CN107658407B - A kind of preparation method of the two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification - Google Patents

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

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CN107658407B
CN107658407B CN201710792594.8A CN201710792594A CN107658407B CN 107658407 B CN107658407 B CN 107658407B CN 201710792594 A CN201710792594 A CN 201710792594A CN 107658407 B CN107658407 B CN 107658407B
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lithium
graphene oxide
porous carbon
sulfur cell
carbon sheet
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CN107658407A (en
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方晓亮
裴非
郑南峰
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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 the two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification, is related to lithium-sulfur cell.In a solvent by graphene oxide and surfactant-dispersed, dispersion liquid is obtained；Resulting dispersion liquid is adjusted into pH, ethyl 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 to be washed with solvent, in a solvent, formaldehyde, phenols, amine and ethyl orthosilicate reaction is added in dispersion, and it is dry, obtain powder；By resulting powder carbonization treatment under an inert atmosphere, carbonized product is obtained；Obtained carbonized product HF solution or sodium hydroxide solution are etched, are centrifuged, is washed, it is dry, obtain two-dimentional porous carbon sheet powder；In a solvent by resulting two-dimentional porous carbon sheet powder and binder ultrasonic disperse, gained dispersion liquid is filtered onto diaphragm, drying obtains the two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification after cutting.

Description

A kind of preparation method of the two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification
Technical field
The present invention relates to lithium-sulfur cells, more particularly, to a kind of two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification Preparation method.
Background technique
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 be applied to the fields such as energy stores and conversion, drug delivery, environmental protection and catalysis, be particularly due to its high-specific surface area with Adjustable duct can provide energy storage site abundant 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.) hot spot (Chem.Rev.2017,117,6225-6331.).Although two-dimentional carbon nanosheet is considered as having very much for electrochemical energy storage The electrode material of prospect, but since two-dimensional material is typically easy to reunite, it is difficult to maintain flat configuration and high specific area special Property, significantly limit the application study development of two-dimentional carbon nanosheet.In addition, in order to further enhance 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) It can application field.Therefore, two-dimentional porous carbon nanometer not easy to reunite, and that there is high-specific surface area and Heteroatom doping characteristic is prepared Piece will effectively promote the application potential of two-dimentional carbon nanosheet.Lithium-sulfur cell (Li-S) is one kind using lithium metal as cathode, Elemental sulfur is the lithium secondary battery of anode, 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 environmental-friendly.Although Li-S battery is in energy There is huge theory advantage in metric density and cost, but still there are many yet unresolved issues, seriously hinder Li- The practical application of S battery.For example, lithium-sulfur cell is during discharge, the intermediate product (polysulfide) of anode reaction can dissolve In electrolyte, cathode of lithium side is diffused to by diaphragm；And during the charging process, these polysulfides again can be from cathode to anode Migration.This " shuttle effect " is the main reason for causing Li-S battery capacity to decay.In addition, being diffused into cathode of lithium by diaphragm Polysulfide also result in the loss of positive active material sulphur, the corrosion of cathode lithium and self-discharge phenomenon (Adv.Mater.2017,1606823.)。
Membrane system is one of the core component in lithium-sulfur cell, and most possibly promotes lithium-sulfur cell from commercial angle The component of application performance.It the use of more diaphragm is at present traditional olefinic polymerization species diaphragm in lithium-sulfur cell, it is predominantly poly- (two layers of PP/PE compound for the multilayer composite membrane of propylene (PP) microporous barrier, polyethylene (PE) microporous barrier and the production of Celgard company Or tri- layers of PP/PE/PP compound).The production cost of polyolefins diaphragm 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 substance " shuttle effect ", it is now septate to solve that there is an urgent need to a kind of new function diaphragms It is insufficient.The barrier layer that one layer of ion sieve is spread as polysulfide is constructed in commercial membrane surface, in transmission Li+While have Effect ground plays the role of inhibiting " shuttle effect " in turn to the physical barriers and chemisorption of soluble polysulfide, is to extend lithium sulphur One effective way of the cycle life of battery.
Summary of the invention
It is an object of the invention to existing lithium-sulfur cell diaphragm there are aiming at the problem that, by simple hard template method close At the method for high-ratio surface, Heteroatom doping two dimension porous carbon sheet, provides easily to be modified commercial cells diaphragm and repair Decorations processing, and further inhibit " the shuttle effect " of polysulfide in lithium-sulfur cell by using the battery diaphragm of this modification, The utilization rate for improving positive electrode, one kind of the height ratio capacity and long circulation life of realizing lithium-sulfur cell is for lithium-sulfur cell diaphragm The preparation method of modified two-dimentional porous carbon sheet.
The present invention the following steps are included:
1) dispersion liquid in a solvent by graphene oxide and surfactant-dispersed, is obtained；
In step 1), the surfactant can be selected from polyvinylpyrrolidone, and second alcohol and water can be used in the solvent Mixed solution, the volume ratio of second alcohol and water can be (2~10) ︰ 1.
2) the resulting dispersion liquid of step 1) is adjusted into pH, adds ethyl orthosilicate, by coated with silica in oxidation stone Product, is centrifuged by black alkene surface after reaction, obtains graphene oxide (the GO@SiO of Silica-coated2)；
In step 2), ammonium hydroxide or aqueous slkali is can be selected in the adjusting pH, and sodium hydroxide or hydrogen can be selected in the aqueous slkali One of potassium oxide etc., the pH can be 8~10；The proportion of the ethyl orthosilicate and graphene oxide can for (10~ 60) 1 ︰, wherein ethyl orthosilicate is 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 the graphene oxide of Silica-coated obtained in step 2) (GO@SiO2) washed with solvent, it is dispersed in In solvent, formaldehyde, phenols, amine and ethyl orthosilicate reaction is added, it is dry, obtain powder；
In step 3), the solvent can be used deionized water or organic solvent, and the organic solvent can be selected from ethyl alcohol, different At least one of propyl alcohol, methylene chloride, methanol etc.；The phenols can be selected from phenol, resorcinol, hydroquinone, isophthalic three At least one of phenol etc., the amine can be selected from least one of melamine, ethamine, ethylenediamine, 1,6- hexamethylene diamine etc.； The temperature of the reaction can be 30~50 DEG C, time of reaction can for 5~for 24 hours；The oxidation of the formaldehyde and Silica-coated Graphene (GO@SiO2) proportion 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 ethyl orthosilicate and Silica-coated2) proportion can for (10~100) ︰ 1, In, ethyl 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 conditions.
4) by the resulting powder of step 3) carbonization treatment under an inert atmosphere, carbonized product is obtained；
In step 4), nitrogen or argon gas etc. is can be used in the inert atmosphere；Tube furnace can be used in the carbonization treatment, rises Warm rate 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 for obtaining step 4) HF solution or sodium hydroxide solution etching, are centrifuged, wash, dry, obtain Two-dimentional porous carbon sheet powder；
In step 5), the etching, it is 10%HF solution or 12M that volume ratio, which can be used, and 80 DEG C of sodium hydroxide solutions are carved The time of erosion can be for for 24 hours；The condition of the drying can 60 DEG C of dryings under vacuum；Gained two dimension porous carbon sheet being capable of single point of height It dissipates, can easily be dispersed in most solvents, the solvent can be deionized water, methanol, ethyl alcohol, isopropanol, N- first One of base pyrrolidones, n,N-Dimethylformamide etc..
6) in a solvent by the resulting two-dimentional porous carbon sheet powder of step 5) and binder ultrasonic disperse, by gained dispersion liquid It filters on diaphragm, drying obtains the two-dimentional porous carbon sheet for lithium-sulfur cell diagram modification after cutting.
In step 6), acrylonitrile multiple copolymer (LA133) or Kynoar (PVDF) is can be used in the binder.
The present invention has the advantages that
1) raw material sources are extensive, low in cost, synthetic method is simple, are easy to amplify；
2) resulting two-dimentional porous carbon sheet has excellent dispersibility and two-dimensional structure, by simply filtering i.e. to commercialization Diaphragm is modified；
3) the two-dimentional porous carbon sheet of gained has the characteristics that high-specific surface area, cellular structure abundant and high nitrogen atom doping；
4) smooth stacked structure is presented in the two-dimentional porous carbon sheet on modified diaphragm, can be able to carry out to polysulfide effectively Blocking and absorption, and then promoted active material specific capacity, extend battery cycle life.
Detailed description of the invention
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 graph 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.
The diaphragm and non-modified business diaphragm that the two-dimentional porous carbon sheet that Fig. 8 is prepared by embodiment 3 is modified assemble Lithium-sulfur cell 0.2C recycle comparison diagram.
Lithium-sulfur cell 1C (the 1C=1675mA that the modified diaphragm of the two-dimentional porous carbon sheet that Fig. 9 is prepared by embodiment 3 assembles g-1) long circulating performance map under the conditions of charge and discharge.
Specific embodiment
Below by embodiment combination attached drawing, the invention will be further described, it will help those skilled in the art into One step understands the present invention, but the invention is not limited in any way.It should be pointed out that coming to those skilled in the art It says, without departing from the inventive concept of the premise, can also make certain adjustments and improvements.These belong to protection of the invention Range, but it is not limited to the protection scope of invention.
Embodiment 1
1) 30mg GO and 0.3g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 15mL deionized water first, is added Enter 6mL ammonia spirit and 4mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, adds 0.3mL formaldehyde, After 0.2g resorcinol, 0.3mL ammonium hydroxide and 0.2mL TEOS, mixed dispersion liquid is futher stirred into 12h at 40 DEG C.From The heart collects intermediate, in N2In 800 DEG C of carbonization 4h under atmosphere, drying is then washed afterwards for 24 hours with 10wt%HF aqueous solution etching, is obtained To two-dimentional porous carbon sheet.
3) by 2) middle gained two dimension porous carbon sheet 9mg and 1mg PVDF ultrasonic disperse in N-Methyl pyrrolidone, then will Dispersion liquid is filtered onto diaphragm, and drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet after cutting.
Embodiment 2
1) 30mg GO and 0.3g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 15mL deionized water first, is added Enter 6mL ammonia spirit and 4mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, add 0.3mL formaldehyde, After 0.2g phenol, 0.6mL ethylenediamine and 1mL TEOS, mixed dispersion liquid is futher stirred into 12h at 40 DEG C.Centrifugation is received Collect intermediate, in N2In 800 DEG C of carbonization 4h under atmosphere, drying is then washed afterwards for 24 hours with 10wt%HF aqueous solution etching, obtains two Tie up porous carbon sheet.
3) by 2) middle gained two dimension porous carbon sheet 9mg and 1mg Kynoar (PVDF) ultrasonic disperse in N- methylpyrrole In alkanone, then by dispersion liquid suction filtration to diaphragm, drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet after cutting.
Embodiment 3
1) 30mg GO and 0.3g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 15mL deionized water first, is added Enter 6mL ammonia spirit and 3mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, add 0.3mL formaldehyde, After 0.2g resorcinol, 0.3mL ethylenediamine and 0.6mL TEOS, mixed dispersion liquid is futher stirred into 12h at 40 DEG C. Intermediate is collected by centrifugation, in N2In 800 DEG C of carbonization 4h under atmosphere, drying is then washed afterwards for 24 hours with 10wt%HF aqueous solution etching, Obtain two-dimentional porous carbon sheet.
3) by 2) middle gained two dimension porous carbon sheet 9mg and 1mg LA133 ultrasonic disperse in N-Methyl pyrrolidone, then will Dispersion liquid is filtered onto diaphragm, and drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet 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 is referring to Fig. 3, the atomic force microscopy diagram of two-dimentional porous carbon sheet referring to fig. 4, The atomic force curve graph 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 diaphragm being modified and not The lithium-sulfur cell 0.2C circulation comparison diagram that modified business diaphragm is assembled is referring to Fig. 8, the modified diaphragm of two-dimentional porous carbon sheet Lithium-sulfur cell 1C (the 1C=1675mA g assembled-1) long circulating performance map under the conditions of charge and discharge is referring to Fig. 9.
Embodiment 4
1) 30mg GO and 0.6g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 15mL deionized water first, is added Enter 6mL ammonia spirit and 1mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, adds 0.3mL formaldehyde, After 0.2g phloroglucin, 0.3mL 1,6- hexamethylene diamine and 1mL TEOS, mixed dispersion liquid is futher stirred at 40 DEG C 24h.Intermediate is collected by centrifugation, in N2In 800 DEG C of carbonization 4h under atmosphere, then washed afterwards for 24 hours with 10wt%HF aqueous solution etching It is dry, obtain two-dimentional porous carbon sheet.
3) 2) middle gained two dimension porous carbon sheet 9mg and 1mg LA133 ultrasonic disperse in ethanol, then by dispersion liquid are filtered Onto diaphragm, drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet after cutting.
Embodiment 5
1) 30mg GO and 0.6g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 15mL deionized water first, is added Enter 6mL ammonia spirit and 4mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, add 0.3mL formaldehyde, After 0.2g resorcinol, 0.3mL mercaptoethylmaine and 1mL TEOS, mixed dispersion liquid is futher stirred for 24 hours at 40 DEG C. Intermediate is collected by centrifugation, in N2In 800 DEG C of carbonization 4h under atmosphere, drying is then washed afterwards for 24 hours with 10wt%HF aqueous solution etching, Obtain two-dimentional porous carbon sheet.
3) 2) middle gained two dimension porous carbon sheet 9mg and 1mg LA133 ultrasonic disperse in ethanol, then by dispersion liquid are filtered Onto diaphragm, drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet after cutting.
Embodiment 6
1) 30mg GO and 0.6g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 15mL deionized water first, is added Enter 6mL ammonia spirit and 4mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, add 0.3mL formaldehyde, After 0.2g hydroquinone, 0.3mL ethamine and 0.6mL TEOS, mixed dispersion liquid is futher stirred for 24 hours at 40 DEG C.From The heart collects intermediate, in N2In 800 DEG C of carbonization 4h under atmosphere, drying is then washed afterwards for 24 hours with 10wt%HF aqueous solution etching, is obtained To two-dimentional porous carbon sheet.
3) 2) middle gained two dimension porous carbon sheet 9mg and 1mg LA133 ultrasonic disperse in ethanol, then by dispersion liquid are filtered Onto diaphragm, drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet after cutting.
Embodiment 7
1) 30mg GO and 0.9g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 20mL deionized water first, is added Enter 6mL ammonia spirit and 1mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, add 0.3mL formaldehyde, After 0.2g hydroquinone, 0.6mL ethamine and 0.6mL TEOS, mixed dispersion liquid is futher stirred for 24 hours at 40 DEG C.From The heart collects intermediate, in N2In 800 DEG C of carbonization 4h under atmosphere, then for 24 hours with aqueous solution (12M, the 80 DEG C) etching of sodium hydroxid After wash drying, obtain two-dimentional porous carbon sheet.
3) 2) middle gained two dimension porous carbon sheet 7mg and 3mg LA133 ultrasonic disperse in ethanol, then by dispersion liquid are filtered Onto diaphragm, drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet after cutting.
Embodiment 8
1) 30mg GO and 0.9g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 20mL deionized water first, is added Enter 6mL ammonia spirit and 1mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, add 0.3mL formaldehyde, After 0.2g hydroquinone, 0.6mL ethamine and 1mL TEOS, mixed dispersion liquid is futher stirred for 24 hours at 40 DEG C.Centrifugation Intermediate is collected, in N2In 800 DEG C of carbonization 4h under atmosphere, after then being etched for 24 hours with the aqueous solution (12M, 80 DEG C) of sodium hydroxid Drying is washed, two-dimentional porous carbon sheet is obtained.
3) 2) middle gained two dimension porous carbon sheet 7mg and 3mg LA133 ultrasonic disperse in ethanol, then by dispersion liquid are filtered Onto diaphragm, drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet after cutting.
Embodiment 9
1) 30mg GO and 0.9g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 20mL deionized water first, is added Enter 6mL ammonia spirit and 1mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, add 0.3mL formaldehyde, After 0.2g hydroquinone, 0.6mL ethamine and 1mL TEOS, mixed dispersion liquid is futher stirred for 24 hours at 40 DEG C.Centrifugation Intermediate is collected, in N2In 800 DEG C of carbonization 4h under atmosphere, after then being etched for 24 hours with the aqueous solution (12M, 80 DEG C) of sodium hydroxid Drying is washed, two-dimentional porous carbon sheet is obtained.
3) by 2) middle gained two dimension porous carbon sheet 7mg and 3mg LA133 ultrasonic disperse in ethyl alcohol and 15mL deionized water, Dispersion liquid is filtered onto diaphragm again, drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet after cutting.
Embodiment 10
1) 30mg GO and 1.2g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 20mL deionized water first, is added Enter 6mL ammonia spirit and 3mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, add 0.3mL formaldehyde, After 0.2g phloroglucin, 0.3mL ethylenediamine and 0.6mL TEOS, mixed dispersion liquid is futher stirred for 24 hours at 40 DEG C. Intermediate is collected by centrifugation, in N2In 800 DEG C of carbonization 4h under atmosphere, then etched with the aqueous solution (12M, 80 DEG C) of sodium hydroxid It washs drying afterwards for 24 hours, obtains two-dimentional porous carbon sheet.
3) 2) middle gained two dimension porous carbon sheet 5mg and 5mg LA133 ultrasonic disperse in ethanol, then by dispersion liquid are filtered Onto diaphragm, drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet after cutting.
Embodiment 11
1) 30mg GO and 1.2g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 20mL deionized water first, is added Enter 6mL ammonia spirit and 3mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, add 0.3mL formaldehyde, After 0.2g phenol, 0.4mL ethamine and 0.6mL TEOS, mixed dispersion liquid is futher stirred for 24 hours at 40 DEG C.Centrifugation is received Collect intermediate, in N2In 800 DEG C of carbonization 4h under atmosphere, then washed afterwards for 24 hours with aqueous solution (12M, the 80 DEG C) etching of sodium hydroxid Drying is washed, two-dimentional porous carbon sheet is obtained.
3) 2) middle gained two dimension porous carbon sheet 5mg and 5mg LA133 ultrasonic disperse in ethanol, then by dispersion liquid are filtered Onto diaphragm, drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet after cutting.
Embodiment 12
1) 30mg GO and 1.2g polyvinylpyrrolidone is added in 120mL ethyl alcohol and 20mL deionized water first, is added Enter 6mL ammonia spirit and 3mL TEOS, is stirred to react 6h at 30 DEG C.It will be spare after product centrifuge washing.
2) 1) product in is added in the mixed solution of 70mL deionized water and 30mL ethyl alcohol, add 0.3mL formaldehyde, After 0.2g phenol, 0.4mL melamine and 0.3mL TEOS, mixed dispersion liquid is futher stirred for 24 hours at 40 DEG C.From The heart collects intermediate, in N2In 800 DEG C of carbonization 4h under atmosphere, then for 24 hours with aqueous solution (12M, the 80 DEG C) etching of sodium hydroxid After wash drying, obtain two-dimentional porous carbon sheet.
3) 2) middle gained two dimension porous carbon sheet 5mg and 5mg LA133 ultrasonic disperse in ethanol, then by dispersion liquid are filtered Onto diaphragm, drying obtains the modified battery diaphragm of two-dimentional porous carbon sheet after cutting.
The present invention relates to a kind of synthetic methods 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 diaphragm, and modified diaphragm 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 outstanding advantages below: 1) raw material sources Extensively, low in cost, synthetic method is simple, be easy to amplify；2) resulting two-dimentional porous carbon sheet have excellent dispersibility and Two-dimensional structure can be modified by simply filtering on diaphragm；3) the two-dimentional porous carbon materials of gained have unique knot (surface area can be more than 2000m to structure advantage2g-1, pore volume be greater than 2cm3g-1, nitrogen atom doping content is up to 5at%).Compared to Unmodified business diaphragm, more vulcanizations using the modified diaphragm of two-dimentional porous carbon sheet to being formed in lithium-sulfur cell charge and discharge process Object is able to carry out effective blocking and chemisorption, prevents polysulfide from passing through diaphragm and reaches cathode, is obviously improved lithium-sulfur cell Specific capacity and cycle life.

Claims (9)

1. a kind of preparation method of lithium-sulfur cell diaphragm, it is characterised in that the following steps are included:
1) dispersion liquid in a solvent by graphene oxide and surfactant-dispersed, is obtained；
2) the resulting dispersion liquid of step 1) is adjusted into pH, ethyl orthosilicate is added, by coated with silica in graphene oxide Product is centrifuged by surface after reaction, obtains the graphene oxide of Silica-coated；
3) graphene oxide of Silica-coated obtained in step 2) is washed with solvent, in a solvent, first is added in dispersion Aldehyde, phenols, amine and ethyl orthosilicate reaction, it is dry, obtain powder；The temperature of the reaction is 30~50 DEG C, the time of reaction For 5~for 24 hours；
The mass ratio of the graphene oxide of the phenols and Silica-coated is (10~80) ︰ 1；The amine and silica The mass ratio of the graphene oxide of package is (10~80) ︰ 1；The graphene oxide of the ethyl orthosilicate and Silica-coated Proportion be (10~100) ︰ 1, wherein ethyl orthosilicate is calculated by volume, and the graphene oxide of Silica-coated presses quality It calculates；The 60 DEG C of dryings under vacuum conditions of the condition of the drying；
The amine is selected from least one of melamine, ethamine, ethylenediamine, 1,6- hexamethylene diamine；
Graphene oxide (the GO@SiO of the formaldehyde and Silica-coated2) proportion be (10~60) ︰ 1, wherein formaldehyde is pressed Volume calculates, graphene oxide (the GO SiO of Silica-coated2) by mass；
4) by the resulting powder of step 3) carbonization treatment under an inert atmosphere, carbonized product is obtained；
5) carbonized product for obtaining step 4) HF solution or sodium hydroxide solution etching, are centrifuged, wash, dry, obtain two-dimentional Porous carbon sheet powder；
6) in a solvent by the resulting two-dimentional porous carbon sheet powder of step 5) and binder ultrasonic disperse, gained dispersion liquid is filtered Onto diaphragm, drying obtains lithium-sulfur cell diaphragm after cutting.
2. a kind of preparation method of lithium-sulfur cell diaphragm as described in claim 1, it is characterised in that in step 1), the surface Activating agent is selected from polyvinylpyrrolidone, and the solvent uses the mixed solution of second alcohol and water, and the volume ratio of second alcohol and water is (2 ~10) ︰ 1.
3. a kind of preparation method of lithium-sulfur cell diaphragm as described in claim 1, it is characterised in that in step 2), the adjusting PH selects ammonium hydroxide or aqueous slkali, and the aqueous slkali selects one of sodium hydroxide or potassium hydroxide, and the pH is 8~10.
4. a kind of preparation method of lithium-sulfur cell diaphragm as described in claim 1, it is characterised in that in step 2), the positive silicon The proportion of acetoacetic ester and graphene oxide is that (10~60) ︰ 1, wherein ethyl orthosilicate is calculated by volume, and graphene oxide presses matter Amount calculates；The temperature of the reaction is 30 DEG C, and the time of reaction is 2~5h.
5. a kind of preparation method of lithium-sulfur cell diaphragm as described in claim 1, it is characterised in that in step 3), the solvent Using deionized water or organic solvent, the organic solvent is selected from least one of ethyl alcohol, isopropanol, methylene chloride, methanol； The phenols is selected from least one of phenol, resorcinol, hydroquinone, phloroglucin.
6. a kind of preparation method of lithium-sulfur cell diaphragm as described in claim 1, it is characterised in that in step 4), the inertia Atmosphere uses nitrogen or argon gas；The carbonization treatment uses tube furnace, and heating rate is 2~10 DEG C of min-1, the carbonization treatment Temperature be 600~1000 DEG C, be down to room temperature naturally.
7. a kind of preparation method of lithium-sulfur cell diaphragm as claimed in claim 6, it is characterised in that the carbonization treatment is at 800 DEG C 1~4h of lower carbonization treatment.
8. a kind of preparation method of lithium-sulfur cell diaphragm as described in claim 1, it is characterised in that in step 5), the quarter Erosion, uses volume ratio for 10%HF solution or 12M, 80 DEG C of sodium hydroxide solutions, and the time of etching is for 24 hours；The item of the drying Part is 60 DEG C of dryings under vacuum.
9. a kind of preparation method of lithium-sulfur cell diaphragm as described in claim 1, it is characterised in that in step 6), the bonding Agent uses acrylonitrile multiple copolymer or Kynoar；The solvent is deionized water, methanol, ethyl alcohol, isopropanol, N- methyl One of pyrrolidones, n,N-Dimethylformamide.
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