CN107994186A - A kind of lithium battery organo-mineral complexing membrane and preparation method - Google Patents
A kind of lithium battery organo-mineral complexing membrane and preparation method Download PDFInfo
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- CN107994186A CN107994186A CN201711107203.0A CN201711107203A CN107994186A CN 107994186 A CN107994186 A CN 107994186A CN 201711107203 A CN201711107203 A CN 201711107203A CN 107994186 A CN107994186 A CN 107994186A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of lithium battery organo-mineral complexing membrane and preparation method, belong to technical field of lithium batteries.Composite diaphragm, includes the inorganic, ceramic layer of centre and the organic layer of its both sides, includes following component in the raw material of the organic layer：Polyolefin, non-conjugated olefin copolymer, surfactant, antioxidant, lubricant, filler, the first solvent；Include following component by weight in the raw material of the inorganic, ceramic layer：Alumina-zirconia/two-dimensional nano titanium carbide composite particles, nano alumina particles, adhesive, non-ionic surface active, the second solvent.Using the lithium battery of organo-mineral complexing membrane provided by the invention, have the advantages that resistance to elevated temperatures is good, intensity is high.
Description
Technical field
The present invention relates to a kind of lithium battery organo-mineral complexing membrane and preparation method, belong to technical field of lithium batteries.
Background technology
The development of lithium ion battery comes from the nineties in last century, and only 20 years so far, be lithium electricity industry at past 20 years
Once leap, with attention of the various countries to environment, new energy, lithium ion battery more has the development advanced by leaps and bounds.
Lithium ion battery has the characteristics that：(1) operating voltage is high.The voltage of lithium ion battery is generally nickel in 3.6V
3 times of cadmium, Ni-MH battery operating voltage.(2) energy density is high.The energy density of lithium ion battery should reach 180Wh/kg, be
3 times of nickel-cadmium cell under equal quality, 1.5 times of Ni-MH battery.(3) have extended cycle life.Lithium ion battery usually has 1000
Multiple cycle life, be ni-Cd, 2 times of Ni-MH battery.(4) self-discharge rate is small.Process of the lithium ion battery in initial charge
In one layer of solid electrolyte passivating film (SEI) can be formed on Carbon anode, it only allow ion by without allow electronics by,
Therefore self discharge can be preferably prevented so that storage life increases, and capacity attenuation reduces.General its month self-discharge rate is 2%
~3%, far below nickel-cadmium cell (25%~30%) and Ni-MH battery (20%).(5) allow temperature range wide, have excellent
High/low temperature discharge performance, can work between -20 DEG C~+60 DEG C.(6) non-environmental-pollution.Lead, cadmium are not contained in lithium ion battery
It is real environmentally protective battery Deng poisonous and harmful substances.(7) memory-less effect.Memory effect refer to battery it is not complete when again
Charge volume can decline during charging, and lithium ion battery there is no ni-Cd, the memory effect of Ni-MH battery, can discharge and recharge at any time, and
Its capacity and cycle life are not influenced.Since lithium ion battery has performance excellent above, therefore it sets in portable electronic
The various aspects such as standby, electric automobile, space technology, national defense industry illustrate wide application prospect and potential tremendous economic effect
Benefit, is referred to as the ideal source of 21 century.
The security of battery diaphragm is to lithium ion battery, and whether the security of high-capacity battery or high-power battery is all
It is most important.It is understood that the lithium battery diaphragm of current commercial applications is PP and PE bilayers or three layers of composite diaphragm, it is such a
The most outstanding problem that membrane is applied now is exactly that melting point polymer is generally relatively low, and PE fusing points are 130 degrees Celsius, and PP fusing points are
180 degrees Celsius.Under abuse conditions, inside battery heat increased dramatically so that great problems occur for battery security.
CN103165841A discloses a kind of production method of diaphragm for lithium ion battery, comprises the following steps：Prepare with
The high-melting plastics particle of nano material blending；To obtain with the high-melting plastics particle of nano material blending carry out extrusion and
Stretching；Thermal finalization；The nano material is one kind in nano silicon dioxide, nano barium sulfate, nano-calcium carbonate, described
High-melting plastics particle is one kind in PEEK, PEI or PPS plastic pellet.CN103915593A discloses a kind of polyimides
Preparation method of nano-lithium ion cell membrane and products thereof, its preparation method comprises the following steps：The system of polyamic acid solution
It is standby：By 4,4', mono- diaminodiphenyl ethers and the double phthalic anhydrides of mono- oxygen of 4,4' by a certain percentage at dimethylacetylamide (DMAc)
Middle polycondensation is made；The preparation of melt：Resulting polymers solution is cured at a certain temperature to obtain solidfied material, then solidfied material is existed
Melted below its fusing point in the range of 20-30 DEG C, obtain hypocrystalline melt；It is prepared by membrane：By obtained melt through melt spinning, again
Crystallization, cold and hot stretching and thermal finalization series of process handle to obtain a nanometer membrane；Membrane post-processes：It is dilute in membrane including removing
Agent and some residual solvent are released, polyamic acid membrane is dried in a vacuum；Imidization is handled：The polyamic acid being prepared is received
Rice membrane carries out high temperature imidization and handles to obtain polyimide nano membrane.
But there is the problem of intensity is low, resistance to elevated temperatures is not high for above-mentioned membrane.
The content of the invention
The purpose of the present invention is：The membrane of lithium battery interior is solved the problems, such as there is intensity is low, resistance to elevated temperatures is not high,
Propose a kind of organo-mineral complexing membrane excellent with high intensity, resistance to elevated temperatures.
Technical solution：
A kind of lithium battery organo-mineral complexing membrane, include centre inorganic, ceramic layer and its both sides it is organic
Layer, following component by weight is included in the raw material of the organic layer：50~70 parts of polyolefin, non-conjugated olefin-copolymerization
10~20 parts of thing, 1~5 part of surfactant, 1~5 part of antioxidant, 1~5 part of lubricant, 1~5 part of filler, the first solvent 15
~30 parts；Include following component by weight in the raw material of the inorganic, ceramic layer：Alumina-zirconia/two dimension
40~60 parts of nano titanium carbide composite particles, 20~40 parts of nano alumina particles, 10~20 parts of adhesive, non-ionic surface are lived
Property 1~5 part, 10~30 parts of the second solvent.
The material shape of the organic layer is non-woven fabrics.
The polyolefin is selected from polypropylene or polyethylene.
The non-conjugated olefin copolymer is selected from Ethylene-Propylene-Diene rubber (EPDM).
The average grain diameter of the alumina-zirconia/two-dimensional nano titanium carbide composite particles and/or nano alumina particles
Scope is 50~200 μm.
One or several kinds of mixing of first solvent in ethyl acetate, butyl acetate, ethanol, propyl alcohol.
A kind of or both mixing of second solvent in water or ethanol.
The preparation method of the alumina-zirconia/two-dimensional nano titanium carbide composite particles, includes the following steps：
1st step, by Ti3AlC2Powder ball milling, then dried after carrying out, the ceramic powder refined；
2nd step, the ceramic powder of refinement is taken in 2g~10g submergence 50mL~200mL hydrofluoric acid solutions and is reacted, will be corroded
Product is cleaned to neutrality with deionized water, then uses washes of absolute alcohol；By obtained solid sample drying, the pottery after being corroded
Porcelain powder；
3rd step, takes 15g~25g to be put into 2~4L absolute ethyl alcohols the ceramic powder after corrosion obtained by step (2), stirs
Mix, add the nitric acid aluminium powder and 1~5g ZrOCl of 5~20g2Powder, then 100~150ml of dilute hydrochloric acid is slowly added dropwise, continue
Stirring reaction, with deionized water eccentric cleaning is used after absolute ethyl alcohol eccentric cleaning again, solid sample is dried, up to Al (OH)3-
Zr(OH)2-Ti3C2Composite material.
In 1st step, 1~10h of Ball-milling Time, rotational speed of ball-mill 400r/min, ball material mass ratio 6:1；Drying temperature
It is 40~60 DEG C.
In 2nd step, 35~45wt% of concentration of hydrofluoric acid solution, 6~12h of reaction time.
In 3rd step, the mass concentration of dilute hydrochloric acid is 1~5wt%；6~12h of reaction time；Drying temperature is 110
~120 DEG C.
The preparation method of the composite diaphragm, includes the following steps：
S1, by polyolefin, non-conjugated olefin copolymer, surfactant, antioxidant, lubricant, filler, the first solvent
Mixing, the melting extrusion at 210~220 DEG C, is sprayed onto on lace curtaining by the spinning head of a diameter of 0.1~0.5mm, 150~160 DEG C
Roll-in is shaped, and obtains the nonwoven layer that thickness is 10~20 μm；
S2, by alumina-zirconia/two-dimensional nano titanium carbide composite particles, nano alumina particles, adhesive, it is non-from
Sub- surface-active, the second solvent are uniformly mixed, and obtain inorganic particle slurry；
S3, the coating inorganic particle slurry in nonwoven layer, then place on the pulp layer of formation another layer of non-woven fabrics
Layer；Again after drying, composite diaphragm is obtained.
The painting method may be selected from spraying, scratch or roller coat in one kind.
Beneficial effect
Lithium battery provided by the invention employs organo-mineral complexing membrane configuration, has that resistance to elevated temperatures is good, intensity is high
The advantages of.
Embodiment
The present invention is described in further detail below by embodiment.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Specific skill is not specified in embodiment
Art or condition person, carry out according to the described technology of document in the art or condition or according to product description.Examination used
Production firm person is not specified in agent or instrument, and being can be with conventional products that are commercially available.
Word " comprising " used herein, "comprising", " having " or its any other variant are intended to cover non-exclusionism
Including.Technique, method, article or the equipment for e.g., including listing key element are not necessarily limited by those key elements, but can include it
He is not explicitly listed or belongs to this technique, method, article or the intrinsic key element of equipment.
Scope is used as using what the value of range format expression should be interpreted as not only including clearly including in a flexible way
The numerical value of limit value, but also including covering all single numbers or subinterval within the range, just as each numerical value and sub-district
Between be expressly recited out.For example, " about 0.1% to about 5% " concentration range should be understood to not only include clearly including
About 0.1% to about 5% concentration, further include in the range of alluding to single concentration (e.g., 1%, 2%, 3% and 4%) and son
Section (for example, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).Percentage in the present invention is in no specified otherwise
In the case of refer to percentage by weight.
The structure of composite diaphragm provided by the present invention, include centre inorganic, ceramic layer and its both sides it is organic
Layer, following component by weight is included in the raw material of the organic layer：50~70 parts of polyolefin, non-conjugated olefin-copolymerization
It is 10~20 parts of thing, 1~5 part of non-ionic surface active, 1~5 part of antioxidant, 1~5 part of lubricant, 1~5 part of filler, first molten
15~30 parts of agent；Include following component by weight in the raw material of the inorganic, ceramic layer：Alumina-zirconia/
40~60 parts of two-dimensional nano titanium carbide composite particles, 20~40 parts of nano alumina particles, 10~20 parts of adhesive, nonionic table
1~5 part of face activity, 10~30 parts of the second solvent.
The polyolefin used in the present invention can for example include polyethylene, polypropylene and by ethene or propylene with it is other
The polymer that the resins such as the copolymer of alpha-olefin are formed.
Polypropylene can be the polymer synthesized using common Ziegler-Natta catalyst, or can also be profit
The polymer synthesized to metallocene for the single site catalysts of representative.As other alpha-olefins, for the alkene of carbon number 3~10
Hydrocarbon, specifically, can include propylene, 1- butylene, 1- amylenes, 1- hexenes, 4-methyl-1-pentene and 1- octenes etc..These can
To be used alone a kind, two or more can also be combined.
Non-conjugated olefin copolymer has been further included in organic layer, it is enhancing ingredients, it acts synergistically with polyolefin,
It is capable of providing excellent compatibility and provides and combines the stronger effect of power between improved adjacent layer.Preferably copolymer uses
Be Ethylene-Propylene-Diene rubber (EPDM), EPDM by by a small amount of third component introduce EP rubbers (EPM) i.e. ethene and
The copolymer of propylene obtains, so as to form double bond in main chain.There is many that there is different amounts of different types of third component
The synthesis rubber of (typically comprising ethylidene norbornene (ENB), 1,4- hexadienes (1,4-HD) and bicyclopentadiene (DCP))
Glue.
As antioxidant, such as triphenyl phosphite, three (4- aminomethyl phenyls) phosphite esters, three (4- can be used
Tert-butyl-phenyl) phosphite ester, three (single nonyl phenyl) phosphite esters, three (2- methyl -4- ethylphenyls) phosphite esters, three
(2- methyl -4- tert-butyl-phenyls) phosphite ester, three (2,4- di-t-butyls phenyl) phosphite esters, three (2,6- di-t-butyls
Phenyl) phosphite ester, three (2,4- di-t-butyl -5- aminomethyl phenyls) phosphite esters, three (single, dinonylphenyl) phosphite esters,
Double (single nonyl phenyl) pentaerythrites-two-phosphite ester, double (2,4- di-t-butyls phenyl) pentaerythrites-two-phosphite ester,
Double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythrites-two-phosphite ester, double (tri--tert-butyl-phenyls of 2,4,6-) seasons penta
Tetrol-two-phosphite ester, double (2,4- di-t-butyl -5- aminomethyl phenyls) pentaerythrites-two-phosphite ester, 2,2- methylene
Double (4,6- 3,5-dimethylphenyls) octyl group phosphite esters, 2,2- di-2-ethylhexylphosphine oxides (the 4- tert-butyl group -6- aminomethyl phenyls) octyl group phosphite ester,
2,2- di-2-ethylhexylphosphine oxides (4,6- di-t-butyls phenyl) octyl group phosphite ester, 2,2- di-2-ethylhexylphosphine oxides (4,6- 3,5-dimethylphenyls) hexyl
Phosphite ester, 2,2- di-2-ethylhexylphosphine oxides (4,6- 3,5-dimethylphenyls) hexyl phosphite ester, 2,2- di-2-ethylhexylphosphine oxides (4,6- di-t-butyls
Phenyl) bi-ester of phosphite such as stearyl phosphite ester；[the 3- (3,5- di-t-butyl 4- hydroxy phenyls) of pentaerythrite base-four
Propionic ester], 1,6-HD-bis- [3- (3,5- di-t-butyl 4- hydroxy phenyls) propionic ester], octadecyl -3- (3,5- bis- -
Tert-butyl-hydroxy phenyl) propionic ester, 1,3,5- trimethyls -2,4,6- three (3,5- di-t-butyl -4- hydroxyphenylmethyls) benzene,
Double { 2- [3- (the 3- tert-butyl group -4- the hydroxyls of triethylene glycol-bis- [3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) propionic ester], 3,9-
Base -5- aminomethyl phenyls) propionyloxy] -1,1- dimethyl ethyls 2,4,8,10- tetra- oxaspiro [5,5] hendecane, 1,1,3- tri-
The fortified phenol classes such as [2- methyl -4- (3,5- di-t-butyl -4- hydroxy phenylpropionyls epoxide) -5- tert-butyl-phenyls] butane
Compound；5,7- di-t-butyl -s 3- (3,4- 3,5-dimethylphenyls) -3H- benzofuran-2-ones etc..These can be used alone or
Two or more is used in combination.
The lubricant used in the present invention is not particularly limited, as long as it is in terms of the mobility of thermoplastic polymer is improved
Play a role, their example includes hydrocarbon lubricants, such as atoleine, solid paraffin, microcrystalline wax and polyethylene
Wax；Fatty acid lubricant, such as stearic acid, behenic acid and 1,2-hydroxystearic acid；And ester lubricant, such as stearic acid
Butyl ester, glyceryl monostearate, pentaerythritol tetrastearate, hardened castor oil and stearyl stearate.
Filler employed in the present invention generally refers to refer to inert solid particle shape material, such as silicic acid in small, broken bits, is such as pyrolyzed
Silicic acid or silica gel, titanium dioxide, hydroxide such as aluminium hydroxide, potassium carbonate, magnesium carbonate and calcium carbonate, silicate such as sodium metasilicate,
Magnesium silicate, talcum, calcium silicates, zinc silicate, aluminosilicate such as sodium aluminosilicate, potassium aluminotrisilicate orthoclase, calcium aluminosilicate, bentonite, kaolin.
These can be used alone can also two or more be used in combination.
The first solvent is used in this reaction.The concrete example for the organic solvent that can be used, can enumerate hexane, hexamethylene,
The alcohol such as the arene compounds such as the alkanes such as heptane, toluene, dimethylbenzene, methanol, ethanol, isopropanol, butanol, hexanol, cyclohexanol
Class.In addition, it can also according to circumstances use ketone, ether, the tetrahydrochysene furans such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cycloheptanone, cyclohexanone
Mutter, the nitrile compound such as ester compounds, the acetonitrile such as ethers, ethyl acetate, butyl acetate, the methyl formate such as dioxane etc..
As particularly preferred solvent, there is the arene compound such as the alkanes such as hexane, hexamethylene, heptane, toluene, dimethylbenzene.It is more excellent
Select one or several kinds of mixing in ethyl acetate, butyl acetate, ethanol, propyl alcohol.
Raw material in inorganic, ceramic layer includes：Alumina-zirconia/two-dimensional nano titanium carbide composite particles 40~60
Part, 20~40 parts of nano alumina particles, 10~20 parts of adhesive, 1~5 part of non-ionic surface active, the second solvent 10~30
Part.
Wherein, alumina-zirconia/two-dimensional nano titanium carbide composite particles can be prepared via a method which to obtain：
1st step, by Ti3AlC2Powder ball milling, then dried after carrying out, the ceramic powder refined；
2nd step, the ceramic powder of refinement is taken in 2g~10g submergence 50mL~200mL hydrofluoric acid solutions and is reacted, will be corroded
Product is cleaned to neutrality with deionized water, then uses washes of absolute alcohol；By obtained solid sample drying, the pottery after being corroded
Porcelain powder；
3rd step, takes 15g~25g to be put into 2~4L absolute ethyl alcohols the ceramic powder after corrosion obtained by step (2), stirs
Mix, add the nitric acid aluminium powder and 1~5g ZrOCl of 5~20g2Powder, then 100~150ml of dilute hydrochloric acid is slowly added dropwise, continue
Stirring reaction, with deionized water eccentric cleaning is used after absolute ethyl alcohol eccentric cleaning again, solid sample is dried, up to Al (OH)3-
Zr(OH)2-Ti3C2Composite material.
In 1st step, 1~10h of Ball-milling Time, rotational speed of ball-mill 400r/min, ball material mass ratio 6:1；Drying temperature is 40~
60℃。
In 2nd step, 35~45wt% of concentration of hydrofluoric acid solution, 6~12h of reaction time.
In 3rd step, the mass concentration of dilute hydrochloric acid is 1~5wt%；6~12h of reaction time；Drying temperature is 110~120
℃。
Adhesive include glycerine, hydroxypropyl methylcellulose, dextrin, polyethylene glycol, syrup, Arabic gum, sorbierite, gelatin or
Polyvinylpyrrolidone etc..
A kind of or both mixing of second solvent in water or ethanol.
The surfactant used in organic layer and inorganic, ceramic layer, can using nonionic surfactant,
For example, line style polyoxyalkylene alkyl class, such as polyethylene glycol oxide hexyl ether, polyoxyethylene octyl ether, polyethylene glycol oxide decyl
Ether, polyoxyethylene lauryl ether and polyethylene glycol oxide cetyl ether；Branched polyoxyalkylenes primary alkyl ethers, such as polyoxygenated
Ethene 2- ethylhexyl ethers, polyethylene glycol oxide isocetyl ether and polyethylene glycol oxide iso stearyl ether；Branched polyoxyalkylene is secondary
Alkyl ether, such as polyethylene glycol oxide 1- hexyl hexyl ethers, polyethylene glycol oxide 1- octyl group hexyl ethers, polyethylene glycol oxide 1- hexyl octyl groups
Ether, polyethylene glycol oxide 1- amyl group heptyl ethers and polyethylene glycol oxide 1- heptyl amyl ethers；Polyoxyalkylene alkenyl ethers class, such as polyoxygenated
Ethene oleyl ether；Polyoxyalkylene alkyl phenyl ethers, such as polyoxyethylene octylphenyl ether, polyoxyethylene nonyl phenyl
Ether, and polyethylene glycol oxide dodecylphenyl ether；Polyoxyalkylene alkyl aryl phenyl ethers, such as polyethylene glycol oxide triphenylethylene base
Phenyl ether, polyethylene glycol oxide diphenylethyllene phenyl ether, polyethylene glycol oxide styrylphenyl ether, polyethylene glycol oxide tribenzyl-benzene
Base, polyethylene glycol oxide dibenzylphenyl ether, and polyethylene glycol oxide benzyl phenyl ether；Polyoxyalkylene fatty acid ester class, such as polyoxy
Change ethene monolaurate, polyethylene glycol oxide monoleate, polyoxyethylene monostearate ester, polyethylene glycol oxide list myristic acid
Ester, polyethylene glycol oxide dilaurate, polyethylene glycol oxide dioleate, two myristinate of polyethylene glycol oxide, and polyoxygenated
Ethene distearate；Sorbitan ester class, such as span 40 and sorbitan list oleic acid
Ester；Polyoxyalkylene sorbitan polyol fatty acid esters, such as TWEEN 60 and polyoxygenated
Ethene dehydrated sorbitol mono-fatty acid ester；Glycerine fatty acid esters, such as glyceryl monostearate, glyceryl monolaurate and glycerine
Monopalmitate；Polyoxyalkylene sorbitan polyol fatty acid esters；Sucrose-fatty esters；Polyoxyalkylene castor oil ethers, it is such as poly-
Ethylene oxide castor oil ether；Polyoxyalkylene hydrogenated castor oil ethers, such as polyoxyethylene hydrogenated castor oil ether；Polyoxyalkylene alkyl
Amino ethers, such as polyoxyethylene lauryl base amino ethers and polyethylene glycol oxide stearyl ether；Ethylene oxide-propylene oxide is embedding
Section or random copolymer；Oxyethylene group-oxypropylene group the block or random copolymer of end alkyl etherificate；With end sugarcane
The ethylene oxide-propylene oxide block or random copolymer of sugar-etherificate.
Embodiment 1
Lithium battery organo-mineral complexing membrane, includes the inorganic, ceramic layer of centre and the organic layer of its both sides, institute
State the following component included in the raw material of organic layer by weight：50 parts of polypropylene, non-conjugated olefin copolymer ethene-the third
10 parts of alkene-diene rubber (EPDM), 1 part of sorbitan ester class surfactant, 1 part of antioxidant, lubricant polyethylene
1 part of wax, 1 part of filler calcium silicates, 15 parts of the first solvent ethyl acetate；Include by weight in the raw material of the inorganic, ceramic layer
The following component of part meter：40 parts of alumina-zirconia/two-dimensional nano titanium carbide composite particles (average particle size range is 50 μm),
20 parts of nano alumina particles (average particle size range is 50 μm), 10 parts of adhesive polyethylene glycol, sorbitan ester class are non-
1 part of ion surface active, 10 parts of the second aqueous solvent；Wherein, the material shape of organic layer is non-woven fabrics；
The preparation method of the alumina-zirconia/two-dimensional nano titanium carbide composite particles, includes the following steps：
1st step, by Ti3AlC2Powder ball milling, then dried after carrying out, the ceramic powder refined；
2nd step, by the ceramic powder of refinement take 2gg submergence 50mL hydrofluoric acid solutions in react, by corrosion product spend from
Sub- water is cleaned to neutrality, then uses washes of absolute alcohol；By obtained solid sample drying, the ceramic powder after being corroded；
3rd step, takes 15g to be put into 2L absolute ethyl alcohols the ceramic powder after corrosion obtained by step (2), stirs, add
The nitric acid aluminium powder and 1gZrOCl of 5g2Powder, then dilute hydrochloric acid 100ml is slowly added dropwise, continues stirring reaction, with absolute ethyl alcohol from
Deionized water eccentric cleaning is used again after heart cleaning, solid sample is dried, up to Al (OH)3-Zr(OH)2-Ti3C2Composite material.
In 1st step, Ball-milling Time 1h, rotational speed of ball-mill 400r/min, ball material mass ratio 6:1；Drying temperature is 40
℃。
In 2nd step, the concentration 35wt% of hydrofluoric acid solution, reaction time 6h.
In 3rd step, the mass concentration of dilute hydrochloric acid is 1wt%；Reaction time 6h；Drying temperature is 110 DEG C.
The preparation method of the composite diaphragm, includes the following steps：
S1, by polyolefin, non-conjugated olefin copolymer, surfactant, antioxidant, lubricant, filler, the first solvent
Mixing, the melting extrusion at 210 DEG C, is sprayed onto on lace curtaining by the spinning head of a diameter of 0.1mm, and 150 DEG C of roll-in sizings, obtain thickness
Spend the nonwoven layer for 10~20 μm；
S2, by alumina-zirconia/two-dimensional nano titanium carbide composite particles, nano alumina particles, adhesive, it is non-from
Sub- surface-active, the second solvent are uniformly mixed, and obtain inorganic particle slurry；
S3, sprays inorganic particle slurry in nonwoven layer, then another layer of non-woven fabrics is placed on the pulp layer of formation
Layer；Again after drying, composite diaphragm is obtained.
Embodiment 2
Lithium battery organo-mineral complexing membrane, includes the inorganic, ceramic layer of centre and the organic layer of its both sides, institute
State the following component included in the raw material of organic layer by weight：70 parts of polypropylene, non-conjugated olefin copolymer ethene-the third
20 parts of alkene-diene rubber (EPDM), 5 parts of sorbitan ester class surfactant, antioxidant triphenyl phosphite 5
Part, 5 parts of lubricant stearic acid, 5 parts of filler bentonite, 15~30 parts of the first solvent ethyl acetate；The inorganic, ceramic layer
Include following component by weight in raw material：Alumina-zirconia/two-dimensional nano titanium carbide composite particles (average grain
Footpath scope is 200 μm) 60 parts, 40 parts of nano alumina particles (average particle size range is 200 μm), adhesive polyethylene glycol 20
Part, 5 parts of sorbitan ester class non-ionic surface active, 30 parts of the second aqueous solvent；Wherein, the material shape of organic layer is nothing
Woven fabric；
The preparation method of the alumina-zirconia/two-dimensional nano titanium carbide composite particles, includes the following steps：
1st step, by Ti3AlC2Powder ball milling, then dried after carrying out, the ceramic powder refined；
2nd step, by the ceramic powder of refinement take 10g submergence 200mL hydrofluoric acid solutions in react, by corrosion product spend from
Sub- water is cleaned to neutrality, then uses washes of absolute alcohol；By obtained solid sample drying, the ceramic powder after being corroded；
3rd step, takes 25g to be put into 4L absolute ethyl alcohols the ceramic powder after corrosion obtained by step (2), stirs, add
The nitric acid aluminium powder and 5gZrOCl of 20g2Powder, then dilute hydrochloric acid 150ml is slowly added dropwise, continues stirring reaction, with absolute ethyl alcohol from
Deionized water eccentric cleaning is used again after heart cleaning, solid sample is dried, up to Al (OH)3-Zr(OH)2-Ti3C2Composite material.
In 1st step, Ball-milling Time 10h, rotational speed of ball-mill 400r/min, ball material mass ratio 6:1；Drying temperature is 60
℃。
In 2nd step, the concentration 45wt% of hydrofluoric acid solution, reaction time 12h.
In 3rd step, the mass concentration of dilute hydrochloric acid is 5wt%；Reaction time 12h；Drying temperature is 120 DEG C.
The preparation method of the composite diaphragm, includes the following steps：
S1, by polyolefin, non-conjugated olefin copolymer, surfactant, antioxidant, lubricant, filler, the first solvent
Mixing, the melting extrusion at 220 DEG C, is sprayed onto on lace curtaining by the spinning head of a diameter of 0.5mm, and 160 DEG C of roll-in sizings, obtain thickness
Spend the nonwoven layer for 10~20 μm；
S2, by alumina-zirconia/two-dimensional nano titanium carbide composite particles, nano alumina particles, adhesive, it is non-from
Sub- surface-active, the second solvent are uniformly mixed, and obtain inorganic particle slurry；
S3, sprays inorganic particle slurry in nonwoven layer, then another layer of non-woven fabrics is placed on the pulp layer of formation
Layer；Again after drying, composite diaphragm is obtained.
Embodiment 3
Lithium battery organo-mineral complexing membrane, includes the inorganic, ceramic layer of centre and the organic layer of its both sides, institute
State the following component included in the raw material of organic layer by weight：60 parts of polypropylene, non-conjugated olefin copolymer ethene-the third
15 parts of alkene-diene rubber (EPDM), 2 parts of sorbitan ester class surfactant, antioxidant triphenyl phosphite 2
Part, 2 parts of lubricating fluid paraffin, 2 parts of filler calcium silicates, 19 parts of the first solvent ethyl acetate；The original of the inorganic, ceramic layer
Include following component by weight in material：Alumina-zirconia/two-dimensional nano titanium carbide composite particles (average grain diameter
Scope is 100 μm) 50 parts, 30 parts of nano alumina particles (average particle size range is 100 μm), 15 parts of adhesive polyethylene glycol,
3 parts of sorbitan ester class non-ionic surface active, 18 parts of the second aqueous solvent；Wherein, the material shape of organic layer is nonwoven
Cloth；
The preparation method of the alumina-zirconia/two-dimensional nano titanium carbide composite particles, includes the following steps：
1st step, by Ti3AlC2Powder ball milling, then dried after carrying out, the ceramic powder refined；
2nd step, by the ceramic powder of refinement take 5g submergence 100mL hydrofluoric acid solutions in react, by corrosion product spend from
Sub- water is cleaned to neutrality, then uses washes of absolute alcohol；By obtained solid sample drying, the ceramic powder after being corroded；
3rd step, takes 18g to be put into 3L absolute ethyl alcohols the ceramic powder after corrosion obtained by step (2), stirs, add
The nitric acid aluminium powder and 3gZrOCl of 10g2Powder, then dilute hydrochloric acid 120ml is slowly added dropwise, continues stirring reaction, with absolute ethyl alcohol from
Deionized water eccentric cleaning is used again after heart cleaning, solid sample is dried, up to Al (OH)3-Zr(OH)2-Ti3C2Composite material.
In 1st step, Ball-milling Time 5h, rotational speed of ball-mill 400r/min, ball material mass ratio 6:1；Drying temperature is 40
~60 DEG C.
In 2nd step, the concentration 40wt% of hydrofluoric acid solution, reaction time 8h.
In 3rd step, the mass concentration of dilute hydrochloric acid is 3wt%；Reaction time 8h；Drying temperature is 115 DEG C.
The preparation method of the composite diaphragm, includes the following steps：
S1, by polyolefin, non-conjugated olefin copolymer, surfactant, antioxidant, lubricant, filler, the first solvent
Mixing, the melting extrusion at 215 DEG C, is sprayed onto on lace curtaining by the spinning head of a diameter of 0.2mm, and 155 DEG C of roll-in sizings, obtain thickness
Spend the nonwoven layer for 10~20 μm；
S2, by alumina-zirconia/two-dimensional nano titanium carbide composite particles, nano alumina particles, adhesive, it is non-from
Sub- surface-active, the second solvent are uniformly mixed, and obtain inorganic particle slurry；
S3, sprays inorganic particle slurry in nonwoven layer, then another layer of non-woven fabrics is placed on the pulp layer of formation
Layer；Again after drying, composite diaphragm is obtained.
Reference examples 1
With embodiment 3 difference lies in：In the preparation process of alumina-zirconia/two-dimensional nano titanium carbide composite particles,
The particle of 2nd step without hydrofluoric acid solution corrosion.
Lithium battery organo-mineral complexing membrane, includes the inorganic, ceramic layer of centre and the organic layer of its both sides, institute
State the following component included in the raw material of organic layer by weight：60 parts of polypropylene, non-conjugated olefin copolymer ethene-the third
15 parts of alkene-diene rubber (EPDM), 2 parts of sorbitan ester class surfactant, antioxidant triphenyl phosphite 2
Part, 2 parts of lubricating fluid paraffin, 2 parts of filler calcium silicates, 19 parts of the first solvent ethyl acetate；The original of the inorganic, ceramic layer
Include following component by weight in material：Alumina-zirconia/two-dimensional nano titanium carbide composite particles (average grain diameter
Scope is 100 μm) 50 parts, 30 parts of nano alumina particles (average particle size range is 100 μm), 15 parts of adhesive polyethylene glycol,
3 parts of sorbitan ester class non-ionic surface active, 18 parts of the second aqueous solvent；Wherein, the material shape of organic layer is nonwoven
Cloth；
The preparation method of the alumina-zirconia/two-dimensional nano titanium carbide composite particles, includes the following steps：
1st step, by Ti3AlC2Powder ball milling, then dried after carrying out, the ceramic powder refined；
2nd step, by the ceramic powder 5g of refinement, is cleaned to neutrality with deionized water, then uses washes of absolute alcohol；By institute
Obtain solid sample drying, the ceramic powder after being cleaned；
3rd step, takes 18g to be put into 3L absolute ethyl alcohols the ceramic powder after cleaning obtained by step (2), stirs, add
The nitric acid aluminium powder and 3gZrOCl of 10g2Powder, then dilute hydrochloric acid 120ml is slowly added dropwise, continues stirring reaction, with absolute ethyl alcohol from
Deionized water eccentric cleaning is used again after heart cleaning, solid sample is dried, up to Al (OH)3-Zr(OH)2-Ti3C2Composite material.
In 1st step, Ball-milling Time 5h, rotational speed of ball-mill 400r/min, ball material mass ratio 6:1；Drying temperature is 40
~60 DEG C.
In 2nd step, the concentration 40wt% of hydrofluoric acid solution, reaction time 8h.
In 3rd step, the mass concentration of dilute hydrochloric acid is 3wt%；Reaction time 8h；Drying temperature is 115 DEG C.
The preparation method of the composite diaphragm, includes the following steps：
S1, by polyolefin, non-conjugated olefin copolymer, surfactant, antioxidant, lubricant, filler, the first solvent
Mixing, the melting extrusion at 215 DEG C, is sprayed onto on lace curtaining by the spinning head of a diameter of 0.2mm, and 155 DEG C of roll-in sizings, obtain thickness
Spend the nonwoven layer for 10~20 μm；
S2, by alumina-zirconia/two-dimensional nano titanium carbide composite particles, nano alumina particles, adhesive, it is non-from
Sub- surface-active, the second solvent are uniformly mixed, and obtain inorganic particle slurry；
S3, sprays inorganic particle slurry in nonwoven layer, then another layer of non-woven fabrics is placed on the pulp layer of formation
Layer；Again after drying, composite diaphragm is obtained.
Reference examples 2
With embodiment 3 difference lies in：Do not add EPDM in organic layer.
Lithium battery organo-mineral complexing membrane, includes the inorganic, ceramic layer of centre and the organic layer of its both sides, institute
State the following component included in the raw material of organic layer by weight：60 parts of polypropylene, sorbitan ester class surface are lived
2 parts of agent of property, 2 parts of antioxidant triphenyl phosphite, 2 parts of lubricating fluid paraffin, 2 parts of filler calcium silicates, the first solvent second
19 parts of acetoacetic ester；Include following component by weight in the raw material of the inorganic, ceramic layer：Alumina-zirconia/
(average particle size range is for 50 parts of two-dimensional nano titanium carbide composite particles (average particle size range is 100 μm), nano alumina particles
100 μm) 30 parts, 15 parts of adhesive polyethylene glycol, 3 parts of sorbitan ester class non-ionic surface active, the second aqueous solvent 18
Part；Wherein, the material shape of organic layer is non-woven fabrics；
The preparation method of the alumina-zirconia/two-dimensional nano titanium carbide composite particles, includes the following steps：
1st step, by Ti3AlC2Powder ball milling, then dried after carrying out, the ceramic powder refined；
2nd step, by the ceramic powder of refinement take 5g submergence 100mL hydrofluoric acid solutions in react, by corrosion product spend from
Sub- water is cleaned to neutrality, then uses washes of absolute alcohol；By obtained solid sample drying, the ceramic powder after being corroded；
3rd step, takes 18g to be put into 3L absolute ethyl alcohols the ceramic powder after corrosion obtained by step (2), stirs, add
The nitric acid aluminium powder and 3gZrOCl of 10g2Powder, then dilute hydrochloric acid 120ml is slowly added dropwise, continues stirring reaction, with absolute ethyl alcohol from
Deionized water eccentric cleaning is used again after heart cleaning, solid sample is dried, up to Al (OH)3-Zr(OH)2-Ti3C2Composite material.
In 1st step, Ball-milling Time 5h, rotational speed of ball-mill 400r/min, ball material mass ratio 6:1；Drying temperature is 40
~60 DEG C.
In 2nd step, the concentration 40wt% of hydrofluoric acid solution, reaction time 8h.
In 3rd step, the mass concentration of dilute hydrochloric acid is 3wt%；Reaction time 8h；Drying temperature is 115 DEG C.
The preparation method of the composite diaphragm, includes the following steps：
S1, polyolefin, surfactant, antioxidant, lubricant, filler, the first solvent are mixed, melted at 215 DEG C
Melt extrusion, be sprayed onto by the spinning head of a diameter of 0.2mm on lace curtaining, 155 DEG C of roll-in sizings, obtain the nothing that thickness is 10~20 μm
Woven fabric layer；
S2, by alumina-zirconia/two-dimensional nano titanium carbide composite particles, nano alumina particles, adhesive, it is non-from
Sub- surface-active, the second solvent are uniformly mixed, and obtain inorganic particle slurry；
S3, sprays inorganic particle slurry in nonwoven layer, then another layer of non-woven fabrics is placed on the pulp layer of formation
Layer；Again after drying, composite diaphragm is obtained.
Performance test
Test battery performance
(1) preparation of cathode
By 100 grams of positive active material LiCoO2, 2 grams of adhesive vinylidene fluorides (PVDF), 3 grams of conductive agent acetylene black
Mixture is added in 40 grams of n-methyl-2-pyrrolidone (NMP), and then stirring forms uniform cathode in de-airing mixer
Slurry.
The slurry is uniformly coated on aluminium foil, then drying, roll-in at 150 DEG C, cut obtained size as 390 millimeters
The cathode of × 40 millimeters × 18 microns (thickness), wherein containing 5.8 grams of active ingredient LiCoO2。
(2) preparation of anode
By 100 grams of negative electrode active material native graphites, 1.5 grams of adhesive polytetrafluoroethylene (PTFE) (PTFE) and 1.5 grams of carboxymethyls
The mixture of cellulose (CMC) is added in 100 grams of water, and then stirring forms uniform cathode size in de-airing mixer.
The cathode size is uniformly coated on the both sides of copper foil, is then dried at 90 DEG C, roll-in, cut obtained ruler
Very little is the anode of 395 millimeters × 41 millimeters × 12 microns (thickness), wherein containing 2.6 grams of active ingredient native graphites.
(3) battery is made with the composite diaphragm of the present invention
4.0 millimeters × 34 millimeters × 46 will be included after cathode obtained above, anode and membrane successively lamination and winding
In the square aluminum hull of millimeter.The membrane is respectively by obtained composite diaphragm in embodiment and reference examples.
Will be in solvent (ethylene carbonate：Methyl ethyl carbonate：Diethyl carbonate (EC/EMC/DEC) volume ratio is 1:1:
1) 1 mole of lithium hexafluoro phosphate (LiPF is contained in6) the above-mentioned batteries of about 2.4 grams of electrolyte injection in, and in a conventional manner
Ageing, sealed cell aluminum hull obtain lithium rechargeable battery.The design capacity of the battery is 750 milliampere hour.
(4) battery resistance to elevated temperatures is tested
Test method is as follows：Battery progress 1C is charged to 100% Charging state, is placed in an oven, oven temperature is with 5
DEG C/min 150 DEG C and 180 DEG C are increased to from room temperature, wherein cell voltage falls is considered as short circuit more than 0.2 volt.
(5) battery life is tested
Test method is as follows：At 25 DEG C ± 5 DEG C, battery is subjected to cycle charge-discharge 500 times, records remaining capacity.It is surplus
Remaining electricity is higher, and battery life is longer.
The battery that will be made of the composite diaphragm made by embodiment and reference examples, battery is carried out according to above-mentioned test method
Resistance to elevated temperatures and life test, obtained the results are shown in Table 1.
Table 1
As can be seen from the above table, battery diaphragm provided by the invention has preferable intensity and resistance to elevated temperatures, more
Still more than 80% remaining capacity can be kept after secondary circulation electric discharge；And have the advantages that conductivity is low.Embodiment 3 is opposite
For reference examples 1, by the way that to ceramic powder in a solution of hydrofluoric acid, the roughening on the surface of powder, Neng Gouyu can be promoted
Organic layer is preferably integrated, and improves the intensity of diaphragm material；Additional embodiment 3 is for reference examples 2, by adding EPDM
It can preferably be merged with inorganic particles, the conductivity of membrane can be reduced.
Claims (8)
- A kind of 1. lithium battery organo-mineral complexing membrane, it is characterised in that include centre inorganic, ceramic layer and its two The organic layer of side, following component by weight is included in the raw material of the organic layer：It is 50~70 parts of polyolefin, non-conjugated 10~20 parts of olefin copolymer, 1~5 part of surfactant, 1~5 part of antioxidant, 1~5 part of lubricant, 1~5 part of filler, One 15~30 parts of solvent；Include following component by weight in the raw material of the inorganic, ceramic layer：Aluminium oxide/oxidation Zirconium/40~60 parts of two-dimensional nano titanium carbide composite particles, 20~40 parts of nano alumina particles, 10~20 parts of adhesive, it is non-from Sub- 1~5 part of surface-active, 10~30 parts of the second solvent.
- 2. lithium battery according to claim 1 organo-mineral complexing membrane, it is characterised in that the material of the organic layer Expect that form is non-woven fabrics.
- 3. lithium battery according to claim 1 organo-mineral complexing membrane, it is characterised in that the polyolefin is selected from Polypropylene or polyethylene；The non-conjugated olefin copolymer is selected from Ethylene-Propylene-Diene rubber (EPDM)；The oxidation The average particle size range of aluminium/zirconium oxide/two-dimensional nano titanium carbide composite particles and/or nano alumina particles is 50~200 μm.
- 4. lithium battery according to claim 1 organo-mineral complexing membrane, it is characterised in that the first solvent choosing From one or several kinds of mixing in ethyl acetate, butyl acetate, ethanol, propyl alcohol；Second solvent be selected from water or A kind of or both mixing in ethanol.
- 5. lithium battery according to claim 1 organo-mineral complexing membrane, it is characterised in that the aluminium oxide/oxidation The preparation method of zirconium/two-dimensional nano titanium carbide composite particles, includes the following steps：1st step, by Ti3AlC2Powder ball milling, then into Dried after row, the ceramic powder refined；2nd step, takes 2g~10g to submerge 50mL~200mL hydrogen the ceramic powder of refinement Reacted in fluorspar acid solution, corrosion product is cleaned to neutrality with deionized water, then uses washes of absolute alcohol；By obtained solid sample Product are dried, the ceramic powder after being corroded；3rd step, takes 15g~25g to be put into the ceramic powder after corrosion obtained by step (2) In 2~4L absolute ethyl alcohols, stir, add the nitric acid aluminium powder and 1~5gZrOCl of 5~20g2Powder, then dilute salt is slowly added dropwise 100~150ml of acid, continues stirring reaction, with deionized water eccentric cleaning is used after absolute ethyl alcohol eccentric cleaning again, by solid sample Drying, up to Al (OH)3-Zr(OH)2-Ti3C2Composite material.
- 6. lithium battery according to claim 5 organo-mineral complexing membrane, it is characterised in that in the 1st step, ball Consume time 1~10h, rotational speed of ball-mill 400r/min, ball material mass ratio 6:1；Drying temperature is 40~60 DEG C；In 2nd step, 35~45wt% of concentration of hydrofluoric acid solution, 6~12h of reaction time；In 3rd step, the mass concentration of dilute hydrochloric acid is 1~ 5wt%；6~12h of reaction time；Drying temperature is 110~120 DEG C.
- 7. claim 1~6 any one of them lithium battery preparation method of organo-mineral complexing membrane, it is characterised in that Include the following steps：S1, by polyolefin, non-conjugated olefin copolymer, surfactant, antioxidant, lubricant, filler, One solvent mixes, and the melting extrusion at 210~220 DEG C, is sprayed onto on lace curtaining, 150 by the spinning head of a diameter of 0.1~0.5mm ~160 DEG C of roll-in sizings, obtain the nonwoven layer that thickness is 10~20 μm；S2, alumina-zirconia/two-dimensional nano is carbonized Titanium composite particles, nano alumina particles, adhesive, non-ionic surface active, the second solvent are uniformly mixed, and obtain inorganic particle Slurry；S3, the coating inorganic particle slurry in nonwoven layer, then place on the pulp layer of formation another layer of nonwoven layer； Again after drying, composite diaphragm is obtained.
- 8. the battery according to claim 7 preparation method of organo-mineral complexing membrane, it is characterised in that the coating Method may be selected from spraying, scratch or roller coat in one kind.
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| CN201711107203.0A CN107994186A (en) | 2017-11-10 | 2017-11-10 | A kind of lithium battery organo-mineral complexing membrane and preparation method |
| PCT/CN2017/115926 WO2019090888A1 (en) | 2017-11-10 | 2017-12-13 | Organic-inorganic composite separator for lithium battery and preparation method therefor |
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|---|---|---|---|---|
| CN113444527A (en) * | 2021-06-29 | 2021-09-28 | 江苏品和石油科技有限公司 | Preparation method of antioxidant stabilizer for lithium ion diaphragm pore-forming oil |
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| US20220231379A1 (en) * | 2019-05-24 | 2022-07-21 | Drexel University | Mxene-polymer separators for li-ion batteries |
| CN111916634A (en) * | 2020-07-30 | 2020-11-10 | 福建巨电新能源股份有限公司 | PTC effect diaphragm for lithium ion battery |
| CN113278310B (en) * | 2021-04-30 | 2022-06-17 | 惠州锂威新能源科技有限公司 | Composite ceramic particle and preparation method and application thereof |
| CN114614201A (en) * | 2022-03-29 | 2022-06-10 | 河北金力新能源科技股份有限公司 | Zebra coating diaphragm and preparation method thereof |
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