CN107452941A - A kind of battery electrode protection materials and preparation method thereof, cell electrode piece and preparation method and lithium battery - Google Patents
A kind of battery electrode protection materials and preparation method thereof, cell electrode piece and preparation method and lithium battery Download PDFInfo
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- CN107452941A CN107452941A CN201610378334.1A CN201610378334A CN107452941A CN 107452941 A CN107452941 A CN 107452941A CN 201610378334 A CN201610378334 A CN 201610378334A CN 107452941 A CN107452941 A CN 107452941A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 invention provides a kind of battery electrode protection materials, the electrode protection material is core shell structure, including kernel and shell, the kernel are carbon material, and the shell is inorganic ceramic material.The battery electrode protection materials can effectively prevent the growth of Li dendrite; improve the security and cycle life of lithium battery; to solve the generation that existing lithium battery electrolytes can not limit Li dendrite; there is corrosiveness to metal lithium electrode; and the SEI films being concatenated to form can lose lithium ion, the problem of so as to cause lithium battery security and cycle life to decline.Present invention also offers the preparation method of the battery electrode protection materials, and cell electrode piece and lithium battery comprising the battery electrode protection materials.
Description
Technical field
The present invention relates to field of lithium, more particularly to a kind of battery electrode protection materials and preparation method thereof, battery
Electrode slice and preparation method thereof and lithium battery.
Background technology
With the popularization of electronic product in recent years, as the lithium battery of its power supply, because with light weight, small volume, work
The advantages that voltage height, energy density height, output power, charge efficiency height and memory-less effect, increasingly it is taken seriously.This
Outside, in fields such as electric tool, electric automobile and large-scale energy storage devices, the lithium ion battery of high safety and high-energy-density
The progress of exploitation also just in full preparation.
Presently commercially available lithium battery is generally made up of positive plate, negative plate, barrier film, electrolyte and shell.Wherein electrolyte
The liquid electrolytes used using organic solvent as solvent, and the solid electrolyte based on polymer and inorganic material more, this
Two kinds of electrolyte can not all limit the generation of Li dendrite, and have corrosiveness to metal lithium electrode, and the SEI films of formation can lose lithium
Ion.Therefore, in order to improve the security of battery, while battery capacity is improved, in lithium battery, the growth to preventing Li dendrite
Both sides research is protected to be particularly important with cathode of lithium battery.
In view of the above-mentioned problems, people are frequently with following methods in studying at this stage, but in place of these methods all Shortcomings：
1st, the level (10 of liquid electrolyte can be basically reached using solid electrolyte, the ionic mobility of solid electrolyte-2S/cm), but
How nonelastic solid electrolyte is, can not be in close contact with cathode of lithium battery, causes ion transmission to be obstructed, and solid electrolyte material
It is more unstable, the charge and discharge cycles number of battery is influenceed, the serious use for limiting battery；2nd, the supplement loss of the means such as lithium powder is added
Lithium ion, this method preparation condition is harsh, can not large-scale use, and the growth of following Li dendrite can not be limited；3rd, by lithium
Passivation of metal surfaces, one layer of metastable diaphragm is generated, by generating inorganic oxide film, Huo Zhetong in metal surface
Bath composition organic matter lithium salts SEI films are overregulated, with elasticity, are not ruptured, however, in charge and discharge process, it is this
Diaphragm is the process rebuild again in rupture all the time, and dendrite, or lithium gold still can be inevitably produced in some sites
Belong to it is exposed in the electrolytic solution.
The content of the invention
In consideration of it, first aspect present invention provides a kind of battery electrode protection materials, the battery electrode protection materials can
The growth of Li dendrite is effectively prevented, improves the security and cycle life of lithium battery, can not to solve existing lithium battery electrolytes
The generation of Li dendrite is limited, and has corrosiveness to metal lithium electrode, the SEI films being concatenated to form can lose lithium ion, so as to lead
The problem of causing lithium battery security and cycle life to decline.
In a first aspect, the invention provides a kind of battery electrode protection materials, the electrode protection material is core shell structure, bag
Kernel and shell are included, the kernel is carbon material, and the shell is inorganic ceramic material.
In first aspect present invention, the carbon material includes graphene, doped graphene, graphene oxide, doping oxidation
At least one of graphene, hard carbon, doping hard carbon, soft carbon material, CNT and doped carbon nanometer pipe.
In first aspect present invention, the inorganic ceramic material includes titanium dioxide, aluminum oxide, zirconium oxide, lithium fluoride, oxygen
SiClx, calcium oxide, magnesia, tantalum oxide, silicon nitride, cubic boron nitride, aluminium nitride, chromium nitride, titanium nitride, carborundum, carbonization
At least one of boron, titanium carbide and chromium carbide.
In first aspect present invention, the quality of the carbon material accounts for the 1-50% of the electrode protection material gross mass.
In first aspect present invention, the thickness of the shell is 1-10nm.
In first aspect present invention, the electrode protection material is spherical core shell structure, a diameter of 0.01-2 microns.
In first aspect present invention, the shell is directly coated on the surface of the kernel.
In first aspect present invention, there is gap between the kernel and shell, the gap is less than 500nm.
First aspect present invention provide battery electrode protection materials, using carbon material as kernel, using inorganic ceramic material as
Shell, because carbon material has higher electron mobility and higher current potential, (such as lithium metal, born using itself and electrode material
Pole graphite etc.) potential difference can effectively prevent growth of the Li dendrite to the direction of electrolyte, so as to overcome in the prior art, lithium electricity
Pond electrolyte can not limit the generation of Li dendrite, there is corrosiveness to metal lithium electrode, and the SEI films loss lithium being concatenated to form
The problem of ion, improve the security and cycle life of lithium battery.
Second aspect, the invention provides a kind of preparation method of battery electrode protection materials, comprise the following steps：
Carbon material is taken, the carbon material is scattered in polymer monomer, included by way of emulsion polymerization
The polymer microballoon of carbon material, the microballoon include carbon material and coat the polymeric outer layer of the carbon material；
The coated inorganic ceramic material on the polymeric outer layer, then removed by the way of dissolving or sintering described poly-
Compound outer layer, that is, obtain battery electrode protection materials, and the electrode protection material is core shell structure, including kernel and shell, institute
It is carbon material to state kernel, and the shell is inorganic ceramic material.
In second aspect of the present invention, the polymer monomer includes styrene, methyl methacrylate, acrylate, vinegar
Vinyl acetate, vinyl chloride or oxirane.
In second aspect of the present invention, the polymer microballoon tool for obtaining including carbon material by way of emulsion polymerization
Body is：After the carbon material is scattered in polymer monomer, solvent, surfactant and initiator are added, in 50-150 DEG C
10-48 hours are reacted, the polymer microballoon emulsion for including carbon material is obtained, after demulsification, separating, washing, drying, obtains institute
State the polymer microballoon for including carbon material.
The preparation method that second aspect of the present invention provides, technique is simple, is adapted to extensive prepare.
The third aspect, the invention provides a kind of cell electrode piece, the cell electrode piece and electrolyte contacts
Electrode protecting layer is provided with simultaneously, the material of the electrode protecting layer includes battery electrode as described in the first aspect of the invention
Protection materials.
In third aspect present invention, the thickness of the electrode protecting layer is 0.1-20 microns.
In third aspect present invention, the material of the electrode protecting layer also includes Kynoar, polyacrylonitrile, poly- methyl
Methyl acrylate, polyvinylidene chloride, polyvinyl sulfone, poly- ethylene glycol diacrylate, polyvinylpyrrolidone and poly- inclined two
One or more in PVF.
The cell electrode piece that third aspect present invention provides can be lithium battery anode piece or cathode pole piece, the electrode pole
Piece can effectively prevent the generation of Li dendrite, improve the battery capacity, security and cycle life of lithium battery.
Fourth aspect, the invention provides a kind of preparation method of cell electrode piece, comprise the following steps：
Battery electrode protection materials as described in the first aspect of the invention are scattered in atent solvent, obtain slurry, will
In one side of the slurry coated in electrode plates and electrolyte contacts, electrode protecting layer is formed, is obtained with electrode protecting layer
The cell electrode piece.
In fourth aspect present invention, the atent solvent includes hexane, heptane, benzene, ether, tetrahydrofuran, 1,2- diformazans
One or more in epoxide ethane, butyl ether and 1-METHYLPYRROLIDONE.
5th aspect, the invention provides a kind of lithium battery, and it includes the battery electrode pole described in third aspect present invention
Piece.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification
, or can be known by the implementation of the embodiment of the present invention.
Brief description of the drawings
Fig. 1 is the battery electrode protection materials structural representation that the embodiment of the present invention one is prepared.
Embodiment
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of principle of the embodiment of the present invention is not departed from, some improvements and modifications can also be made, these improvement
The protection domain of the embodiment of the present invention is also considered as with retouching.
In field, high safety and high-energy-densities such as electronic product, electric tool, electric automobile and large-scale energy storage devices
Lithium battery chased always by people.Presently commercially available lithium battery is generally by positive plate, negative plate, barrier film, electrolyte and outer
Shell forms, and wherein electrolyte uses the liquid electrolyte using organic solvent as solvent, and polymer and inorganic material to be more
Main solid electrolyte, but both electrolyte can not all limit the generation of Li dendrite, and there is corrosion to make metal lithium electrode
With, and the SEI films being concatenated to form can lose lithium ion, so as to cause the security of lithium battery and battery capacity to substantially reduce.
In order to effectively solve this problem, the embodiments of the invention provide a kind of battery electrode protection materials, be positioned in electrode and
It between electrolyte, can effectively prevent Li dendrite from being grown to the direction of electrolyte, improve the security and cycle life of lithium battery.
Specifically, the embodiments of the invention provide a kind of battery electrode protection materials, the electrode protection material is nucleocapsid knot
Structure, including kernel and shell, the kernel are carbon material, and the shell is inorganic ceramic material.
Battery electrode of embodiment of the present invention protection materials, which use, has very high mobility and opposing negative polarity graphite and lithium metal
Deng the carbon material with high potential as inner nuclear material, it is placed in when by the battery electrode protection materials between electrode and electrolyte
When forming electrode protecting layer, direction of the Li dendrite to electrolyte can be prevented using the potential difference of electrode protecting layer and electrode material
Growth.Alternatively, in embodiment of the present invention, the carbon material includes graphene, doped graphene, graphene oxide, doping
At least one of graphene oxide, hard carbon, doping hard carbon, soft carbon material, CNT and doped carbon nanometer pipe.Wherein, mix
Miscellaneous element can be the one or more in N, P, B, O, S, F, Cl, H.The graphene, doped graphene, graphene oxide,
It can be single or multiple lift structure to adulterate graphene oxide.
Because the shape of the carbon materials such as graphene is relatively irregular, it is not easy to form the film of uniform ground in electrode surface,
And the projection of the carbon material surface such as graphene, it is also possible to influence the contact of each boundary layer in battery system, the final ion that influences passes
It is defeated, therefore the embodiment of the present invention is wrapped up carbon material using inorganic ceramic material as shell, obtains the cause of uniform ground
Close shell, avoid carbon material kernel because it is exposed outside with electrolyte contacts.Meanwhile inorganic ceramic material shell also improves electricity
The intensity of pond electrode protection material.In embodiment of the present invention, the inorganic ceramic material include but is not limited to be titanium dioxide,
Aluminum oxide, zirconium oxide, lithium fluoride, silica, calcium oxide, magnesia, tantalum oxide, silicon nitride, cubic boron nitride, aluminium nitride, nitrogen
Change at least one of chromium, titanium nitride, carborundum, boron carbide, titanium carbide and chromium carbide.
In embodiment of the present invention, the quality of the carbon material accounts for the 1-50% of the electrode protection material gross mass.Can
Selection of land, the quality of the carbon material account for 1-10%, 12-30%, 35%-50% of the electrode protection material gross mass.
In order that electrode protection material conductivity is unaffected, but also chondritic can be formed well, the present invention is implemented
In mode, the thickness of the shell may be configured as 1-10nm, or be arranged to 3-7nm.
In embodiment of the present invention, the electrode protection material is spherical core shell structure, and diameter can be 0.01-2 microns,
Can be 0.1-1 microns.Electrode protection material shape rule is easy to arrange film forming, coat is made with solvent is scattered, for lithium electricity
Pond assembles.
In embodiment of the present invention, electrode protection material can be that shell is directly coated on the surface of kernel, can also
It is that there is gap between kernel and shell, its gap is less than 500nm.Both concrete structures can be by using different preparation methods
Obtain.
The battery electrode protection materials of the above-mentioned offer of the embodiment of the present invention, using carbon material as kernel, with inorganic ceramic material
For shell, growth of the Li dendrite to the direction of electrolyte can be effectively prevented, the security and cycle life of lithium battery is improved, overcomes
Lithium battery electrolytes can not limit the generation of Li dendrite in the prior art, and have corrosiveness to metal lithium electrode, repeatedly
The problem of SEI films loss lithium ion of formation.
Correspondingly, the embodiments of the invention provide a kind of preparation method of battery electrode protection materials, comprise the following steps：
Carbon material is taken, the carbon material is scattered in polymer monomer, included by way of emulsion polymerization
The polymer microballoon of carbon material, the microballoon include carbon material and coat the polymeric outer layer of the carbon material；
The coated inorganic ceramic material on the polymeric outer layer, then removed by the way of dissolving or sintering described poly-
Compound outer layer, that is, obtain battery electrode protection materials, and the electrode protection material is core shell structure, including kernel and shell, institute
It is carbon material to state kernel, and the shell is inorganic ceramic material.
The embodiment of the present invention makes the carbon materials such as graphene be initially formed polymer microballoon by way of emulsion polymerization, then carries out
The cladding of inorganic ceramic material, the battery electrode protection materials of the relatively regular spherical core shell structure of shape can be obtained.
Alternatively, in embodiment of the present invention, the carbon material includes graphene, doped graphene, graphene oxide, mixed
At least one of miscellaneous graphene oxide, hard carbon, doping hard carbon, soft carbon material, CNT and doped carbon nanometer pipe.Wherein,
Doped chemical can be the one or more in N, P, B, O, S, F, Cl, H.The graphene, doped graphene, graphite oxide
Alkene, doping graphene oxide can be single or multiple lift structure.
In embodiment of the present invention, the polymer monomer includes styrene, methyl methacrylate, acrylate, vinegar
Vinyl acetate, vinyl chloride or oxirane.
In embodiment of the present invention, the polymer microballoon tool for obtaining including carbon material by way of emulsion polymerization
Body is：After the carbon material is scattered in polymer monomer, solvent, surfactant and initiator are added, in 50-150 DEG C
10-48 hours are reacted, the polymer microballoon emulsion for including carbon material is obtained, after demulsification, separating, washing, drying, obtains institute
State the polymer microballoon for including carbon material.
In embodiment of the present invention, solvent, surfactant, initiator etc. are depending on different reaction systems.For example,
Solvent can be water, and surfactant can be neopelex, and initiator can be potassium peroxydisulfate, Ammonium Persulfate 98.5.
In embodiment of the present invention, PH conditioning agents and some other auxiliary agent can be also added during emulsion polymerization, the PH is adjusted
It can be alundum (Al2O3), sodium hydroxide, potassium hydroxide, ammoniacal liquor, hydrochloric acid to save agent.The demulsification can be by adding mass fraction
50% lithium chloride solution is realized.
In embodiment of the present invention, the inorganic ceramic material includes but is not limited to be titanium dioxide, aluminum oxide, oxidation
Zirconium, lithium fluoride, silica, calcium oxide, magnesia, tantalum oxide, silicon nitride, cubic boron nitride, aluminium nitride, chromium nitride, titanium nitride,
At least one of carborundum, boron carbide, titanium carbide and chromium carbide.In embodiment of the present invention, inorganic ceramic material it is specific
Depending on method for coating species of inorganic ceramic material selected by, the embodiment of the present invention is not particularly limited.
In embodiment of the present invention, polymeric outer layer can carry out dissolving removal by adding organic solvent, or using sintering
Mode remove.Wherein, depending on the selection of organic solvent is by specific type of polymer, the temperature of sintering can be 450~700
℃。
In embodiment of the present invention, the quality of the carbon material accounts for the 1-50% of the electrode protection material gross mass.Can
Selection of land, the quality of the carbon material account for 1-10%, 12-30%, 35%-50% of the electrode protection material gross mass.
In order that electrode protection material conductivity is unaffected, but also chondritic can be formed well, the present invention is implemented
In mode, the thickness of the shell may be configured as 1-10nm, or be arranged to 3-7nm.
In embodiment of the present invention, the electrode protection material is spherical core shell structure, and diameter can be 0.01-2 microns,
Can be 0.1-1 microns.
The preparation method of the battery electrode protection materials of the above-mentioned offer of the embodiment of the present invention, technique is simple, is adapted to extensive
Prepare.
In addition, the embodiments of the invention provide a kind of cell electrode piece, the one of the electrode plates and electrolyte contacts
Electrode protecting layer is provided with face, the material of the electrode protecting layer includes as above-mentioned battery electrode protection such as the embodiment of the present invention
Material.
In embodiment of the present invention, the thickness of the electrode protecting layer may be configured as 0.1-20 microns, may be alternatively provided as 1-2
Micron.
In embodiment of the present invention, the material of the electrode protecting layer can also further comprise Kynoar, polypropylene
Nitrile, polymethyl methacrylate, polyvinylidene chloride, polyvinyl sulfone, poly- ethylene glycol diacrylate, polyvinylpyrrolidone
With the one or more in polyvinylidene fluoride.These above-mentioned polymer are added in the material of electrode protecting layer, can be electricity
Pond electrode protection material provides decentralized medium, enable electrode protection material more preferably, spread more evenly across in electrode protecting layer.
The above-mentioned cell electrode piece of the embodiment of the present invention, lithium battery anode piece or cathode pole piece can be used as, can be effective
The generation of Li dendrite is prevented, improves the battery capacity, security and cycle life of lithium battery.
Correspondingly, the embodiments of the invention provide a kind of preparation method of cell electrode piece, comprise the following steps：
The above-mentioned battery electrode protection materials of the embodiment of the present invention are scattered in atent solvent, obtain slurry, by described in
In one side of the slurry coated in electrode plates and electrolyte contacts, electrode protecting layer is formed, obtains the cell electrode piece.
In embodiment of the present invention, the atent solvent includes hexane, heptane, benzene, ether, tetrahydrofuran, 1,2- diformazans
One or more in epoxide ethane, butyl ether and 1-METHYLPYRROLIDONE.
In embodiment of the present invention, after slurry is coated on electrode plates, electrode plates are placed in inert gas gas
Drying at room temperature 10~24 hours under atmosphere.Further can in vacuum drying oven 60~100 DEG C of dry 12~48h.
In embodiment of the present invention, the thickness of the electrode protecting layer may be configured as 0.1-20 microns, may be alternatively provided as 1-2
Micron.
In embodiment of the present invention, Kynoar, polyacrylonitrile, polymethyl are still further comprised in the slurry
Sour methyl esters, polyvinylidene chloride, polyvinyl sulfone, poly- ethylene glycol diacrylate, polyvinylpyrrolidone and poly- inclined difluoro second
One or more polymeric materials in alkene.
In addition, the embodiment of the present invention additionally provides a kind of lithium battery, it includes the above-mentioned battery electrode of the embodiment of the present invention
Pole piece.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.Wherein, the embodiment of the present invention is unlimited
Due to following specific embodiment.In the range of constant principal right, can be suitably carry out change implementation.
Embodiment one
A kind of preparation method of battery electrode protection materials, comprises the following steps：
(1) styrene coated graphite alkene microballoon is prepared：1g nanoscale graphite alkene is scattered in 20mL styrene liquid, obtained
To the first dispersion liquid；0.9g neopelexes and 10g alundum (Al2O3)s are dissolved in 250mL deionized waters, obtained
Mixed solution；The dispersion liquid of gained first is added in the above-mentioned mixed solution being stirred vigorously, stirring and emulsifying, then add 0.5g mistakes
Potassium sulfate, 70 DEG C are warming up to, stirring reaction stops reaction after 14 hours, the pipe/polyhenylethylene nano level for obtaining including graphene is micro-
Ball emulsion, the lithium chloride solution that a small amount of mass fraction is 50% is added into emulsion and is demulsified, filtering, after washing is dried, is obtained
6.5g graphenes-polystyrene microsphere is stand-by.
(2) cladding titanium dioxide：Graphene-polystyrene microsphere of the above-mentioned preparations of 3g is taken to be dispersed in 30mL ethanol, then
Add 0.6gKH550 coupling agents to stir, obtain the second dispersion liquid, the 6mL ethanol for being dispersed with 0.6mL butyl titanates is molten
Liquid is slowly added into the second dispersion liquid, and is filtered after being stirred vigorously 2h, obtains being coated with the graphene of compact titanium dioxide-poly-
Phenylethylene micro ball mixed liquor.
(3) dissolving removes polystyrene：Take the graphene for being coated with compact titanium dioxide-polyphenyl second of the above-mentioned preparations of 10mL
The mixed liquor of alkene microballoon, it is added in 20mL tetrahydrofurans, magnetic agitation 2h is filtrated to get cladding to dissolve removal polystyrene
There is the graphene nano particle of titanium dioxide, that is, obtain battery electrode protection materials.As shown in figure 1, battery obtained by the present embodiment
Electrode protection material is spherical core shell structure, including kernel 1 and shell 2, wherein, kernel 1 is graphene, and shell 2 is titanium dioxide
Titanium, there is gap 3, the particle diameter of the battery electrode protection materials is 0.01~2 micron between graphene kernel 1 and shell 2.
The preparation of lithium ion battery electrode piece
After taking graphite to be mixed with conductive black, polyvinylidene fluoride with 85: 10: 5 in 1-METHYLPYRROLIDONE, uniformly apply
It is overlying in copper foil current collector, 120 DEG C of vacuum dryings, obtains electrode plates.Take 2g is manufactured in the present embodiment to be coated with titanium dioxide
Graphene nano particle, be added in 20mL hexanes and be dispersed with stirring uniformly, obtain slurry, by the slurry coated in being provided with
In the one side of active material, then drying at room temperature 16 hours under an argon atmosphere, then 90 DEG C of dry 36h in vacuum drying oven, shape
Into electrode protecting layer, lithium ion battery negative electrode is finally given.
The preparation of lithium ion battery
Anode, the lithium ion battery negative electrode of the above-mentioned preparation of the present embodiment and dielectric film are assembled into all solid state
Secondary lithium cell, then it is packaged into battery and by being melted into aluminum plastic film, obtains lithium ion battery.
Embodiment two
A kind of preparation method of battery electrode protection materials, comprises the following steps：
(1) styrene coated graphite alkene microballoon is prepared：1g nanoscale nitrogen-doped graphenes are scattered in 20mL styrene liquid
In body, the first dispersion liquid is obtained；0.9g neopelexes and 3g sodium hydroxides are dissolved in 250mL deionized waters,
Obtain mixed solution；The dispersion liquid of gained first is added in the above-mentioned mixed solution being stirred vigorously, stirring and emulsifying, then added
0.5g Ammonium Persulfate 98.5s, 80 DEG C are warming up to, stirring reaction stops reaction after 24 hours, obtain the polyphenyl for including nitrogen-doped graphene
Ethene nanoscale microballoon emulsion, the lithium chloride solution that a small amount of mass fraction is 50% is added into emulsion and is demulsified, filtering, washing is done
After dry, it is stand-by to obtain 6.8g nitrogen-doped graphenes-polystyrene microsphere.
(2) cladding titanium dioxide：Nitrogen-doped graphene-polystyrene microsphere of the above-mentioned preparations of 3g is taken to be dispersed in 30mL ethanol
In, add 0.6gKH550 coupling agents and stir, obtain the second dispersion liquid, the 6mL of 0.6mL butyl titanates will be dispersed with
Ethanol solution is slowly added into the second dispersion liquid, and is filtered after being stirred vigorously 2h, obtains being coated with the nitrogen of compact titanium dioxide
Doped graphene-polystyrene microsphere mixed liquor.
(3) dissolving removes polystyrene：Take the nitrogen-doped graphenes for being coated with compact titanium dioxide of the above-mentioned preparations of 10mL-
The mixed liquor of polystyrene microsphere, it is added in 20mL tetrahydrofurans, magnetic agitation 2h is filtered with dissolving removal polystyrene
To the nitrogen-doped graphene nano-particle for being coated with titanium dioxide, that is, obtain battery electrode protection materials.Electricity obtained by the present embodiment
Pond electrode protection material is spherical core shell structure, a diameter of 0.01~2 micron.
The preparation of lithium battery cathode pole piece
The 2g nitrogen-doped graphene nano-particles manufactured in the present embodiment for being coated with titanium dioxide are taken, are added in 20mL benzene
It is dispersed with stirring uniformly, obtains slurry, by the slurry coated in lithium piece, lithium piece is then placed into room temperature under an argon atmosphere and done
Dry 16 hours, electrode protecting layer is formed, finally gives lithium battery cathode pole piece.
The preparation of lithium battery
Anode, the lithium battery cathode pole piece of the above-mentioned preparation of the present embodiment and dielectric film are assembled into all solid state secondary
Lithium cell, then it is packaged into battery and by being melted into aluminum plastic film, obtains lithium battery.
Embodiment three
A kind of preparation method of battery electrode protection materials, is both embodiment two.
The preparation of electrode plates of lithium cell：The 2g nitrogen-doped graphenes manufactured in the present embodiment for being coated with titanium dioxide are taken to receive
Rice corpuscles and 0.2g Kynoar, it is added in 20mL tetrahydrofurans and is dispersed with stirring uniformly, obtain slurry, the slurry is applied
Overlay in lithium piece, lithium piece is then placed into drying at room temperature 16 hours under an argon atmosphere, form electrode protecting layer, finally give lithium
Cell electrode piece.
The preparation of lithium battery
Anode, the electrode plates of lithium cell of the above-mentioned preparation of the present embodiment and dielectric film are assembled into all solid state secondary
Lithium cell, then it is packaged into battery and by being melted into aluminum plastic film.
Example IV
A kind of preparation method of battery electrode protection materials, comprises the following steps：
(1) styrene cladding graphene oxide microballoon is prepared：1g nano-scale carbon nanotubes are scattered in 20mL styrene liquid
In body, the first dispersion liquid is obtained；0.9g neopelexes and 10g alundum (Al2O3)s are dissolved in 250mL deionized waters
In, obtain mixed solution；The dispersion liquid of gained first is added in the above-mentioned mixed solution being stirred vigorously, stirring and emulsifying, Ran Houjia
Enter 0.5g potassium peroxydisulfates, be warming up to 70 DEG C, stirring reaction stops reaction after 14 hours, obtain the polyphenyl second for including CNT
Alkene nanoscale microballoon emulsion, the lithium chloride solution that a small amount of mass fraction is 50% is added into emulsion and is demulsified, filtering, washs drying
Afterwards, it is stand-by to obtain 7.5g CNTs-polystyrene microsphere.
(2) coated aluminum oxide and removal polystyrene：By 5g Al (OOC8H15)2(OC3H7)2It is dissolved in 50ml isopropanols
In, 1g CNTs-polystyrene microsphere is added, stirs 20h, evaporation solvent obtains 20ml concentrates at 130 DEG C, then will
The 500ml n-hexanes that concentrate cooling is instilled in stirring, are filtrated to get and are coated with Al (OOC8H15)2(OC3H7)2CNT-
Polystyrene microsphere, it is then sintered into 4h at 700 DEG C, obtain the nucleocapsid knot that shell is aluminum oxide, kernel is CNT
Structure material, that is, obtain battery electrode protection materials.
The preparation of electrode plates of lithium cell
The 2g carbon nanotube particles manufactured in the present embodiment for being coated with aluminum oxide are taken, are added to stirring point in 20mL benzene
Dissipate uniformly, obtain slurry, by the slurry coated in lithium piece, it is small that lithium piece is then placed into drying at room temperature 16 under an argon atmosphere
When, electrode protecting layer is formed, finally gives electrode plates of lithium cell.
The preparation of lithium battery
Anode, the electrode plates of lithium cell of the above-mentioned preparation of the present embodiment and dielectric film are assembled into all solid state secondary
Lithium cell, then it is packaged into battery and by being melted into aluminum plastic film.
Claims (15)
1. a kind of battery electrode protection materials, it is characterised in that the electrode protection material is core shell structure, including kernel and outer
Shell, the kernel are carbon material, and the shell is inorganic ceramic material.
2. electrode protection material as claimed in claim 1, it is characterised in that the carbon material includes graphene, doped graphite
In alkene, graphene oxide, doping graphene oxide, hard carbon, doping hard carbon, soft carbon material, CNT and doped carbon nanometer pipe
At least one.
3. electrode protection material as claimed in claim 1 or 2, it is characterised in that the inorganic ceramic material includes titanium dioxide
Titanium, aluminum oxide, zirconium oxide, lithium fluoride, silica, calcium oxide, magnesia, tantalum oxide, silicon nitride, cubic boron nitride, aluminium nitride,
At least one of chromium nitride, titanium nitride, carborundum, boron carbide, titanium carbide and chromium carbide.
4. the electrode protection material as described in claim any one of 1-3, it is characterised in that the quality of the carbon material accounts for described
The 1-50% of electrode protection material gross mass.
5. the electrode protection material as described in claim any one of 1-4, it is characterised in that the thickness of the shell is 1-
10nm。
6. the electrode protection material as described in claim any one of 1-5, it is characterised in that the electrode protection material is spherical
Core shell structure, a diameter of 0.01-2 microns.
7. a kind of preparation method of battery electrode protection materials, it is characterised in that comprise the following steps：
Carbon material is taken, the carbon material is scattered in polymer monomer, obtains including carbon materials by way of emulsion polymerization
The polymer microballoon of material, the microballoon include carbon material and coat the polymeric outer layer of the carbon material；
The coated inorganic ceramic material on the polymeric outer layer, then remove the polymer by the way of dissolving or sintering
Outer layer, that is, obtain battery electrode protection materials, and the electrode protection material is core shell structure, including kernel and shell, it is described in
Core is carbon material, and the shell is inorganic ceramic material.
8. preparation method as claimed in claim 7, it is characterised in that the polymer monomer includes styrene, metering system
Sour methyl esters, acrylate, vinylacetate, vinyl chloride or oxirane.
9. preparation method as claimed in claim 7 or 8, it is characterised in that described to be included by way of emulsion polymerization
The polymer microballoon for having carbon material is specially：After the carbon material is scattered in polymer monomer, solvent, surface-active are added
Agent and initiator, 10-48 hours are reacted in 50-150 DEG C, obtain the polymer microballoon emulsion for including carbon material, after demulsification, warp
Separation, washing, dry, obtain the polymer microballoon for including carbon material.
10. a kind of cell electrode piece, it is characterised in that be provided with the one side of the cell electrode piece and electrolyte contacts
Electrode protecting layer, the material of the electrode protecting layer include the battery electrode protection materials as described in claim any one of 1-6.
11. cell electrode piece as claimed in claim 10, it is characterised in that the thickness of the electrode protecting layer is 0.1-20
Micron.
12. the cell electrode piece as described in claim 10 or 11, it is characterised in that the material of the electrode protecting layer also wraps
Include Kynoar, polyacrylonitrile, polymethyl methacrylate, polyvinylidene chloride, polyvinyl sulfone, poly- diacrylate second two
One or more in alcohol ester, polyvinylpyrrolidone and polyvinylidene fluoride.
13. a kind of preparation method of cell electrode piece, it is characterised in that comprise the following steps：
Battery electrode protection materials as described in claim any one of 1-6 are scattered in atent solvent, obtain slurry, by institute
State in one side of the slurry coated in electrode plates and electrolyte contacts, form electrode protecting layer, obtain that there is electrode protecting layer
The cell electrode piece.
14. the preparation method of cell electrode piece as claimed in claim 13, it is characterised in that the atent solvent includes oneself
One or more in alkane, heptane, benzene, ether, tetrahydrofuran, 1,2- dimethoxy-ethanes, butyl ether and 1-METHYLPYRROLIDONE.
15. a kind of lithium battery, it is characterised in that include the cell electrode piece as described in claim any one of 10-12.
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