CN110407203A - A kind of highly conductive graphite foam and preparation method thereof - Google Patents
A kind of highly conductive graphite foam and preparation method thereof Download PDFInfo
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- CN110407203A CN110407203A CN201910492403.5A CN201910492403A CN110407203A CN 110407203 A CN110407203 A CN 110407203A CN 201910492403 A CN201910492403 A CN 201910492403A CN 110407203 A CN110407203 A CN 110407203A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to porous carbon and preparation method thereof more particularly to a kind of preparation methods of highly conductive graphite foam, and using polyurethane foam as template, using soluble mesophase pitch as raw material, by secondary liquid impregnation and graphitization processing, graphite foam is made.Highly conductive graphite foam prepared by the present invention has the following characteristics that hole based on 0.1~0.5 μm of macropore, uniform pore diameter, 20~50nm of hole wall, through-hole rate >=90%, carries sulfur content >=85%；Degree of graphitization >=90%, p owder resistivity≤25m Ω cm.The present invention solves the problems, such as that the load sulfur content of positive carrier in the prior art is lower and electric conductivity is bad simultaneously.
Description
Technical field
The present invention relates to the highly conductive graphite of sulphur anode carrier in porous carbon and preparation method thereof, especially lithium-sulfur cell to steep
Foam and preparation method thereof.
Background technique
Lithium-sulfur cell is the secondary cell of a kind of high-energy, environmental protection, is expected to become next-generation electric car first choice battery class
Type.The technical bottleneck of lithium-sulfur cell industrialization is that positive sulphur has dissolubility in the electrolytic solution, and this aspect can reduce anode
Active material quality destroys the cycle performance of battery；On the other hand it will lead to the increase of electrolyte viscosity, Ion transfer speed becomes
Slowly, so that the internal resistance of cell increases severely, battery is directly scrapped.
In order to solve this problem, sulphur is generally placed in porous carbon support by people, although this mode can alleviate sulphur
Dissolution, but also result in sulphur and collector poor contact.This is because the sulphur in porous carbon be with gas procedure enter it is porous
Carbon, conductive agent can not be mixed into sulphur powder under the technique, therefore its electric conductivity is completely dependent on porous carbon support.However, more
Hole carbon is mostly amorphous carbon material, electric conductivity itself is general, and after being made into porous structure, electric conductivity becomes worse, this
Outside, porous carbon materials toughness is insufficient, and crack conditions are had in pole piece nipping process, has further been destroyed sulphur and collector
Electric conductivity.Therefore, exploitation high conduction performance porous carbon support just becomes a key of lithium-sulfur cell.
There are many reports of porous carbon electric conductivity ameliorative way at present, the study found that in porous carbon surface or inside
The electric conductivity of sulphur can be improved by adding a certain amount of conductive agent, but effect is limited, be unable to satisfy lithium-sulfur cell high power charging-discharging
It is required that；Using graphited porous carbon, and can occur hole during heat treatment and shrink problem, carry sulfur content and substantially decay；With swollen
Swollen graphite is to carry sulphur body, although can solve electric conductivity, and hole is flourishing, the hole of expanded graphite be it is tubaeform, it is inner small
It is outer big, it is poor to the constraint of sulphur.
In consideration of it, the present invention provides one kind using macropore polyurethane foam as template, pass through two step impregnation technologies and later period
The method with porous, highly conductive graphite foam is made in heat treatment.
Summary of the invention
Anode in lithium-sulfur cell is commonly sulphur or copolymerization sulphur, and it is existing that dissolution easily occurs in lipid or ethers electrolyte
As in order to inhibit the dissolution of sulphur in the electrolytic solution, it is carrier that people, which mostly use greatly porous carbon,.However, sulphur enters porous carbon use
Be vapour deposition process, conductive agent during which can not be added in sulphur powder, carries sulfur content and high conductivity to meet the high of porous carbon
Can, the present invention provides a kind of highly conductive foam material of graphite and preparation method thereof.
The present invention is achieved by the following technical programs:
A kind of preparation method of highly conductive graphite foam, which comprises the following steps: using polyurethane foam as mould
Using soluble mesophase pitch as raw material, by secondary liquid impregnation and graphitization processing, graphite foam is made in plate.
Further, a kind of preparation method of highly conductive graphite foam, comprising the following steps:
It impregnates for the first time: using quinoline for solvent, soluble mesophase pitch is dissolved in quinoline, then by polyurethane foam
It is placed in cold primer-oil, curing process is carried out after standing, the curing process carries out under an inert atmosphere, natural after curing process
It is cooling, curing material is obtained, curing material is broken up to obtain secondary template by machinery；
Second of dipping: it uses the pure quinoline of analysis for solvent, soluble mesophase pitch is dissolved in quinoline, by secondary mould
Plate is placed in cold primer-oil, and curing process is carried out after standing, and the curing process carries out under an inert atmosphere, after curing process certainly
So cooling, curing material is broken up to obtain graphite foam presoma through machinery；
Graphitization: above-mentioned graphite foam presoma is subjected to ordinary graphite processing, obtains highly conductive graphite foam.
Further, a kind of preparation method of highly conductive graphite foam, comprising the following steps:
It impregnates for the first time: using the pure quinoline of analysis for solvent, soluble mesophase pitch is dissolved in the pure quinoline of analysis, shape
At cold primer-oil, the mass percent for controlling soluble mesophase pitch in solution is 10%, then polyurethane foam is placed in drip
In green solution, the mass ratio of the polyurethane foam and soluble mesophase pitch is (10~20): 1, it is carried out after standing 1~3h
Curing process, the curing process carry out under an inert atmosphere, and solidification heating rate is 0.2~1 DEG C/min, solidify maximum temperature
It is 700~1300 DEG C, solidification process 10~60min of constant temperature at the maximum temperature, then natural cooling, obtains curing material, will
Curing material is broken up to obtain secondary template by machinery；
Second of dipping: using the pure quinoline of analysis for solvent, soluble mesophase pitch is dissolved in the pure quinoline of analysis, shape
At cold primer-oil, the mass percent for controlling soluble mesophase pitch in solution is 20%, and it is molten that secondary template is placed in pitch
In liquid, the mass ratio of secondary template and soluble mesophase pitch is (5~10): 1, curing process, institute are carried out after standing 1~3h
It states curing process to carry out under an inert atmosphere, solidification heating rate is 0.5~3 DEG C/min, and solidification maximum temperature is 900~1300
DEG C, solidification process 10~60min of constant temperature at the maximum temperature, after natural cooling, curing material is broken up to obtain graphite through machinery to be steeped
Foam presoma；
Graphitization: by above-mentioned graphite foam presoma 3200 DEG C of graphitization processings for 24 hours, obtain highly conductive graphite foam.
Preferably, the D50 of the polyurethane foam is 20 μm, and the aperture of the polyurethane foam is 0.8 μm, the poly- ammonia
The purity of ester foam is that analysis is pure.
Preferably, the softening point of the soluble mesophase pitch be 220~270 DEG C, intermediate Phase Proportion >=60%, in quinoline
There is good dissolubility in quinoline solvent.
Preferably, the soluble mesophase pitch is made of new mesophase pitch and pre- mesophase pitch.
A kind of highly conductive graphite foam, which is characterized in that the highly conductive graphite foam is highly conductive according to above-mentioned one kind
The preparation method preparation of graphite foam.
A kind of highly conductive graphite foam, which is characterized in that the highly conductive graphite foam have the following characteristics that hole with
Based on 0.1~0.5 μm of macropore, uniform pore diameter, 20~50nm of hole wall, through-hole rate >=90%, carry sulfur content >=85%；Degree of graphitization >=
90%, p owder resistivity≤25m Ω cm.
Compared with prior art, the invention has the following advantages:
To realize that graphite foam meets the high requirement for carrying sulfur content and high conductivity simultaneously, the present invention is using polyurethane foam as mould
Plate is invested pitch on the skeleton of polyurethane foam by a liquid phase impregnation using soluble mesophase pitch as raw material,
It is impregnated again after solidification as secondary template, the controllable graphite foam presoma of hole can be obtained.Most afterwards through being graphitized
Obtain highly conductive graphite foam.The innovative point of the technique is: 1. raw material selects: plain asphalt can not meet easy graphitization simultaneously
The requirement of (highly conductive), good dipping (height carries sulfur content), therefore patent and document do not have using pitch as raw material, pass through template
Prepare the report of highly conductive graphite foam.The present invention has selected a kind of special pitch for the first time: in soluble (dissolving in quinoline)
Between asphalt phase, which only includes new mesophase pitch and pre- mesophase pitch, and this pitch has high softening-point (220~270
DEG C), intermediate Phase Proportion high (>=60%), there is good dissolubility in quinoline solvent.
2. impregnation technology: since polyurethane is low carbon residue material, can disappear substantially in solidification process, therefore the mould of the material
Plate will disappear after acting on experience one-step solidification, and want that the technique for just reaching strict control of material hole by single-steeping is
Difficult to realize.Therefore, present invention employs two step impregnation technologies, first step dipping mainly allows soluble mesophase pitch suitable
Amount is attached on polyurethane skeleton, and stable template is formed after solidification；The purpose of double-steeping is before regulating and controlling graphite foam repeatedly
Drive the pore structure of body；The pitch concentration impregnated twice has larger difference, and second of dipping pitch concentration used is higher.
The present invention prepares graphite foam using unique technique, solves the positive carrier of lithium-sulfur cell in the prior art
Load sulfur content is lower and the bad problem of electric conductivity.The advantages of graphite foam prepared by the present invention, is: sulfur content height is 1. carried, it can
Up to 85% or more；2. undergoing graphitization processing, resulting material has good electric conductivity, p owder resistivity≤25m Ω cm.
Specific embodiment
Embodiment 1
By 10g softening point be 220 DEG C, the new mesophase pitch of intermediate Phase Proportion 70% is dissolved in 90g quinoline, is completely dissolved
It by the commercially available D50 of 100g is again afterwards 20 μm, aperture is that 0.8 μm of the pure polyurethane foam of analysis (similarly hereinafter) is dipped in cold primer-oil, quiet
Curing process, condition of cure are carried out after setting 1h are as follows: 0.2 DEG C nitrogen atmosphere, heating rate/min, solidification maximum temperature are 750 DEG C,
Constant temperature time 20min.Solidifying substance is broken up to obtain secondary template through machinery.
By 10g softening point be 220 DEG C, the new mesophase pitch of intermediate Phase Proportion 80% is dissolved in 40g quinoline, is completely dissolved
50g polyurethane foam is dipped in cold primer-oil again afterwards, carries out curing process, condition of cure after standing 1h are as follows: nitrogen atmosphere, liter
Warm 0.5 DEG C/min of speed, solidification maximum temperature are 1200 DEG C, constant temperature time 60min.Solidifying substance is broken up to obtain graphite bubble through machinery
The presoma of foam.
It is most graphitized for 24 hours through 3200 DEG C afterwards, obtains graphite foam 1# sample.
Embodiment 2
By 10g softening point be 250 DEG C, the new mesophase pitch of intermediate Phase Proportion 80% is dissolved in 90g quinoline, is completely dissolved
200g polyurethane foam is dipped in cold primer-oil again afterwards, carries out curing process, condition of cure after standing 3h are as follows: argon atmosphere,
0.5 DEG C/min of heating rate, solidification maximum temperature are 900 DEG C, constant temperature time 30min.Solidifying substance is broken up to obtain secondary through machinery
Template.
By 10g softening point be 220 DEG C, the new mesophase pitch of intermediate Phase Proportion 80% is dissolved in 40g quinoline, is completely dissolved
100g polyurethane foam is dipped in cold primer-oil again afterwards, carries out curing process, condition of cure after standing 3h are as follows: argon atmosphere,
0.5 DEG C/min of heating rate, solidification maximum temperature are 1250 DEG C, constant temperature time 60min.Solidifying substance is broken up to obtain graphite through machinery
The presoma of foam.
It is most graphitized for 24 hours through 3200 DEG C afterwards, obtains graphite foam 2# sample.
Embodiment 3
By 10g softening point be 250 DEG C, the pre- mesophase pitch of intermediate Phase Proportion 60% is dissolved in 90g quinoline, is completely dissolved
100g polyurethane foam is dipped in cold primer-oil again afterwards, carries out curing process, condition of cure after standing 2h are as follows: nitrogen atmosphere,
0.3 DEG C/min of heating rate, solidification maximum temperature are 800 DEG C, constant temperature time 10min.Solidifying substance is broken up to obtain secondary through machinery
Template.
By 10g softening point be 250 DEG C, the pre- mesophase pitch of intermediate Phase Proportion 60% is dissolved in 40g quinoline, is completely dissolved
50g polyurethane foam is dipped in cold primer-oil again afterwards, carries out curing process, condition of cure after standing 1h are as follows: nitrogen atmosphere, liter
Warm 3 DEG C/min of speed, solidification maximum temperature are 1300 DEG C, constant temperature time 60min.Solidifying substance is broken up to obtain graphite foam through machinery
Presoma.
It is most graphitized for 24 hours through 3200 DEG C afterwards, obtains graphite foam 3# sample.
Embodiment 4
By 10g softening point be 270 DEG C, the pre- mesophase pitch of intermediate Phase Proportion 70% is dissolved in 90g quinoline, is completely dissolved
200g polyurethane foam is dipped in cold primer-oil again afterwards, carries out curing process, condition of cure after standing 3h are as follows: argon atmosphere,
0.5 DEG C/min of heating rate, solidification maximum temperature are 900 DEG C, constant temperature time 30min.Solidifying substance is broken up to obtain secondary through machinery
Template.
By the soft softening point of 10g be 270 DEG C, the pre- mesophase pitch of intermediate Phase Proportion 70% is dissolved in 40g quinoline, completely molten
100g polyurethane foam is dipped in cold primer-oil by Xie Houzai, carries out curing process, condition of cure after standing 3h are as follows: argon gas gas
0.5 DEG C atmosphere, heating rate/min, solidification maximum temperature are 1250 DEG C, constant temperature time 60min.Solidifying substance is broken up to obtain through machinery
The presoma of graphite foam.
It is most graphitized for 24 hours through 3200 DEG C afterwards, obtains graphite foam 4# sample.
Comparative example: the low resistance porous carbon of Kuraray Co., Ltd. production, YP-80F.
The performance comparison of the low resistance porous carbon of the graphite foam and comparative example of embodiment 1-4 preparation is as shown in the table:
Comparison is it is found that either load sulfur content or electric conductivity, the embodiment of the present invention sample are superior to comparative example.
The advantages of graphite foam prepared by the present invention, is: sulfur content height is 1. carried, up to 85% or more；2. undergoing at graphitization
Reason, resulting material have good electric conductivity, p owder resistivity≤25m Ω cm.
Why the present invention can obtain highly conductive graphite foam, and one of core is raw material selection.Used in the present invention
Raw material has compared with high softening-point and intermediate phase constituent, while it is soluble to be also equipped with ideal quinoline.High softening-point ensure that pitch
In solidifying slow temperature-rise period, bubble will not be generated because fugitive constituent escapes again；Phase constituent guarantees that material has between senior middle school
Easily graphitization characteristic, it is ensured that gained graphite foam has good conductive property；Quinoline solubility is before realizing liquid impregnation
It mentions.
Further, since polyurethane is almost without carbon residue, therefore the template is only capable of undergoing primary heat treatment, and only by one
Secondary dipping-curing process is the pore performance for being difficult to control graphite foam, therefore, present invention employs two step impregnation technologies, first
Step dipping is impregnated using the lower solution of pitch concentration, it is therefore an objective to obtain stable carbon template, second step dipping can be very good
The pore structure for controlling graphite foam presoma, facilitates the lot stability of technique.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.It should be pointed out that for those skilled in the art, without departing from the principles of the present invention several change
Into and retouching, also should be regarded as protection scope of the present invention.The available prior art of each component part being not known in the present embodiment
It is realized.
Claims (8)
1. a kind of preparation method of highly conductive graphite foam, which comprises the following steps: using polyurethane foam as mould
Using soluble mesophase pitch as raw material, by secondary liquid impregnation and graphitization processing, graphite foam is made in plate.
2. a kind of preparation method of highly conductive graphite foam according to claim 1, which is characterized in that including following step
It is rapid:
It impregnates for the first time: using quinoline for solvent, soluble mesophase pitch is dissolved in quinoline, then polyurethane foam is placed in
In cold primer-oil, curing process is carried out after standing, the curing process carries out under an inert atmosphere, naturally cold after curing process
But, curing material is obtained, curing material is broken up to obtain secondary template by machinery；
Second of dipping: it uses the pure quinoline of analysis for solvent, soluble mesophase pitch is dissolved in quinoline, secondary template is set
In cold primer-oil, curing process is carried out after standing, the curing process carries out under an inert atmosphere, naturally cold after curing process
But, curing material is broken up to obtain graphite foam presoma through machinery；
Graphitization: above-mentioned graphite foam presoma is subjected to ordinary graphite processing, obtains highly conductive graphite foam.
3. a kind of preparation method of highly conductive graphite foam according to claim 2, which is characterized in that including following step
It is rapid:
It impregnates for the first time: using the pure quinoline of analysis for solvent, soluble mesophase pitch is dissolved in quinoline, control and dripped in solution
Green mass percent is 10%, then polyurethane foam is placed in cold primer-oil, the quality of the polyurethane foam and pitch
Than for (10~20): carrying out curing process after 1,1~3h of standing, the curing process carries out under an inert atmosphere, solidification heating
Speed be 0.2~1 DEG C/min, solidification maximum temperature be 700~1300 DEG C, solidification process at the maximum temperature constant temperature 10~
60min, then natural cooling, obtains curing material, and curing material is broken up to obtain secondary template by machinery；
Second of dipping: it uses the pure quinoline of analysis for solvent, soluble mesophase pitch is dissolved in quinoline, control and dripped in solution
Green mass percent is 20%, and secondary template is placed in cold primer-oil, and secondary template and asphalt quality ratio are (5~10):
1, curing process is carried out after standing 1~3h, the curing process carries out under an inert atmosphere, and solidification heating rate is 0.5~3
DEG C/min, solidification maximum temperature is 900~1300 DEG C, solidification process 10~60min of constant temperature at the maximum temperature, natural cooling
Afterwards, curing material is broken up to obtain graphite foam presoma through machinery；
Graphitization: by above-mentioned graphite foam presoma 3200 DEG C of graphitization processings for 24 hours, obtain highly conductive graphite foam.
4. a kind of preparation method of highly conductive graphite foam according to claim 1-3, it is characterised in that: described
The D50 of polyurethane foam is 20 μm, and the aperture of the polyurethane foam is 0.8 μm, and the purity of the polyurethane foam is analysis
It is pure.
5. a kind of preparation method of highly conductive graphite foam according to claim 1-3, it is characterised in that: described
The softening point of soluble mesophase pitch is 220~270 DEG C, intermediate Phase Proportion >=60%, have in quinoline solvent it is good
Dissolubility.
6. a kind of preparation method of highly conductive graphite foam according to claim 5, it is characterised in that: in the solubility
Between asphalt phase be made of new mesophase pitch and pre- mesophase pitch.
7. a kind of highly conductive graphite foam, it is characterised in that: the highly conductive graphite foam is according to claim 1 any one of -6
A kind of preparation method preparation of highly conductive graphite foam.
8. a kind of highly conductive graphite foam according to claim 7, it is characterised in that: the highly conductive graphite foam has
Following characteristics: hole based on 0.1~0.5 μm of macropore, uniform pore diameter, 20~50nm of hole wall, through-hole rate >=90%, carry sulfur content >=
85%；Degree of graphitization >=90%, p owder resistivity≤25m Ω cm.
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| CN201910492403.5A CN110407203B (en) | 2019-06-06 | 2019-06-06 | High-conductivity graphite foam and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910492403.5A CN110407203B (en) | 2019-06-06 | 2019-06-06 | High-conductivity graphite foam and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049928A (en) * | 2006-04-04 | 2007-10-10 | 中国矿业大学(北京) | Method for manufacturing high heat conducting foam material of graphite with even apertures |
| CN102134068A (en) * | 2011-04-24 | 2011-07-27 | 大连理工大学 | Preparation method of graphitic carbon foam with high aperture ratio |
| CN103626153A (en) * | 2013-11-29 | 2014-03-12 | 哈尔滨工程大学 | Method for preparing graphitized foam carbon by using boron-based catalyst |
-
2019
- 2019-06-06 CN CN201910492403.5A patent/CN110407203B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049928A (en) * | 2006-04-04 | 2007-10-10 | 中国矿业大学(北京) | Method for manufacturing high heat conducting foam material of graphite with even apertures |
| CN102134068A (en) * | 2011-04-24 | 2011-07-27 | 大连理工大学 | Preparation method of graphitic carbon foam with high aperture ratio |
| CN103626153A (en) * | 2013-11-29 | 2014-03-12 | 哈尔滨工程大学 | Method for preparing graphitized foam carbon by using boron-based catalyst |
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