CN107658407A - A kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification - Google Patents

A kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification Download PDF

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CN107658407A
CN107658407A CN201710792594.8A CN201710792594A CN107658407A CN 107658407 A CN107658407 A CN 107658407A CN 201710792594 A CN201710792594 A CN 201710792594A CN 107658407 A CN107658407 A CN 107658407A
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porous carbon
carbon sheet
lithium
dimentional porous
sulfur cell
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CN107658407B (en
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方晓亮
裴非
郑南峰
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Xiamen University
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Xiamen University
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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
    • 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
    • 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
    • H01M50/411—Organic material
    • 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
    • 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
    • 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

A kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification, is related to lithium-sulfur cell.By graphene oxide and surfactant-dispersed in a solvent, dispersion liquid is obtained；The dispersion liquid of gained is adjusted into pH, tetraethyl orthosilicate is added, product is centrifuged by coated with silica after surface of graphene oxide, reaction, obtains the graphene oxide of Silica-coated；The graphene oxide of obtained Silica-coated is washed with solvent, disperses in a solvent, to add formaldehyde, phenols, amine and tetraethyl orthosilicate reaction, dry, obtain powder；By the powder of gained carbonization treatment under an inert atmosphere, carbonized product is obtained；Obtained carbonized product is etched with HF solution or sodium hydroxide solution, centrifuges, washs, dry, obtain two-dimentional porous carbon sheet powder；By the two-dimentional porous carbon sheet powder of gained and binding agent ultrasonic disperse in a solvent, gained dispersion liquid is filtered onto barrier film, drying obtains the two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification after cutting.

Description

A kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification
Technical field
The present invention relates to lithium-sulfur cell, more particularly, to a kind of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification Preparation method.
Background technology
In past 10 years, two-dimentional carbon nanosheet (also referred to as two-dimentional carbon plate) is because of its unique structure and characteristic electron, extensively Ground is applied to the field such as energy stores and conversion, drug delivery, environmental protection and catalysis, be particularly due to its high-specific surface area and Adjustable duct can provide abundant energy storage site and good mass transfer approach, have become in electrochemical energy storage technical field The research object of (lithium ion battery, lithium-sulfur cell, fuel cell, hybrid super capacitor and electro-catalysis etc.) focus (Chem.Rev.2017,117,6225-6331.).Although two-dimentional carbon nanosheet is considered as to be used to electrochemical energy storage have very much The electrode material of prospect, but because two-dimensional material is typically easy to reunite, it is difficult to maintain flat configuration and specific area special Property, it significantly limit the application study development of two-dimentional carbon nanosheet.In addition, in order to further lift two-dimentional carbon nanosheet electrification Performance is learned, is doped the storage for being widely used in two-dimentional carbon nanosheet to two-dimentional carbon nanosheet using hetero atom (such as N, S and B) Can application field.Therefore, prepare and be not easy to reunite, and the two-dimentional porous carbon nanometer with high-specific surface area and Heteroatom doping characteristic Piece can will effectively lift the application potential of two-dimentional carbon nanosheet.Lithium-sulfur cell (Li-S) be one kind using lithium metal as negative pole, Elemental sulfur is the lithium secondary battery of positive pole, has high theoretical energy density (2600Wh kg-1).The sulphur simple substance used is relatively existing Anode material for lithium-ion batteries is compared, and has the characteristics that rich reserves, cheap and environment-friendly.Although Li-S batteries are in energy There is huge theory advantage in metric density and cost, but still many yet unresolved issues be present, seriously hinder Li- The practical application of S batteries.For example, lithium-sulfur cell, in discharge process, the intermediate product (polysulfide) of positive pole reaction can dissolve In electrolyte, cathode of lithium side is diffused to by barrier film；And in charging process, these polysulfides again can be from negative pole to positive pole Migration.This " shuttle effect " is the main reason for causing Li-S battery capacities to decay.In addition, cathode of lithium is diffused into by barrier film Polysulfide also result in the loss of positive active material sulphur, the corrosion of negative pole lithium and self-discharge phenomenon (Adv.Mater.2017,1606823.)。
Membrane system is one of core component in lithium-sulfur cell, and most possibly lifts lithium-sulfur cell from commercial angle The component of application performance.The use of more barrier film is at present traditional olefinic polymerization species barrier film in lithium-sulfur cell, it is predominantly poly- (two layers of PP/PE is compound for the multilayer composite membrane of propylene (PP) microporous barrier, polyethylene (PE) microporous barrier and the production of Celgard companies Or tri- layers of PP/PE/PP is compound).The production cost of TPO barrier film is low, aperture size is adjustable, has good electrochemistry steady Qualitative and mechanical strength, thus be widely used in commercial batteries.But in lithium-sulfur cell system, conventional membrane can not be effective The more lithium sulfides of inhibitory activity material " shuttle effect ", it is now septate to solve there is an urgent need to a kind of new function barrier film Deficiency.The barrier layer that one layer of ion sieve spread as polysulfide is constructed in commercial membrane surface, in transmission Li+While have Ground is imitated to the physical barriers and chemisorbed of soluble polysulfide and then plays suppression " shuttle effect " effect, is to extend lithium sulphur One effective way of the cycle life of battery.
The content of the invention
The problem of it is an object of the invention to exist for existing lithium-sulfur cell barrier film, closed by simple hard template method Into the method for high-ratio surface, Heteroatom doping two dimension porous carbon sheet, there is provided easily commercial cells barrier film is modified and repaiied Decorations processing, and " the shuttle effect " of polysulfide in lithium-sulfur cell is further suppressed by using the battery diaphragm of this modification, The utilization rate of positive electrode is improved, realizes that the height ratio capacity of lithium-sulfur cell and one kind of long circulation life are used for lithium-sulfur cell barrier film The preparation method of modified two-dimentional porous carbon sheet.
The present invention comprises the following steps：
1) dispersion liquid by graphene oxide and surfactant-dispersed in a solvent, is obtained；
In step 1), the surfactant may be selected from polyvinylpyrrolidone, and the solvent can use second alcohol and water Mixed solution, the volume ratio of second alcohol and water can be (2~10) ︰ 1.
2) dispersion liquid obtained by step 1) is adjusted into pH, adds tetraethyl orthosilicate, by coated with silica in oxidation stone Black alkene surface, centrifuges product after reaction, obtains graphene oxide (the GO@SiO of Silica-coated2)；
In step 2), ammoniacal liquor or aqueous slkali can be selected in the regulation pH, and sodium hydroxide or hydrogen can be selected in the aqueous slkali One kind in potassium oxide etc., the pH can be 8~10；The proportioning of the tetraethyl orthosilicate and graphene oxide can be (10~ 60) ︰ 1, wherein tetraethyl orthosilicate are calculated by volume, and graphene oxide is by mass；The temperature of the reaction can be 30 DEG C, instead The time answered can be 2~5h.
3) by graphene oxide (the GO@SiO of the Silica-coated obtained in step 2)2) washed with solvent, it is dispersed in In solvent, formaldehyde, phenols, amine and tetraethyl orthosilicate reaction are added, dries, obtains powder；
In step 3), the solvent can use deionized water or organic solvent, and the organic solvent may be selected from ethanol, different At least one of propyl alcohol, dichloromethane, methanol etc.；The phenols may be selected from phenol, resorcinol, hydroquinones, isophthalic three At least one of phenol etc., the amine may be selected from least one of melamine, ethamine, ethylenediamine, 1,6- hexamethylene diamines etc.； The temperature of the reaction can be 30~50 DEG C, and the time of reaction can be 5~24h；The oxidation of the formaldehyde and Silica-coated Graphene (GO@SiO2) proportioning can be (10~60) ︰ 1, wherein, formaldehyde is calculated by volume, the oxidation stone of Silica-coated Black alkene (GO@SiO2) by mass；Graphene oxide (the GO@SiO of the phenols and Silica-coated2) mass ratio can For (10~80) ︰ 1；Graphene oxide (the GO@SiO of the amine and Silica-coated2) mass ratio can be (10~80) ︰ 1；Graphene oxide (the GO@SiO of the tetraethyl orthosilicate and Silica-coated2) proportioning can be (10~100) ︰ 1, its In, tetraethyl orthosilicate is calculated by volume, graphene oxide (the GO@SiO of Silica-coated2) by mass；The drying Condition can 60 DEG C of dryings under vacuum.
4) by the carbonization treatment under an inert atmosphere of the powder obtained by step 3), carbonized product is obtained；
In step 4), the inert atmosphere can use nitrogen or argon gas etc.；The carbonization treatment can use tube furnace, rise Warm speed can be 2~10 DEG C of min-1, the temperature of the carbonization treatment can be carbonization treatment 1 at 600~1000 DEG C, preferably 800 DEG C ~4h, is down to room temperature naturally.
5) carbonized product that step 4) obtains is etched with HF solution or sodium hydroxide solution, centrifuged, washed, dried, obtain Two-dimentional porous carbon sheet powder；
In step 5), the etching, volume ratio can be used as 10%HF solution or 12M, 80 DEG C of sodium hydroxide solutions, carved The time of erosion can be 24h；The condition of the drying can 60 DEG C of dryings under vacuo；Gained two dimension porous carbon sheet can highly single point Dissipate, can easily be dispersed in most solvents, the solvent can be deionized water, methanol, ethanol, isopropanol, N- first One kind in base pyrrolidones, DMF etc..
6) by the two-dimentional porous carbon sheet powder obtained by step 5) and binding agent ultrasonic disperse in a solvent, by gained dispersion liquid Filter on barrier film, drying obtains the two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification after cutting.
In step 6), the binding agent can use acrylonitrile multiple copolymer (LA133) or Kynoar (PVDF).
The advantage of the invention is that：
1) raw material sources are extensive, cost is cheap, synthetic method is simple, are easy to amplify；
2) the two-dimentional porous carbon sheet obtained by has excellent dispersiveness and two-dimensional structure, by simply filtering i.e. to commercialization Barrier film is modified；
3) the two-dimentional porous carbon sheet of gained has the characteristics that high-specific surface area, abundant pore passage structure and high nitrogen atom doping；
4) smooth stacked structure is presented in the two-dimentional porous carbon sheet on modified diaphragm, polysulfide can be carried out effectively Stop and absorption, and then lifted active material specific capacity, extend battery cycle life.
Brief description of the drawings
Fig. 1 is the synthesis schematic diagram of two-dimentional porous carbon sheet prepared by embodiment 3.
Fig. 2 is the scanning electron microscope (SEM) photograph of two-dimentional porous carbon sheet prepared by embodiment 3.
Fig. 3 is the transmission electron microscope picture of two-dimentional porous carbon sheet prepared by embodiment 3.
Fig. 4 is the atomic force microscopy diagram of two-dimentional porous carbon sheet prepared by embodiment 3.
Fig. 5 is the atomic force curve map of two-dimentional porous carbon sheet prepared by embodiment 3.
Fig. 6 is the N of two-dimentional porous carbon sheet prepared by embodiment 32Adsorption desorption curve and graph of pore diameter distribution.
Fig. 7 is the pictorial diagram and sectional view of two-dimentional porous carbon sheet modified diaphragm prepared by embodiment 3.
Fig. 8 is assembled by barrier film that two-dimentional porous carbon sheet prepared by embodiment 3 is modified and non-modified business barrier film Lithium-sulfur cell 0.2C circulation comparison diagram.
Lithium-sulfur cell 1C (the 1C=1675mA that the barrier film that Fig. 9 is modified by two-dimentional porous carbon sheet prepared by embodiment 3 assembles g-1) long circulating performance map under the conditions of discharge and recharge.
Embodiment
Below by embodiment combination accompanying drawing, the invention will be further described, it will help those skilled in the art enters One step understands the present invention, but the invention is not limited in any way.It should be pointed out that one of ordinary skill in the art is come Say, without departing from the inventive concept of the premise, can also make certain adjustments and improvements.These belong to the protection of the present invention Scope, but it is not limited to the protection domain of invention.
Embodiment 1
1) 30mg GO and 0.3g polyvinylpyrrolidones are added in 120mL ethanol and 15mL deionized waters first, added Enter 6mL ammonia spirits and 4mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, adds 0.3mL formaldehyde, After 0.2g resorcinols, 0.3mL ammoniacal liquor and 0.2mL TEOS, the dispersion liquid of mixing is further stirred into 12h at 40 DEG C.From The heart collects intermediate, in N2Be carbonized 4h under atmosphere at 800 DEG C, washs drying after then etching 24h with the 10wt%HF aqueous solution, obtains To two-dimentional porous carbon sheet.
3) by 2) the two-dimentional porous carbon sheet 9mg of middle gained and 1mg PVDF ultrasonic disperses in 1-METHYLPYRROLIDONE, then will Dispersion liquid is filtered onto barrier film, and drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
Embodiment 2
1) 30mg GO and 0.3g polyvinylpyrrolidones are added in 120mL ethanol and 15mL deionized waters first, added Enter 6mL ammonia spirits and 4mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, add 0.3mL formaldehyde, After 0.2g phenol, 0.6mL ethylenediamines and 1mL TEOS, the dispersion liquid of mixing is further stirred into 12h at 40 DEG C.Centrifugation is received Collect intermediate, in N2Be carbonized 4h under atmosphere at 800 DEG C, washs drying after then etching 24h with the 10wt%HF aqueous solution, obtains two Tie up porous carbon sheet.
3) by 2) the two-dimentional porous carbon sheet 9mg of middle gained and 1mg Kynoar (PVDF) ultrasonic disperse in N- methylpyrroles In alkanone, then by dispersion liquid suction filtration to barrier film, drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
Embodiment 3
1) 30mg GO and 0.3g polyvinylpyrrolidones are added in 120mL ethanol and 15mL deionized waters first, added Enter 6mL ammonia spirits and 3mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, add 0.3mL formaldehyde, After 0.2g resorcinols, 0.3mL ethylenediamines and 0.6mL TEOS, the dispersion liquid of mixing is further stirred into 12h at 40 DEG C. Intermediate is collected by centrifugation, in N2Be carbonized 4h under atmosphere at 800 DEG C, and drying is washed after then etching 24h with the 10wt%HF aqueous solution, Obtain two-dimentional porous carbon sheet.
3) by 2) the two-dimentional porous carbon sheet 9mg of middle gained and 1mg LA133 ultrasonic disperses in 1-METHYLPYRROLIDONE, then will Dispersion liquid is filtered onto barrier film, and drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
The synthesis schematic diagram of two-dimentional porous carbon sheet prepared by embodiment 3 is referring to Fig. 1, the scanning electron microscope (SEM) photograph of two-dimentional porous carbon sheet Referring to Fig. 2, the transmission electron microscope picture of two-dimentional porous carbon sheet referring to Fig. 3, the atomic force microscopy diagram of two-dimentional porous carbon sheet referring to Fig. 4, The atomic force curve map of two-dimentional porous carbon sheet is referring to Fig. 5, the N of two-dimentional porous carbon sheet2Adsorption desorption curve and graph of pore diameter distribution referring to Fig. 6, the pictorial diagram and sectional view of two-dimentional porous carbon sheet modified diaphragm are referring to Fig. 7, two-dimentional porous carbon sheet barrier film being modified and not The barrier film that the lithium-sulfur cell 0.2C circulation comparison diagrams that modified business barrier film is assembled are modified referring to Fig. 8, two-dimentional porous carbon sheet Lithium-sulfur cell 1C (the 1C=1675mA g assembled-1) long circulating performance map under the conditions of discharge and recharge is referring to Fig. 9.
Embodiment 4
1) 30mg GO and 0.6g polyvinylpyrrolidones are added in 120mL ethanol and 15mL deionized waters first, added Enter 6mL ammonia spirits and 1mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, adds 0.3mL formaldehyde, After 0.2g phloroglucins, 0.3mL 1,6- hexamethylene diamines and 1mL TEOS, the dispersion liquid of mixing is further stirred at 40 DEG C 24h.Intermediate is collected by centrifugation, in N2Be carbonized 4h under atmosphere at 800 DEG C, is washed after then etching 24h with the 10wt%HF aqueous solution Dry, obtain two-dimentional porous carbon sheet.
3) 2) the middle two-dimentional porous carbon sheet 9mg of gained is filtered in ethanol, then by dispersion liquid with 1mg LA133 ultrasonic disperses Onto barrier film, drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
Embodiment 5
1) 30mg GO and 0.6g polyvinylpyrrolidones are added in 120mL ethanol and 15mL deionized waters first, added Enter 6mL ammonia spirits and 4mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, add 0.3mL formaldehyde, After 0.2g resorcinols, 0.3mL mercaptoethylmaines and 1mL TEOS, the dispersion liquid of mixing is further stirred into 24h at 40 DEG C. Intermediate is collected by centrifugation, in N2Be carbonized 4h under atmosphere at 800 DEG C, and drying is washed after then etching 24h with the 10wt%HF aqueous solution, Obtain two-dimentional porous carbon sheet.
3) 2) the middle two-dimentional porous carbon sheet 9mg of gained is filtered in ethanol, then by dispersion liquid with 1mg LA133 ultrasonic disperses Onto barrier film, drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
Embodiment 6
1) 30mg GO and 0.6g polyvinylpyrrolidones are added in 120mL ethanol and 15mL deionized waters first, added Enter 6mL ammonia spirits and 4mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, add 0.3mL formaldehyde, After 0.2g hydroquinones, 0.3mL ethamine and 0.6mL TEOS, the dispersion liquid of mixing is further stirred into 24h at 40 DEG C.From The heart collects intermediate, in N2Be carbonized 4h under atmosphere at 800 DEG C, washs drying after then etching 24h with the 10wt%HF aqueous solution, obtains To two-dimentional porous carbon sheet.
3) 2) the middle two-dimentional porous carbon sheet 9mg of gained is filtered in ethanol, then by dispersion liquid with 1mg LA133 ultrasonic disperses Onto barrier film, drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
Embodiment 7
1) 30mg GO and 0.9g polyvinylpyrrolidones are added in 120mL ethanol and 20mL deionized waters first, added Enter 6mL ammonia spirits and 1mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, add 0.3mL formaldehyde, After 0.2g hydroquinones, 0.6mL ethamine and 0.6mL TEOS, the dispersion liquid of mixing is further stirred into 24h at 40 DEG C.From The heart collects intermediate, in N2Be carbonized 4h under atmosphere at 800 DEG C, then etches 24h with the aqueous solution (12M, 80 DEG C) of sodium hydroxid After wash drying, obtain two-dimentional porous carbon sheet.
3) 2) the middle two-dimentional porous carbon sheet 7mg of gained is filtered in ethanol, then by dispersion liquid with 3mg LA133 ultrasonic disperses Onto barrier film, drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
Embodiment 8
1) 30mg GO and 0.9g polyvinylpyrrolidones are added in 120mL ethanol and 20mL deionized waters first, added Enter 6mL ammonia spirits and 1mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, add 0.3mL formaldehyde, After 0.2g hydroquinones, 0.6mL ethamine and 1mL TEOS, the dispersion liquid of mixing is further stirred into 24h at 40 DEG C.Centrifugation Intermediate is collected, in N2Be carbonized 4h under atmosphere at 800 DEG C, then with after the aqueous solution (12M, 80 DEG C) the etching 24h of sodium hydroxid Drying is washed, obtains two-dimentional porous carbon sheet.
3) 2) the middle two-dimentional porous carbon sheet 7mg of gained is filtered in ethanol, then by dispersion liquid with 3mg LA133 ultrasonic disperses Onto barrier film, drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
Embodiment 9
1) 30mg GO and 0.9g polyvinylpyrrolidones are added in 120mL ethanol and 20mL deionized waters first, added Enter 6mL ammonia spirits and 1mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, add 0.3mL formaldehyde, After 0.2g hydroquinones, 0.6mL ethamine and 1mL TEOS, the dispersion liquid of mixing is further stirred into 24h at 40 DEG C.Centrifugation Intermediate is collected, in N2Be carbonized 4h under atmosphere at 800 DEG C, then with after the aqueous solution (12M, 80 DEG C) the etching 24h of sodium hydroxid Drying is washed, obtains two-dimentional porous carbon sheet.
3) by 2) the two-dimentional porous carbon sheet 7mg of middle gained and 3mg LA133 ultrasonic disperses in ethanol and 15mL deionized waters, Dispersion liquid is filtered onto barrier film again, drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
Embodiment 10
1) 30mg GO and 1.2g polyvinylpyrrolidones are added in 120mL ethanol and 20mL deionized waters first, added Enter 6mL ammonia spirits and 3mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, add 0.3mL formaldehyde, After 0.2g phloroglucins, 0.3mL ethylenediamines and 0.6mL TEOS, the dispersion liquid of mixing is further stirred into 24h at 40 DEG C. Intermediate is collected by centrifugation, in N2Be carbonized 4h under atmosphere at 800 DEG C, is then etched with the aqueous solution (12M, 80 DEG C) of sodium hydroxid Drying is washed after 24h, obtains two-dimentional porous carbon sheet.
3) 2) the middle two-dimentional porous carbon sheet 5mg of gained is filtered in ethanol, then by dispersion liquid with 5mg LA133 ultrasonic disperses Onto barrier film, drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
Embodiment 11
1) 30mg GO and 1.2g polyvinylpyrrolidones are added in 120mL ethanol and 20mL deionized waters first, added Enter 6mL ammonia spirits and 3mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, add 0.3mL formaldehyde, After 0.2g phenol, 0.4mL ethamine and 0.6mL TEOS, the dispersion liquid of mixing is further stirred into 24h at 40 DEG C.Centrifugation is received Collect intermediate, in N2Be carbonized 4h under atmosphere at 800 DEG C, is washed after then etching 24h with the aqueous solution (12M, 80 DEG C) of sodium hydroxid Drying is washed, obtains two-dimentional porous carbon sheet.
3) 2) the middle two-dimentional porous carbon sheet 5mg of gained is filtered in ethanol, then by dispersion liquid with 5mg LA133 ultrasonic disperses Onto barrier film, drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
Embodiment 12
1) 30mg GO and 1.2g polyvinylpyrrolidones are added in 120mL ethanol and 20mL deionized waters first, added Enter 6mL ammonia spirits and 3mL TEOS, stirring reaction 6h at 30 DEG C.Will be standby after product centrifuge washing.
2) product in 1) is added in the mixed solution of 70mL deionized waters and 30mL ethanol, add 0.3mL formaldehyde, After 0.2g phenol, 0.4mL melamines and 0.3mL TEOS, the dispersion liquid of mixing is further stirred into 24h at 40 DEG C.From The heart collects intermediate, in N2Be carbonized 4h under atmosphere at 800 DEG C, then etches 24h with the aqueous solution (12M, 80 DEG C) of sodium hydroxid After wash drying, obtain two-dimentional porous carbon sheet.
3) 2) the middle two-dimentional porous carbon sheet 5mg of gained is filtered in ethanol, then by dispersion liquid with 5mg LA133 ultrasonic disperses Onto barrier film, drying obtains the battery diaphragm that two-dimentional porous carbon sheet is modified after cutting.
The present invention relates to a kind of synthetic method using easy hard template method synthesizing high specific surface area two dimension porous carbon sheet. The carbon nanosheet can be used for the modification of commercial batteries barrier film, and modified barrier film can be obviously improved lithium-sulfur cell performance.This hair Bright to provide a kind of synthetic method of lithium-sulfur cell diagram modification material, this method has following outstanding advantages：1) raw material sources Extensively, cost is cheap, synthetic method is simple, is easy to amplify；2) the two-dimentional porous carbon sheet obtained by have excellent dispersiveness and Two-dimensional structure, it can be modified by simply filtering on barrier film；3) the two-dimentional porous carbon materials of gained have unique knot (surface area can exceed 2000m to structure advantage2g-1, pore volume be more than 2cm3g-1, nitrogen atom doping content is up to 5at%).Compared to Unmodified business barrier film, more vulcanizations of the barrier film being modified using two-dimentional porous carbon sheet to being formed in lithium-sulfur cell charge and discharge process Thing can effectively be stopped and chemisorbed, prevents polysulfide from reaching negative pole through barrier film, is obviously improved lithium-sulfur cell Specific capacity and cycle life.

Claims (10)

1. the preparation method of a kind of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification, it is characterised in that including following step Suddenly：
1) dispersion liquid by graphene oxide and surfactant-dispersed in a solvent, is obtained；
2) dispersion liquid obtained by step 1) is adjusted into pH, tetraethyl orthosilicate is added, by coated with silica in graphene oxide Surface, product is centrifuged after reaction, obtain graphene oxide (the GO@SiO of Silica-coated2)；
3) by graphene oxide (the GO@SiO of the Silica-coated obtained in step 2)2) washed with solvent, it is dispersed in solvent In, formaldehyde, phenols, amine and tetraethyl orthosilicate reaction are added, dries, obtains powder；
4) by the carbonization treatment under an inert atmosphere of the powder obtained by step 3), carbonized product is obtained；
5) carbonized product that step 4) obtains is etched with HF solution or sodium hydroxide solution, centrifuged, washed, dried, obtain two-dimentional Porous carbon sheet powder；
6) by the two-dimentional porous carbon sheet powder obtained by step 5) and binding agent ultrasonic disperse in a solvent, gained dispersion liquid is filtered Onto barrier film, drying obtains the two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification after cutting.
2. a kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification as claimed in claim 1, its feature It is in step 1), the surfactant is selected from polyvinylpyrrolidone, and the solvent is molten using the mixing of second alcohol and water Liquid, the volume ratio of second alcohol and water is (2~10) ︰ 1.
3. a kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification as claimed in claim 1, its feature It is in step 2), the regulation pH selects ammoniacal liquor or aqueous slkali, and the aqueous slkali is from sodium hydroxide or potassium hydroxide One kind, the pH be 8~10.
4. a kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification as claimed in claim 1, its feature It is in step 2), the proportioning of the tetraethyl orthosilicate and graphene oxide is (10~60) ︰ 1, wherein tetraethyl orthosilicate are pressed Volume calculates, and graphene oxide is by mass；The temperature of the reaction is 30 DEG C, and the time of reaction is 2~5h.
5. a kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification as claimed in claim 1, its feature It is in step 3), the solvent uses deionized water or organic solvent, and the organic solvent is selected from ethanol, isopropanol, two At least one of chloromethanes, methanol；The phenols in phenol, resorcinol, hydroquinones, phloroglucin at least one Kind, the amine is selected from least one of melamine, ethamine, ethylenediamine, 1,6- hexamethylene diamines.
6. a kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification as claimed in claim 1, its feature It is in step 3), the temperature of the reaction is 30~50 DEG C, and the time of reaction is 5~24h；The formaldehyde and silica Graphene oxide (the GO@SiO of parcel2) proportioning for (10~60) ︰ 1, wherein, formaldehyde is calculated by volume, Silica-coated Graphene oxide (GO@SiO2) by mass.
7. a kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification as claimed in claim 1, its feature It is in step 3), graphene oxide (the GO@SiO of the phenols and Silica-coated2) mass ratio be (10~80) ︰ 1；Graphene oxide (the GO@SiO of the amine and Silica-coated2) mass ratio be (10~80) ︰ 1；The positive silicic acid The graphene oxide of ethyl ester and Silica-coated (GO@SiO2) proportioning for (10~100) ︰ 1, wherein, tetraethyl orthosilicate is pressed Volume calculates, graphene oxide (the GO SiO of Silica-coated2) by mass；The condition of the drying is in vacuum condition Lower 60 DEG C of dryings.
8. a kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification as claimed in claim 1, its feature It is in step 4), the inert atmosphere uses nitrogen or argon gas；The carbonization treatment uses tube furnace, heating rate 2 ~10 DEG C of min-1, the temperature of the carbonization treatment is 1~4h of carbonization treatment at 600~1000 DEG C, preferably 800 DEG C, is down to naturally Room temperature.
9. a kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification as claimed in claim 1, its feature Be in step 5), the etching, use volume ratio as 10%HF solution or 12M, 80 DEG C of sodium hydroxide solutions, etching when Between be 24h；The condition of the drying is 60 DEG C of dryings under vacuo；The solvent be deionized water, methanol, ethanol, isopropanol, One kind in 1-METHYLPYRROLIDONE, DMF.
10. a kind of preparation method of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification as claimed in claim 1, its feature It is in step 6), the binding agent uses acrylonitrile multiple copolymer or Kynoar.
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CN110911619A (en) * 2019-12-19 2020-03-24 昆山宝创新能源科技有限公司 Lithium battery diaphragm, preparation method thereof and lithium battery
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