CN110078053A - A kind of porous carbon materials and its preparation method and application applied to battery diaphragm coating - Google Patents
A kind of porous carbon materials and its preparation method and application applied to battery diaphragm coating Download PDFInfo
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- CN110078053A CN110078053A CN201910408439.0A CN201910408439A CN110078053A CN 110078053 A CN110078053 A CN 110078053A CN 201910408439 A CN201910408439 A CN 201910408439A CN 110078053 A CN110078053 A CN 110078053A
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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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
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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
Abstract
The porous carbon materials and its preparation method and application that the purpose of the present invention is to provide a kind of applied to battery diaphragm coating, belong to the technical field of the new material of electrochemistry.Preparation method includes the following steps: adenine, 4,4- diphenyl dicarboxylic acid 1) is taken to dissolve respectively spare；2) zinc acetate, cobalt acetate, cetyl trimethylammonium bromide mixing are taken, mixture A is obtained；3) it takes mixture A, carbon nano-tube solution, methanol and deionized water to be mixed, obtains mixture B；4) mixture B is centrifuged, obtains grey powder, MOF-CNT composite material will be dried to obtain after the washing of grey powder；5) MOF-CNT composite material made from step 4) is calcined under nitrogen atmosphere to get Co-NCN-CNT composite material.Co-NCN-CNT composite material of the invention is applied in lithium-sulfur cell, can effectively be catalyzed the conversion of more lithium sulfides, to inhibit shuttle effect, the cyclical stability and high rate performance of battery is greatly improved.
Description
Technical field
The invention belongs to the technical fields of electrochemistry new material, and in particular to a kind of applied to the porous of battery diaphragm coating
Carbon material and its preparation method and application.
Background technique
With electric car industry, mancarried electronic aid industry flourishes and various clean energy resource such as wind energies, the sun
Can, the more large-scale application of tide energy, lithium ion battery has been difficult to meet the chargeable stocking system of next-generation high-energy density
Demand.Lithium-sulfur cell due to high theoretical energy density (2600Wh/Kg) and high theoretical specific capacity (1675mAh/g),
And as the sulphur rich reserves and economy of positive electrode, these advantages all allow lithium-sulfur cell to become current most development prospect
One of secondary cell system.But lithium-sulfur cell, apart from traditional business application also very long a distance, first, sulphur and sulphur exist
The lithium sulfide generated in cell reaction is all insulation, so as to cause active material utilization is very low and dynamics of oxidation reduction
Slowly；Second, more lithium sulfides dissolution that reaction process generates generates unnecessary parasitic reaction and lithium Zhi Jing in the electrolytic solution
Generation can all severely impact battery performance even result in battery death.Active material utilization existing for lithium-sulfur cell at present
Low, the problems such as cycle life is low, high rate performance is poor low with safety, all seriously hinders its application.For these problems, scientist
Corresponding exploration has all been carried out in terms of anode, diaphragm, electrolyte, to improve the cycle performance of lithium-sulfur cell.Wherein set
Meter new function diaphragm effectively and can slow down the shuttle effects of more lithium sulfides, so that the cycle performance of battery be substantially improved.Cause
This develop a kind of simple preparation process, abundant raw materials and economy, good conductivity and can effectively inhibit shuttle effect every
Membrane coat is just great to be of practical significance.It much combines physical absorption however, although the membrane material to grow up at this stage has, change
Catalysis and good electric conductivity are learned, but in sulphur carrying capacity very greatly and under high current density, battery can not play excellent long circulating
Performance and high initial discharge specific capacity.In addition, often price is competitiveless for their raw material, synthetic method is also very complicated.
In recent years, metal organic framework (MOFs) and using MOFs be the carbon material of presoma as novel sulfur-donor and function
Energy film coating materials have obtained extensive research in lithium battery.MOFs be by metal ion/cluster node for infinitely arranging and
The crystalline material of organic chain junctor composition, large specific surface area, size and aperture are adjustable, by the concern of people.The hole of MOFs
Hole can carry chemical active sites, such as Lewis-acid sites and function organo-functional group, these can be to sulphur and more sulphur
Changing lithium has suction-operated, and not only remains active site as the carbon material of precursor using MOFs but also improve the conductor wire of material
With reduce weight.
Summary of the invention
The purpose of the present invention is to provide a kind of porous carbon materials applied to battery diaphragm coating, to contain Co and N
Porous carbon materials Co-NCN-CNT composite material, be rich in Co and N element.
The present invention also provides the preparation methods for the porous carbon materials for being applied to battery diaphragm coating, include the following steps:
1) adenine, 4,4- diphenyl dicarboxylic acid is taken to dissolve respectively spare；
2) zinc acetate, cobalt acetate, cetyl trimethylammonium bromide mixing are taken, mixture A is obtained；
3) it takes mixture A, carbon nano-tube solution, methanol and deionized water to be mixed, reaction raw materials and carbon nanotube is filled
Divide mixing, reaction, obtains mixture B；
4) mixture B is centrifuged, obtains grey powder, grey powder is washed, by washing away unreacted impurity, it
After be dried to obtain MOF-CNT composite material；
5) MOF-CNT composite material made from step 4) is calcined under nitrogen atmosphere, by being carbonized under an inert atmosphere,
The porous carbon materials of cobalt, N doping are obtained to get products C o-NCN-CNT composite material.
Wherein, dissolution described in step 1) includes n,N-Dimethylformamide (DMF) using reagent, so that organic ligand
Adenine and 4,4- diphenyl dicarboxylic acid sufficiently dissolves, so that reaction raw materials sufficiently dissolve；
It is dissolved respectively before zinc acetate described in step 2, cobalt acetate, cetyl trimethylammonium bromide mixing, the use of dissolution
Reagent includes N,N-dimethylformamide；
Carbon nano-tube solution in step 3) is to disperse activated solution in N,N-dimethylformamide solution in advance；By carbon
Nanotube is scattered in advance can to make the more uniform growth of nano particle on the carbon nanotubes；
Washing described in step 4) includes N,N-dimethylformamide, methanol using reagent (its English abbreviation is MeOH).
The present invention also provides the applications for the porous carbon materials for being applied to battery diaphragm coating, are applied to battery diaphragm
Coating material, battery include lithium-sulfur cell；
The preparation method of the coating material of battery diaphragm includes the following steps: to take Co-NCN-CNT composite material, conductive agent, bonding
Agent and the mixing of normal propyl alcohol solution are tuned into slurry, as coating material, are coated on battery diaphragm, dry, slice to get
To the coated separator of Co-NCN-CNT；The carbon composite prepared is coated on diaphragm, and assembled battery, to test painting
Material is covered to the improvement situation of battery performance.
Further, the conductive agent includes conductive black, and the binder includes LA132 binder；The effect of carbon black
It is to improve electric conductivity, the effect of binder is to be adhered to material on diaphragm.
Beneficial effects of the present invention are as follows:
The three-dimensional adsoption catalysis conductive network structure that Co-NCN-CNT composite material of the invention is formed has high specific discharge capacity
And the feature of high stability etc., and maintain nearly 100% coulombic efficiency (discharging efficiency), in the prior art, when by common PP
Diaphragm is applied in lithium-sulfur cell, can not effectively obstruct more lithium sulfide migrations, also can not adsorb or convert more lithium sulfides, cause
Battery discharge specific capacity decays rapidly, can not also support the long circulating under big sulphur carrying capacity and high current density；And it will be of the invention
Co-NCN-CNT composite material is applied in lithium-sulfur cell as diaphragm coating, can effectively be catalyzed the conversion of more lithium sulfides,
To inhibit shuttle effect, the cyclical stability and high rate performance of battery is greatly improved；
The present invention design it is a kind of based on MOFs be presoma be carbonized it is resulting to more lithium sulfides have catalytic action Co-NCN-
CNT composite material, preparation method is simple, easily operated, and raw material are cheap and abundant.
Figure of description
Fig. 1 is the preparation flow schematic diagram of porous carbon materials Co-NCN-CNT composite material of the invention；
Fig. 2 is the structure chart of Co-NCN-CNT composite material of the invention；
The coated separator and the diaphragm figure after slice that Fig. 3 is Co-NCN-CNT of the invention；
Fig. 4 is that the electrochemistry of the coated separator of Co-NCN-CNT of the invention recycles schematic diagram.
Specific embodiment
Below by way of specific case study on implementation and Detailed description of the invention, the present invention is described in further detail, it should be understood that this
A little embodiments are merely to illustrate the present invention rather than limit the scope of the invention, after the present invention has been read, ability
It is as defined in the appended claims that field technique personnel fall within the application to the modification of various equivalent forms of the invention.
If all raw materials and reagents of the invention are the raw material of conventional market, reagent without specified otherwise.
Embodiment 1
A kind of preparation method of the porous carbon materials applied to battery diaphragm coating:
1) adenine, 4,4- diphenyl dicarboxylic acid is taken to be dissolved in same volume N,N-dimethylformamide respectively with the molar ratio of 1:1
Middle ultrasonic dissolution is spare；
2) zinc acetate, cobalt acetate, cetyl trimethylammonium bromide is taken to be dissolved in N, N- dimethyl formyl with the molar ratio of 9:1:1
Ultrasonic dissolution is spare in amine, and three of the above is dissolved in the solution in n,N-Dimethylformamide and is mixed, mixture A is obtained；
3) taking mixture A, volume ratio is added is that the activated carbon nanotube being dispersed in N,N-dimethylformamide of 5:4:1 is molten
Mixture B is stirred at room temperature to obtain in liquid, methanol and deionized water；
4) after reaction stops, mixture B is centrifuged, grey powder (MOF of Co and N doping) is obtained, it is successively used to N, N-
After dimethylformamide, methanol washing, MOF-CNT composite material is obtained after drying in an oven；
5) it will be calcined in the tube furnace of MOF-CNT composite material under nitrogen atmosphere made from step 4), calcination condition is 800 degree
8h, heating rate are 5 DEG C/min, and calcined product is named as Co-NCN-CNT to get products C o-NCN-CNT composite material.
Co-NCN-CNT composite material that Example 1 synthesizes, Super-P(conductive black), LA132 binder is according to 6:
The ratio of 2:2 is dispersed to be tuned into slurry, is coated onto PP(Celgard-2400 using normal propyl alcohol solution) on diaphragm,
Drying for 24 hours, is cut into the disk size that diameter is 19mm using slicer to get Co- is arrived in 60 DEG C of vacuum oven
The coated separator of NCN-CNT.
Embodiment 2
A kind of preparation method of the porous carbon materials applied to battery diaphragm coating:
1) adenine, 4,4- diphenyl dicarboxylic acid is taken to be dissolved in same volume N,N-dimethylformamide respectively with the molar ratio of 1:1
Middle ultrasonic dissolution is spare；
2) zinc acetate, cobalt acetate, cetyl trimethylammonium bromide is taken to be dissolved in N, N- dimethyl formyl with the molar ratio of 8:1:1
Ultrasonic dissolution is spare in amine, and three of the above is dissolved in the solution in n,N-Dimethylformamide and is mixed, mixture A is obtained；
3) taking mixture A, volume ratio is added is that the activated carbon nanotube being dispersed in N,N-dimethylformamide of 5:4:1 is molten
Mixture B is stirred at room temperature to obtain in liquid, methanol and deionized water；
4) after reaction stops, mixture B is centrifuged, grey powder (MOF of Co and N doping) is obtained, it is successively used to N, N-
After dimethylformamide, methanol washing, MOF-CNT composite material is obtained after drying in an oven；
5) it will be calcined in the tube furnace of MOF-CNT composite material under nitrogen atmosphere made from step 4), calcination condition is 800 degree
8h, heating rate are 5 DEG C/min, and calcined product is named as Co-NCN-CNT to get products C o-NCN-CNT composite material.
Co-NCN-CNT composite material that Example 2 synthesizes, Super-P(conductive black), LA132 binder is according to 6:
The ratio of 2:2 is dispersed to be tuned into slurry, is coated onto PP(Celgard-2400 using normal propyl alcohol solution) on diaphragm,
Drying for 24 hours, is cut into the disk size that diameter is 19mm using slicer to get Co- is arrived in 60 DEG C of vacuum oven
The coated separator of NCN-CNT.
Embodiment 3
A kind of preparation method of the porous carbon materials applied to battery diaphragm coating:
1) adenine, 4,4- diphenyl dicarboxylic acid is taken to be dissolved in same volume N,N-dimethylformamide respectively with the molar ratio of 1:1
Middle ultrasonic dissolution is spare；
2) zinc acetate, cobalt acetate, cetyl trimethylammonium bromide is taken to be dissolved in N, N- dimethyl formyl with the molar ratio of 7:1:1
Ultrasonic dissolution is spare in amine, and three of the above is dissolved in the solution in n,N-Dimethylformamide and is mixed, mixture A is obtained；
3) taking mixture A, volume ratio is added is that the activated carbon nanotube being dispersed in N,N-dimethylformamide of 5:4:1 is molten
Mixture B is stirred at room temperature to obtain in liquid, methanol and deionized water；
4) after reaction stops, mixture B is centrifuged, grey powder (MOF of Co and N doping) is obtained, it is successively used to N, N-
After dimethylformamide, methanol washing, MOF-CNT composite material is obtained after drying in an oven；
5) it will be calcined in the tube furnace of MOF-CNT composite material under nitrogen atmosphere made from step 4), calcination condition is 800 degree
8h, heating rate are 5 DEG C/min, and calcined product is named as Co-NCN-CNT to get products C o-NCN-CNT composite material.
Co-NCN-CNT composite material that Example 3 synthesizes, Super-P(conductive black), LA132 binder is according to 6:
The ratio of 2:2 is dispersed to be tuned into slurry using normal propyl alcohol solution, be coated onto PP diaphragm (as Celgard-2400 every
Film) on, in 60 DEG C of vacuum oven it is dry for 24 hours, using slicer be cut into the disk size that diameter is 19mm to get
To the coated separator of Co-NCN-CNT.
As shown in Figure 1, it is the simple of porous carbon materials of the invention, that is, Co-NCN-CNT composite material preparation method
Exemplary flow；
Fig. 3 is the coated separator figure for the Co-NCN-CNT that the embodiment of the present invention obtains.
Comparative experiments: by S(sulfur material) and Ketjen black (conductive black) it is anti-in 155 DEG C of reaction kettles according to the ratio of 1:4
It answers 24 hours and is prepared into C/S compound, by C/S compound, Super-P, LA132 binder according to the ratio of 8:1:1 using just
Propanol solution dispersion is prepared into slurry, is coated on aluminium foil, dries for 24 hours in 60 DEG C of vacuum oven.Utilize slice
Machine is cut into the electrode disk that diameter is 12 mm, and being prepared into sulphur carrying capacity respectively using the scraper of different-thickness is 2 mg/cm2、
5 mg/cm2With 9 mg/cm2Pole piece.In glove box, with prepared pole piece be anode, lithium piece is to cathode, PP
(Celgard-2400) diaphragm or be coated with the PP(Celgard-2400 of material) for diaphragm, 1.0 M LiTFSI DOL/DME
(v:v, 1:1) is electrolyte, is assembled into CR-2302 button cell, and wherein coat is towards C/S anode.
With the chemical property of battery test system test battery:
Such as Fig. 3, it can be seen that in 5 mg/cm of sulphur carrying capacity2With current density be the mAh/g of 1C(1C=1675) in the case where, PP every
Film modified lithium-sulfur cell is dead in 100 circle rapid decays, and pole significantly CE wave occurs since circulation is at the very start
It is dynamic, it was demonstrated that so high current density and the big battery carried under sulfur content can not be supported, decays to 47.2 mAh/g in 100 circle left and right,
And the three-dimensional adsoption catalysis conductive network (as shown in Figure 2) that Co-NCN-CNT is formed then further illustrates its superiority；Such as
It is 5 mg/cm carrying sulfur content shown in Fig. 42With the high electric discharge ratio that can still keep 795.5 mAh/g under the high current density of 1C
Capacity and 500 circles can be steadily recycled, and finally also maintain the specific discharge capacity of 498.6 mAh/g, rate of decay
Only 0.07%, and maintain nearly 100% coulombic efficiency always, under so big load sulfur content and current density, this hair
Bright Co-NCN-CNT composite material has still played efficiently absorption and catalytic action, highly effective that more lithium sulfides is inhibited to wear
Shuttle.
Claims (9)
1. a kind of porous carbon materials applied to battery diaphragm coating, which is characterized in that it is the porous carbon containing Co and N
Material, the porous carbon materials are Co-NCN-CNT composite material.
2. a kind of preparation method of the porous carbon materials applied to battery diaphragm coating, which comprises the steps of:
1) adenine, 4,4- diphenyl dicarboxylic acid is taken to dissolve respectively spare；
2) zinc acetate, cobalt acetate, cetyl trimethylammonium bromide mixing are taken, mixture A is obtained；
3) it takes mixture A, carbon nano-tube solution, methanol and deionized water to be mixed, obtains mixture B；
4) mixture B is centrifuged, obtains grey powder, MOF-CNT composite material will be dried to obtain after the washing of grey powder；
5) MOF-CNT composite material made from step 4) is calcined under nitrogen atmosphere and is answered to get products C o-NCN-CNT
Condensation material.
3. by the preparation method of the porous carbon materials as claimed in claim 2 applied to battery diaphragm coating, which is characterized in that step
It is rapid 1) described in dissolution using reagent include N,N-dimethylformamide.
4. by the preparation method of the porous carbon materials described in claim 2 or 3 applied to battery diaphragm coating, feature exists
In zinc acetate described in step 2, cobalt acetate, cetyl trimethylammonium bromide mixing are dissolved respectively before, the use of dissolution
Reagent includes N,N-dimethylformamide.
5. by the preparation method of the porous carbon materials as claimed in claim 4 applied to battery diaphragm coating, which is characterized in that step
It is rapid 3) in carbon nano-tube solution be disperse activated solution in N,N-dimethylformamide solution in advance.
6. the preparation method as described in claim 5 applied to the porous carbon materials of battery diaphragm coating, which is characterized in that step
It is rapid 4) described in washing using reagent include N,N-dimethylformamide, methanol.
7. a kind of application of the porous carbon materials applied to battery diaphragm coating, which is characterized in that it is applied to battery diaphragm
Coating material, battery include lithium-sulfur cell.
8. by the application of the porous carbon materials as claimed in claim 7 applied to battery diaphragm coating, which is characterized in that the electricity
The preparation method of the coating material of pond diaphragm includes the following steps: to take Co-NCN- made from preparation method described in claim 2
CNT composite material, conductive agent, binder and the mixing of normal propyl alcohol solution are tuned into slurry, as coating material, are coated onto electricity
It is dry on the diaphragm of pond, it is sliced to get the coated separator of Co-NCN-CNT is arrived.
9. the application as described in claim 7 or 8 applied to the porous carbon materials of battery diaphragm coating, which is characterized in that institute
In the preparation method for stating the coating material of battery diaphragm, conductive agent includes conductive black, and binder includes LA132 binder.
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| CN111682147A (en) * | 2020-04-30 | 2020-09-18 | 华南师范大学 | Double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and shuttle effect and preparation method thereof |
| CN111697236A (en) * | 2020-04-30 | 2020-09-22 | 华南师范大学 | Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof |
| CN111697236B (en) * | 2020-04-30 | 2021-12-14 | 华南师范大学 | Three-dimensional current collector with multi-level structure for protecting lithium metal negative electrode and preparation method thereof |
| CN111682147B (en) * | 2020-04-30 | 2022-11-18 | 华南师范大学 | Double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and shuttle effect and preparation method thereof |
| CN112670669A (en) * | 2020-12-23 | 2021-04-16 | 华南农业大学 | Nitrogen-doped carbon-coated Co and/or Co3Application of ZnC composite material in preparation of lithium-sulfur battery diaphragm |
| CN114069159B (en) * | 2021-11-09 | 2024-03-01 | 广东工业大学 | Diaphragm based on nitrogen-rich column layer structure MOF, and preparation method and application thereof |
| CN114583389A (en) * | 2022-02-25 | 2022-06-03 | 广东工业大学 | Co-based MOF-derived metal/carbon composite (Co/C) membrane and preparation method and application thereof |
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