CN108963156A - Method of modifying of the aluminate coupling agent to coating film - Google Patents
Method of modifying of the aluminate coupling agent to coating film Download PDFInfo
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- CN108963156A CN108963156A CN201810751874.9A CN201810751874A CN108963156A CN 108963156 A CN108963156 A CN 108963156A CN 201810751874 A CN201810751874 A CN 201810751874A CN 108963156 A CN108963156 A CN 108963156A
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- coupling agent
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- aluminate coupling
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- 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 aluminate coupling agents to the method for modifying of coating film, it is characterised in that preparation step is as follows: coating agent is mixed with solvent, aluminate coupling agent, by cleaning, filtering, vacuum drying and etc. modified coating agent is made.In a kettle, mixed and modified coating agent, dimethylformamide, Kynoar-hexafluoropropene and polymethyl methacrylate, make solution in reaction kettle be changed into thick liquid；Thick liquid is coated on the surface by radiation treatment basement membrane, it is dry that coating diaphragm is made.
Description
Technical field
The present invention relates to aluminate coupling agents to the method for modifying of coating film, and in particular to one kind can be used for lithium battery, lithium
The preparation method of the coated polymer film of ion battery, polymer battery and supercapacitor belongs to the skill of battery diaphragm preparation
Art field.
Technical background
Lithium ion battery has many advantages, such as that big voltage height, capacity, memory-less effect, service life are long, is widely used in mobile electricity
In the power tools such as the digital products such as words, digital camera, laptop and electric vehicle, hybrid electric vehicle.Diaphragm is lithium ion
The important component of battery.In battery system, diaphragm plays a part of to obstruct electrical communication, conducting ion between anode and cathode.
Diaphragm has important role to battery performance and safe handling.It is distinguished according to the production technology of diaphragm, the diaphragm of lithium ion battery
Film by dry method, wet process film and composite membrane can be divided into.Commercialized film by dry method, wet process film and composite membrane are mainly polyolefin type.
Mainly there are polyethylene (PE), polypropylene (PP) and polyolefin composite film (e.g., PP/PE/PP, PE/PP).In abuse conditions, lithium
Ion battery may be in 100~300 DEG C of high-temperature regions.These polyalkene diaphragms at high temperature can contraction distortion, cause polyene
There are security risks for the lithium ion battery of hydrocarbon film.
The nano materials such as coating alumina on polyolefin film form coating film, can be obviously improved polyalkene diaphragm
Performance.Coating film has been applied to power battery system, improves the heat resistance and imbibition water retainability and battery of diaphragm
Security performance.Organic material assigns diaphragm flexibility in coating film, meets the matching requirements of battery.Under the high temperature conditions, it coats
Organic component can melt in film, block the hole of diaphragm, slow down or prevent cell reaction, to ensure the safety of battery.It applies
Inorganic material is distributed in the outer layer of diaphragm in overlay film, plays the effect of rigid backbone, can ensure the safety of lithium ion battery.
Coating film is generally made of basement membrane, adhesive, inorganic nano material.
From the point of view of applying coating, the inorganic nano material studied includes nanometer Al2O3、ZrO2、SiO2、TiO2、MgO、
CaO、CaCO3、BaSO4, zeolite, boehmite, clay etc..[Takemura D., the et al. J. Power such as Takemura
Sources, 2005,146 (1/2): 779-783.] investigate Al2O3Influence of the partial size to membrane properties.They have found, apply
Cover Al2O3Particle can improve the high temperature resistance of diaphragm.Choi etc. [Choi E. S., et al. J. Mater. Chem.,
2011, (38): 14747-14754.] use partial size 40nm SiO2PE microporous barrier is coated, coating film is prepared.Researcher goes back apparatus
There is the inorganic material in special duct to replace nanometer Al2O3, it is prepared for ceramic diaphragm.
From the point of view of basement membrane, bonding is to be in close contact adhesive and adherend by wetting, relies primarily on intermolecular interaction
Power plays effect.Since the surface inertness of polyolefin base membrane is stronger, bonded between the applying coating and basement membrane on coating film not closely,
So that untreated polymer is difficult to be bonded.During the long-time charge and discharge cycles of battery system, coating film is easy
Now lose powder phenomenon.In order to improve this phenomenon, [Chen H., the et al. Plasma activation and such as Chen
atomic layer deposition of TiO2 on polypropylene membranes for improved
Performances of lithium-ion batteries, J. Membr. Sci., 2014,458,217-224.] it uses
Plasma technique handles the surface of PP film, is then coated with TiO2, prepare coating film.Studies have shown that plasma treatment can make
PP film surface generates polar group, is conducive to TiO2Disperse in membrane surface.Modified diaphragm has higher imbibition rate, higher
Ionic conductivity, lower thermal contraction, the lithium ion battery being assembled into it can significantly improve performance.In order to solve
The coat of coating film and the adhesion problem of basement membrane, it is contemplated that coupling agent can be coupled by chemical reaction and inorganic particle surfaces
In conjunction with, and effect is crosslinked with high molecular polymer, so that two kinds of substances of different nature be combined.Forefathers have adopted
With silane coupling agent to SiO2Study on the modification is carried out, and with modified SiO2As coating agent, it is prepared for coating diaphragm.
Although by the studies above effort, currently, coating film is applied in battery system has problem.Such as, it coats
Film will increase the internal resistance of cell, and the capacity of battery is made to be difficult to play, and picking influences performance, applying coating and anode, cathode, electrolyte
There are matching problem, the inorganic nano material in coating film is easy to happen reunion, keeps the uniformity of coating film bad.Due to silane
Coupling agent needs hydrone to participate in reaction in the reaction of modification, and water is avoiding greatly for lithium-ion battery system, can be serious
Influence the performance of battery.
In order to improve problem above, it is contemplated that aluminate coupling agent is reacted with water to fail, using aluminate coupling agent
System can avoid the influence of moisture.It will be applied in diaphragm coating layer by the modified coating agent of aluminate coupling agent, Aluminate
Hydrophilic radical can react or be formed tangled structure, the group meeting of oil and binder with coating agent surface in coupling agent molecule
And basement membrane reacts or is formed tangled structure, it, can not only so as to improve the interface compatibility of coating agent and binder and basement membrane
Enough improve processing performance, the mechanical performance of coating film, hence it is evident that the water absorption rate for reducing the coating film of preparation is applying modified coating agent
The uniformity of overlay film Dispersion on surface is significantly improved, to be obviously improved the batch of the battery using this coating film preparation
Consistency has apparent economic benefit.
The technical solution adopted in the present invention comprises the steps of:
By coating agent with solvent according to weight ratio 1:(1~100) it is mixed in back flow reaction kettle, it is warming up to 90~140 DEG C of temperature
Any temperature in section is added the aluminate coupling agent of 1~100% weight of coating agent, is stirred 1~100h, is cleaned with solvent
And centrifugal filtration, it is dried in vacuo and modified coating agent is made.
In a kettle, according to weight ratio (0.1~50): 1000 mixed and modified coating agents and dimethylformamide are made
Mixed solution.Kynoar-hexafluoropropene of modified 1~200% weight of coating agent is added, adds modified coating agent weight
1~200% weight polymethyl methacrylate, 10~50min of supersonic oscillations, at 50~90 DEG C stir 8~12 h,
Solution in reaction kettle is set to be changed into thick liquid.
Thick liquid is coated on the surface by radiation treatment basement membrane, in any temperature of 70~110 DEG C of temperature ranges
Coating diaphragm is made in degree vacuum drying or forced air drying.
The solvent is benzene,toluene,xylene, industrial naptha or isopropanol.
The coating agent be partial size the aluminium oxide of the μ m of 1nm~5, titanium dioxide, zinc oxide, magnesia, zinc borate,
Boehmite, zeolite, sericite, muscovite, synthetic mica, Conductive mica, phlogopite, biotite or paragonite.
The aluminate coupling agent be distearyl acyl-oxygen isopropyl Aluminate, three isopropyl ester of aluminic acid, three benzyl ester of aluminic acid or
Aluminic acid trimethyl.
Three isopropyl ester of aluminic acid is that molecular formula is [Al (OC3H7)3]nCompound.
Three benzyl ester of aluminic acid is that molecular formula is [Al (OC6H5CH2)3]nCompound.
The process radiation treatment basement membrane is placed in basement membrane under corona discharge, cold plasma discharge or glow discharge
Handle the monofilm or multilayer film of 1s~10min.
Kynoar-the hexafluoropropene is Kynoar-hexafluoro of the average molecular weight in 20~2,800,000 ranges
Propylene.
The polymethyl methacrylate is polymethyl methacrylate of the average molecular weight in 60~1,600,000 ranges.
The basement membrane is monofilm or multilayer film containing polypropylene or polyethylene layer.
The multilayer film is the diaphragm that the number of plies is formed in the monofilm of 2~10 ranges.
Cost of material of the invention is lower, and preparation process is simple, easy to operate, and time-consuming is few.The coating agent and bonding of preparation
The interface compatibility of agent and basement membrane is improved.This method can not only improve the processing performance of coating film, mechanical performance, hence it is evident that
The water absorption rate for reducing the coating film of preparation makes modified coating agent be significantly improved in the uniformity of coating film Dispersion on surface,
To be obviously improved the batch consistency of the battery using this coating film, there is apparent economic benefit.
Specific embodiment
The present invention is further detailed below with reference to embodiment.Embodiment is only to further supplement of the invention
And explanation, rather than the limitation to invention.
Embodiment 1
The technical solution adopted in the present invention comprises the steps of:
Partial size 10nm aluminium oxide is mixed in back flow reaction kettle with toluene according to weight ratio 1:50, is warming up to 110 DEG C, is added
The distearyl acyl-oxygen isopropyl Aluminate of 50% weight of aluminium oxide, is stirred 30h, is cleaned with toluene and centrifugal filtration, vacuum are dry
Dry obtained modified aluminas.
In a kettle, according to the mixed and modified aluminium oxide of weight ratio 40:1000 and dimethylformamide, it is molten that mixing is made
Liquid.Kynoar-hexafluoropropene of 80% weight of modified aluminas and average molecular weight 1,100,000 is added, adds modified oxidized
The polymethyl methacrylate of 20% weight of aluminium and average molecular weight 1,200,000, supersonic oscillations 30min stir 10 at 60 DEG C
H makes solution in reaction kettle be changed into thick liquid.
Thick liquid is coated on the surface by the polypropylene monofilm of Corona discharge Treatment 50s, in 90 DEG C of vacuum
It is dry, coating diaphragm is made.
Li will be formed1.05Ni0.5Co0.2Mn0.3O2Tertiary cathode material, acetylene black and the PVDF binder of type are according to 85:10:
5 weight ratio weighs, and using N-Methyl pyrrolidone as grinding aid, uniform sizing material is made in ball milling mixing 3h.Uniform sizing material is coated
In aluminum foil current collector, positive plate is made after drying.By lithium metal, coating diaphragm, positive plate, battery case and the electrolyte of preparation
It is placed in the glove box full of argon atmosphere, is assembled into CR2025 type button cell.To system on new Weir battery test system
Standby button cell carries out charge and discharge and cycle performance test.Test temperature is room temperature (25 ± 1 DEG C).The section of charge and discharge is
2.5~4.3V.Charge and discharge cycles experiment carries out under 1C multiplying power electric current, and the discharge capacity of the 1st circulation is 170mAh/g.
Embodiment 2
The technical solution adopted in the present invention comprises the steps of:
Partial size 1nm zinc oxide is mixed in back flow reaction kettle with dimethylbenzene according to weight ratio 1:1, is warming up to 90 DEG C, oxygen is added
Three isopropyl ester of aluminic acid for changing 1% weight of zinc, is stirred 1h, is cleaned with dimethylbenzene and modification is made in centrifugal filtration, vacuum drying
Zinc oxide.
In a kettle, according to the mixed and modified zinc oxide of weight ratio 0.1:1000 and dimethylformamide, it is molten that mixing is made
Liquid.Kynoar-hexafluoropropene of 1% weight of modified zinc oxide and average molecular weight 200,000 is added, adds modified zinc oxide
The polymethyl methacrylate of 1% weight and average molecular weight 1,600,000, supersonic oscillations 10min make anti-in 50 DEG C of 8 h of stirring
Solution in kettle is answered to be changed into thick liquid.
Thick liquid is coated on the surface by 2 tunic of PP/PE of cold plasma discharge processing 10min, in 70
DEG C vacuum drying, be made coating diaphragm.
Embodiment 3
The technical solution adopted in the present invention comprises the steps of:
5 μm of magnesia of partial size are mixed in back flow reaction kettle with industrial naptha according to weight ratio 1:100,150 DEG C is warming up to, adds
Enter 100% weight of magnesia and molecular formula [Al (OC6H5CH2)3]nCompound, be stirred 100h, with industrial naptha clean
And modified oxidized magnesium is made in centrifugal filtration, vacuum drying.
In a kettle, according to the mixed and modified magnesia of weight ratio 50:1000 and dimethylformamide, it is molten that mixing is made
Liquid.Kynoar-hexafluoropropene of modified oxidized 200% weight of magnesium and average molecular weight 2,800,000 is added, adds modified oxygen
Change the polymethyl methacrylate of 200% weight of magnesium and average molecular weight 600,000, supersonic oscillations 50min stirs 12 at 90 DEG C
H makes solution in reaction kettle be changed into thick liquid.
Thick liquid is coated in the PE/PP/PP/PE/PP/PE/PE/ by discharge of plasma in low temperature processing 5min
On the surface of 10 tunics of PP/PP/PP, in 110 DEG C of forced air dryings, coating diaphragm is made.
Embodiment 4
The technical solution adopted in the present invention comprises the steps of:
1 μm of magnesia of partial size is mixed in back flow reaction kettle with isopropanol according to weight ratio 1:20, is warming up to 95 DEG C, oxygen is added
Three benzyl ester of aluminic acid for changing 10% weight of magnesium, is stirred 80h, is cleaned with isopropanol and modified oxygen is made in centrifugal filtration, vacuum drying
Change magnesium.
In a kettle, according to the mixed and modified magnesia of weight ratio 20:1000 and dimethylformamide, it is molten that mixing is made
Liquid.Kynoar-hexafluoropropene of modified oxidized 50% weight of magnesium and average molecular weight 800,000 is added, adds modified oxidized
The polymethyl methacrylate of 100% weight of magnesium and average molecular weight 1,600,000, supersonic oscillations 10min stir 9h at 50 DEG C,
Solution in reaction kettle is set to be changed into thick liquid.
Thick liquid is coated on the surface by the polypropylene monofilm of cold plasma discharge processing 1s, in 70 DEG C
Coating diaphragm is made in forced air drying.
Embodiment 5
The technical solution adopted in the present invention comprises the steps of:
Partial size 1nm sericite is mixed in back flow reaction kettle with industrial naptha according to weight ratio 1:100,90 DEG C is warming up to, adds
The aluminic acid trimethyl for entering 20% weight of sericite, is stirred 20h, is cleaned with industrial naptha and centrifugal filtration, vacuum drying are made
Modified sericite.
In a kettle, according to the mixed and modified sericite of weight ratio 50:1000 and dimethylformamide, it is molten that mixing is made
Liquid.Kynoar-hexafluoropropene of modified 1% weight of sericite and average molecular weight 200,000 is added, adds modified sericite
The polymethyl methacrylate of 80% weight and average molecular weight 1,000,000, supersonic oscillations 22min stir 8 h at 65 DEG C, make
Solution is changed into thick liquid in reaction kettle.
Thick liquid is coated on the surface by 3 tunic of PP/PE/PP of Corona discharge Treatment 150s, in 110 DEG C
Coating diaphragm is made in vacuum drying.
Embodiment 6
The technical solution adopted in the present invention comprises the steps of:
5 μm of partial size of sericite is mixed in back flow reaction kettle with industrial naptha according to weight ratio 1: 15, is warming up to 150 DEG C,
Three isopropyl ester of aluminic acid of 1% weight of sericite is added, is stirred 1h, is cleaned with industrial naptha and centrifugal filtration, vacuum drying is made
Sericite must be modified.
In a kettle, according to the mixed and modified sericite of weight ratio 50:1000 and dimethylformamide, it is molten that mixing is made
Liquid.Kynoar-hexafluoropropene of modified 200% weight of sericite and average molecular weight 2,000,000 is added, adds modified thin,tough silk
The polymethyl methacrylate of 1% weight of mica and average molecular weight 600,000, supersonic oscillations 10min make in 50 DEG C of stirring 8h
Solution is changed into thick liquid in reaction kettle.
Thick liquid is coated on the surface by the polypropylene monofilm of Corona discharge Treatment 10min, in 70 DEG C of drums
Air-dry dry, obtained coating diaphragm.
Embodiment 7
The technical solution adopted in the present invention comprises the steps of:
2 μm of synthetic micas of partial size are mixed in back flow reaction kettle with isopropanol according to weight ratio 1:20,140 DEG C is warming up to, adds
Enter 70% weight of synthetic mica and molecular formula is [Al (OC3H7)3]nCompound, be stirred 100h, with isopropanol clean and from
Heart filtering, is dried in vacuo and modified synthesis mica is made.
In a kettle, according to the mixed and modified synthetic mica of weight ratio 2:1000 and dimethylformamide, it is molten that mixing is made
Liquid.Kynoar-hexafluoropropene of 120% weight of modified synthesis mica and average molecular weight 2,800,000 is added, adds modification
The polymethyl methacrylate of 1% weight of synthetic mica and average molecular weight 600,000, supersonic oscillations 50min are stirred at 90 DEG C
12 h make solution in reaction kettle be changed into thick liquid.
Thick liquid is coated on the surface by 3 tunic of PE/PP/PP of Corona discharge Treatment 10min, in 110
DEG C vacuum drying, be made coating diaphragm.
Claims (10)
1. aluminate coupling agent is to the method for modifying of coating film, it is characterised in that preparation step is as follows: coating agent and solvent are pressed
According to weight ratio 1:(1~100) it is mixed in back flow reaction kettle, it is warming up to any temperature of 90~140 DEG C of temperature ranges, is added and applies
The aluminate coupling agent for covering 1~100% weight of agent, is stirred 1~100h, is cleaned with solvent and centrifugal filtration, vacuum drying are made
Coating agent must be modified；
In a kettle, according to weight ratio (0.1~50): mixing is made in 1000 mixed and modified coating agents and dimethylformamide
Solution；Kynoar-hexafluoropropene of modified 1~200% weight of coating agent is added, add modified coating agent weight 1~
The polymethyl methacrylate of 200% weight, 10~50min of supersonic oscillations stir 8~12 h at 50~90 DEG C, make to react
Solution is changed into thick liquid in kettle；
Thick liquid is coated on the surface by radiation treatment basement membrane, it is true in any temperature of 70~110 DEG C of temperature ranges
Coating diaphragm is made in empty drying or forced air drying.
2. aluminate coupling agent according to claim 1 is to the method for modifying of coating film, it is characterised in that the coating
Agent is partial size in the aluminium oxide of the μ m of 1nm~5, titanium dioxide, zinc oxide, magnesia, zinc borate, boehmite, zeolite, thin,tough silk cloud
Mother, muscovite, synthetic mica, Conductive mica, phlogopite, biotite or paragonite.
3. aluminate coupling agent according to claim 1 is to the method for modifying of coating film, it is characterised in that the aluminic acid
Ester coupling agent is distearoyl oxygen isopropyl Aluminate, three isopropyl ester of aluminic acid, three benzyl ester of aluminic acid or aluminic acid trimethyl.
4. aluminate coupling agent according to claim 1 is to the method for modifying of coating film, it is characterised in that described is poly- inclined
Vinyl fluoride-hexafluoropropene is Kynoar-hexafluoropropene of the average molecular weight in 20~2,800,000 ranges.
5. aluminate coupling agent according to claim 1 is to the method for modifying of coating film, it is characterised in that the poly- first
Base methyl acrylate is polymethyl methacrylate of the average molecular weight in 60~1,600,000 ranges.
6. aluminate coupling agent according to claim 1 is to the method for modifying of coating film, it is characterised in that the basement membrane
It is monofilm or multilayer film containing polypropylene or polyethylene layer.
7. aluminate coupling agent according to claim 1 is to the method for modifying of coating film, it is characterised in that the process
Radiation treatment basement membrane is the single layer that basement membrane is passed through to corona discharge, cold plasma discharge or glow discharge process 1s~10min
Film or multilayer film.
8. aluminate coupling agent according to claim 6 is to the method for modifying of coating film, it is characterised in that the multilayer
Film is the diaphragm that the number of plies is formed in the monofilm of 2~10 ranges.
9. aluminate coupling agent according to claim 1 is to the method for modifying of coating film, it is characterised in that the solvent
For benzene,toluene,xylene, industrial naptha or isopropanol.
10. aluminate coupling agent according to claim 3 is to the method for modifying of coating film, it is characterised in that the aluminic acid
Three isopropyl esters are that molecular formula is [Al (OC3H7)3]nCompound；Three benzyl ester of aluminic acid is that molecular formula is [Al
(OC6H5CH2)3]nCompound.
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| CN111653715A (en) * | 2020-06-16 | 2020-09-11 | 合肥国轩高科动力能源有限公司 | Modified ceramic diaphragm, preparation method thereof and lithium ion battery |
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| CN112436234A (en) * | 2019-08-09 | 2021-03-02 | 宁德卓高新材料科技有限公司 | Ceramic micro-composite diaphragm and preparation method thereof |
| CN113913728A (en) * | 2021-09-28 | 2022-01-11 | 德清创智科技股份有限公司 | Method for improving bonding strength of plasma spraying AT coating on surface of overfeed roller disc |
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| CN111653715A (en) * | 2020-06-16 | 2020-09-11 | 合肥国轩高科动力能源有限公司 | Modified ceramic diaphragm, preparation method thereof and lithium ion battery |
| CN113913728A (en) * | 2021-09-28 | 2022-01-11 | 德清创智科技股份有限公司 | Method for improving bonding strength of plasma spraying AT coating on surface of overfeed roller disc |
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Application publication date: 20181207 |