carbon material；If temperature is too low, the time is too short, and the degree of graphitization of porous carbon materials is low, poorly conductive.It is typical
But it is non-first to limit, the temperature of secondary carbonization can for 900 DEG C, 1000 DEG C, 1100 DEG C, 1200 DEG C, 1300 DEG C, 1400 DEG C or
1500℃；The time of secondary carbonization can be 2h, 3h, 4h or 5h.
The present invention is not particularly limited the heating rate of calcining.Typical but unrestricted, heating rate can be 2
DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min or 7 DEG C/min.In addition, calcining need under protective atmosphere into
Row, protective gas can be argon gas, nitrogen etc..
In a preferred embodiment, the preparation method of porous carbon materials, includes the following steps:
Phenol, low-carbon aldehyde, concentrated hydrochloric acid are mixed at 80-100 DEG C with foam zinc, makes that home position polymerization reaction occurs, obtains
The foam zinc of phenolic resin cladding, the foam zinc that phenolic resin coats once is carbonized at 400-600 DEG C, then in 900-
1000 DEG C carry out secondary carbonization, and porous carbon materials are made.
Firstly, the three-dimensional structure of foam zinc, ensure that the porous carbon materials being subsequently generated have self-support functions.This
Outside, in the range of 400-600 DEG C, the foam zinc as template can provide a melt environment, the melt conditions warrant
The homogeneity for the porous carbon materials being subsequently generated.In the range of 900-1000 DEG C, foam zinc can realize itself by evaporation
Removal, and then the synthesis of porous carbon materials and the removal of template are realized simultaneously, achieve the effect that get twice the result with half the effort.
The relevant parameter for the foam zinc that the present invention uses is as follows:
Aperture: 100 μm -1000 μm；Porosity: 50%-98%；Through-hole rate: >=98%；Bulk density: 0.1-0.8g/
cm3。
It should be noted that the dosage of concentrated hydrochloric acid is appropriate.The concentrated hydrochloric acid for playing catalytic effect determines home position polymerization reaction
Carry out degree.If concentrated hydrochloric acid is very few, home position polymerization reaction carries out incomplete；If concentrated hydrochloric acid is excessive, extra acid can be to foam
Zinc causes to corrode, and destroys template.
In a preferred embodiment, low-carbon aldehyde includes any one in formaldehyde, acetaldehyde or propionic aldehyde or at least two
The combination of kind；
Preferably, the low-carbon aldehyde is formaldehyde and/or acetaldehyde.
Due to the growth with carbochain, the activity of organic matter can decline, therefore the present invention selects low-carbon aldehyde as synthesis phenol
A kind of raw material of urea formaldehyde.Typical but unrestricted, low-carbon aldehyde can choose formaldehyde, also can choose acetaldehyde, it is also an option that
Formaldehyde and the mixed aldehyde of acetaldehyde etc..
Second aspect provides a kind of porous carbon materials at least one embodiment, using the system of above-mentioned porous carbon materials
Preparation Method is made；
The aperture of porous carbon materials be 100-400 μm, porous carbon materials have three dimensional skeletal structure, skeleton with a thickness of
50-150μm。
Porous carbon materials made from preparation method using porous carbon materials provided by the invention, the porous carbon materials have
Good homogeneity and ionic conductivity are applied in secondary cell field, are conducive to the cyclical stability for improving secondary cell.
It is to be appreciated that the thickness in the aperture of porous carbon materials, structure and its skeleton is golden with the foam as template
Belong to related.Typical but unrestricted, the aperture of porous carbon materials is 100 μm, 200 μm, 300 μm or 400 μm；Skeleton with a thickness of
50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm or 150 μm.
The third aspect provides a kind of self-supporting secondary battery negative pole, self-supporting secondary cell at least one embodiment
Cathode is porous carbon materials or above-mentioned porous carbon materials made from the preparation method of above-mentioned porous carbon materials.
It can be directly as certainly after suitable size and shape it should be noted that the pressing of above-mentioned porous carbon materials is cut into
It supports negative electrode of lithium ion battery to use, does not need metal collector, also do not need to add additional binder and conductive agent, favorably
In the energy density for further increasing secondary cell.
Fourth aspect, provides a kind of secondary cell at least one embodiment, including anode, cathode, between anode and
Diaphragm and electrolyte between cathode；
Wherein, cathode is above-mentioned self-supporting secondary battery negative pole.
It is understood that the present invention remaining part in addition to cathode of secondary cell is not done it is specifically limited, should
The core of secondary cell is to contain porous carbon materials of the invention, remaining composition or component can refer to the prior art.
It should be noted that porous carbon materials provided by the invention can be applied to include lithium ion battery, sodium-ion battery
Self-supporting secondary battery negative pole is used as in equal secondary cells.
It is mainly further described in detail by taking lithium ion battery as an example below the present invention, it is understood, however, that,
Secondary cell includes but is not limited to lithium ion battery.
5th aspect provides a kind of electronic device comprising above-mentioned secondary cell, electronic at least one embodiment
Tool, electric vehicle or electric power storage system.
Electronic device is the electronics for using secondary cell to perform various functions (for example, performing music) as the power supply of operation
Device.Electric tool is the electric tool for using secondary cell to carry out moving parts (for example, drill bit) as driving power.Electric vehicle
It is the electric vehicle run by secondary cell as driving power, and can be and be also equipped with other than secondary cell
The automobile (including hybrid electric vehicle) of other driving sources.Electric power storage system is to use secondary cell as the electricity of electric power storage source
Power stocking system.For example, electric power is stored in the secondary cell as electric power storage source in household power stocking system,
And consumption stores electric power in the secondary battery to be able to use the various devices of such as domestic electronic appliances as needed.
Combined with specific embodiments below, comparative example and attached drawing, the invention will be further described.
Embodiment 1
A kind of preparation method of porous carbon materials is present embodiments provided, its step are as follows:
4g phenol, 2.5mL formalin are placed in a beaker, 10mL concentrated hydrochloric acid is added thereto, stirs evenly.By foam
Zinc is immersed in above-mentioned mixed solution, 20 DEG C at a temperature of react 30mins, after the completion of home position polymerization reaction, by product into
Row low-temperature vacuum drying obtains the foam zinc of phenolic resin cladding (volume ratio of phenolic resin and foam zinc is 10:1).By institute
The foam zinc for obtaining phenolic resin cladding is heated to 500 DEG C under ar gas environment with the heating rate of 5 DEG C/min, keeps the temperature 6h, carries out
Primary carbonization；1000 DEG C then are heated to the heating rate of 5 DEG C/min, 2h is kept the temperature, carries out secondary carbonization.Decline to temperature
Afterwards to get arrived porous carbon materials (as shown in Figure 1, porous carbon materials be three dimensional skeletal structure, skeleton with a thickness of 50-150
μm, aperture is 100-400 μm).
Embodiment 2
A kind of preparation method of porous carbon materials is present embodiments provided, its step are as follows:
3g phenol, 2mL formalin are placed in a beaker, 5mL concentrated hydrochloric acid is added thereto, stirs evenly.By foam zinc
Be immersed in above-mentioned mixed solution, 10 DEG C at a temperature of react 120mins, after the completion of home position polymerization reaction, by product into
Row low-temperature vacuum drying obtains the foam zinc of phenolic resin cladding (volume ratio of phenolic resin and foam zinc is 8:1).By gained
The foam zinc of phenolic resin cladding is heated to 600 DEG C under ar gas environment with the heating rate of 3 DEG C/min, keeps the temperature 3h, carries out one
Secondary carbonization；1000 DEG C then are heated to the heating rate of 5 DEG C/min, 3h is kept the temperature, carries out secondary carbonization.After temperature decline,
Porous carbon materials are obtained.
Embodiment 3
A kind of preparation method of porous carbon materials is present embodiments provided, its step are as follows:
4g phenol, 2.5mL formalin are placed in a beaker, 7mL concentrated hydrochloric acid is added thereto, stirs evenly.By foam
Zinc is immersed in above-mentioned mixed solution, 40 DEG C at a temperature of react 100mins, after the completion of home position polymerization reaction, by product
It carries out low-temperature vacuum drying, obtains the foam zinc of phenolic resin cladding (volume ratio of phenolic resin and foam zinc is 10:1).It will
The foam zinc of gained phenolic resin cladding is heated to 400 DEG C under ar gas environment with the heating rate of 3 DEG C/min, keeps the temperature 4h, into
The primary carbonization of row；900 DEG C then are heated to the heating rate of 5 DEG C/min, 5h is kept the temperature, carries out secondary carbonization.Decline to temperature
Afterwards to get having arrived porous carbon materials.
Embodiment 4
A kind of preparation method of porous carbon materials is present embodiments provided, its step are as follows:
4mL pyrroles is placed in a beaker, foam zinc is immersed in above-mentioned chromium solution, 50 DEG C at a temperature of react
Product is carried out low-temperature vacuum drying after the completion of home position polymerization reaction by 60mins, and the foam zinc for obtaining polypyrrole cladding is (poly-
The volume ratio of pyrroles and foam zinc is 5:1).The foam zinc that gained polypyrrole is coated is in a nitrogen environment with the liter of 5 DEG C/min
Warm rate is heated to 700 DEG C, keeps the temperature 7h, is once carbonized；1500 DEG C then are heated to the heating rate of 5 DEG C/min, is protected
Warm 2h carries out secondary carbonization.To get having arrived porous carbon materials after temperature decline.
Embodiment 5
The preparation method for present embodiments providing a kind of porous carbon materials, the amount in addition to changing phenol are the amount of 1g, formaldehyde
For 2mL, the volume ratio 4:1 of phenolic resin and foam zinc, remaining preparation step and reality in the foam zinc for coating phenolic resin
It is identical to apply example 1.
Embodiment 6
The preparation method for present embodiments providing a kind of porous carbon materials, the amount in addition to changing phenol are 1.5g, formaldehyde
Amount be 2mL, make phenolic resin coat foam zinc in phenolic resin and foam zinc volume ratio 5:1, remaining preparation step and
Embodiment 1 is identical.
Embodiment 7
The preparation method for present embodiments providing a kind of porous carbon materials, the amount in addition to changing phenol are the amount of 2g, formaldehyde
For 2.5mL, the volume ratio 7:1 of phenolic resin and foam zinc in the foam zinc that coats phenolic resin, remaining preparation step and
Embodiment 1 is identical.
Embodiment 8
The preparation method for present embodiments providing a kind of porous carbon materials, the amount in addition to changing phenol are the amount of 3g, formaldehyde
For 2mL, the volume ratio 8:1 of phenolic resin and foam zinc, remaining preparation step and reality in the foam zinc for coating phenolic resin
It is identical to apply example 1.
Embodiment 9
The preparation method for present embodiments providing a kind of porous carbon materials, the amount in addition to changing phenol are the amount of 3g, formaldehyde
For 2.5mL, the volume ratio 9:1 of phenolic resin and foam zinc in the foam zinc that coats phenolic resin, remaining preparation step and
Embodiment 1 is identical.
Embodiment 10
The preparation method for present embodiments providing a kind of porous carbon materials, in addition to change organic monomer is dopamine 2 g, urges
Agent is dilute sulfuric acid so that the foam zinc of poly-dopamine cladding is made, remaining preparation step is same as Example 1.
Embodiment 11
The preparation method for present embodiments providing a kind of porous carbon materials is aniline 1.5g to make in addition to changing organic monomer
The foam zinc of polyaniline-coated is obtained, remaining preparation step is same as Example 1.
Embodiment 12
The preparation method for present embodiments providing a kind of porous carbon materials, in addition to formalin is replaced with acetaldehyde solution,
Remaining preparation step is same as Example 1.
Embodiment 13
The preparation method for present embodiments providing a kind of porous carbon materials, in addition to formalin is replaced with propionic aldehyde solution,
Remaining preparation step is same as Example 1.
Note: the porous carbon materials that the above various embodiments is prepared can be achieved self-support functions, can directly as lithium from
Sub- battery cathode.
Comparative example 1
This comparative example provides a kind of preparation method of porous carbon materials, in addition to foam zinc is directly immersed in phenolic resin
30mins is stirred in solution, product is subjected to low-temperature vacuum drying, obtains foam zinc (phenolic resin and the bubble of phenolic resin cladding
The volume ratio of foam zinc is 10:1), remaining preparation step is same as Example 1.
The experimental result of this comparative example are as follows: the porous carbon materials that this comparative example is prepared cannot achieve phenolic resin pair
The complete cladding of foam zinc, and then can not achieve self-support functions, after the porous carbon materials smear for needing to prepare as lithium from
The cathode of sub- battery.
Comparative example 2
This comparative example provides a kind of preparation method of porous carbon materials, and it is molten that foam zinc is immersed in glucose in addition to directly
In liquid (volume ratio of glucose and foam zinc is 10:1), remaining preparation step is same as Example 1.
The experimental result of this comparative example are as follows: the porous carbon materials that this comparative example is prepared cannot achieve glucose to bubble
The complete cladding of foam zinc, and then can not achieve self-support functions, lithium ion is used as after the porous carbon materials smear for needing to prepare
The cathode of battery.
Comparative example 3
This comparative example provides a kind of preparation method of porous carbon materials, in addition to replacing foam zinc with zinc particle, remaining system
Standby step is same as Example 1.
The experimental result of this comparative example are as follows: the porous carbon materials that this comparative example is prepared can not form three-dimensional framework knot
Structure, and then can not achieve self-support functions needs the cathode after the porous carbon materials smear that will be prepared as lithium ion battery.
Experimental example
The porous carbon materials that the porous carbon materials provided respectively with embodiment 1-5 are provided directly as cathode, comparative example 1-3
Cathode is used as after smear, with LiFePO4As anode assembling button cell after smear, in the voltage window range of 2.5-4.5V
Loop test is carried out under interior, 1C current density, (wherein, Fig. 2 is the preparation method provided with embodiment 1 to performance as shown in table 1
Porous carbon materials obtained are directly as the cycle performance figure of cathode assembling lithium ion battery, and after the circle of circulation 200, specific capacity is protected
Hold in 342mAh/g):
The performance data of the button cell of the assembling of porous carbon materials made from each embodiment of table 1 and comparative example
The related data from table, it can be deduced that draw a conclusion: it can smoothly be prepared using preparation method of the invention
Porous carbon materials with self-support functions are shown excellent with the porous carbon materials directly as the cathode of lithium ion battery
Different cyclical stability and high energy density.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of porous carbon materials, which comprises the steps of:
Organic monomer, foam metal are mixed with optionally catalyst, makes that home position polymerization reaction occurs, obtains polymer overmold
Foam metal, calcining, obtains porous carbon materials.
2. the preparation method of porous carbon materials according to claim 1, which is characterized in that in the bubble of the polymer overmold
In foam metal, the volume ratio of polymer and foam metal is (5-10): 1, preferably (8-10): 1.
3. the preparation method of porous carbon materials according to claim 1, which is characterized in that the polymer includes: phenolic aldehyde
In resin, polyaniline, polypyrrole, polythiophene or poly-dopamine any one or at least two combination；
Preferably, the foam metal includes foam zinc；
Preferably, the catalyst includes inorganic acid, and the inorganic acid includes concentrated hydrochloric acid and/or dilute sulfuric acid.
4. the preparation method of porous carbon materials according to claim 1-3, which is characterized in that the mixed temperature
Degree is 10-50 DEG C, preferably 20-40 DEG C；
Preferably, the mixed time is 30-120min, preferably 60-100min；
Preferably, the calcining includes the steps that once being carbonized and secondary carbonization；
Preferably, the temperature being once carbonized is 400-700 DEG C, preferably 400-600 DEG C；
Preferably, the time being once carbonized is 3-7h, preferably 4-6h；
Preferably, the temperature of the secondary carbonization is 900-1500 DEG C, preferably 900-1000 DEG C；
Preferably, the time of the secondary carbonization is 2-5h, preferably 3-5h.
5. the preparation method of porous carbon materials according to claim 1-3, which is characterized in that including walking as follows
It is rapid:
Phenol, low-carbon aldehyde, concentrated hydrochloric acid are mixed at 80-100 DEG C with foam zinc, makes that home position polymerization reaction occurs, obtains phenolic aldehyde
The foam zinc of resin cladding, the foam zinc that phenolic resin coats once is carbonized at 400-600 DEG C, then in 900-1000
DEG C secondary carbonization is carried out, porous carbon materials are made.
6. the preparation method of porous carbon materials according to claim 5, which is characterized in that the low-carbon aldehyde include formaldehyde,
In acetaldehyde or propionic aldehyde any one or at least two combination；
Preferably, the low-carbon aldehyde is formaldehyde and/or acetaldehyde.
7. a kind of porous carbon materials, which is characterized in that using the preparation side of porous carbon materials described in any one of claims 1-6
Method is made；
The aperture of the porous carbon materials is 100-400 μm, and the porous carbon materials have three dimensional skeletal structure, the skeleton
With a thickness of 50-150 μm.
8. a kind of self-supporting secondary battery negative pole, which is characterized in that the self-supporting secondary battery cathode extremely claim 1-6 appoints
Porous carbon materials made from the preparation method of porous carbon materials described in one or porous carbon materials as claimed in claim 7.
9. a kind of secondary cell, which is characterized in that including anode, cathode, the diaphragm between anode and cathode and electrolysis
Liquid；
Wherein, the cathode is self-supporting secondary battery negative pole according to any one of claims 8.
10. including electronic device, electric tool, electric vehicle or the electric power storage system of secondary cell as claimed in claim 9.
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