CN103035866A - 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
- Publication number
- CN103035866A CN103035866A CN2013100069426A CN201310006942A CN103035866A CN 103035866 A CN103035866 A CN 103035866A CN 2013100069426 A CN2013100069426 A CN 2013100069426A CN 201310006942 A CN201310006942 A CN 201310006942A CN 103035866 A CN103035866 A CN 103035866A
- Authority
- CN
- China
- Prior art keywords
- ceramic diaphragm
- methyl
- ceramic
- methacrylate
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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 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 comprise organic-inorganic composition with nucleocapsid structure as the ceramic diaphragm of ceramic coating, the invention still further relates to this kind ceramic diaphragm in the application of the chemical power source systems such as lithium ion battery and contain the battery of this ceramic diaphragm.
Background technology
Lithium ion battery is as a kind of energy density is high, output voltage is high, memory-less effect, excellent, the eco-friendly chemical power source system of cycle performance, have 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 the effect that prevents the both positive and negative polarity contact and allow ionic conduction, is the important part of battery.At present, what adopt in the commercial lithium ion battery mainly is the TPO diaphragm material with microcellular structure, such as the single or multiple lift film of polyethylene (Polyethylene, PE), polypropylene (Polypropylene, PP).Because the characteristics of polymer itself, although polyalkene diaphragm can provide enough mechanical strength and chemical stability at normal temperatures, but show larger thermal contraction in that hot conditions is next, thereby cause the both positive and negative polarity contact and gather rapidly large calorimetric, melt the micropore that blocks in the polymer although can PE at first occur at lower temperature (120 ° of C) such as the PP/PE composite diaphragm, blocking-up ionic conduction and PP still plays the further generation that the effect of support prevents electrode reaction, but because the melting temperature of PP also only has 150 ° of C, when temperature rises rapidly, the melting temperature that surpasses PP, the barrier film melting can cause the large tracts of land short circuit and cause thermal runaway, the aggravation thermal accumlation, produce the inside battery hyperbar, cause battery burning or blast.Internal short-circuit of battery is the maximum hidden danger of lithium ion battery security.In order to satisfy 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 make it become one of main selection that replaces the conventional polyolefins barrier film.
Ceramic diaphragm (Ceramic-coated Separators) is on the surface of existing polyolefin micropore film base material, single or double coating one deck uniformly, by the protective layer that ceramic microparticle etc. consists of, form porous security functions barrier film.On the basis that guarantees the original fundamental characteristics of polyolefin micropore barrier diaphragm, give barrier film high heat-resisting function, reduce the heat-shrinkable of barrier film, thereby more effectively reduce the inside lithium ion cell short circuit, prevent the battery thermal runaway that causes because of internal short-circuit of battery.
At present, the preparation method of ceramic diaphragm mainly is (mainly to be the oxide powder of nanometer or sub-micron, such as Al with ceramic powder
2O
3, SiO
2, TiO
2Deng), binding agent etc. is dispersed in and forms slurry in the solvent, forms ceramic coating (referring to Journal of Power Sources195 (2010) 6192 – 6196, CN200580036709.6, CN200780035135.X etc.) by the tape casting or infusion process at the polyalkene diaphragm substrate surface again.But, because the 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 relatively poor, has significantly " dry linting " phenomenon, and this can affect the serviceability of ceramic diaphragm in lithium ion battery greatly.In addition, ceramic diaphragm is because the coating of powder can improve the blind date ability with electrolyte, but because barrier film base material itself and electrolyte wetting capacity are relatively 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 absorption and the hold facility of electrolyte, the potential safety hazard that the leakage that the existing ceramic diaphragm of solution may exist causes, the present invention has inorganic matter for examining by constructing in advance, the acrylate based polyalcohol is the compound of shell and its pattern and space structure is carried out good design and control, with the ceramic powder in the existing ceramic diaphragm of this compound replacement, improve its coating uniformity on the diaphragm material base material, improve the ability of ceramic diaphragm absorption and maintenance electrolyte, thereby 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 nuclear, the acrylate based polyalcohol replaces the ceramic diaphragm that ceramic powder obtains in the barrier film coating as the nucleocapsid structure compound of shell.
Another object of the present invention provides the application of this ceramic diaphragm in battery.
Another object of the present invention provides the battery that comprises this ceramic diaphragm.
A kind of ceramic diaphragm provided by the invention; comprise the diaphragm material base material; it is characterized in that: be coated with protective layer at the diaphragm material substrate surface; the main component of described protective layer for take inorganic matter as nuclear, the acrylate based polyalcohol is as the nucleocapsid structure compound of shell, other components of described protective layer such as bonding agent and solvent can adopt the conventional component of using in the prior art.
The nuclear of nucleocapsid structure compound is inorganic matter, is selected from alundum (Al2O3), titanium dioxide, silicon dioxide, zirconium dioxide, tin ash, magnesium oxide, zinc oxide, barium sulfate, boron nitride, aluminium nitride, the magnesium nitride one or more.The particles of inorganic material particle diameter is 5nm-50 μ m, for the uniformity that applies and the validity of application, is preferably 50nm-10 μ m.
Described acrylate based polyalcohol, by being selected from methyl methacrylate, EMA, butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, the Ethylene Glycol Methyl methyl acrylate, polyethylene glycol dimethacrylate, the 3-methoxy-methyl acrylate, methyl acrylate, ethyl acrylate, lauryl methacrylate, the 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, the ammediol ester, trimethyl silicon based methacrylate, TEGDMA, 1,1,1,3,3,3-hexafluoro isopropylacrylic acid ester, the acrylic acid trifluoro ethyl ester, tetraethylene glycol diacrylate, 2,2,3,3-tetrafluoro propyl methyl acid esters, the acrylic acid tetrahydrofuran ester, 2-(2-ethoxy ethyoxyl) a kind of monomer polymerization in the ethyl propylene acid esters or two or more monomer copolymerization is crosslinked obtains, shell thickness is 1nm-10 μ m.
The present invention is polymethyl methacrylate particularly preferably, polymethyl methacrylate (PMMA) is a kind of thermoplastics that is commonly used for the polymer dielectric matrix, because the acrylate-functional groups that contains is similar to the functional group of carbonates electrolyte, therefore has preferably compatibility with electrolyte, pick up is high, its impalpable structure also is conducive to ionic conduction, and unlike polyethylene glycol oxide (PEO) class matrix can with electrolyte in Li
+Crystallization on every side.In addition, the gel polymer electrolyte material of PMMA base also shows good interface stability to the lithium metal, according to some reports, thereby the PMMA base gel electrolyte that PMMA more easily forms the chemical crosslinking structure to be increased its mechanical strength and have a cross-linked structure can suppress the formation of Li dendrite.Used diaphragm material base material both can be commercial TPO apertured polymeric film (such as polyethylene or polyacrylic single or multiple lift composite membrane), nonwoven fabrics, it also can be the polymeric material that is applied to the secondary cell polymer dielectric, such as polyethylene glycol oxide, polyacrylonitrile, polymethyl methacrylate, Kynoar, Kynoar-hexafluoropropylene copolymer, polyvinyl alcohol etc., and comprise blend, the copolymerization system of being derived by above system, such as acrylonitrile methyl meth acrylat copolymer etc.The coating thickness of nucleocapsid compound on the barrier film base material is 0.1 micron to 20 microns, can be coated with at barrier film base material single face, also can be at barrier film base material double spread.
The application of ceramic diaphragm provided by the invention in battery replaces existing ceramic diaphragm.
Battery provided by the invention comprises positive electrode, negative material, it is characterized in that: ceramic diaphragm provided by the invention is arranged between positive electrode and negative material.
Usually the positive electrode of lithium ion battery use can use in the present invention.The positive active material that positive pole relates to can use reversibly occlusion-emit the compound of (Infix and desfix) lithium ion, for example, can enumerate and use Li
xMO
2Or Li
yM
2O
4The metal chalcogenide of the lithium-contained composite oxide of (in the formula, M is transition metal, 0≤x≤1,0≤y≤2) expression, the oxide of spinelle shape, layer structure, olivine structural etc.
As its object lesson, can enumerate LiCoO
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; Has LiMPO
4Material of olivine-type crystalline textures such as (M=Fe, Mn, Ni) etc.
The lithium-contained composite oxide that particularly adopts layer structure or spinelle shape structure is preferred, LiCoO
2, LiMn
2O
4, LiNiO
2, LiNi
1/2Mn
1/2O
2Deng being the li-mn-ni compound oxide of representative, LiNi
L/3Mn
1/3Co
1/3O
2, LiNi
0.6Mn
0.2Co
0.2O
2Deng being lithium manganese nickel cobalt composite oxides or the LiNi of representative
1-x-y-zCo
xAl
yMg
zO
2Lithium-contained composite oxides such as (in the formulas, 0≤x≤1,0≤y≤0.1,0≤z≤0.1,0≤1-x-y-z≤1).In addition, the part of the Constitution Elements in the above-mentioned lithium-contained composite oxide is also comprised wherein by lithium-contained composite oxide that the interpolation element replaced of Ge, Ti, Zr, Mg, Al, Mo, Sn etc. etc.
These positive active materials both can use separately a kind, also can more than 2 kinds and use.For example, the lithium-contained composite oxide by using simultaneously layer structure and the lithium-contained composite oxide of spinel structure can seek to take into account the raising of high capacity and fail safe.
Be used for consisting of the positive pole of nonaqueous electrolytic solution secondary battery, for example, in above-mentioned positive active material, suitably add the conductive auxiliary agents such as carbon black, acetylene black, or the adhesives such as Kynoar, poly(ethylene oxide) etc., the preparation anode mixture uses it after with the banded formed body coating of the current-collecting members such as aluminium foil as core.But anodal manufacture method is not limited only to example.
Usually the negative material of lithium ion battery use can use in the present invention.The negative electrode active material that negative pole relates to can use and can embed-compound of removal lithium embedded metal, lithium.Can be used as negative electrode active material such as the alloy of aluminium, silicon, tin etc. or the various materials such as oxide, material with carbon element etc.Oxide can be enumerated titanium dioxide etc., and material with carbon element can be enumerated sintered body, mesophase-carbon micro-beads of graphite, RESEARCH OF PYROCARBON class, coke class, vitreous carbon class, organic high molecular compound etc.
Be used for consisting of the negative pole of nonaqueous electrolytic solution secondary battery, for example, in above-mentioned negative electrode active material, suitably add the conductive auxiliary agents such as carbon black, acetylene black, or the adhesives such as Kynoar, poly(ethylene oxide) etc., the preparation cathode agent uses it after with the banded formed body coating of the current-collecting members such as Copper Foil 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 be enumerated ethylene carbonate, propene carbonate, butylene, gamma-butyrolacton, sulphur class ester (ethylene glycol sulfide etc.) etc.Linear carbonate can be enumerated dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate etc. and be the low viscous polarity linear carbonate of representative, aliphat branched chain type carbonats compound.Cyclic carbonate (particularly ethylene carbonate) is particularly preferred with the mixed solvent of linear carbonate.
Ethers can be enumerated dimethyl ether tetraethylene glycol (TEGDME), glycol dimethyl ether (DME), 1,3-dioxolane (DOL) etc.
In addition, except above-mentioned nonaqueous solvents, can adopt the chain phosphotriesters such as chain-like alkyl ester class, trimethyl phosphate such as methyl propionate; The nitrile solvents such as 3-methoxypropionitrile; The nonaqueous solventss (organic solvent) such as branched chain type compound with ehter bond take dendrimer as representative.
In addition, also can adopt the fluorine kind solvent.
As the fluorine kind solvent, for example, can enumerate H (CF
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 ethers, 4-trifluoromethyl ten fluorine amyl group ether, 4-trifluoromethyl ten fluorine amyl group propyl ether, 5-trifluoromethyl ten difluoro hexyl methyl ethers, 5-trifluoromethyl ten difluoro hexyl ether, 5-trifluoromethyl ten difluoro hexyl propyl ether, 6-trifluoromethyl ten tetrafluoro heptyl methyl ethers, 6-trifluoromethyl ten tetrafluoro heptyl ether, 6-trifluoromethyl ten tetrafluoro heptyl propyl ether, 7-trifluoromethyl ten hexafluoro octyl group methyl ethers, 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 be used.
As the electrolytic salt that uses in the nonaqueous electrolytic solution, the lithium salts such as the lithium salts of the perchlorate of preferred lithium, organic boron lithium salts, fluorochemical, lithium imide salts.
As the example of such electrolytic salt, for example, can enumerate LiClO
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 the formula, Rf is fluoroalkyl) etc.In these lithium salts, fluorine-containing organic lithium salt is particularly preferred.Fluorine-containing organic lithium salt is because the large and easily separated one-tenth ion of anionic property is soluble in nonaqueous electrolytic solution.
The concentration of electrolyte lithium salt in nonaqueous electrolytic solution for example, is preferred more than the 0.3mol/L (mol/L), more preferably more than the 0.7mol/L, below the preferred 1.7mol/L, more preferably below the 1.2mol/L.Cross when low when the concentration of electrolyte lithium salt, ionic conduction is spent little, when too high, worries to fail the electrolytic salt of dissolve complete to separate out.
In addition, in nonaqueous electrolytic solution, also can add the various additives of the performance that can improve the battery that adopts it, not be particularly limited.
Usefulness of the present invention is: because acrylate-based shell can adsorb more electrolyte, realize the quick conduction of lithium ion, therefore can improve the cycle performance of battery under the high current charge-discharge condition that uses this kind ceramic diaphragm; In addition, because acrylate based polyalcohol anticathode shows preferably interface stability, generation that therefore can also the establishment Li dendrite when coat and graphite cathode one side contacts.
Description of drawings
Fig. 1 is the used SiO of embodiment 1
2For nuclear, PMMA are the nucleocapsid compound transmission electron microscope photo of shell.
Fig. 2 by embodiment 1 the stereoscan photograph of acquisition ceramic diaphragm.
Fig. 3 by embodiment 1 the electrolyte wettability relatively (left side: polyethylene barrier film, the right side: embodiment 1 ceramic diaphragm) of acquisition ceramic diaphragm and polyethylene barrier film.
Before Fig. 4 a is the pyrocondensation test, embodiment 1 ceramic diaphragm that obtains and polyethylene barrier film (left side: polyethylene barrier film, the right side: embodiment 1 ceramic diaphragm); After Fig. 4 b is the pyrocondensation test, embodiment 1 ceramic diaphragm that obtains and polyethylene barrier film (left side: polyethylene barrier film, the right side: embodiment 1 ceramic diaphragm).
Fig. 5 is that embodiment 7 adopts the battery of ceramic diaphragm of the present invention and the cycle performance of battery correlation curve that Comparative Examples 2 adopts the conventional ceramic barrier film.
Embodiment
The below will be described in more detail by embodiment, but protection scope of the present invention is not limited to these embodiment.
At normal temperatures the 30ml tetraethoxysilane is joined in the 350mL absolute ethyl alcohol, then add fast 30ml water and 12ml14mol/L ammonia water mixture, obtain the silicon dioxide granule dispersion liquid behind the speed stirring reaction 3h with 200r/min, silicon dioxide granule is about 400nm.At N
2Carry out under the gas protection; in the reactor with condensing unit; add above-mentioned nano-silicon dioxide particle dispersion liquid, deionized water and methacrylate monomer; begin to heat up after stirring 60min; add an amount of ammonium persulfate when 75 ° of C, be warmed up to 85 ° of C behind the constant temperature 6h and continue reaction 60min, then cooling obtains silicon dioxide/methyl acrylate nucleocapsid compound; characterize by transmission electron microscope, shell thickness can be controlled at 2nm-1 μ m by the input amount of regulating methacrylate monomer.Get 4g nucleocapsid compound, 1g vinylidene (binding agent) is scattered in the 50mlN-methyl pyrrolidone, adopts the tape casting at 1m
2The polyethylene barrier film on be coated with, namely obtain ceramic diaphragm after the drying.
The ceramic diaphragm that obtains and the polyethylene barrier film that is used for applying are immersed respectively the commercial lithium-ion batteries electrolyte (LiPF of 1mol/L
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 following formula:
Diaphragm quality before pick up=(diaphragm quality before the quality-imbibition of imbibition metacneme)/imbibition
The ceramic diaphragm pick up of embodiment 1 preparation reaches 80%, and the polyethylene barrier film is 45% only, ceramic diaphragm be described since with the existence of the better polymethyl methacrylate of electrolyte characterization of adsorption, the ability of adsorbing electrolyte significantly improves.
The electrolyte adsorption capacity of the ceramic diaphragm excellence that the present invention obtains can intuitively embody from accompanying drawing 3, the left side is the photo after the commercially available polyethylene barrier film infiltrates in electrolyte in the accompanying drawing 3, the right side is the photo after ceramic diaphragm that the present invention obtains infiltrates in electrolyte, and the electrolyte adsorption capacity of the ceramic diaphragm that the present invention obtains obviously is better than the commercially available polyethylene barrier film.
The heat resistanceheat resistant contracting performance of the ceramic diaphragm excellence that the present invention obtains can intuitively embody from accompanying drawing 4a and accompanying drawing 4b, and the left side is the photo of the front commercially available polyethylene barrier film of pyrocondensation experiment among the accompanying drawing 4a, and the right side is the ceramic diaphragm photo that the present invention obtains; The left side is the photo of the rear commercially available polyethylene barrier film of pyrocondensation experiment (experiment condition is that 145 ° of C keep 0.5h) among the accompanying drawing 4b, and the right side is the ceramic diaphragm photo that the present invention obtains; Can find out that the heat resistanceheat resistant contracting performance of the ceramic diaphragm that the present invention obtains obviously is better than the commercially available polyethylene barrier film.
Comparative Examples 1
Get the silicon dioxide granule (not having nucleocapsid structure) that obtains among the 4g embodiment 1, direct and 1g vinylidene (binding agent) is scattered in the 50mlN-methyl pyrrolidone, adopts the tape casting at 1m
2The polyethylene barrier film on be coated with, namely obtain the conventional ceramic barrier film after the drying.
Embodiment 2
In the three-neck flask of 2000ml capacity, mix the 1000ml deionized water; the 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 the 15g butyl methacrylate; react after 2 hours; add the 1.5g molecular weight and be 1500 polyethylene glycol dimethacrylate and carry out chemical crosslinking; continue reaction and stop reaction after 2 hours, the product centrifugation that obtains is washed respectively three times with ethanol and water; in room temperature; dry under the vacuum condition, obtain titanium dioxide/butyl methacrylate nucleocapsid compound.Get 8g nucleocapsid compound, 2g Kynoar-hexafluoropropylene (binding agent) is scattered in the 100ml acetone, adopts the tape casting at 1m
2Polypropylene diaphragm on be coated with, namely obtain ceramic diaphragm after the drying.
Embodiment 3
Mixing 3000ml deionized water, 100g particle diameter are zirconium dioxide and the 1g neopelex of 10 μ m in the three-neck flask of 5000ml capacity; 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 and stop reaction after 4 hours; the product centrifugation that obtains; wash respectively three times with ethanol and water; under room temperature, vacuum condition, dry, obtain zirconium dioxide/polyethylene glycol methyl methacrylate nucleocapsid compound.Get 10g nucleocapsid compound, 0.2g CMC and 0.3g butadiene-styrene rubber and be scattered in the 100ml water, the polyethylene barrier film at 20cm * 6m on small size coating machine is coated with, and namely obtains ceramic diaphragm after the drying.
Embodiment 4
In the three-neck flask of 5000ml capacity, mix 3000ml toluene, 50g particle diameter and be the zinc oxide mechanical agitation 1 hour of 2 μ m, be warming up to 60 ° of C, adding 100g3-methoxy-methyl acrylate and 1 drips, react and stop reaction after 4 hours, the product centrifugation that obtains, wash respectively three times with ethanol and water, under room temperature, vacuum condition, dry, obtain zinc oxide/methyl acrylate nucleocapsid compound.Get 10g nucleocapsid compound, 0.2g CMC and 0.3g butadiene-styrene rubber and be scattered in the 100ml water, the polyethylene barrier film at 20cm * 6m on small size coating machine is coated with, and namely obtains ceramic diaphragm after the drying.
Embodiment 5
Get the alundum (Al2O3) of 20g mist projection granulating preparation/lauryl methacrylate nucleocapsid compound, wherein the particle diameter of alundum (Al2O3) is about 1 μ m, get this kind compound 1g, 0.1g Kynoar-hexafluoropropylene (binding agent) is scattered in 10ml N, in the dinethylformamide, the mode that adopts immersion coating is on the polymer film of Kynoar of 20 μ m at thickness with its double spread, namely obtains ceramic diaphragm after the drying.
Embodiment 6
Get the barium sulfate of 20g mist projection granulating preparation/butyl methacrylate nucleocapsid compound, wherein the particle diameter of barium sulfate is about 10 μ m, get this kind compound 1g, 0.1g Kynoar-hexafluoropropylene (binding agent) is scattered in 10ml N, in the dinethylformamide, adopting the mode of immersion coating is on the poly barrier film of 20 μ m, namely to obtain ceramic diaphragm after the drying at thickness with its double spread.
Comparative Examples 2
A kind of battery comprises positive electrode and negative material, and the conventional ceramic barrier film of Comparative Examples 1 preparation is arranged between positive electrode and negative material.
Embodiment 7
A kind of battery comprises positive electrode and negative material, and the ceramic diaphragm of embodiment 1 preparation is arranged between positive electrode and negative material.
The cycle performance of battery that test implementation example 7 and Comparative Examples 2 obtain, as shown in Figure 5.Can find out, use the cycle performance of battery of the ceramic diaphragm that the present invention obtains, obviously improve than the cycle performance of battery of the conventional ceramic barrier film that uses prior art.
Embodiment 8
A kind of battery comprises positive electrode and negative material, and the ceramic diaphragm of embodiment 2 preparations is arranged between positive electrode and negative material.
Embodiment 9
A kind of battery comprises positive electrode and negative material, and the ceramic diaphragm of embodiment 3 preparations is arranged between positive electrode and negative material.
A kind of battery comprises positive electrode and negative material, and the ceramic diaphragm of embodiment 4 preparations is arranged between positive electrode and negative material.
A kind of battery comprises positive electrode and negative material, and the ceramic diaphragm of embodiment 5 preparations is arranged between positive electrode and negative material.
A kind of battery comprises positive electrode and negative material, and the ceramic diaphragm of embodiment 6 preparations is arranged between positive electrode and negative material.
Claims (10)
1. a ceramic diaphragm comprises the diaphragm material base material, it is characterized in that: be coated with protective layer at the diaphragm material substrate surface, the main component of described protective layer for take inorganic matter as nuclear, the acrylate based polyalcohol is as the nucleocapsid structure compound of shell.
2. ceramic diaphragm according to claim 1, it is characterized in that: the nuclear 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, the magnesium nitride.
3. ceramic diaphragm according to claim 2, it is characterized in that: the particle diameter of the nuclear of described nucleocapsid structure compound is 5nm-50 μ m.
4. ceramic diaphragm according to claim 2, it is characterized in that: the particle diameter of the nuclear of described nucleocapsid structure compound is 50nm-10 μ m.
5. ceramic diaphragm according to claim 1, it is characterized in that: described acrylate based polyalcohol, by being selected from methyl methacrylate, EMA, butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, the Ethylene Glycol Methyl methyl acrylate, polyethylene glycol dimethacrylate, the 3-methoxy-methyl acrylate, methyl acrylate, ethyl acrylate, lauryl methacrylate, the 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, the ammediol ester, trimethyl silicon based methacrylate, TEGDMA, 1,1,1,3,3,3-hexafluoro isopropylacrylic acid ester, the acrylic acid trifluoro ethyl ester, tetraethylene glycol diacrylate, 2,2,3,3-tetrafluoro propyl methyl acid esters, the acrylic acid tetrahydrofuran ester, 2-(2-ethoxy ethyoxyl) a kind of monomer polymerization in the ethyl propylene acid esters or two or more monomer copolymerization is crosslinked obtains, shell thickness is 1nm-10 μ m.
6. ceramic diaphragm according to claim 1 is characterized in that: described diaphragm material base material is TPO apertured polymeric film, nonwoven fabrics or is selected from polyethylene glycol oxide, polyacrylonitrile, polymethyl methacrylate, Kynoar, Kynoar-hexafluoropropylene copolymer, polyvinyl alcohol and the blend of being derived by aforementioned polymer, one or several in the copolymerized polymer.
7. ceramic diaphragm according to claim 1, it is characterized in that: described protective layer thickness is 0.5-20 μ m.
8. ceramic diaphragm according to claim 1, it is characterized in that: described protective layer is coated with at described diaphragm material base material single or double.
9. according to claim 1-8 application of the described ceramic diaphragm of arbitrary claim in secondary cell.
10. a battery comprises positive electrode, negative material, it is characterized in that: the described ceramic diaphragm of the arbitrary claim of with good grounds claim 1-8 between positive electrode and negative material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310006942.6A CN103035866B (en) | 2013-01-09 | 2013-01-09 | Ceramic membrane, application of ceramic membrane to battery and battery comprising ceramic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310006942.6A CN103035866B (en) | 2013-01-09 | 2013-01-09 | Ceramic membrane, application of ceramic membrane to battery and battery comprising ceramic membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103035866A true CN103035866A (en) | 2013-04-10 |
| CN103035866B CN103035866B (en) | 2015-01-07 |
Family
ID=48022536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310006942.6A Active CN103035866B (en) | 2013-01-09 | 2013-01-09 | Ceramic membrane, application of ceramic membrane to battery and battery comprising ceramic membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103035866B (en) |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103545475A (en) * | 2013-10-29 | 2014-01-29 | 淄博众品鑫化学膜应用技术有限公司 | Barium sulfate diaphragm of lithium ion battery and preparation method thereof |
| CN103956451A (en) * | 2014-05-16 | 2014-07-30 | 中国东方电气集团有限公司 | Composite ceramic membrane for lithium ion batteries and preparation method thereof |
| CN104269505A (en) * | 2014-10-27 | 2015-01-07 | 沧州明珠隔膜科技有限公司 | Composite lithium ion battery diaphragm and preparation method thereof |
| CN104362275A (en) * | 2014-12-01 | 2015-02-18 | 东莞市卓高电子科技有限公司 | Manufacturing method of lithium ion battery diaphragm as well as battery diaphragm prepared by manufacturing method and battery |
| CN104600231A (en) * | 2014-12-31 | 2015-05-06 | 北京鼎能开源电池科技股份有限公司 | Diaphragm provided with active nano boron nitride coating, and preparation method of diaphragm |
| CN104868084A (en) * | 2015-05-06 | 2015-08-26 | 东莞市魔方新能源科技有限公司 | Isolation membrane for lithium ion secondary battery |
| 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 |
| CN105140453A (en) * | 2015-08-26 | 2015-12-09 | 厦门大学 | Ceramic composite membrane with thermal-shutdown function and application thereof |
| CN105304850A (en) * | 2015-09-17 | 2016-02-03 | 中航锂电（洛阳）有限公司 | Mixed paint for composite membrane of lithium ion battery, composite membrane and preparation method thereof, and lithium ion battery |
| CN105324870A (en) * | 2013-10-31 | 2016-02-10 | 株式会社Lg化学 | Organic-inorganic complex porous membrane, separator comprising same, and electrode structure body |
| CN105390642A (en) * | 2015-11-06 | 2016-03-09 | 中国第一汽车股份有限公司 | Preparation method for poly-dopamine modified ceramic particle nonwoven diaphragm |
| CN105406008A (en) * | 2015-11-04 | 2016-03-16 | 东莞市特瑞斯电池科技有限公司 | Solid-state polymer lithium ion battery core and preparation method thereof |
| CN105428571A (en) * | 2015-11-06 | 2016-03-23 | 中国第一汽车股份有限公司 | PVDF-HFP based polymer membrane prepared from polydopamine modified ceramic particles and preparation method |
| CN105440770A (en) * | 2014-06-30 | 2016-03-30 | 成都中科来方能源科技有限公司 | Water based composition used for modifying diaphragm for lithium ion battery and modified diaphragm and battery |
| CN105957999A (en) * | 2016-07-05 | 2016-09-21 | 东莞市卓高电子科技有限公司 | Nano ceramic particle doped PE diaphragm and preparation method thereof |
| CN106207049A (en) * | 2016-08-24 | 2016-12-07 | 合肥国轩高科动力能源有限公司 | A kind of ceramic diaphragm and the application in lithium ion battery |
| CN106663789A (en) * | 2014-06-06 | 2017-05-10 | 罗伯特·博世有限公司 | Cathode material for lithium sulphur cells |
| CN106920919A (en) * | 2017-01-23 | 2017-07-04 | 浙江钱江锂电科技有限公司 | A kind of stacked soft-package battery |
| CN108051136A (en) * | 2017-12-08 | 2018-05-18 | 马鞍山合力仪表有限责任公司 | A kind of preparation method of diaphragm pressure gage isolation diaphragm |
| CN108305972A (en) * | 2017-12-29 | 2018-07-20 | 深圳中兴创新材料技术有限公司 | A kind of ceramic-coated separator and preparation method and application |
| CN109167008A (en) * | 2018-09-05 | 2019-01-08 | 江苏安瑞达新材料有限公司 | Lithium battery low moisture ceramic diaphragm preparation method, aqueous slurry and ceramic diaphragm |
| WO2020000164A1 (en) * | 2018-06-26 | 2020-01-02 | 深圳市星源材质科技股份有限公司 | Composite lithium battery separator and preparation method therefor |
| CN110854339A (en) * | 2018-08-20 | 2020-02-28 | 广东美联隔膜有限公司 | In-situ composite ceramic diaphragm with core-shell structure and preparation method and application thereof |
| CN111048720A (en) * | 2019-12-06 | 2020-04-21 | 深圳市新非泽科技有限公司 | Coating slurry for lithium battery diaphragm and coating process |
| CN112646303A (en) * | 2021-03-15 | 2021-04-13 | 江苏厚生新能源科技有限公司 | Al with high adhesion and high wetting efficiency2O3-PMMA composite material, preparation method thereof and polyolefin composite diaphragm |
| TWI734918B (en) * | 2017-06-15 | 2021-08-01 | 日商綠淨星球股份有限公司 | Heating device and heating method |
| CN113921992A (en) * | 2021-09-16 | 2022-01-11 | 河北金力新能源科技股份有限公司 | High-heat-resistance lithium battery diaphragm and preparation method and application thereof |
| CN114552002A (en) * | 2020-11-24 | 2022-05-27 | 天津大学 | Organic electrolyte additive for battery |
| CN117477168A (en) * | 2023-12-26 | 2024-01-30 | 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 |
| 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 |
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 |
Cited By (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2015024479A1 (en) * | 2013-08-23 | 2015-02-26 | 江苏华东锂电技术研究院有限公司 | Composite membrane and preparation method thereof, and lithium ion battery |
| CN103545475A (en) * | 2013-10-29 | 2014-01-29 | 淄博众品鑫化学膜应用技术有限公司 | Barium sulfate diaphragm of lithium ion battery and preparation method thereof |
| 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 |
| CN105324870A (en) * | 2013-10-31 | 2016-02-10 | 株式会社Lg化学 | Organic-inorganic complex porous membrane, separator comprising same, and electrode structure body |
| US10797287B2 (en) | 2013-10-31 | 2020-10-06 | Lg Chem, Ltd. | Organic/inorganic composite porous membrane, and separator and electrode structure comprising the same |
| TWI557169B (en) * | 2013-10-31 | 2016-11-11 | Ｌｇ化學股份有限公司 | Organic/inorganic composite porous membrane, and separator and electrode structure comprising the same |
| 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 |
| CN103956451A (en) * | 2014-05-16 | 2014-07-30 | 中国东方电气集团有限公司 | Composite ceramic membrane for lithium ion batteries and preparation method thereof |
| CN103956451B (en) * | 2014-05-16 | 2017-01-04 | 中国东方电气集团有限公司 | A kind of lithium ion battery composite ceramics barrier film and preparation method thereof |
| CN106663789A (en) * | 2014-06-06 | 2017-05-10 | 罗伯特·博世有限公司 | Cathode material for lithium sulphur cells |
| CN105440770A (en) * | 2014-06-30 | 2016-03-30 | 成都中科来方能源科技有限公司 | Water based composition used for modifying diaphragm for lithium ion battery and modified diaphragm and battery |
| CN104269505A (en) * | 2014-10-27 | 2015-01-07 | 沧州明珠隔膜科技有限公司 | Composite lithium ion battery diaphragm and preparation method thereof |
| CN104269505B (en) * | 2014-10-27 | 2016-09-14 | 沧州明珠隔膜科技有限公司 | A kind of composite lithium ion cell barrier film and preparation method thereof |
| CN104362275A (en) * | 2014-12-01 | 2015-02-18 | 东莞市卓高电子科技有限公司 | Manufacturing method of lithium ion battery diaphragm as well as battery diaphragm prepared by manufacturing method and battery |
| CN104600231A (en) * | 2014-12-31 | 2015-05-06 | 北京鼎能开源电池科技股份有限公司 | Diaphragm provided with active nano boron nitride coating, and preparation method of diaphragm |
| CN104868084A (en) * | 2015-05-06 | 2015-08-26 | 东莞市魔方新能源科技有限公司 | Isolation membrane for lithium ion secondary battery |
| CN105140453A (en) * | 2015-08-26 | 2015-12-09 | 厦门大学 | Ceramic composite membrane with thermal-shutdown function and application thereof |
| CN105304850A (en) * | 2015-09-17 | 2016-02-03 | 中航锂电（洛阳）有限公司 | Mixed paint for composite membrane of lithium ion battery, composite membrane and preparation method thereof, and lithium ion battery |
| CN105406008A (en) * | 2015-11-04 | 2016-03-16 | 东莞市特瑞斯电池科技有限公司 | Solid-state polymer lithium ion battery core and preparation method thereof |
| CN105406008B (en) * | 2015-11-04 | 2018-10-16 | 永州聚力新能源科技有限公司 | A kind of solid polymer lithium ion battery cell and preparation method thereof |
| CN105428571A (en) * | 2015-11-06 | 2016-03-23 | 中国第一汽车股份有限公司 | PVDF-HFP based polymer membrane prepared from polydopamine modified ceramic particles and preparation method |
| CN105390642A (en) * | 2015-11-06 | 2016-03-09 | 中国第一汽车股份有限公司 | Preparation method for poly-dopamine modified ceramic particle nonwoven diaphragm |
| CN105957999A (en) * | 2016-07-05 | 2016-09-21 | 东莞市卓高电子科技有限公司 | Nano ceramic particle doped PE diaphragm and preparation method thereof |
| CN106207049B (en) * | 2016-08-24 | 2018-09-18 | 合肥国轩高科动力能源有限公司 | A kind of ceramic diaphragm and the application in lithium ion battery |
| CN106207049A (en) * | 2016-08-24 | 2016-12-07 | 合肥国轩高科动力能源有限公司 | A kind of ceramic diaphragm and the application in lithium ion battery |
| CN106920919A (en) * | 2017-01-23 | 2017-07-04 | 浙江钱江锂电科技有限公司 | A kind of stacked soft-package battery |
| TWI734918B (en) * | 2017-06-15 | 2021-08-01 | 日商綠淨星球股份有限公司 | Heating device and heating method |
| TWI788901B (en) * | 2017-06-15 | 2023-01-01 | 日商綠淨星球股份有限公司 | Heating device and heating method |
| CN108051136A (en) * | 2017-12-08 | 2018-05-18 | 马鞍山合力仪表有限责任公司 | A kind of preparation method of diaphragm pressure gage isolation diaphragm |
| CN108305972A (en) * | 2017-12-29 | 2018-07-20 | 深圳中兴创新材料技术有限公司 | A kind of ceramic-coated separator and preparation method and application |
| WO2020000164A1 (en) * | 2018-06-26 | 2020-01-02 | 深圳市星源材质科技股份有限公司 | Composite lithium battery separator and preparation method therefor |
| CN110859053A (en) * | 2018-06-26 | 2020-03-03 | 深圳市星源材质科技股份有限公司 | Composite lithium battery diaphragm and preparation method thereof |
| KR20210021585A (en) * | 2018-06-26 | 2021-02-26 | 셴젠 시니어 테크놀로지 매테리얼 씨오., 엘티디. | Composite lithium battery separator and manufacturing method thereof |
| KR102543254B1 (en) * | 2018-06-26 | 2023-06-13 | 셴젠 시니어 테크놀로지 매테리얼 씨오., 엘티디. | Composite lithium battery separator and its manufacturing method |
| CN110854339A (en) * | 2018-08-20 | 2020-02-28 | 广东美联隔膜有限公司 | In-situ composite ceramic diaphragm with core-shell structure and preparation method and application thereof |
| CN110854339B (en) * | 2018-08-20 | 2022-07-12 | 安徽美芯新材料有限公司 | In-situ composite ceramic diaphragm with core-shell structure and preparation method and application thereof |
| CN109167008A (en) * | 2018-09-05 | 2019-01-08 | 江苏安瑞达新材料有限公司 | Lithium battery low moisture ceramic diaphragm preparation method, aqueous slurry and ceramic diaphragm |
| CN109167008B (en) * | 2018-09-05 | 2021-05-11 | 江苏安瑞达新材料有限公司 | Preparation method of low-moisture ceramic diaphragm for lithium battery, aqueous slurry and ceramic diaphragm |
| CN111048720A (en) * | 2019-12-06 | 2020-04-21 | 深圳市新非泽科技有限公司 | Coating slurry for lithium battery diaphragm and coating process |
| CN114552002A (en) * | 2020-11-24 | 2022-05-27 | 天津大学 | Organic electrolyte additive for battery |
| CN112646303A (en) * | 2021-03-15 | 2021-04-13 | 江苏厚生新能源科技有限公司 | Al with high adhesion and high wetting efficiency2O3-PMMA composite material, preparation method thereof and polyolefin composite diaphragm |
| CN113921992A (en) * | 2021-09-16 | 2022-01-11 | 河北金力新能源科技股份有限公司 | High-heat-resistance lithium battery diaphragm and preparation method and application thereof |
| 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 |
| CN117477168A (en) * | 2023-12-26 | 2024-01-30 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103035866B (en) | 2015-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103035866B (en) | Ceramic membrane, application of ceramic membrane to battery and battery comprising ceramic membrane | |
| CN105070868B (en) | A kind of dopamine modified ceramic composite diaphragm and its application | |
| CN105826603B (en) | A kind of polymerized thylene carbonate vinyl ester lithium ion battery polymer electrolyte and its preparation method and application | |
| CN105140453B (en) | A kind of Ceramic Composite barrier film and its application with Thermal shutdown function | |
| CN108475772A (en) | Anode of secondary cell and lithium secondary battery comprising the anode | |
| CN108604674A (en) | Anode of secondary cell, its manufacturing method and the lithium secondary battery comprising the anode | |
| WO2017032304A1 (en) | Modified ceramic composite separator film and manufacturing method thereof | |
| CN103633367B (en) | A kind of gel polymer electrolyte and polymer Li-ion battery and preparation method thereof | |
| CN106784558A (en) | Ceramic diaphragm with aeroge as powder and its application in lithium ion battery | |
| CN104466062B (en) | A kind of ceramic diaphragm of boracic and preparation method and application | |
| CN108666511B (en) | High-temperature-resistant polymer modified ceramic diaphragm and application thereof | |
| JP2010097696A (en) | Lithium-ion battery | |
| CN104916802A (en) | Composite membrane and application thereof | |
| CN106654125A (en) | Method for preparing modified ceramic diaphragm through dopamine compound adhesive and application thereof | |
| CN105161658A (en) | Polymer-modified ceramic-coated composite separator and application thereof | |
| CN104600233A (en) | Thermal shutdown composite diaphragm and application thereof | |
| JP2023508451A (en) | Polyoxymethylene-based all-solid-state polymer electrolyte prepared by in-situ ring-opening polymerization and its use | |
| CN111697266B (en) | Electrolyte solution, and electrochemical device and electronic device including the same | |
| CN106848163A (en) | A kind of ceramic coating membrane and its preparation method and application | |
| CN107507950A (en) | The ceramic diaphragm of the compound binding agent containing dopamine and the application in lithium ion battery | |
| KR20210081303A (en) | Electrolytes and electrochemical devices | |
| CN111834620A (en) | Lithium metal battery positive electrode, lithium metal battery and preparation method thereof | |
| KR20190128140A (en) | Manufacturing method of secondary battery | |
| CN112615111A (en) | High-liquid-retention self-repairing diaphragm, preparation method thereof and lithium ion battery | |
| CN106207049B (en) | A kind of ceramic diaphragm and the application in lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: CHINA AVIATION LITHIUM BATTERY CO., LTD. Effective date: 20140115 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20140115 Address after: Siming District of Xiamen city in Fujian Province, 361005 South Siming Road No. 422 Applicant after: Xiamen University Applicant after: China Aviation Lithium Battery Co., Ltd. Address before: Siming District of Xiamen city in Fujian Province, 361005 South Siming Road No. 422 Applicant before: Xiamen University |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |