CN106207049B - Ceramic diaphragm and application thereof in lithium ion battery - Google Patents
Ceramic diaphragm and application thereof in lithium ion battery Download PDFInfo
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- CN106207049B CN106207049B CN201610719500.XA CN201610719500A CN106207049B CN 106207049 B CN106207049 B CN 106207049B CN 201610719500 A CN201610719500 A CN 201610719500A CN 106207049 B CN106207049 B CN 106207049B
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- diaphragm
- ceramic
- coated
- ceramic diaphragm
- sialon
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- 239000000919 ceramic Substances 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 238000005524 ceramic coating Methods 0.000 claims abstract description 6
- -1 hydroxyl ethyl Chemical group 0.000 claims description 24
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- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- 238000005253 cladding Methods 0.000 claims description 8
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
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- 229910002804 graphite Inorganic materials 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical class [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KPMFJARPXKCVHQ-UHFFFAOYSA-N methyl prop-2-enoate Chemical compound COC(=O)C=C.COC(=O)C=C KPMFJARPXKCVHQ-UHFFFAOYSA-N 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
the invention discloses a ceramic diaphragm, which comprises a diaphragm material substrate and is characterized in that a ceramic coating is coated on at least one side surface of the diaphragm material substrate, the ceramic coating contains L i- α -sialon powder, the surface of L i- α -sialon powder is coated with a polymer layer, the particle size of L i- α -sialon powder is 5nm-50 um., the surface of the diaphragm is coated with L i- α -sialon powder coated with a polymer, the rapid conduction of lithium ions is realized, the cycle performance of a battery using the ceramic diaphragm under the condition of high-current charging and discharging can be improved, in addition, the acrylate-based polymer coated on the surface has better interface stability for a negative electrode, the generation of lithium dendrites can be effectively inhibited, the qualification rate of a laminated battery is improved, the production efficiency and the product quality of the laminated battery are improved, the market application of the laminated battery is improved, and the production guidance significance and the economic effect are increased.
Description
Technical field
The invention belongs to electrochemical technology field, specifically a kind of ceramic diaphragm and preparation method are further related in takeup type
Application in laminated batteries system.
Background technology
With the continuous development that low-carbon globalizes, electrical equipment supplies system based on the decentralized power supply of solar energy and wind energy
System, peak load regulation network, redundant electrical power, green building, portable medical electronic devices, Industry Control, aerospace, robot, state
The rapid development in the fields such as family's safety, there is an urgent need to higher energy density, higher power density, more long circulation life and more
High security can charge and discharge energy storage device.Meanwhile high power capacity power-type lithium ion secondary cell becomes the head of the following environmentally friendly vehicle
Choosing, countries in the world have accordingly formulated the policy state basic policy of future development green energy resource, increasingly to the safety requirements of lithium ion battery
Height, and the reason that short circuit is then most general in all safety accidents occurs in battery.Therefore, it is to prevent electricity in the world in recent years
Security risk caused by the internal short-circuit of pond, battery diaphragm coating, pole piece coating, high safety be electro-hydraulic etc., various aspects have done a large amount of works
Make, to prevent the security risk because of caused by battery internal short-circuit.
In addition, wretched insufficiency is showed in terms of low temperature charge and discharge and cycle, especially at -20 DEG C hereinafter, battery under low temperature
Internal resistance increase apparent, power supply can may not put electricity directly.And at 0 DEG C or less all there is battery impedance increase in charging, cathode
Lithium, poor circulation are analysed in surface, and short life limits its use in cold district.Low temperature rechargeable battery polarizing voltage increases, by
Unstable in the SEI membrane structures of negative terminal surface, battery can on fire, explosion in safety tests such as needle thorn, extruding.For current
Lithium ion battery separator is more to be suitable for a certain range of process route, still, in the stabilization of battery pole group structure
Property, coating ionic conductivity, multiplying power property etc. Shortcomings, in addition rubberized material is more single, has generally comprised poly- inclined
Vinyl fluoride, the Kynoar have that defluorinate etc. is unstable after long-time stores, seriously affect lithium ion battery
Overall performance, be easy to make lithium ion battery that the security risks such as short circuit occur.
Battery core currently on the market is typically all winding method, but this lithium battery is due to, high current big with internal resistance
The shortcomings of poor performance, temperature is high, and safety is poor, cannot be satisfied the performance requirement of some special occasions, in terms of power battery.For
Overcome these disadvantages, especially meets the safe handling in terms of electric vehicle.Lithium ion battery on traditional structure is in ruler
After very little amplification, some internal adverse reactions caused by specific structure are also amplified therewith, and there is an urgent need to a kind of more excellent at this time
The core strueture of change meets the design requirement of high capacity cell, and on this basis, laminated batteries come into being.But laminated battery
The low production efficiency in pond, pole piece will be punched, and section is more, easily pierces through diaphragm, easily short circuit, be also easy to produce side reaction, the tension of battery
It is not easy to control, so that battery reduced performance or security problems is occurred.
Invention content
In view of the deficiencies of the prior art, the present invention proposes a kind of ceramic diaphragm and preparation method, improve ceramic powder with every
The binding ability of film base material improves absorption and ownership of the ceramic powder to electrolyte, improve existing ceramic diaphragm there may be
Leakage caused by security risk, in addition, can be also takeup type laminated batteries ceramic diaphragm, the present invention passes through Li- α-
The tower structure of sialon own materials, surface are coated with polymer, are replaced in existing ceramic diaphragm with this compound
Ceramic powder improves its coating homogeneity on diaphragm material base material, in high/low temperature cyclic process, utilizes its frame structure
Improve due to internal short-circuit to improve the overall performance and stability in use of ceramic diaphragm with the regulating power to lithium ion
Caused by electrochemical appliance safety.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of ceramic diaphragm, including diaphragm material base material, which is characterized in that a diaphragm material base material at least side surface
It is coated with ceramic coating, contains Li- α-sialon powders in institute's ceramic coating, the Li- α-sialon powder surfaces are coated with
The grain size of polymeric layer, the Li- α-sialon powders is 5nm-50um.
The grain size of the Li- α-sialon powders is 10nm-2um.
Li- α-sialon powder surface the coated polymers are selected from methyl methacrylate, ethyl methacrylate, first
Base butyl acrylate, Isobutyl methacrylate, hydroxyethyl methacrylate, Ethylene Glycol Methyl methyl acrylate, polyethylene glycol
Dimethylacrylate, 3- methoxy-methyl acrylates, methyl acrylate, ethyl acrylate, lauryl methacrylate, propylene
Sour trifluoro ethyl ester, glycidyl methacrylate, trimethylol-propane trimethacrylate, trimethylolpropane tris propylene
Acid esters, trimethyl silicane methyl acrylate, triethylene glycol dimethacrylate, 1,1,1,3,3,3- hexafluoro isopropyl of acrylic acid
Ester, acrylic acid trifluoro ethyl ester, tetraethylene glycol diacrylate, 2,2,3,3- tetrafluoro propyl methacrylates, acrylic acid tetrahydrochysene furan
Mutter ester, a kind of monomer polymerization in 2- (2- ethoxyethoxies) ethyl propylene acid esters or two or more monomer crosslinking copolymerizations obtains,
Polymer layer of thickness is 2nm-2um.
The polymer layer of thickness is 1nm-5um.
The diaphragm material base material be polyolefins apertured polymeric film, non-woven fabrics or selected from polyethylene glycol oxide, poly- third
Alkene nitrile, polymethyl methacrylate, Kynoar, Kynoar-hexafluoropropylene copolymer, polyvinyl alcohol and by aforementioned poly-
It closes and is blended derived from object, is in copolymerized polymer one or more.
Another object of the present invention is to provide a kind of preparation method of ceramic diaphragm, poly- the method includes that will be coated with
Li- α-sialon the powders for closing object are coated on as ceramic powder on diaphragm material base material, form ceramic diaphragm.
It is another object of the present invention to provide a kind of secondary cells of ceramic diaphragm.
Another object of the present invention is to provide a kind of application of ceramic diaphragm in the secondary battery.
Beneficial effects of the present invention：Membrane surface coating of the present invention is coated with the Li- α-sialon powders of polymer, realizes
The quick conduction of lithium ion can improve cyclicity under the conditions of high current charge-discharge using the battery of this kind of ceramic diaphragm
Energy；Further, since surface coated acrylate based polyalcohol shows preferable interface stability to cathode, moreover it is possible to effectively suppression
The generation of Li dendrite processed improves the qualification rate of laminated batteries, is conducive to the production efficiency and product quality that improve laminated batteries, carries
The market of high laminated batteries is applied, and is had important operation instruction meaning and is increased economic benefit effect.
Description of the drawings
Fig. 1 ceramic diaphragms（1#）With common diaphragm（2#）Cycle performance comparison diagram in the secondary battery.
Specific implementation mode
Polymethyl methacrylate specifically preferred according to the invention, polymethyl methacrylate (PMMA) are that one kind is commonly used for polymerizeing
The thermoplastic of object electrolyte matrix, due to containing acrylate-functional groups and carbonates electrolyte functional group's phase
Seemingly, therefore with electrolyte there is preferable compatibility, imbibition rate is high, and impalpable structure is also beneficial to ionic conduction, rather than
Polyoxyethylene alkenes matrix can be with the Li+ surrounding crystallines in electrolyte.In addition, the gel polymer electrolyte material pair of PMMA bases
Lithium metal also shows good interface stability, and according to some reports, PMMA is easier to be formed chemical crosslinking structure to increase
Its mechanical strength and the formation that there is the PMMA bases gel electrolyte of cross-linked structure can inhibit Li dendrite.Diaphragm material used
Base material either commercialization polyolefins apertured polymeric film (such as polyethylene or polyacrylic single-layer or multi-layer composite membrane),
Non-woven fabrics can also be the polymer material applied to secondary cell polymer dielectric, as polyethylene glycol oxide, polyacrylonitrile,
Polymethyl methacrylate, Kynoar, one hexafluoropropylene copolymer of Kynoar, polyvinyl alcohol etc., and include by with
It is blended derived from upper system, copolymerization system, such as acrylonitrile monomethyl methyl acrylate copolymer.It can be in barrier film base material single side
Coating, can also be in barrier film base material double spread.
Secondary cell provided by the invention, including positive electrode, negative material, it is characterised in that：In positive electrode and bear
There is ceramic diaphragm provided by the invention between the material of pole.
The positive electrode that usual lithium ion battery uses can be used in the present invention.The positive electrode active material that anode is related to
Matter can use the reversibly embedded compound with deintercalate lithium ions, LixMO is used for example, can enumerate2Or LiyM2O4。
Oxide, the layer of lithium-contained composite oxide, spinel structure that (in formula, M is transition metal, 0≤x≤1,0≤y≤2) indicates
Metal chalcogenide, olivine structural of shape structure etc..Such as LiCoO2Equal lithium and cobalt oxides, LiMn2O4Equal lithium manganese oxides,
LiNiO2Equal lithium nickel oxides, Li4/3Ti5/3O4Equal Li-Ti oxides, li-mn-ni compound oxide, lithium nickel cobalt manganese oxide；
Material with olivine-types crystalline textures such as LiMPO4 (M=Fe, Mn, Ni)；Using containing for layer structure or spinelle shape structure
Lithium composite xoide is preferred, LiCoO2, LiMn2O4、LiNiO2、LiNi1/2Mn1/2O2Deng the lithium manganese nickel combined oxidation for representative
Object, LiNi1/3Mn1/3Co1/3O2、LiNi0.6Mn0.2Co0.2O2Deng the lithium nickel cobalt manganese oxide or LiNi for representative1-x-y- zCoxAlxMgzO2Lithium-contained composite oxides such as (in formulas, 0≤x≤1,0≤y≤0.1,0≤z≤0.1,0≤1-x-y-z≤1).Separately
Outside, a part for the constitution element in above-mentioned lithium-contained composite oxide, is taken by the addition element of Ti, Zr, Mg, Al, Mo etc.
The lithium-contained composite oxide in generation etc. also includes wherein.These positive active materials, both can be used alone one kind, also can be two or more
It is used in combination.
Anode for constituting nonaqueous electrolytic solution secondary battery, for example, being properly added charcoal in above-mentioned positive active material
Adhesives such as the conductive auxiliary agents such as black, acetylene black or Kynoar, polyethylene oxide etc., by it with current-collecting members such as aluminium foils
As on the band-like formed body of core material be coated with after use.But positive production method is not limited only to example.
The negative material that usual lithium ion battery uses can be used in the present invention.The negative electrode active material that cathode is related to
Matter, which can use, can be embedded in a deintercalation lithium metal, the compound of lithium.Such as the alloy or oxide, carbon material of aluminium, silicon, tin etc.
Etc. a variety of materials etc. may be used as negative electrode active material.Oxide can enumerate titanium dioxide etc., carbon material can enumerate graphite,
It is pyrolyzed carbons, coke class, glassy carbons, the sintered body of organic high molecular compound, mesophase-carbon micro-beads etc..
Cathode for constituting nonaqueous electrolytic solution secondary battery, for example, being properly added charcoal in above-mentioned negative electrode active material
Adhesives such as the conductive auxiliary agents such as black, acetylene black or Kynoar, polyethylene oxide etc. prepare cathode agent, by it with copper
The current-collecting members such as foil as on the band-like formed body of core material be coated with after use.But the production method of cathode is not limited only to
Example.
In nonaqueous electrolytic solution secondary battery provided by the invention, using nonaqueous solvents (organic solvent) as non-aqueous solution electrolysis
Liquid.Nonaqueous solvents includes carbonates, ethers etc..Carbonates include cyclic carbonate and linear carbonate, cyclic carbonate
Ethylene carbonate, propene carbonate, butylene, gamma-butyrolacton, sulphur class ester (ethylene glycol sulfide etc.) etc. can be enumerated.
Linear carbonate can enumerate the polarity chain for the low viscosity that dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate etc. are representative
Carbonic ester, aliphatic branched chain type carbonats compound.Cyclic carbonate (especially ethylene carbonate) and linear carbonate
Mixed solvent is particularly preferred.Ethers can enumerate dimethyl ether tetraethylene glycol (TEGDME), glycol dimethyl ether (DME), and 1,3-
Dioxolane (DOL) etc..
In addition, in addition to above-mentioned nonaqueous solvents, the chains such as the chain-like alkyls such as methyl propionate esters, trimethyl phosphate may be used
Phosphotriester；The nitrile solvents such as 3- methoxypropionitriles；Using dendrimer as the branched chain type compound with ehter bond of representative
Equal nonaqueous solvents (organic solvent).As fluorine solvent, for example, H (CF2)2OCH3、C4F9OCH3、H(CF2)2OCH2CH3、H
(CF2)2OCH2CF3、H(CF2)2CH2O(CF2)2H etc., or CF3CHFCF2OCH3、CF3CHFCF2OCH2CH3Etc. linear chain structures it is (complete
Fluoroalkyl) alkyl ether, i.e. 2- trifluoromethyls hexafluoro propyl methyl ether, 2- trifluoromethyl hexafluoro propyl ether, 2- trifluoromethyl hexafluoros
Propyl propyl ether, 3- trifluoromethyl octafluoros butyl methyl ether, 3- trifluoromethyl octafluoro butyl ether, 3- trifluoromethyl octafluoros butyl third
Ether, ten fluorine amyl group methyl ether of 4- trifluoromethyls, ten fluorine amyl group ether of 4- trifluoromethyls, ten fluorine amyl group propyl ether of 4- trifluoromethyls, 5- tri-
Ten difluoro hexyl methyl ether of methyl fluoride, ten difluoro hexyl ether of 5- trifluoromethyls, ten difluoro hexyl propyl ether of 5- trifluoromethyls, 6- trifluoros
Ten tetrafluoro heptyl methyl ether of methyl, ten tetrafluoro heptyl ether of 6- trifluoromethyls, ten tetrafluoro heptyl propyl ether of 6- trifluoromethyls, 7- fluoroforms
Ten hexafluoro octyl methyl ether of base, ten hexafluoro octyl ether of 7- trifluoromethyls, ten hexafluoro octyl propyl ether of 7- trifluoromethyls etc..On in addition,
Stating different (perfluoroalkyl) alkyl ether and (perfluoroalkyl) alkyl ether of above-mentioned linear chain structure can also be used in combination.
As the electrolytic salt used in nonaqueous electrolytic solution, the preferably perchlorate of lithium, organic boron lithium salts, fluorochemical
The lithium salts such as lithium salts, lithium imide salts.For example, LiClO can be enumerated4、LiPF6、LiBF4、LiAsF6、LiSbF6、LiCF3SO3、
LiCF3CO2、LiC2F4(SO3)2、LiN(C2F5SO2)2、LiC(CF3SO2)3、LiCnF2n+1SO3(n≥2)、LiN(RfOSO2)2(formula
In, Rf is fluoroalkyl) etc..In these lithium salts, fluorine-containing organic lithium salt is particularly preferred.Fluorine-containing organic lithium salt, due to the moon from
Sub- property is big and easily separated at ion, soluble in nonaqueous electrolytic solution.
Concentration of the electrolyte lithium salt in nonaqueous electrolytic solution, for example, 0.3mol/L or more is preferred, more preferable 0.7ml/
L or more, preferably 1.7mol/L are hereinafter, more preferably 1.2mol/L or less.When the concentration of electrolyte lithium salt is too low, ion conductivity
Too small, when excessively high, worry fails to dissolve complete electrolytic salt precipitation.In addition, in nonaqueous electrolytic solution, can also add can carry
Height is not particularly limited using the various additives of the performance of its battery.
In description of the invention, particle, powder and powder indicate identical meaning.
Embodiment 1
In the reactor with condensing unit, Li- α-sialon powders, deionized water and methacrylate monomer is added,
It is started to warm up after stirring 60min, suitable ammonium persulfate is added at 75 DEG C, 85 DEG C are warming up to after constant temperature 6h, and the reaction was continued
60min, then cooling obtain the Li- α-sialon powders of methyl acrylate cladding, and coating thickness can be by adjusting propylene
The input amount of sour methylmethacrylate monomer is controlled in 2nm-1um.Take Li- α-sialon powders, the inclined fluorine second of 1g of 4g methyl acrylates cladding
Alkene (binder) is scattered in the N-Methyl pyrrolidone of 50ml, using the tape casting in 1m2Polyethylene diagrams on be coated,
Ceramic diaphragm is obtained after drying.
Obtained ceramic diaphragm and the polyethylene diagrams for coating are immersed into commercial lithium-ion batteries electrolyte respectively
In (LiPF6 of 1mol/L be dissolved in mass ratio be 1：1：In 1 ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate), pottery
Porcelain diaphragm imbibition rate reaches 85%, and polyethylene diagrams are only 47%, illustrates ceramic diaphragm due to better with electrolyte characterization of adsorption
The presence of polymethyl methacrylate, the ability for adsorbing electrolyte significantly improve.
In the secondary battery by two kinds of diaphragms, through 55 DEG C, 1C charge and discharge, high temperature cyclic performance is shown in Fig. 1.
Embodiment 2
1000ml deionized waters are mixed in the three-neck flask of 2000ml capacity, the Li- α-sialon that 10g grain sizes are 50nm
Powder and 0.1g neopelexes, under nitrogen protection, 0.3g ammonium persulfates and 0.3g is added in mechanical agitation 1 hour
Sodium sulfite is warming up to 80 DEG C, and 15g butyl methacrylates are added, and after reacting 2 hours, it is 1500 that 1.5g molecular weight, which is added,
Polyethylene glycol dimethacrylate is chemically crosslinked, and stops reaction after the reaction was continued 2 hours, obtained product centrifugation point
From, washed three times with ethyl alcohol and water, dried under room temperature, vacuum condition respectively, obtain butyl methacrylate cladding Li- α-
Sialon powders.Li- α-sialon powders, 2g Kynoar-hexafluoropropene that 8g butyl methacrylates coat is taken (to bond
Agent) it is scattered in 100ml acetone, using the tape casting in 1m2Polypropylene diaphragm on be coated, obtained after dry ceramics every
Film.
Embodiment 3
3000ml deionized waters are mixed in the three-neck flask of 5000ml capacity, the Li- α-that 100g grain sizes are 10um
Sialon powders and 1g neopelexes, under nitrogen protection, 3g ammonium persulfates and 3g is added in mechanical agitation 1 hour
Sodium sulfite is warming up to 80 DEG C, and 100g Ethylene Glycol Methyl methyl acrylates are added, and stops reaction, obtained product after reacting 4h
It centrifuges, is washed three times with ethyl alcohol and water, dried under room temperature, vacuum condition respectively, obtain polyethylene glycol methacrylic acid
Li- α-sialon the powders of methyl esters cladding.Take Li- α-sialon powders, the 0.2g that 10g Ethylene Glycol Methyl methyl acrylates coat
Hydroxymethyl cellulose and 0.3g butadiene-styrene rubber are scattered in 100ml water, on small size coating machine the polyethylene of 20cm × 6m every
It is coated on film, ceramic diaphragm is obtained after dry.
Embodiment 4
3000ml toluene is mixed in the three-neck flask of 5000ml capacity, the Li- α-sialon powders that 50g grain sizes are 2um
Mechanical agitation 1 hour is warming up to 60 DEG C, and 100g 3- methoxy-methyl acrylates and 1 are added and drip, and stops reaction after reacting 4h,
Obtained product centrifuges, and is washed three times with ethyl alcohol and water, is dried under room temperature, vacuum condition respectively, obtains 3- methoxyl groups
Li- α-sialon the powders of methyl acrylate methyl acrylate cladding.The Li- α-for taking 10g 3- methoxy-methyl acrylates to coat
Sialon powders, 0.2g hydroxymethyl celluloses and 0.3g butadiene-styrene rubber are scattered in 100ml water, in 20cm on small size coating machine
It is coated on the polyethylene diagrams of × 6m, ceramic diaphragm is obtained after dry.
Embodiment 5
The powder of the lauryl methacrylate cladding of 20g mist projection granulatings preparation, wherein Li- α-sialon powder are produced first
The grain size of body is about 1um, this kind of one hexafluoropropene (binder) of compound 1g, 0.1g Kynoar is taken to be scattered in the N of 10ml,
In dinethylformamide, use the mode of immersion coating by its double spread in thickness for the polymerization of the Kynoar of 20um
On object film, ceramic diaphragm is obtained after dry.
Embodiment 6
Li- α-sialon the powders of the butyl methacrylate cladding of 20g mist projection granulatings preparation, wherein Li- are produced first
The grain size of α-sialon powders is about 100nm, takes this kind of compound 1g, 0.1g Kynoar-hexafluoropropene (binder) point
Dissipate in the n,N-Dimethylformamide of 10ml, use the mode of immersion coating by its double spread in thickness for the poly- second of 20um
On the diaphragm of alkene, ceramic diaphragm is obtained after dry.
Above content is only to structure of the invention example and explanation, affiliated those skilled in the art couple
Described specific embodiment does various modifications or additions or substitutes by a similar method, without departing from invention
Structure or beyond the scope defined by this claim, is within the scope of protection of the invention.
Claims (8)
1. a kind of ceramic diaphragm, including diaphragm material base material, which is characterized in that a diaphragm material base material at least side surface applies
It is furnished with ceramic coating, contains Li- α-sialon powders in institute's ceramic coating, the Li- α-sialon powder surfaces are coated with poly-
Nitride layer is closed, the grain size of the Li- α-sialon powders is 5nm-50um.
2. ceramic diaphragm according to claim 1, which is characterized in that the grain size of the Li- α-sialon powders is 10nm-
2um。
3. ceramic diaphragm according to claim 1, which is characterized in that the Li- α-sialon powder surfaces cladding polymerization
Object is selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, Isobutyl methacrylate, metering system
Sour hydroxyl ethyl ester, Ethylene Glycol Methyl methyl acrylate, polyethylene glycol dimethacrylate, 3- methoxy-methyl acrylates, propylene
Sour methyl esters, ethyl acrylate, lauryl methacrylate, acrylic acid trifluoro ethyl ester, glycidyl methacrylate, three hydroxyl first
Base propane trimethyl acrylic ester, trimethylolpropane trimethacrylate, trimethyl silicane methyl acrylate, triethylene glycol two
Methacrylate, 1,1,1,3,3,3- hexafluoro isopropyl ester of acrylic acid, acrylic acid trifluoro ethyl ester, tetraethylene glycol diacrylate, 2,
In 2,3,3- tetrafluoro propyl methacrylates, acrylic acid tetrahydrofuran ester, 2- (2- ethoxyethoxies) ethyl propylene acid esters
A kind of monomer polymerization or two or more monomer crosslinking copolymerizations obtain, polymer layer of thickness 2nm-2um.
4. ceramic diaphragm according to claim 3, which is characterized in that the polymer layer of thickness is 1nm-5um.
5. ceramic diaphragm according to claim 1, which is characterized in that the diaphragm material base material is that polyolefins is porous poly-
Compound film, non-woven fabrics are selected from polyethylene glycol oxide, polyacrylonitrile, polymethyl methacrylate, Kynoar, polyvinylidene fluoride
It is one or more in alkene-hexafluoropropylene copolymer, polyvinyl alcohol and blending, copolymerized polymer derived from aforementioned polymer.
6. a kind of method preparing ceramic diaphragm as described in claim 1, which is characterized in that the method includes being coated with
Li- α-sialon the powders of polymer are coated on as ceramic powder on diaphragm material base material, form ceramic diaphragm.
7. a kind of secondary cell including ceramic diaphragm as described in claim 1.
8. a kind of application of ceramic diaphragm as described in claim 1 in the secondary battery.
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| KR102378583B1 (en) * | 2018-03-20 | 2022-03-23 | 주식회사 엘지에너지솔루션 | Separator Having Coating Layer of Lithium-Containing Composite, and Lithium Secondary Battery Comprising the Separator and Preparation Method Thereof |
| CN114464950B (en) * | 2021-12-23 | 2024-02-27 | 惠州锂威新能源科技有限公司 | High-ion conductive diaphragm, preparation method of diaphragm and battery |
| CN117477168B (en) * | 2023-12-26 | 2024-03-08 | 新乡华锐锂电新能源股份有限公司 | Isolation film for sodium ion battery and preparation method thereof |
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| CN103035866A (en) * | 2013-01-09 | 2013-04-10 | 厦门大学 | Ceramic membrane, application of ceramic membrane to battery and battery comprising ceramic membrane |
| CN104425788A (en) * | 2013-08-28 | 2015-03-18 | 比亚迪股份有限公司 | Lithium-ion battery diaphragm, preparation method of lithium-ion battery diaphragm, as well as lithium-ion battery comprising diaphragm |
| CN105140453A (en) * | 2015-08-26 | 2015-12-09 | 厦门大学 | Ceramic composite membrane with thermal-shutdown function and application thereof |
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| US20120231321A1 (en) * | 2011-03-11 | 2012-09-13 | GM Global Technology Operations LLC | Integral bi-layer separator-electrode construction for lithium-ion batteries |
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| CN103035866A (en) * | 2013-01-09 | 2013-04-10 | 厦门大学 | Ceramic membrane, application of ceramic membrane to battery and battery comprising ceramic membrane |
| CN104425788A (en) * | 2013-08-28 | 2015-03-18 | 比亚迪股份有限公司 | Lithium-ion battery diaphragm, preparation method of lithium-ion battery diaphragm, as well as lithium-ion battery comprising diaphragm |
| CN105140453A (en) * | 2015-08-26 | 2015-12-09 | 厦门大学 | Ceramic composite membrane with thermal-shutdown function and application thereof |
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