CN103035866B - Ceramic membrane, application of ceramic membrane to battery and battery comprising ceramic membrane - Google Patents
Ceramic membrane, application of ceramic membrane to battery and battery comprising ceramic membrane Download PDFInfo
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- CN103035866B CN103035866B CN201310006942.6A CN201310006942A CN103035866B CN 103035866 B CN103035866 B CN 103035866B CN 201310006942 A CN201310006942 A CN 201310006942A CN 103035866 B CN103035866 B CN 103035866B
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- 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 belongs to the field of electrochemistry and in particular relates to a ceramic membrane. Particularly, the invention also relates to a ceramic membrane with a core-shell structure and prepared by substituting an organic-inorganic composite for ceramic powder. The invention further relates to application of the ceramic membrane to a chemical power supply system such as a lithium ion battery and a battery comprising the ceramic membrane. The ceramic powder with the core-shell composite structure is favorable for improvement of the electrolyte adsorbing and maintaining ability of the ceramic membrane. The ceramic membrane can serve as a high-safety membrane material of secondary batteries such as a lithium ion battery, and has excellent electrochemical performance and heat stability. According to the invention, the operability is high; the cost is low compared with that of other methods; the reproducibility is high; and the obtained product quality is stable.
Description
Technical field
The invention belongs to electrochemical field, be specifically related to a kind of ceramic diaphragm.More specifically, the present invention relates to the organic-inorganic composition that comprises and there is nucleocapsid structure as the ceramic diaphragm of ceramic coating, the invention still further relates to this kind of ceramic diaphragm at the application of the chemical power source systems such as lithium ion battery and the battery containing this ceramic diaphragm.
Background technology
Lithium ion battery is high as a kind of energy density, output voltage is high, memory-less effect, cycle performance excellent, eco-friendly chemical power source system, there is good economic benefit, social benefit and strategic importance, be widely used in the every field such as mobile communication, digital product, and very likely become the topmost power-supply system of energy storage and electric automobile field.
In lithium ion battery, barrier film mainly plays and prevents both positive and negative polarity from contacting and the effect allowing ionic conduction, is the important part of battery.At present, the TPO diaphragm material mainly with microcellular structure adopted in commercial lithium ion battery, as the single or multiple lift film of polyethylene (Polyethylene, PE), polypropylene (Polypropylene, PP).Due to the feature of polymer itself, although polyalkene diaphragm can provide enough mechanical strengths and chemical stability at normal temperatures, but then show larger thermal contraction under the high temperature conditions, thus cause both positive and negative polarity contact and gather rapidly large calorimetric, although first such as can there is the micropore in PE fusing obstruction polymer in PP/PE composite diaphragm at lower temperature (120 ° of C), block the further generation that effect that ionic conduction and PP still play support prevents electrode reaction, but because the melting temperature of PP also only has 150 ° of C, when temperature rises rapidly, more than the melting temperature of PP, barrier film melting can cause large area short circuit and cause thermal runaway, aggravation thermal accumlation, produce inside battery hyperbar, cause cells burst or blast.Internal short-circuit of battery is the maximum hidden danger of lithium ion battery security.In order to meet the needs of high capacity lithium ion battery development, exploitation high security barrier film has become the task of top priority of industry.At this wherein, the temperature tolerance of ceramic diaphragm excellence and high security become one of main selection replacing conventional polyolefins barrier film.
Ceramic diaphragm (Ceramic-coated Separators) is on the surface of existing polyolefin micropore film base material, and single or double is coated with the protective layer that one deck is uniform, be made up of ceramic microparticle etc., forms porous security functions barrier film.On the basis ensureing the original fundamental characteristics of polyolefin micropore barrier diaphragm, give barrier film high heat-resisting function, reduce the heat-shrinkable of barrier film, thus more effectively reduce inside lithium ion cell short circuit, prevent the battery thermal runaway caused because of internal short-circuit of battery.
At present, mainly by ceramic powder, (the mainly oxide powder of nanometer or sub-micron, as Al for the preparation method of ceramic diaphragm
2o
3, SiO
2, TiO
2deng), binding agent etc. is dispersed in solvent and forms slurry, then form ceramic coating (see Journal of Power Sources195 (2010) 6192 – 6196, CN200580036709.6, CN200780035135.X etc.) by the tape casting or infusion process at polyalkene diaphragm substrate surface.But, because ceramic powder specific surface energy is larger, be easy to reunite, and its surface is generally water-wet behavior, and polyolefin film is hydrophobic material, therefore, from great majority research report, the uniformity of ceramic powder coating is poor, and there is significantly " dry linting " phenomenon, this can affect the serviceability of ceramic diaphragm in lithium ion battery greatly.In addition, ceramic diaphragm can improve the blind date ability with electrolyte due to the coating of powder, but due to barrier film base material itself and electrolyte wetting capacity poor, therefore, still there is certain leakage risk in existing ceramic diaphragm.
Summary of the invention
In order to improve the affinity of ceramic powder and barrier film base material, improve ceramic powder to the absorption of electrolyte and hold facility, solve the potential safety hazard that leakage that existing ceramic diaphragm may exist causes, by to construct in advance, to have inorganic matter be core in the present invention, acrylate based polyalcohol is the compound of shell and carries out good design and control to its pattern and space structure, the ceramic powder in existing ceramic diaphragm is replaced with this compound, improve its coating homogeneity on diaphragm material base material, improve the ability of ceramic diaphragm absorption and maintenance electrolyte, thus improve overall performance and the stability in use of ceramic diaphragm.
Therefore, an object of the present invention is to provide a kind of based on take inorganic matter as core, acrylate based polyalcohol is shell nucleocapsid structure compound replaces the ceramic diaphragm that ceramic powder is coated with acquisition on barrier film.
Another object of the present invention is to provide the application in the battery of this ceramic diaphragm.
Another object of the present invention is to provide the battery comprising this ceramic diaphragm.
A kind of ceramic diaphragm provided by the invention; comprise diaphragm material base material; it is characterized in that: be coated with protective layer at diaphragm material substrate surface; the nucleocapsid structure compound that the main component of described protective layer is take inorganic matter as core, acrylate based polyalcohol is shell, other components such as bonding agent and the solvent of described protective layer can adopt the conventional constituents used in prior art.
The core of nucleocapsid structure compound is inorganic matter, is selected from one or more in alundum (Al2O3), titanium dioxide, silicon dioxide, zirconium dioxide, tin ash, magnesium oxide, zinc oxide, barium sulfate, boron nitride, aluminium nitride, magnesium nitride.Particles of inorganic material particle diameter is 5nm-50 μm, for the uniformity of coating and the validity of application, is preferably 50nm-10 μm.
Described acrylate based polyalcohol, by being selected from methyl methacrylate, EMA, butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, Ethylene Glycol Methyl methyl acrylate, polyethylene glycol dimethacrylate, 3-methoxy-methyl acrylate, methyl acrylate, ethyl acrylate, lauryl methacrylate, acrylic acid trifluoro ethyl ester, glycidyl methacrylate, 2-methyl-2-acrylic acid-2-ethyl-2-[[(2-methyl isophthalic acid-oxo-2-acrylic) oxygen] methyl]-1,3-PD ester, trimethyl silicane methyl acrylate, TEGDMA, 1,1,1,3,3,3-hexafluoro isopropyl acrylate, acrylic acid trifluoro ethyl ester, tetraethylene glycol diacrylate, 2,2,3,3-tetrafluoro propyl methacrylate, acrylic acid tetrahydrofuran ester, 2-(2-ethoxyethoxy) a kind of monomer polymerization in ethyl propylene acid esters or two or more monomer copolymerization is crosslinked obtains, shell thickness is 1nm-10 μm.
The present invention is polymethyl methacrylate particularly preferably, polymethyl methacrylate (PMMA) is a kind of thermoplastics being commonly used for polymer electrolyte matrix, because the acrylate-functional groups contained is similar to the functional group of carbonates electrolyte, therefore with electrolyte, there is good compatibility, pick up is high, its impalpable structure is also conducive to ionic conduction, and can with the Li in electrolyte unlike polyethylene glycol oxide (PEO) class matrix
+surrounding crystalline.In addition, the gel polymer electrolyte material of PMMA base also shows good interface stability to lithium metal, according to some reports, PMMA more easily forms chemical crosslinking structure thus increases its mechanical strength and the PMMA base gel electrolyte with cross-linked structure can suppress the formation of Li dendrite.Diaphragm material base material used both can be commercial TPO apertured polymeric film (as polyethylene or polyacrylic single or multiple lift composite membrane), nonwoven fabrics, also can be the polymeric material being applied to secondary cell polymer dielectric, as polyethylene glycol oxide, polyacrylonitrile, polymethyl methacrylate, Kynoar, Kynoar-hexafluoropropylene copolymer, polyvinyl alcohol etc., and comprise blended, the copolymerization system that are derived by above system, as acrylonitrile methyl meth acrylat copolymer etc.The coating thickness of nucleocapsid compound on barrier film base material is 0.1 micron to 20 microns, can be coated with at barrier film base material one side, also can at barrier film base material double spread.
Ceramic diaphragm provided by the invention application in the battery, replaces existing ceramic diaphragm.
Battery provided by the invention, comprises positive electrode, negative material, it is characterized in that: between positive electrode and negative material, have ceramic diaphragm provided by the invention.
The positive electrode that usual lithium ion battery uses can use in the present invention.The positive active material that positive pole relates to, can use the compound of reversibly occlusion-releasing (Infix and desfix) lithium ion, such as, can enumerate and use Li
xmO
2or Li
ym
2o
4lithium-contained composite oxide, the oxide of spinelle shape, the metal chalcogenide, olivine structural etc. of layer structure that (in formula, M is transition metal, 0≤x≤1,0≤y≤2) represents.
As its object lesson, LiCoO can be enumerated
2deng lithium and cobalt oxides, LiMn
2o
4deng lithium manganese oxide, LiNiO
2deng lithium nickel oxide, Li
4/3ti
5/3o
4deng Li-Ti oxide, li-mn-ni compound oxide, lithium manganese nickel cobalt composite oxides; There is LiMPO
4material of olivine-type crystalline textures such as (M=Fe, Mn, Ni) etc.
The lithium-contained composite oxide particularly adopting layer structure or spinelle shape structure is preferred, LiCoO
2, LiMn
2o
4, LiNiO
2, LiNi
1/2mn
1/2o
2deng li-mn-ni compound oxide, LiNi for representative
l/3mn
1/3co
1/3o
2, LiNi
0.6mn
0.2co
0.2o
2deng being the lithium manganese nickel cobalt composite oxides of representative or LiNi
1-x-y-zco
xal
ymg
zo
2lithium-contained composite oxides such as (in formulas, 0≤x≤1,0≤y≤0.1,0≤z≤0.1,0≤1-x-y-z≤1).In addition, a part for the constitution element in above-mentioned lithium-contained composite oxide, the lithium-contained composite oxide etc. that replaces by the Addition ofelements of Ge, Ti, Zr, Mg, Al, Mo, Sn etc. also comprise wherein.
These positive active materials, both can be used alone a kind, but also two or more are also used.Such as, by the lithium-contained composite oxide of the lithium-contained composite oxide and spinel structure that use layer structure simultaneously, the raising taking into account high capacity and fail safe can be sought.
For forming the positive pole of nonaqueous electrolytic solution secondary battery, such as, the conductive auxiliary agent such as carbon black, acetylene black is suitably added in above-mentioned positive active material, or the adhesive such as Kynoar, poly(ethylene oxide) etc., preparation anode mixture, uses after it being coated with on the banded formed body using current-collecting members such as aluminium foils as core.But the manufacture method of positive pole is not limited only to example.
The negative material that usual lithium ion battery uses can use in the present invention.The negative electrode active material that negative pole relates to can use the compound that can embed-removal lithium embedded metal, lithium.The alloy of such as aluminium, silicon, tin etc. or the various materials such as oxide, material with carbon element etc. can be used as negative electrode active material.Oxide can enumerate titanium dioxide etc., and material with carbon element can enumerate the sintered body, mesophase-carbon micro-beads etc. of graphite, RESEARCH OF PYROCARBON class, coke class, vitreous carbon class, organic high molecular compound.
For forming the negative pole of nonaqueous electrolytic solution secondary battery, such as, the conductive auxiliary agent such as carbon black, acetylene black is suitably added in above-mentioned negative electrode active material, or the adhesive such as Kynoar, poly(ethylene oxide) etc., preparation cathode agent, uses after it being coated with on the banded formed body using current-collecting members such as Copper Foils as core.But the manufacture method of negative pole is not limited only to example.
In nonaqueous electrolytic solution secondary battery provided by the invention, use nonaqueous solvents (organic solvent) as nonaqueous electrolytic solution.Nonaqueous solvents comprises carbonates, ethers etc.
Carbonates comprises cyclic carbonate and linear carbonate, and cyclic carbonate can enumerate ethylene carbonate, propene carbonate, butylene, gamma-butyrolacton, sulphur class ester (ethylene glycol sulfide etc.) etc.Linear carbonate can enumerate low viscous polarity linear carbonate, the aliphat branched chain type carbonats compound that dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate etc. are representative.Cyclic carbonate (particularly ethylene carbonate) is particularly preferred with the mixed solvent of linear carbonate.
Ethers can enumerate dimethyl ether tetraethylene glycol (TEGDME), glycol dimethyl ether (DME), 1,3-dioxolane (DOL) etc.
In addition, except above-mentioned nonaqueous solvents, the chain phosphotriesters such as chain-like alkyl ester class, trimethyl phosphate such as methyl propionate can be adopted; The nitrile solvents such as 3-methoxypropionitrile; With dendrimer be representative there is the nonaqueous solventss (organic solvent) such as the branched chain type compound of ehter bond.
In addition, also fluorine kind solvent can be adopted.
As fluorine kind solvent, such as, H (CF can be enumerated
2)
2oCH
3, C
4f
9oCH
3, H (CF
2)
2oCH
2cH
3, H (CF
2)
2oCH
2cF
3, H (CF
2)
2cH
2o (CF
2)
2h etc. or CF
3cHFCF
2oCH
3, CF
3cHFCF
2oCH
2cH
3etc. (perfluoroalkyl) alkyl ether of linear chain structure, i.e. 2-trifluoromethyl hexafluoro propyl methyl ether, 2-trifluoromethyl hexafluoro propyl group ether, 2-trifluoromethyl hexafluoro propyl group propyl ether, 3-trifluoromethyl octafluoro butyl methyl ether, 3-trifluoromethyl octafluoro butyl ether, 3-trifluoromethyl octafluoro butyl propyl ether, 4-trifluoromethyl ten fluorine amyl group methyl ether, 4-trifluoromethyl ten fluorine amyl group ether, 4-trifluoromethyl ten fluorine amyl group propyl ether, 5-trifluoromethyl ten difluoro hexyl methyl ether, 5-trifluoromethyl ten difluoro hexyl ether, 5-trifluoromethyl ten difluoro hexyl propyl ether, 6-trifluoromethyl ten tetrafluoro heptyl methyl ether, 6-trifluoromethyl ten tetrafluoro heptyl ether, 6-trifluoromethyl ten tetrafluoro heptyl propyl ether, 7-trifluoromethyl ten hexafluoro octyl group methyl ether, 7-trifluoromethyl ten hexafluoro octyl group ether, 7-trifluoromethyl ten hexafluoro octyl group propyl ether etc.
In addition, (perfluoroalkyl) alkyl ether of above-mentioned different (perfluoroalkyl) alkyl ether and above-mentioned linear chain structure also can and use.
As the electrolytic salt used in nonaqueous electrolytic solution, the lithium salts such as lithium salts, lithium imide salts of the perchlorate of preferred lithium, organic boron lithium salts, fluorochemical.
As the example of such electrolytic salt, such as, LiClO can be enumerated
4, LiPF
6, LiBF
4, LiAsF
6, LiSbF
6, LiCF
3sO
3, LiCF
3cO
2, LiC
2f
4(SO
3)
2, LiN (C
2f
5sO
2)
2, LiC (CF
3sO
2)
3, LiC
nf
2n+1sO
3(n>=2), LiN (RfOSO
2)
2(in formula, Rf is fluoroalkyl) etc.In these lithium salts, fluorine-containing organic lithium salt is particularly preferred.Fluorine-containing organic lithium salt, due to the large and easily separated one-tenth ion of anionic property, soluble in nonaqueous electrolytic solution.
The concentration of electrolyte lithium salt in nonaqueous electrolytic solution, such as, more than 0.3mol/L (mol/L) is preferred, more preferably more than 0.7mol/L, preferred below 1.7mol/L, more preferably below 1.2mol/L.When the concentration of electrolyte lithium salt is too low, ionic conduction is spent little, time too high, worries that failing to dissolve electrolytic salt completely separates out.
In addition, in nonaqueous electrolytic solution, also can add the various additives of the performance that can improve the battery adopting it, not be particularly limited.
Usefulness of the present invention is: because acrylate-based shell can adsorb more electrolyte, realizes the quick conduction of lithium ion, therefore can improve the cycle performance of battery under high current charge-discharge condition using this kind of ceramic diaphragm; In addition, because acrylate based polyalcohol anticathode shows good interface stability, the generation of Li dendrite can also therefore effectively be suppressed when coat and graphite cathode one side contacts.
Accompanying drawing explanation
Fig. 1 is embodiment 1 SiO used
2for the nucleocapsid compound transmission electron microscope photo that core, PMMA are shell.
The stereoscan photograph of Fig. 2 is embodiment 1 acquisition ceramic diaphragm.
Fig. 3 is embodiment 1, and acquisition ceramic diaphragm compares with the electrolyte wettability of polyethylene diagrams (left: polyethylene diagrams, right: embodiment 1 ceramic diaphragm).
Fig. 4 a is before pyrocondensation test, embodiment 1 obtains ceramic diaphragm and polyethylene diagrams (left side: polyethylene diagrams, the right side: embodiment 1 ceramic diaphragm); Fig. 4 b is after pyrocondensation test, embodiment 1 obtains ceramic diaphragm and polyethylene diagrams (left side: polyethylene diagrams, the right side: embodiment 1 ceramic diaphragm).
Fig. 5 is that embodiment 7 adopts the battery of ceramic diaphragm of the present invention and comparative example 2 to adopt the cycle performance of battery correlation curve of conventional ceramic barrier film.
Embodiment
To be described in more detail by embodiment below, but protection scope of the present invention is not limited to these embodiments.
Embodiment 1
At normal temperatures 30ml tetraethoxysilane is joined in 350mL absolute ethyl alcohol, then 30ml water and 12ml14mol/L ammonia water mixture is added fast, to obtain silicon dioxide granule dispersion liquid after the speed stirring reaction 3h of 200r/min, silicon dioxide granule is at about 400nm.At N
2carry out under gas shielded; in the reactor of band condensing unit; add above-mentioned nano-silicon dioxide particle dispersion liquid, deionized water and methacrylate monomer; start after stirring 60min to heat up; add appropriate ammonium persulfate when 75 ° of C, be warmed up to 85 ° of C after constant temperature 6h and continue reaction 60min, then cooling obtains silicon dioxide/methyl acrylate nucleocapsid compound; characterized by transmission electron microscope, shell thickness can control at 2nm-1 μm by regulating the input amount of methacrylate monomer.Get 4g nucleocapsid compound, 1g vinylidene (binding agent) is scattered in 50mlN-methyl pyrrolidone, adopt the tape casting at 1m
2polyethylene diagrams on be coated with, namely obtain ceramic diaphragm after drying.
The ceramic diaphragm obtained and the polyethylene diagrams that is used for applying are immersed (the LiPF of 1mol/L in commercial lithium-ion batteries electrolyte respectively
6be dissolved in ethylene carbonate, dimethyl carbonate and the methyl ethyl carbonate that mass ratio is 1:1:1), measure pick up (Electrolyte Uptake) according to the following formula:
Diaphragm quality before pick up=(before the quality-imbibition of imbibition metacneme diaphragm quality)/imbibition
Ceramic diaphragm pick up prepared by embodiment 1 reaches 80%, and polyethylene diagrams is only 45%, illustrates that ceramic diaphragm is due to the existence with the better polymethyl methacrylate of electrolyte characterization of adsorption, and the ability of absorption electrolyte significantly improves.
The electrolyte adsorption capacity of the ceramic diaphragm excellence that the present invention obtains intuitively can embody from accompanying drawing 3, in accompanying drawing 3, left side is the photo after commercially available polyethylene barrier film infiltrates in the electrolytic solution, photo after the ceramic diaphragm that right side obtains for the present invention infiltrates in the electrolytic solution, the electrolyte adsorption capacity of the ceramic diaphragm that the present invention obtains obviously is better than commercially available polyethylene barrier film.
The heat resistanceheat resistant contracting performance of the ceramic diaphragm excellence that the present invention obtains intuitively can embody from accompanying drawing 4a and accompanying drawing 4b, and in accompanying drawing 4a, left side is the photo of commercially available polyethylene barrier film before pyrocondensation experiment, and right side is the ceramic diaphragm photo that the present invention obtains; In accompanying drawing 4b, left side is the photo of pyrocondensation experiment (experiment condition is 145 ° of C maintenance 0.5h) commercially available polyethylene barrier film afterwards, and right side is the ceramic diaphragm photo that the present invention obtains; Can find out, the heat resistanceheat resistant contracting performance of the ceramic diaphragm that the present invention obtains obviously is better than commercially available polyethylene barrier film.
Comparative example 1
Get the silicon dioxide granule (not having nucleocapsid structure) obtained in 4g embodiment 1, direct and 1g vinylidene (binding agent) is scattered in 50mlN-methyl pyrrolidone, adopts the tape casting at 1m
2polyethylene diagrams on be coated with, namely obtain conventional ceramic barrier film after drying.
Embodiment 2
1000ml deionized water is mixed in the three-neck flask of 2000ml capacity, 10g particle diameter is titanium dioxide and the 0.1g neopelex of 50nm, under nitrogen protection, mechanical agitation 1 hour, add 0.3g ammonium persulfate and 0.3g sodium sulfite, be warming up to 80 ° of C, add 15g butyl methacrylate, react after 2 hours, add 1.5g molecular weight be 1500 polyethylene glycol dimethacrylate carry out chemical crosslinking, continue reaction and after 2 hours, stop reaction, the product centrifugation obtained, three times are washed respectively with ethanol and water, in room temperature, dry under vacuum condition, obtain titanium dioxide/butyl methacrylate nucleocapsid compound.Get 8g nucleocapsid compound, 2g Kynoar-hexafluoropropylene (binding agent) is scattered in 100ml acetone, adopt the tape casting at 1m
2polypropylene diaphragm on be coated with, namely obtain ceramic diaphragm after drying.
Embodiment 3
In the three-neck flask of 5000ml capacity, mix 3000ml deionized water, 100g particle diameter is zirconium dioxide and the 1g neopelex of 10 μm; under nitrogen protection; mechanical agitation 1 hour; add 3g ammonium persulfate and 3g sodium sulfite; be warming up to 80 ° of C; add 100g Ethylene Glycol Methyl methyl acrylate; react after 4 hours and stop reaction; the product centrifugation obtained; three times are washed respectively with ethanol and water; dry under room temperature, vacuum condition, obtain zirconium dioxide/polyethylene glycol methyl methacrylate nucleocapsid compound.Getting 10g nucleocapsid compound, 0.2g CMC and 0.3g butadiene-styrene rubber is scattered in 100ml water, small size coating machine is coated with on the polyethylene diagrams of 20cm × 6m, namely obtains ceramic diaphragm after drying.
Embodiment 4
In the three-neck flask of 5000ml capacity, mix 3000ml toluene, 50g particle diameter is the zinc oxide mechanical agitation 1 hour of 2 μm, be warming up to 60 ° of C, add 100g3-methoxy-methyl acrylate and 1 to drip, react after 4 hours and stop reaction, the product centrifugation obtained, wash three times respectively with ethanol and water, dry under room temperature, vacuum condition, obtain zinc oxide/methyl acrylate nucleocapsid compound.Getting 10g nucleocapsid compound, 0.2g CMC and 0.3g butadiene-styrene rubber is scattered in 100ml water, small size coating machine is coated with on the polyethylene diagrams of 20cm × 6m, namely obtains ceramic diaphragm after drying.
Embodiment 5
Get alundum (Al2O3)/lauryl methacrylate nucleocapsid compound prepared by 20g mist projection granulating, wherein the particle diameter of alundum (Al2O3) is about 1 μm, get this kind of compound 1g, 0.1g Kynoar-hexafluoropropylene (binding agent) is scattered in 10ml N, in dinethylformamide, its double spread is on the polymer film of the Kynoar of 20 μm at thickness by the mode adopting immersion coating, namely obtains ceramic diaphragm after drying.
Embodiment 6
Get barium sulfate/butyl methacrylate nucleocapsid compound prepared by 20g mist projection granulating, wherein the particle diameter of barium sulfate is about 10 μm, get this kind of compound 1g, 0.1g Kynoar-hexafluoropropylene (binding agent) is scattered in 10ml N, in dinethylformamide, its double spread is on the poly barrier film of 20 μm at thickness by the mode adopting immersion coating, namely obtains ceramic diaphragm after drying.
Comparative example 2
A kind of battery, comprises positive electrode and negative material, has conventional ceramic barrier film prepared by comparative example 1 between positive electrode and negative material.
Embodiment 7
A kind of battery, comprises positive electrode and negative material, has ceramic diaphragm prepared by embodiment 1 between positive electrode and negative material.
The cycle performance of battery that testing example 7 and comparative example 2 obtain, as shown in Figure 5.Can find out, the cycle performance of battery of the ceramic diaphragm using the present invention to obtain, obviously improves than the cycle performance of battery of the conventional ceramic barrier film using prior art.
Embodiment 8
A kind of battery, comprises positive electrode and negative material, has ceramic diaphragm prepared by embodiment 2 between positive electrode and negative material.
Embodiment 9
A kind of battery, comprises positive electrode and negative material, has ceramic diaphragm prepared by embodiment 3 between positive electrode and negative material.
Embodiment 10
A kind of battery, comprises positive electrode and negative material, has ceramic diaphragm prepared by embodiment 4 between positive electrode and negative material.
Embodiment 11
A kind of battery, comprises positive electrode and negative material, has ceramic diaphragm prepared by embodiment 5 between positive electrode and negative material.
Embodiment 12
A kind of battery, comprises positive electrode and negative material, has ceramic diaphragm prepared by embodiment 6 between positive electrode and negative material.
Claims (8)
1. a ceramic diaphragm, comprises diaphragm material base material, it is characterized in that: be coated with protective layer at diaphragm material substrate surface, the nucleocapsid structure compound that the main component of described protective layer is take inorganic matter as core, acrylate based polyalcohol is shell; Described protective layer thickness is 0.5 ~ 20 μm; The particle diameter of described core is 5nm ~ 50 μm, and the thickness of described shell is 1nm ~ 10 μm.
2. ceramic diaphragm according to claim 1, is characterized in that: the core of described nucleocapsid structure compound is selected from one or more in alundum (Al2O3), titanium dioxide, silicon dioxide, zirconium dioxide, tin ash, magnesium oxide, zinc oxide, barium sulfate, boron nitride, aluminium nitride, magnesium nitride.
3. ceramic diaphragm according to claim 1, is characterized in that: the particle diameter of described core is 50nm ~ 10 μm.
4. ceramic diaphragm according to claim 1, is characterized in that: described acrylate based polyalcohol, by being selected from methyl methacrylate, EMA, butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, Ethylene Glycol Methyl methyl acrylate, polyethylene glycol dimethacrylate, 3-methoxy-methyl acrylate, methyl acrylate, ethyl acrylate, lauryl methacrylate, acrylic acid trifluoro ethyl ester, glycidyl methacrylate, 2-methyl-2-acrylic acid-2-ethyl-2-[[(2-methyl isophthalic acid-oxo-2-acrylic) oxygen] methyl]-1,3-PD ester, trimethyl silicane methyl acrylate, TEGDMA, 1,1,1,3,3,3-hexafluoro isopropyl acrylate, acrylic acid trifluoro ethyl ester, tetraethylene glycol diacrylate, 2,2,3,3-tetrafluoro propyl methacrylate, acrylic acid tetrahydrofuran ester, a kind of monomer polymerization in 2-(2-ethoxyethoxy) ethyl propylene acid esters or two or more monomer copolymerization are cross-linked and obtain.
5. ceramic diaphragm according to claim 1, is characterized in that: described diaphragm material base material be TPO apertured polymeric film, nonwoven fabrics or be selected from polyethylene glycol oxide, polyacrylonitrile, polymethyl methacrylate, Kynoar, Kynoar-hexafluoropropylene copolymer, polyvinyl alcohol and blended, the copolymerized polymer that derived by aforementioned polymer one or several.
6. ceramic diaphragm according to claim 1, is characterized in that: described protective layer is coated with at described diaphragm material base material single or double.
7. according to the arbitrary described ceramic diaphragm application in the secondary battery of claim 1 ~ 6.
8. a battery, comprises positive electrode, negative material, it is characterized in that: the arbitrary described ceramic diaphragm of with good grounds claim 1 ~ 6 between positive electrode and negative material.
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| CN103236512A (en) * | 2013-04-19 | 2013-08-07 | 厦门大学 | Ceramic diaphragm and application of same to lithium ion battery |
| CN103474601A (en) * | 2013-08-23 | 2013-12-25 | 江苏华东锂电技术研究院有限公司 | Composite membrane, preparation method of composite membrane, and lithium-ion battery |
| CN103545475B (en) * | 2013-10-29 | 2015-04-15 | 山东正华隔膜技术有限公司 | Barium sulfate diaphragm of lithium ion battery and preparation method thereof |
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| CN104934646A (en) * | 2014-03-21 | 2015-09-23 | 深圳市沃特玛电池有限公司 | Method for improving security of ternary-material polymer lithium ion battery |
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| WO2024031519A1 (en) * | 2022-08-11 | 2024-02-15 | 宁德时代新能源科技股份有限公司 | Separator and preparation method therefor, and related secondary battery, battery module, battery pack and electric device |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325145A (en) * | 2000-04-10 | 2001-12-05 | 思凯德公司 | Partition board for high-energy charged lithium cells |
| US6488721B1 (en) * | 2000-06-09 | 2002-12-03 | Moltech Corporation | Methods of preparing electrochemical cells |
| CN102122704A (en) * | 2010-12-29 | 2011-07-13 | 中科院广州化学有限公司 | Composite microporous membrane used as lithium ion battery diaphragm as well as preparation method and application thereof |
| CN102299286A (en) * | 2011-08-01 | 2011-12-28 | 华为技术有限公司 | Battery diaphragm and preparation method and lithium ion battery thereof |
| CN102766241A (en) * | 2011-05-06 | 2012-11-07 | 北京化工大学 | Core-shell structured nano-silica/polyacrylate emulsion and its preparation method |
-
2013
- 2013-01-09 CN CN201310006942.6A patent/CN103035866B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325145A (en) * | 2000-04-10 | 2001-12-05 | 思凯德公司 | Partition board for high-energy charged lithium cells |
| US6488721B1 (en) * | 2000-06-09 | 2002-12-03 | Moltech Corporation | Methods of preparing electrochemical cells |
| CN102122704A (en) * | 2010-12-29 | 2011-07-13 | 中科院广州化学有限公司 | Composite microporous membrane used as lithium ion battery diaphragm as well as preparation method and application thereof |
| CN102766241A (en) * | 2011-05-06 | 2012-11-07 | 北京化工大学 | Core-shell structured nano-silica/polyacrylate emulsion and its preparation method |
| CN102299286A (en) * | 2011-08-01 | 2011-12-28 | 华为技术有限公司 | Battery diaphragm and preparation method and lithium ion battery thereof |
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