CN109411678A - A kind of high security ceramic diaphragm and preparation method for lithium ion battery - Google Patents
A kind of high security ceramic diaphragm and preparation method for lithium ion battery Download PDFInfo
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- CN109411678A CN109411678A CN201811199572.1A CN201811199572A CN109411678A CN 109411678 A CN109411678 A CN 109411678A CN 201811199572 A CN201811199572 A CN 201811199572A CN 109411678 A CN109411678 A CN 109411678A
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- Prior art keywords
- lithium ion
- ion battery
- high security
- ceramic diaphragm
- thickener
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Cell Separators (AREA)
Abstract
The present invention is a kind of high security ceramic diaphragm for lithium ion battery, including basement membrane and coated in the ceramic slurry of membrane surface, the ceramic slurry includes following components according to parts by weight: 1 part of aluminium oxide, 0.0125 part of dispersing agent, 0.3-0.4 parts of thickener, 0.1-0.2 parts of aqueous binder and wetting agent, and wetting agent and the weight fraction ratio containing aluminium oxide, dispersing agent, thickener and aqueous binder mixed liquor are 0.001:1.Grammes per square metre enhancing of the present invention improves the thermal contraction performance of diaphragm, and the puncture strength of diaphragm enhances, not cracky.
Description
Technical field
The present invention relates to battery material fields, more particularly to a kind of high security ceramic diaphragm for lithium ion battery
And preparation method.
Background technique
Lithium ion battery separator is mainly porous polyolefin class, uses widely predominantly polyethylene or polypropylene at present,
Play the role of electronic isolation in the anode and cathode of battery, in addition the free migration also for electrolyte intermediate ion provides channel.Mesh
Preceding lithium ion battery separator there are the problem of mainly have: 1, in the use process of battery, since exothermic temperature is higher, diaphragm from
Row closed pore, but with the further raising of temperature, the thermal contraction that diaphragm generates will lead to battery positive and negative polarities contact short circuit to
It sets off an explosion；2, in charge and discharge process repeatedly, the tip crystal that electrode surface generates be easy to cause diaphragm breakage to lead
Cause short circuit.Furthermore, it is contemplated that diaphragm crimping by stretching and the assembling of battery in process of production, also easily punctures diaphragm.
Summary of the invention
A kind of the object of the present invention is to provide intensity high, not cracky high security ceramics for lithium ion battery every
Film and preparation method.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of high security ceramic diaphragm for lithium ion battery, including basement membrane and coated in the ceramic slurry of membrane surface,
The ceramic slurry includes following components according to parts by weight: 1 part of aluminium oxide, 0.0125 part of dispersing agent, thickener 0.3-0.4
Part, 0.1-0.2 parts of aqueous binder and wetting agent, wetting agent are mixed with containing aluminium oxide, dispersing agent, thickener and aqueous binder
The weight fraction ratio for closing liquid is 0.001:1.
Further, the basement membrane with a thickness of 5-12um.
Further, the alumina ratio surface area is 5-10m2/g, partial size 0.1-5um.
Further, the dispersing agent includes ionic and non-ionic.
Further, the ionic dispersant includes polyacrylate, phosphate ester salt, sulphonic acid ester salt and sulfuric acid.
Further, the polyacrylate is ammonium polyacrylate.
Further, the thickener include cellulose family and polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone,
Polyacrylic acid, Sodium Polyacrylate.
Further, the cellulose thickener is carboxymethyl cellulose.
Further, the aqueous binder is polyacrylate.
A kind of preparation method of the high security ceramic diaphragm for lithium ion battery, comprising the following steps:
(1), dispersing agent is dispersed with aqueous solvent, dispersion stirring then is added in aluminium oxide, the time is 50-70 minutes, and revolving speed is
1400-1600rpm is ground again after being dispersed with stirring uniformly；
(2), carboxymethyl cellulose thickener is added in the lysate obtained in step (1), and is 20- with stirring rate
The Rate Dispersion of 40rpm 20-40 minutes；
(3), aqueous binder is added in the mixed dissolution liquid in step (2), and is the speed of 20-40rpm with stirring rate
Dispersion 20-40 minutes, stirs evenly；
(4), wetting agent is added and is Rate Dispersion 20-40 minutes of 20-40rpm with stirring rate, stirs evenly, it will be acquired
Slurry be coated to membrane surface, by being dried to obtain ceramic diaphragm.
Compared with prior art, the present invention is used for the high security ceramic diaphragm and preparation method and application of lithium ion battery
Beneficial effect be: grammes per square metre enhancing improves the thermal contraction performance of diaphragm, the puncture strength enhancing of diaphragm, not cracky.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the high security ceramic diaphragm for lithium ion battery.
Specific embodiment
As shown in Figure 1, a kind of high security ceramic diaphragm for lithium ion battery, including basement membrane 1 and it is coated in basement membrane 1
The ceramic slurry 2 on surface, ceramic slurry 2 include aluminium oxide, dispersing agent, thickener, aqueous binder and wetting agent.The thickness of basement membrane
Degree is 5-12um.
Alumina ratio surface area is 5-10m2/g, and partial size 0.1-5um, particle diameter distribution relatively concentration, accumulation is closer, can increase
Strong puncture strength.
Dispersing agent includes ionic and non-ionic.
Ionic dispersant is ionized into electrically charged or hydrophilic and hydrophobic grouping in water, forms electronics in solid particles surface
Layer, it is mutually exclusive between particle to be difficult to happen reunion due to electrostatic interaction and space behavior, as polyacrylate, phosphate ester salt,
Sulphonic acid ester salt and sulfuric acid etc..Presently preferred dispersing agent of the present invention is ammonium polyacrylate, and molecular formula is [CH2CHCOONH4] n,
Ammonium polyacrylate is in process of production by heating, the decomposable removal of ammonium ion, can be with compared with sodium polyacrylate disperant
The introducing of sodium ion is reduced, cycle performance of battery is improved.The effect of ammonium polyacrylate is that ammonium polyacrylate is dissociated into ammonium in water
Radical ion and polyacrylic acid radical ion form adsorption layer in oxidation aluminium surface, make Membranes On Alumina Particles Surface with charge, due to quiet
Electricity repels and steric hindrance effect, can keep grain spacing appropriate, reduce the reunion of alumina particle, divide aluminium oxide uniformly
It dissipates.
Non-ionic dispersing agent does not ionize in water, does not exist in the form of an ion, such as polyoxyethylene-type and polyalcohol
Type.
Thickener includes cellulose family and polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, poly- third
Olefin(e) acid sodium etc..Cellulose thickener includes methylcellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose etc., the present invention
Preferred thickener is carboxymethyl cellulose (CMC), is obtained by carboxymethyl cellulose, aqueous solution have thickening, bonding and
The effects of stablizing, for aluminium oxide after dispersion grinding, carboxymethyl cellulose, which is added, makes aluminium oxide keep rock-steady structure.
Aqueous binder is polyacrylate, and effect is to be firmly bonded basement membrane and ceramic slurry coating.Polyacrylic
Aqueous binder is formed by monomer polymerization, and the carboxyl in monomer can make polymer have water solubility with alkaline matter at salt.In addition
It is environmentally protective with extremely low VOC content.
Wetting agent includes type siloxane and fatty alcohols, and main function is the surface tension for reducing water, adjusts coating surface
Enhance the wettability of coating, currently preferred wetting agent is polyether siloxane copolymer.
Embodiment one
A kind of preparation method of the high security ceramic diaphragm for lithium ion battery, comprising the following steps:
(1), ammonium polyacrylate dispersant to be dispersed with aqueous solvent, dispersion stirring then is added in aluminium oxide, the time is 60 minutes,
Revolving speed is 1500rpm, is ground again after being dispersed with stirring uniformly, and the weight fraction ratio of dispersing agent and aluminium oxide is 0.0125:1.
(2), carboxymethyl cellulose thickener is added in the lysate obtained in step (1), and is with stirring rate
The weight fraction ratio of the Rate Dispersion of 30rpm 30 minutes, thickener and aluminium oxide is 0.4:1.
(3), polyacrylate aqueous binder is added in the mixed dissolution liquid in step (2), and is with stirring rate
The Rate Dispersion of 30rpm 30 minutes, stirs evenly, and the weight fraction ratio of aqueous binder and aluminium oxide is 0.2:1.
(4), wetting agent is added and is Rate Dispersion 30 minutes of 30rpm with stirring rate, stirs evenly.Wetting agent and step
Suddenly the weight fraction ratio of gained mixed liquor is 0.001:1 in (3).Obtained slurry is coated to membrane surface, by drying
Obtain ceramic diaphragm.
Embodiment two
A kind of preparation method of the high security ceramic diaphragm for lithium ion battery, comprising the following steps:
(1), ammonium polyacrylate dispersant to be dispersed with aqueous solvent, dispersion stirring then is added in aluminium oxide, the time is 50 minutes,
Revolving speed is 1400rpm, is ground again after being dispersed with stirring uniformly, and the weight fraction ratio of dispersing agent and aluminium oxide is 0.0125:1.
(2), carboxymethyl cellulose thickener is added in the lysate obtained in step (1), and is with stirring rate
The weight fraction ratio of the Rate Dispersion of 20rpm 40 minutes, thickener and aluminium oxide is 0.3:1.
(3), polyacrylate aqueous binder is added in the mixed dissolution liquid in step (2), and is with stirring rate
The Rate Dispersion of 20rpm 40 minutes, stirs evenly, and the weight fraction ratio of aqueous binder and aluminium oxide is 0.1:1.
(4), wetting agent is added and is Rate Dispersion 40 minutes of 20rpm with stirring rate, stirs evenly.Wetting agent and step
Suddenly the weight fraction ratio of gained mixed liquor is 0.001:1 in (3).Obtained slurry is coated to membrane surface, by drying
Obtain ceramic diaphragm.
Embodiment three
A kind of preparation method of the high security ceramic diaphragm for lithium ion battery, comprising the following steps:
(1), ammonium polyacrylate dispersant to be dispersed with aqueous solvent, dispersion stirring then is added in aluminium oxide, the time is 70 minutes,
Revolving speed is 1600rpm, is ground again after being dispersed with stirring uniformly, and the weight fraction ratio of dispersing agent and aluminium oxide is 0.0125:1.
(2), carboxymethyl cellulose thickener is added in the lysate obtained in step (1), and is with stirring rate
The weight fraction ratio of the Rate Dispersion of 40rpm 20 minutes, thickener and aluminium oxide is 0.35:1.
(3), polyacrylate aqueous binder is added in the mixed dissolution liquid in step (2), and is with stirring rate
The Rate Dispersion of 40rpm 20 minutes, stirs evenly, and the weight fraction ratio of aqueous binder and aluminium oxide is 0.15:1.
(4), wetting agent is added and is Rate Dispersion 20 minutes of 40rpm with stirring rate, stirs evenly.Wetting agent and step
Suddenly the weight fraction ratio of gained mixed liquor is 0.001:1 in (3).Obtained slurry is coated to membrane surface, by drying
Obtain ceramic diaphragm.
For ceramic diaphragm of the invention compared with the ceramic diaphragm of comparative example, grammes per square metre enhancing improves the heat-shrinkable of diaphragm
Can, the puncture strength of diaphragm enhances, not cracky.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention, for this field skill
For art personnel, it is clear that invention is not limited to the details of the above exemplary embodiments, and without departing substantially from spirit of the invention or
In the case where essential characteristic, the present invention can be realized in other specific forms.Therefore, in all respects, should all incite somebody to action
Embodiment regards exemplary as, and is non-limiting, the scope of the present invention by appended claims rather than on state
Bright restriction, it is intended that including all changes that fall within the meaning and scope of the equivalent elements of the claims in the present invention
It is interior.Any reference signs in the claims should not be construed as limiting the involved claims.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (10)
1. a kind of high security ceramic diaphragm for lithium ion battery, it is characterised in that: including basement membrane and be coated in basement membrane table
The ceramic slurry in face, the ceramic slurry include following components according to parts by weight: 1 part of aluminium oxide, 0.0125 part of dispersing agent,
0.3-0.4 parts of thickener, 0.1-0.2 parts of aqueous binder and wetting agent, wetting agent with contain aluminium oxide, dispersing agent, thickener
Weight fraction ratio with aqueous binder mixed liquor is 0.001:1.
2. the high security ceramic diaphragm according to claim 1 for lithium ion battery, it is characterised in that: the basement membrane
With a thickness of 5-12um.
3. the high security ceramic diaphragm according to claim 1 for lithium ion battery, it is characterised in that: the oxidation
Aluminium specific surface area is 5-10m2/g, partial size 0.1-5um。
4. the high security ceramic diaphragm according to claim 1 for lithium ion battery, it is characterised in that: the dispersion
Agent includes ionic and non-ionic.
5. the high security ceramic diaphragm according to claim 4 for lithium ion battery, it is characterised in that: the ion
Type dispersing agent includes polyacrylate, phosphate ester salt, sulphonic acid ester salt and sulfuric acid.
6. the high security ceramic diaphragm according to claim 5 for lithium ion battery, it is characterised in that: described poly- third
Olefin(e) acid salt is ammonium polyacrylate.
7. the high security ceramic diaphragm according to claim 1 for lithium ion battery, it is characterised in that: the thickening
Agent includes cellulose family and polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, Sodium Polyacrylate.
8. the high security ceramic diaphragm according to claim 7 for lithium ion battery, it is characterised in that: the fiber
Plain class thickener is carboxymethyl cellulose.
9. the high security ceramic diaphragm according to claim 1 for lithium ion battery, it is characterised in that: described aqueous
Adhesive is polyacrylate.
10. a kind of preparation method of the high security ceramic diaphragm for lithium ion battery, which is characterized in that including following step
It is rapid:
(1), dispersing agent is dispersed with aqueous solvent, dispersion stirring then is added in aluminium oxide, the time is 50-70 minutes, and revolving speed is
1400-1600rpm is ground again after being dispersed with stirring uniformly；
(2), carboxymethyl cellulose thickener is added in the lysate obtained in step (1), and is 20- with stirring rate
The Rate Dispersion of 40rpm 20-40 minutes；
(3), aqueous binder is added in the mixed dissolution liquid in step (2), and is the speed of 20-40rpm with stirring rate
Dispersion 20-40 minutes, stirs evenly；
(4), wetting agent is added and is Rate Dispersion 20-40 minutes of 20-40rpm with stirring rate, stirs evenly, it will be acquired
Slurry be coated to membrane surface, by being dried to obtain ceramic diaphragm.
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| CN201811199572.1A CN109411678A (en) | 2018-10-16 | 2018-10-16 | A kind of high security ceramic diaphragm and preparation method for lithium ion battery |
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| CN201811199572.1A CN109411678A (en) | 2018-10-16 | 2018-10-16 | A kind of high security ceramic diaphragm and preparation method for lithium ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110797496A (en) * | 2019-11-08 | 2020-02-14 | 新乡市中科科技有限公司 | Lithium battery coating film and preparation method thereof |
| CN110845957A (en) * | 2019-11-22 | 2020-02-28 | 上海大学 | Aqueous aramid fiber coating liquid and preparation method thereof, lithium ion battery and diaphragm thereof |
| CN111370623A (en) * | 2020-03-18 | 2020-07-03 | 江苏厚生新能源科技有限公司 | Alumina ceramic diaphragm, preparation method thereof, powder, ceramic slurry and lithium battery |
| CN111769239A (en) * | 2019-04-02 | 2020-10-13 | 河北金力新能源科技股份有限公司 | Heat-resistant high-strength composite lithium battery diaphragm and preparation method and application thereof |
| CN113087445A (en) * | 2021-04-01 | 2021-07-09 | 昆山宝创新能源科技有限公司 | Preparation method of ceramic slurry, ceramic diaphragm and lithium ion battery |
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Application publication date: 20190301 |