CN109037564A - A kind of coating of lithium-ion battery diaphragm ceramic slurry and preparation method thereof - Google Patents
A kind of coating of lithium-ion battery diaphragm ceramic slurry and preparation method thereof Download PDFInfo
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- CN109037564A CN109037564A CN201810966053.7A CN201810966053A CN109037564A CN 109037564 A CN109037564 A CN 109037564A CN 201810966053 A CN201810966053 A CN 201810966053A CN 109037564 A CN109037564 A CN 109037564A
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- parts
- dispersing agent
- lithium
- ion battery
- ceramic slurry
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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
-
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of coating of lithium-ion battery diaphragm ceramic slurries and preparation method thereof, preparation including inorganic particle hydrophobically modified and ceramic slurry, preparation method are to be dissolved in soluble polytetrafluoroethylgranule granule in solvent with inorganic particle to be modified and be dried in vacuo；Hydrophobically modified inorganic particle, fluorine carbon dispersing agent, thickener, water are added in ball mill disperse according to the proportion again, obtains dispersion liquid；Binder is added into dispersion liquid again, disperses that ceramic slurry is made using dispersion machine.The present invention not only can guarantee that diaphragm had lower thermal contraction, preferable electrolyte wellability, but also can significantly reduce the moisture value of diaphragm, enhance the stability and safety of lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of coating of lithium-ion battery diaphragm ceramic slurries
Preparation method.
Background technique
Lithium ion battery due to it is big with specific energy, have extended cycle life, self-discharge rate is low, memory-less effect, to environment friend
The advantages that good, has a wide range of applications in the fields such as space flight and aviation, national defence, automobile, 3C.Pass of the diaphragm as lithium ion battery
Key member, performance determine the interfacial structure of battery, internal resistance etc., directly affect the use and security performance of battery.Polyolefin
Microporous barrier is answered extensively due to having many advantages, such as excellent insulating properties, ion permeability, chemical stability and mechanical strength
With；But there is also biggish defects, such as high high-temp stability is poor, electrolyte wetability difference, these defects it is easier that
The internal resistance of cell increases, cycle performance reduces, even results in internal short-circuit of battery, causes serious safety accident.
In order to improve a series of this problem, the current most common method is in polyalkene diaphragm surface coating inorganic ceramics
Coating can not only significantly improve diaphragm to the wetability of electrolyte, but also have preferable thermal contraction performance at high temperature.
But since the hydrophily of aluminium oxide is stronger, surface is hygroscopic, causes the moisture value of diaphragm higher, this is for lithium ion battery
It is unfavorable for stability and safety.Therefore, it is badly in need of developing a kind of novel lithium ion battery diaphragm to meet lithium-ion electric
The requirements of pond diaphragm.
Summary of the invention
Based on background above technology there are the problem of, the purpose of the present invention is to propose to a kind of coating of lithium-ion battery diaphragm use
Ceramic slurry and preparation method while guaranteeing diaphragm compared with low thermal shrinkage, preferable electrolyte wellability, and can significantly reduce lithium
The moisture value of ion battery diaphragm.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of coating of lithium-ion battery diaphragm ceramic slurry, feature are that the ceramic slurry is prepared by following components by mass fraction
It forms:
Hydrophobically modified inorganic particle: 20-50 parts
Fluorine carbon dispersing agent: 0.01-1 parts
Thickener: 0.1-2 parts
Water: 20-100 parts
Binder: 0.5-8 parts
The hydrophobically modified inorganic particle is prepared by soluble poly tetrafluoroethene modified inorganic particles.
The inorganic particle is one of aluminium oxide, boehmite or two kinds of mixing.
The fluorine carbon dispersing agent is anion fluorine carbon dispersing agent, cation fluorine carbon dispersing agent, non-ionic fluorocarbon dispersing agent, two
One of property fluorine carbon dispersing agent or several mixing.
The thickener is methylpropene sodium sulfonate, acrylamide, N- hydroxyethyl acrylamide, acrylic acid, acrylic acid hydroxyl
The copolymer of at least two kinds of monomers of propyl ester, maleic anhydride, n-vinyl pyrrolidone.
The binder be styrene-butadiene emulsion, polyacrylic binder, oleic series resinoid bond, polyvinyl alcohol,
The mixing of one or more of acrylonitrile multiple copolymer.
A kind of preparation method of coating of lithium-ion battery diaphragm ceramic slurry, this method include step in detail below,
Raw material is in terms of mass fraction:
(1) 0.02-2.5 parts of soluble polytetrafluoroethylgranule granules and 20-50 parts of inorganic particles are dissolved in 20-100 parts of solvents, are mixed
Stirring 0.5-5h is closed, is then dried in vacuo, obtains hydrophobically modified inorganic particle；
(2) by 20-50 parts of hydrophobically modified inorganic particles, 0.01-1 parts of fluorine carbon dispersing agents, 0.1-2 parts of thickeners, 20-100 parts of water
It is added in ball mill and carries out dispersion 10-120min, obtain dispersion liquid；
(3) 0.5-8 parts of binders are added in the dispersion liquid obtained to step (2), 2-60min is dispersed in dispersion machine, obtains lithium
Ion battery applies cloth diaphragm ceramic slurry；
The solvent is the mixing of one or more of water, ethyl alcohol, tetrahydrofuran, N-Methyl pyrrolidone, ethyl acetate；
The inorganic particle is one of aluminium oxide, boehmite or two kinds of mixing；
The fluorine carbon dispersing agent is anion fluorine carbon dispersing agent, cation fluorine carbon dispersing agent, non-ionic fluorocarbon dispersing agent, both sexes fluorine
One of carbon dispersing agent or several mixing；
The thickener be methylpropene sodium sulfonate, acrylamide, N- hydroxyethyl acrylamide, acrylic acid, hydroxypropyl acrylate,
The copolymer of at least two kinds of monomers of maleic anhydride, n-vinyl pyrrolidone；
The binder is styrene-butadiene emulsion, polyacrylic binder, oleic series resinoid bond, polyvinyl alcohol, propylene
The mixing of one or more of nitrile multiple copolymer.
The beneficial effects of the present invention are:
Compared to the prior art, prepared by the method lithium ion battery separator ceramic slurry, so that inorganic particle surfaces
It with preferable hydrophobic performance, ensure that outside the advantage with coating inorganic particles diaphragm, also having prevents inorganic coating from inhaling
The problem of water, significantly reduces the moisture value of diaphragm, substantially increases the stability and security performance of diaphragm.
Specific embodiment
Following embodiment does not limit the present invention convenient for better understanding the present invention.
Embodiment 1
0.02 part of soluble polytetrafluoroethylgranule granule and 20 parts of aluminium oxide are dissolved in 20 parts of water, mixing 0.5h, then into
Row vacuum drying, obtains hydrophobically modified inorganic particle；By 20 parts of hydrophobically modified inorganic particles, 0.02 part of anion fluorine carbon dispersion
Agent, 0.1 part of methylpropene sodium sulfonate and acrylamide copolymer, 20 parts of water are added in ball mill and carry out dispersion 10min, are divided
Dispersion liquid；0.5 part of styrene-butadiene emulsion is added into dispersion liquid, 5min is dispersed in dispersion machine, obtains coating of lithium-ion battery diaphragm use
Ceramic slurry.
Embodiment 2
2.5 parts of soluble polytetrafluoroethylgranule granules and 50 parts of aluminium oxide are dissolved in 100 parts of ethyl alcohol, mixing 5h, then into
Row vacuum drying, obtains hydrophobically modified inorganic particle；By 50 parts of hydrophobically modified inorganic particles, 1 part of anion fluorine carbon dispersing agent, 2
Part methylpropene sodium sulfonate, acrylamide and N- hydroxyethyl acrylamide copolymer, 100 parts of water are added in ball mills and are dispersed
120min obtains dispersion liquid；8 parts of polyacrylic binders are added into dispersion liquid, 60min is dispersed in dispersion machine, is obtained
Coating of lithium-ion battery diaphragm ceramic slurry.
Embodiment 3
0.5 part of soluble polytetrafluoroethylgranule granule and 30 parts of boehmites are dissolved in 50 parts of ethyl alcohol, 1h is mixed, then carries out
Vacuum drying, obtains hydrophobically modified inorganic particle；By 30 parts of hydrophobically modified inorganic particles, 0.1 part of cation fluorine carbon dispersing agent,
0.5 part of acrylamide, N- hydroxyethyl acrylamide and acrylic copolymer, 50 parts of water are added in ball mill and carry out dispersion 30min,
Obtain dispersion liquid；Into dispersion liquid be added 2 portions of oleic series resinoid bonds, 10min is dispersed in dispersion machine, obtain lithium from
Sub- cell coating diaphragm ceramic slurry.
Embodiment 4
0.5 part of soluble polytetrafluoroethylgranule granule and 30 parts of boehmites are dissolved in 50 parts of tetrahydrofurans, 2h is mixed, then
It is dried in vacuo, obtains hydrophobically modified inorganic particle；By 30 parts of hydrophobically modified inorganic particles, 0.3 part of non-ionic fluorocarbon dispersion
Agent, 1 part of acrylamide, N- hydroxyethyl acrylamide and n-vinyl pyrrolidone copolymer, 50 parts of water be added in ball mills into
Row dispersion 60min, obtains dispersion liquid；Into dispersion liquid be added 2 parts of polyvinyl alcohol, 20min is dispersed in dispersion machine, obtain lithium from
Sub- cell coating diaphragm ceramic slurry.
Embodiment 5
1 part of soluble polytetrafluoroethylgranule granule and 40 parts of aluminium oxide are dissolved in 60 parts of N-Methyl pyrrolidones, 2h is mixed,
Then it is dried in vacuo, obtains hydrophobically modified inorganic particle；By 40 parts of hydrophobically modified inorganic particles, 0.8 part of both sexes fluorine carbon point
Powder, 1 part of N- hydroxyethyl acrylamide, maleic anhydride and n-vinyl pyrrolidone copolymer, 60 parts of water are added in ball mill
Dispersion 60min is carried out, dispersion liquid is obtained；4 parts of acrylonitrile multiple copolymers are added into dispersion liquid, disperse in dispersion machine
30min obtains coating of lithium-ion battery diaphragm ceramic slurry.
Comparative example 1
By 20 parts of boehmites, 0. 2 parts of Sodium Polyacrylates, 0.5 part of methylpropene sodium sulfonate and acrylamide copolymer, 30 parts of water
It is added in ball mill and disperses 30min, obtain dispersion liquid；1 part of styrene-butadiene emulsion is added into dispersion liquid, disperses in dispersion machine
5min obtains coating of lithium-ion battery diaphragm ceramic slurry.
Comparative example 2
30 parts of aluminium oxide, 0.3 part of Sodium Polyacrylate, 0.5 part of methylpropene sodium sulfonate and acrylamide copolymer, 45 parts of water are added
Enter and disperse 30min in ball mill, obtains dispersion liquid；2 parts of styrene-butadiene emulsions are added into dispersion liquid, 5min is dispersed in dispersion machine,
Obtain coating of lithium-ion battery diaphragm ceramic slurry.
Slurry in embodiment 1-5 and comparative example is coated on to the PE film of 12 μ m-thicks by the way of micro- gravure roller coating
On one side, coating layer thickness is dry 20min at 4 μm, 60 DEG C, and ceramic diaphragm, the thermal contraction performance and water of obtained diaphragm is made
Score value is as shown in table 1；Wherein, MD and TD respectively represents horizontal and vertical thermal contraction.
Table 1
| Type | MD/%(130 DEG C/1h) | TD/%(130 DEG C/1h) | Moisture value ppm |
| Comparative example 1 | 3.5 | 2.8 | 1350 |
| Comparative example 2 | 3.1 | 2.6 | 1682 |
| Embodiment 1 | 2.2 | 1.4 | 895 |
| Embodiment 2 | 2.6 | 1.5 | 391 |
| Embodiment 3 | 2.5 | 1.4 | 456 |
| Embodiment 4 | 2.4 | 1.2 | 478 |
| Embodiment 5 | 2.1 | 1.0 | 425 |
Claims (7)
1. a kind of coating of lithium-ion battery diaphragm ceramic slurry, which is characterized in that the ceramic slurry presses quality by following components
Number is prepared:
Hydrophobically modified inorganic particle: 20-50 parts
Fluorine carbon dispersing agent: 0.01-1 parts
Thickener: 0.1-2 parts
Water: 20-100 parts
Binder: 0.5-8 parts.
2. a kind of coating of lithium-ion battery diaphragm ceramic slurry according to claim 1, which is characterized in that described hydrophobic
Modified inorganic particles are prepared by soluble poly tetrafluoroethene modified inorganic particles.
3. hydrophobically modified inorganic particle according to claim 2, which is characterized in that the inorganic particle is for aluminium oxide and suddenly
One of nurse stone or two kinds of mixing.
4. a kind of coating of lithium-ion battery diaphragm ceramic slurry according to claim 1, which is characterized in that the fluorine carbon
Dispersing agent is in anion fluorine carbon dispersing agent, cation fluorine carbon dispersing agent, non-ionic fluorocarbon dispersing agent and both sexes fluorine carbon dispersing agent
One or several kinds of mixing.
5. a kind of coating of lithium-ion battery diaphragm ceramic slurry according to claim 1, which is characterized in that the thickening
Agent is methylpropene sodium sulfonate, acrylamide, N- hydroxyethyl acrylamide, acrylic acid, hydroxypropyl acrylate, maleic anhydride and N-
The copolymer of at least two kinds of monomers in vinyl pyrrolidone.
6. a kind of coating of lithium-ion battery diaphragm ceramic slurry according to claim 1, which is characterized in that the bonding
Agent is styrene-butadiene emulsion, polyacrylic binder, oleic series resinoid bond, polyvinyl alcohol and acrylonitrile multiple copolymer
One or more of mixing.
7. a kind of preparation method of coating of lithium-ion battery diaphragm ceramic slurry described in claim 1, which is characterized in that should
Method includes step in detail below, and raw material is in terms of mass fraction:
(1) 0.02-2.5 parts of soluble polytetrafluoroethylgranule granules and 20-50 parts of inorganic particles are dissolved in 20-100 parts of solvents, are mixed
Stirring 0.5-5h is closed, is then dried in vacuo, obtains hydrophobically modified inorganic particle；
(2) by 20-50 parts of hydrophobically modified inorganic particles, 0.01-1 parts of fluorine carbon dispersing agents, 0.1-2 parts of thickeners, 20-100 parts of water
It is added in ball mill and carries out dispersion 10-120min, obtain dispersion liquid；
(3) 0.5-8 parts of binders are added in the dispersion liquid obtained to step (2), 2-60min is dispersed in dispersion machine, obtains lithium
Ion battery applies cloth diaphragm ceramic slurry；
The solvent is the mixing of one or more of water, ethyl alcohol, tetrahydrofuran, N-Methyl pyrrolidone, ethyl acetate；
The inorganic particle is one of aluminium oxide, boehmite or two kinds of mixing；
The fluorine carbon dispersing agent is anion fluorine carbon dispersing agent, cation fluorine carbon dispersing agent, non-ionic fluorocarbon dispersing agent and both sexes
One of fluorine carbon dispersing agent or several mixing；
The thickener be methylpropene sodium sulfonate, acrylamide, N- hydroxyethyl acrylamide, acrylic acid, hydroxypropyl acrylate,
The copolymer of at least two kinds of monomers in maleic anhydride and n-vinyl pyrrolidone；
The binder is styrene-butadiene emulsion, polyacrylic binder, oleic series resinoid bond, polyvinyl alcohol and propylene
The mixing of one or more of nitrile multiple copolymer.
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| CN201810966053.7A CN109037564A (en) | 2018-08-23 | 2018-08-23 | A kind of coating of lithium-ion battery diaphragm ceramic slurry and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112290161A (en) * | 2020-09-28 | 2021-01-29 | 佛山市金辉高科光电材料股份有限公司 | Ultralow-moisture ceramic-coated lithium ion battery diaphragm and preparation method thereof |
| CN112670662A (en) * | 2020-12-02 | 2021-04-16 | 乐凯胶片股份有限公司 | Method for coating ceramic particles with polymer and application thereof |
| CN113261153A (en) * | 2019-01-04 | 2021-08-13 | 三星Sdi株式会社 | Separator for lithium secondary battery and lithium secondary battery including the same |
| CN113659286A (en) * | 2021-08-10 | 2021-11-16 | 惠州亿纬锂能股份有限公司 | Boehmite slurry, boehmite coated diaphragm, preparation method of boehmite coated diaphragm and lithium ion battery |
| CN115117559A (en) * | 2022-06-30 | 2022-09-27 | 中材锂膜有限公司 | Coating slurry of battery diaphragm, preparation method of coating slurry, battery diaphragm and lithium ion battery |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113261153A (en) * | 2019-01-04 | 2021-08-13 | 三星Sdi株式会社 | Separator for lithium secondary battery and lithium secondary battery including the same |
| CN113261153B (en) * | 2019-01-04 | 2023-10-20 | 三星Sdi株式会社 | Separator for lithium secondary battery and lithium secondary battery comprising same |
| CN112290161A (en) * | 2020-09-28 | 2021-01-29 | 佛山市金辉高科光电材料股份有限公司 | Ultralow-moisture ceramic-coated lithium ion battery diaphragm and preparation method thereof |
| CN112290161B (en) * | 2020-09-28 | 2023-08-04 | 佛山市金辉高科光电材料股份有限公司 | Ultralow-moisture ceramic-coated lithium ion battery diaphragm and preparation method thereof |
| CN112670662A (en) * | 2020-12-02 | 2021-04-16 | 乐凯胶片股份有限公司 | Method for coating ceramic particles with polymer and application thereof |
| CN112670662B (en) * | 2020-12-02 | 2022-12-23 | 乐凯胶片股份有限公司 | Method for coating ceramic particles with polymer and application thereof |
| CN113659286A (en) * | 2021-08-10 | 2021-11-16 | 惠州亿纬锂能股份有限公司 | Boehmite slurry, boehmite coated diaphragm, preparation method of boehmite coated diaphragm and lithium ion battery |
| CN113659286B (en) * | 2021-08-10 | 2023-06-30 | 惠州亿纬锂能股份有限公司 | Boehmite slurry, boehmite coated separator, preparation method of boehmite coated separator and lithium ion battery |
| CN115117559A (en) * | 2022-06-30 | 2022-09-27 | 中材锂膜有限公司 | Coating slurry of battery diaphragm, preparation method of coating slurry, battery diaphragm and lithium ion battery |
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