CN109449354A - Ceramic slurry, Ceramic Composite diaphragm and lithium ion battery - Google Patents
Ceramic slurry, Ceramic Composite diaphragm and lithium ion battery Download PDFInfo
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- CN109449354A CN109449354A CN201811249684.3A CN201811249684A CN109449354A CN 109449354 A CN109449354 A CN 109449354A CN 201811249684 A CN201811249684 A CN 201811249684A CN 109449354 A CN109449354 A CN 109449354A
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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
- H01M50/44—Fibrous material
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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
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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
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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
- 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
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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
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Abstract
The present invention relates to lithium ion battery separator preparation technical field, a kind of ceramic slurry, Ceramic Composite diaphragm and lithium ion battery are disclosed.The slurry includes deionized water, ceramic particle, thickener, binder, dispersing agent and wetting agent, and the dispersing agent is the amphipathy macromolecule compound with comb-type structure.Ceramic Composite diaphragm thermal stability is good as made from the slurry, puncture resistance is good, imbibition ability is strong, and when being used for lithium ion battery, ceramic coating is not easily to fall off in the electrolytic solution, can increase battery cycle life, improves battery core consistency and battery security.
Description
Technical field
The present invention relates to lithium ion battery separator preparation technical fields, more specifically, be related to a kind of aqueous ceramic slurry,
The composite diaphragm prepared by the slurry and the lithium ion battery comprising the composite diaphragm.
Background technique
Lithium ion battery has high-energy-density, long circulation life, the characteristic of memory-less effect and safe and reliable and energy fast
The advantages that fast charge and discharge, becomes the research hotspot of novel power supply technology in recent years.The composition of lithium ion battery includes positive, negative
Pole, diaphragm and electrolyte, diaphragm play vital work as performance of the barrier between positive and negative anodes to lithium ion battery
With performance directly influences the capacity and circulation of battery, an important factor for especially influencing battery safety, in diaphragm
It is the effective ways for improving diaphragm safety that surface, which carries out coating,.
In order to improve the heat resistance of diaphragm, ceramic particle, still, ceramic particle are usually added in diaphragm coating slurry
Dispersion effect is not ideal enough, there are part agglomeration, leads to that Stability of Slurry is poor, easily very fast sedimentation layering, to storage condition
It is more demanding, and can further influence subsequent coating processes, lead to that Ceramic Composite membrane surface is coarse, is easy picking, thickness not
The problems such as equal, so that the security performance to lithium ion battery brings hidden danger.
Summary of the invention
Disperse uneven problem in diaphragm coating slurry for above-mentioned ceramic particle, the present invention provides one kind containing dispersion
The ceramic slurry of agent, the dispersing agent are the amphipathy macromolecule compound with comb-type structure, pass through dispersing agent and ceramics
The interaction of grain is not necessarily to pre-dispersed and ball milling, so that it may reach the finely dispersed effect of ceramic particle.As made from the slurry
Ceramic Composite diaphragm thermal stability is good, puncture resistance is good, imbibition ability is strong, and be used for lithium ion battery when, ceramic coating
It is not easily to fall off in the electrolytic solution, battery cycle life can be increased, improve battery core consistency and battery security.
In order to achieve the above objectives, The technical solution adopted by the invention is as follows:
On the one hand, the present invention provides a kind of ceramic slurry, and the slurry includes deionized water, ceramic particle, thickener, glues
Agent, dispersing agent and wetting agent are tied, the dispersing agent is the amphipathy macromolecule compound with comb-type structure.
Preferably, the slurry includes the component of following mass percent:
Preferably, the dispersing agent is the combination of one or both of Tersperse2500, Tersperse2700.
Preferably, the ceramic particle is Al2O3Particle, partial size are 0.1~1 μm.
Preferably, the thickener is methylcellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl fibre
Tie up one of plain sodium or more than one combination.
Preferably, the binder is SBR emulsion, polyvinyl alcohol, ethylene vinyl acetate, hydroxymethyl cellulose
One of sodium, polyvinylpyrrolidone or more than one combination.
Preferably, one of the wetting agent octadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide or
The combination of the two.
Another aspect of the present invention provides a kind of preparation method of ceramic slurry, which is characterized in that the method includes such as
Lower step:
Thickener, dispersing agent and wetting agent are added in deionized water and stir to get solution；
Ceramic particle is added in above-mentioned solution, is dispersed with stirring to obtain ceramics dispersion liquid；
Binder is added in above-mentioned ceramics dispersion liquid, is dispersed with stirring, then defoams, filter, obtain ceramic slurry.
Another aspect of the present invention additionally provides a kind of Ceramic Composite diaphragm, and the composite diaphragm includes basement membrane and is coated on institute
State epilamellar ceramic coating, the ceramic coating by the way that above-mentioned ceramic slurry is coated on the basement membrane one or both sides,
It is dried and is formed.
Another aspect of the present invention also provides a kind of lithium ion battery, the lithium ion battery include above-mentioned Ceramic Composite every
Film.
Beneficial effects of the present invention:
(1) present invention is used as dispersing agent using the amphipathy macromolecule compound with comb-type structure, by dispersing agent and
The interaction of ceramic particle is not necessarily to pre-dispersed and ball milling, so that it may reach the finely dispersed effect of ceramic particle, obtained slurry
Material can be stored for a long time without settling.
(2) Ceramic Composite diaphragm provided by the invention is using PE diaphragm or PP diaphragm as basement membrane, upper and lower surface coated ceramic
Layer forms three layers of symmetrical structure, and ceramic particle is uniformly distributed in basement membrane upper and lower surface, and coating stripping intensity is high, and caking property is good not
Picking, and the permeability of diaphragm is not influenced.
(3) Ceramic Composite diaphragm provided by the invention, ceramic coating is compared with the Li dendrite that can both keep out growth for basement membrane
Puncture, improve the puncture resistance of diaphragm, and the thermal stability of diaphragm can be significantly improved, reduce percent thermal shrinkage, 170
Under DEG C test condition, shrinking percentage minimum 2%.
(4) Ceramic Composite diaphragm provided by the invention reduces membrane surface due to preparing using aqueous ceramic slurry
Power, improves the electrolyte absorbability of diaphragm, and when being used for lithium ion battery, coating is not easy ceramic coating in the electrolytic solution
It falls off, battery cycle life can be increased, improve battery core consistency and battery security.
Detailed description of the invention
Fig. 1 shows the Ceramic Composite diaphragm SEM figure of the preparation of the embodiment of the present invention 5；
Fig. 2 shows the Ceramic Composite diaphragm SEM figures of comparative example 1 of the present invention preparation；
Fig. 3 shows the schematic diagram of the amphipathy macromolecule compound with comb-type structure.
Specific embodiment
The present invention disperses uneven problem for existing ceramic particle in diaphragm coating slurry, provide it is a kind of containing point
The ceramic slurry of powder, the dispersing agent are the amphipathy macromolecule compound with comb-type structure, pass through dispersing agent and ceramics
The interaction of particle is not necessarily to pre-dispersed and ball milling, so that it may reach the finely dispersed effect of ceramic particle.It is made by the slurry
Ceramic Composite diaphragm thermal stability it is good, puncture resistance is good, imbibition ability is strong, and be used for lithium ion battery when, ceramics apply
Coating is not easily to fall off in the electrolytic solution for layer, can increase battery cycle life, improves battery core consistency and battery security.
The present invention provides a kind of ceramic slurry, and the slurry includes deionized water, ceramic particle, thickener, binder, divides
Powder and wetting agent, the dispersing agent are the amphipathy macromolecule compound with comb-type structure.
According to certain embodiments of the present invention, the slurry includes the component of following mass percent: deionized water 50
~80%；Ceramic particle 20~45%；Thickener 0.4~1%；Binder 3~10%；Dispersing agent 0.4~1%；Wetting agent 0.1
~0.5%.Comprehensive performance by the Ceramic Composite diaphragm of the ceramic slurry preparation under the proportion is more preferable.
According to certain embodiments of the present invention, the ceramic particle is Al2O3Particle, partial size are 0.1~1 μm.By this
The Al of particle size2O3The stability for the slurry that particle preparation obtains is more preferable.
In certain embodiments of the present invention, the Al2O3The partial size of particle is 0.5 μm.
Ceramic slurry can be improved in membrane surface wettability in wetting agent, and ceramic slurry is promoted to sprawl in membrane surface
It opens.According to certain embodiments of the present invention, the wetting agent is alkylammonium salt, alkylnaphthalene sulfonate, the work of type siloxane surface
One of property agent or more than one combination.In some embodiments of the present invention, optimizing alkyl ammonium salt is as wetting agent,
Such as octadecyltrimethylammonium chloride (1831) or Cetyltrimethylammonium bromide (CTAB), ceramic slurry can be significantly improved
Expect the wetting effect in membrane surface.
Dispersing agent can effectively improve the dispersion effect of ceramic particle in the slurry, and wetting agent can be improved in system
Degree of scatter, further improve ceramic slurry membrane surface wetting effect.In some embodiments of the present invention, excellent
It is selected as the amphipathy macromolecule compound with comb-type structure, shown in the following attached drawing 3 of structure.
In some embodiments of the present invention, the dispersing agent is one in Tersperse2500, Tersperse2700
The combination of kind or both.
Tersperse 2500 is that by one there is lipophilic skeleton long-chain and hydrophilic anion low molecule to be grafted
The macromolecular grafted copolymer of polypropylene acids with comb-type structure being copolymerized into.This unique chemical structure makes
Tersperse 2500 plays its uniqueness for being totally different from conventional dispersant point in the solid-liquid two-phase system of ceramic particle
Dissipate effect, it may be assumed that the space obstacle that lipophilic skeleton long-chain forms the abundant cladding and hydrophily comb-type structure of ceramic particle
Performance can make scattered ceramic particle stable suspersion in water, will not occur to reunite in a long time and settle.
Tersperse 2700 is that have the skeleton long-chain with strong-hydrophobicity to be grafted altogether with hydrophilic anion low molecule
Combinate form at the polycarboxylate polymeric graft copolymerization object with comb-type structure feature.It is hydrophobic when applied to water dispersible granular
Property skeleton long-chain can form abundant cladding to ceramic particle, and the charge of a large amount of hydrophily low molecule interdigitated electrode structure structures and its institute's band
Effective charge layer repelling effect can be formed, to effectively prevent intergranular reunion and sedimentation, obtains ceramic slurry steady
Fixed reliable suspendability.
In some embodiments of the invention, the dosage of the dispersing agent be ceramic particle quality 0.4~1%, example
Such as: 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc..
Thickener can be the viscosity for adjusting ceramic slurry with main function, be allowed to viscosity and be relatively suitble to coating, while can be with
Reduce the defect of coating surface.According to certain embodiments of the present invention, the thickener is cellulose family, such as Methyl cellulose
One of element, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethylcellulose or more than one combination.At this
In some embodiments of invention, preferably carboxymethyl cellulose sodium (CMC).
In certain embodiments of the present invention, any suitable bonding known in the art can be used in the binder
Agent, such as SBR emulsion (SBR), polyvinyl alcohol, ethylene vinyl acetate, sodium cellulose glycolate, polyvinylpyrrolidone
One of or more than one combination.The combination of polymer paste and membrane surface or ceramic coating surface can be improved in binder
Power, to improve the stability of membrane configuration.
The present invention also provides the preparation methods of the ceramic slurry, include the following steps:
Thickener, dispersing agent and wetting agent are added in deionized water and stir to get solution；
Ceramic particle is added in above-mentioned solution, is dispersed with stirring to obtain ceramics dispersion liquid；
Binder is added in above-mentioned ceramics dispersion liquid, is dispersed with stirring, then defoams, filter, obtain ceramic slurry.
According to certain embodiments of the present invention, the preparation method of the ceramic slurry, including the following steps: first will thickening
Agent, dispersing agent and wetting agent are added in deionized water, with the stirring of 300~600r/min revolving speed in zigzag stirring dispersion machine
0.5h obtains solution；By Al2O3Particle is added in the solution, and is first stirred 3h with 3000~4000r/min revolving speed, is made pottery
Porcelain dispersion liquid；Revolving speed is adjusted to 1500~2000r/min, binder is added, 1h is stirred, revolving speed is finally down to 100~200r/
Min defoaming, filtering obtain ceramic slurry.
In above-mentioned ceramic slurry preparation process, it is firstly added dispersing agent and wetting agent is carried out pre-dispersed, while thickening is added
Agent and the generation that bubble can be greatly decreased with the stirring of lower revolving speed；Al is added2O3Powerful shearing is generated with the stirring of high revolving speed afterwards
The bulky grain of aggregation can be quickly dispersed as smaller particle by power, reinforce dispersion effect；Bonding is added after ceramic particle is scattered
Agent only needs to be mixed uniformly, therefore can suitably reduce revolving speed；Finally the defoaming stage need to can only be incited somebody to action with very low revolving speed
Bubble inside ceramic slurry is suspended into liquid level or more and is filtered removal.
Another aspect of the present invention additionally provides a kind of Ceramic Composite diaphragm, and institute is compound to be stated diaphragm and include basement membrane and be coated on institute
State epilamellar ceramic coating, the ceramic coating by the way that above-mentioned ceramic slurry is coated on the basement membrane one or both sides,
It is dried and is formed.The ceramic coating is conducive to improve the thermal stability of diaphragm.
The basement membrane is polyolefin basement membrane, and preferably polyethylene (PE) basement membrane, polypropylene (PP) basement membrane or PE's and PP is compound
Film.
In certain embodiments of the present invention, the basement membrane with a thickness of 10-20 μm, the ceramic coating with a thickness of
2-5 μm, the diaphragm of preparation should not be too thick, and diaphragm is too thick to be easy to be unfavorable for battery fast charging and discharging, simultaneously so that resistance is too big
Also the winding times of diaphragm can be made to reduce, increase the volume of battery, charge/discharge capacity is caused to decline.
In some embodiments of the present invention, any suitable coating method known in the art can be used, such as make
The ceramic slurry of acquisition is coated on basement membrane with any coating method such as dip-coating, brushing, blade coating or dimple version painting
Then one or both sides are dried using any suitable drying equipment in this field and drying condition, such as are placed in 50-90
DEG C vacuum oven in dry 0.5-2h, Ceramic Composite diaphragm can be obtained.
Above-mentioned preparation method haves no need to change existing device for coating, easily promotes.And use water as preparing polymer paste institute
The solvent needed, production process is environmentally friendly, highly-safe, and production cost is low.
Another aspect of the present invention additionally provides a kind of lithium ion battery, the lithium ion battery include the Ceramic Composite every
Film.Composite diaphragm thermal stability prepared by the present invention is good, puncture resistance is good, imbibition ability is strong, and is used for lithium ion battery
When, coating is not easily to fall off in the electrolytic solution for ceramic coating, can increase battery cycle life, improves battery core consistency and battery peace
Quan Xing.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing and specific implementation
Example, the present invention will be described in further detail.
Embodiment 1:
100g deionized water is added in stainless steel agitator tank, zigzag stirring dispersion machine revolving speed is opened to 500r/min,
0.4g thickener CMC, 0.1g dispersing agent Tersperse2500 and 0.1g wetting agent 1831 is weighed respectively be added in agitator tank stir
Mix dissolution 0.5h；Add 25g Al2O3Particle (partial size is 0.5 μm), and blender is adjusted to 3000r/min high-speed stirred point
3h is dissipated, then revolving speed is adjusted to be added 1g binder SBR stirring 1h after 2000r/min to stir evenly, is finally down to revolving speed
100r/min stirs at low speed the bubble in 1h elimination slurry, then the aqueous ceramic slurry (partial size prepared with filter-cloth filtering
Be 0.6 μm) storage it is spare.
Using dimple type automatic coating machine, above-mentioned aqueous ceramic slurry is uniformly coated on PE membrane surface, PE diaphragm
The speed of service be 10.0m/min, heated-air drying temperature is 60 DEG C, and preparing single side thickness of ceramic coating is 2.0 ± 0.5 μm
Ceramic Composite diaphragm.It is painted with the coating and drying for carrying out same operation after one side to the another side of PE diaphragm again, prepares lithium ion
Battery double-surface ceramics composite diaphragm.
Embodiment 2:
100g deionized water is added in stainless steel agitator tank, zigzag stirring dispersion machine revolving speed is opened to 500r/min,
0.5g thickener CMC, 0.2g dispersing agent Tersperse2500 and 0.2g wetting agent 1831 is weighed respectively be added in agitator tank stir
Mix dissolution 0.5h；Add 35g Al2O3Particle (partial size is 0.5 μm), and blender is adjusted to 3000r/min high-speed stirred point
3h is dissipated, then revolving speed is adjusted to be added 2g binder SBR stirring 1h after 2000r/min to stir evenly, is finally down to revolving speed
100r/min stirs at low speed the bubble in 1h elimination slurry, then the aqueous ceramic slurry (partial size prepared with filter-cloth filtering
Be 0.8 μm) storage it is spare.
Using dimple type automatic coating machine, above-mentioned aqueous ceramic slurry is uniformly coated on PE membrane surface, basement membrane fortune
Scanning frequency degree is 8.0m/min, and heated-air drying temperature is 60 DEG C, prepares the ceramics that single side thickness of ceramic coating is 3.0 ± 0.5 μm
Composite diaphragm.It is painted with the coating and drying for carrying out same operation after one side to the another side of PE diaphragm again, prepares single side ceramics
Coating layer thickness is 3.0 ± 0.5 μm of lithium ion battery double-surface ceramics composite diaphragms.
Embodiment 3:
100g deionized water is added in stainless steel agitator tank, zigzag stirring dispersion machine revolving speed is opened to 500r/min,
0.6g thickener CMC, 0.3g dispersing agent Tersperse2500 and 0.3g wetting agent 1831 is weighed respectively be added in agitator tank stir
Mix dissolution 0.5h；Add 45g Al2O3Particle (partial size is 0.5 μm), and blender is adjusted to 3000r/min high-speed stirred point
3h is dissipated, then revolving speed is adjusted to be added 3g binder SBR stirring 1h after 2000r/min to stir evenly, is finally down to revolving speed
100r/min stirs at low speed the bubble in 1h elimination slurry, then the aqueous ceramic slurry (partial size prepared with filter-cloth filtering
Be 0.8 μm) storage it is spare.
Using dimple type automatic coating machine, above-mentioned aqueous ceramic slurry is uniformly coated on PE membrane surface, PE diaphragm
The speed of service be 6.0m/min, heated-air drying temperature is 60 DEG C, and preparing single side thickness of ceramic coating is 4.0 ± 0.5 μm
Ceramic Composite diaphragm.Be painted with after one side and to carry out the coating and drying of same operation to the another side of PE diaphragm again, prepare lithium from
Sub- battery double-surface ceramics composite diaphragm.
Embodiment 4:
100g deionized water is added in stainless steel agitator tank, zigzag stirring dispersion machine revolving speed is opened to 500r/min,
0.7g thickener CMC, 0.4g dispersing agent Tersperse2500 and 0.4g wetting agent 1831 is weighed respectively be added in agitator tank stir
Mix dissolution 0.5h；Add 55g Al2O3Particle (partial size is 0.5 μm), and blender is adjusted to 3000r/min high-speed stirred point
3h is dissipated, then revolving speed is adjusted to be added 4g binder SBR stirring 1h after 2000r/min to stir evenly, is finally down to revolving speed
100r/min stirs at low speed the bubble in 1h elimination slurry, then the aqueous ceramic slurry (partial size prepared with filter-cloth filtering
Be 0.9 μm) storage it is spare.
Using dimple type automatic coating machine, above-mentioned aqueous ceramic slurry is uniformly coated on PE membrane surface, PE diaphragm
The speed of service be 6.0m/min, heated-air drying temperature is 70 DEG C, and preparing single side thickness of ceramic coating is 4.0 ± 0.5 μm
Ceramic Composite diaphragm.Be painted with the coating and drying for carrying out same operation after one side to the another side of PE diaphragm again, prepare lithium from
Sub- battery double-surface ceramics composite diaphragm.
Embodiment 5:
100g deionized water is added in stainless steel agitator tank, zigzag stirring dispersion machine revolving speed is opened to 500r/min,
0.8g thickener CMC, 0.5g dispersing agent Tersperse2500 and 0.5g wetting agent 1831 is weighed respectively be added in agitator tank stir
Mix dissolution 0.5h；Add 65g Al2O3Particle (partial size is 0.5 μm), and blender is adjusted to 3000r/min high-speed stirred point
3h is dissipated, then revolving speed is adjusted to be added 5g binder SBR stirring 1h after 2000r/min to stir evenly, is finally down to revolving speed
100r/min stirs at low speed the bubble in 1h elimination slurry, then the aqueous ceramic slurry (partial size prepared with filter-cloth filtering
Be 1.0 μm) storage it is spare.
Using dimple type automatic coating machine, above-mentioned aqueous ceramic slurry is uniformly coated on PE membrane surface, PE diaphragm
The speed of service be 4.0m/min, heated-air drying temperature is 70 DEG C, and preparing single side thickness of ceramic coating is 5.0 ± 0.5 μm
Ceramic Composite diaphragm.Be painted with the coating and drying for carrying out same operation after one side to the another side of PE diaphragm again, prepare lithium from
Sub- battery double-surface ceramics composite diaphragm.
Embodiment 6:
100g deionized water is added in stainless steel agitator tank, zigzag stirring dispersion machine revolving speed is opened to 500r/min,
0.8g thickener CMC, 0.5g dispersing agent Tersperse2700 and 0.5g wetting agent 1831 is weighed respectively be added in agitator tank stir
Mix dissolution 0.5h；Add 80g Al2O3Particle (partial size is 0.5 μm), and blender is adjusted to 3000r/min high-speed stirred point
3h is dissipated, then revolving speed is adjusted to be added 8g binder SBR stirring 1h after 2000r/min to stir evenly, is finally down to revolving speed
100r/min stirs at low speed the bubble in 1h elimination slurry, then the aqueous ceramic slurry (partial size prepared with filter-cloth filtering
Be 1.0 μm) storage it is spare.
Using dimple type automatic coating machine, above-mentioned aqueous ceramic slurry is uniformly coated on PE membrane surface, PE diaphragm
The speed of service be 5.0m/min, heated-air drying temperature is 80 DEG C, and preparing single side thickness of ceramic coating is 5.0 ± 0.5 μm
Ceramic Composite diaphragm.Be painted with after one side and to carry out the coating and drying of same operation to the another side of PE diaphragm again, prepare lithium from
Sub- battery double-surface ceramics composite diaphragm.
Comparative example 1
100g deionized water is added in stainless steel agitator tank, zigzag stirring dispersion machine revolving speed is opened to 500r/min,
0.8g thickener CMC, 0.5g dispersant acrylate copolymer ammonium salt is weighed respectively and 0.5g wetting agent 1831 is added to stirring
Stirring and dissolving 0.5h in tank；Add 65g Al2O3Particle (partial size is 0.5 μm), and blender is adjusted to 3000r/min high speed
It is dispersed with stirring 3h, then revolving speed is adjusted to be added 5g binder SBR stirring 1h after 2000r/min to stir evenly, finally by revolving speed
It is down to 100r/min and stirs at low speed 1h and eliminate bubble in slurry, then the aqueous ceramic slurry prepared with filter-cloth filtering
(partial size is 1.2 μm) storage is spare (the very fast sedimentation in for 24 hours of the ceramic slurry of preparation is not suitable for storing for a long time).
Using dimple type automatic coating machine, above-mentioned aqueous ceramic slurry is uniformly coated on PE membrane surface, PE diaphragm
The speed of service be 4.0m/min, heated-air drying temperature is 70 DEG C, and preparing single side thickness of ceramic coating is 5.0 ± 0.5 μm
Ceramic Composite diaphragm.Be painted with after one side and to carry out the coating and drying of same operation to the another side of PE diaphragm again, prepare lithium from
Sub- battery double-surface ceramics composite diaphragm.
Performance test and evaluation
The obtained Ceramic Composite diaphragm of embodiment 1-6 and comparative example 1 and commercially available PE diaphragm are subjected to gas permeability, coating
Peel strength, punctured resistance, percent thermal shrinkage test, the specific test method is as follows, and test result is shown in Table 1.
A. gas permeability
Using the permeability of 4110 type permeating degree tester of Gurley test composite diaphragm.
B. coating stripping intensity and punctured resistance
The coating stripping intensity and punctured resistance of Ceramic Composite diaphragm are tested using universal tensile testing machine, are used
Standard be " test of GB/T1040.32-2006 plastic tensile performance ".
C. percent thermal shrinkage
The membrane sample that composite diaphragm is cut out to 100 × 100mm measures its longitudinal length (MDBefore) and lateral length
(TDBefore), it is put into vacuum drying oven under determined temperature and toasts 1h, take out diaphragm sample, be cooled to room temperature, measure its longitudinal direction again
Length (MDAfterwards) and lateral length (TDAfterwards), percent thermal shrinkage δ is calculated as follows:
δMD=(MDBefore- MDAfterwards)/MDBefore× 100%
δTD=(TDBefore- TDAfterwards)/TDBefore× 100%
Table 1: the performance of commercially available PE diaphragm and the Ceramic Composite diaphragm of different formulations preparation
As it can be seen from table 1 the heat of the Ceramic Composite diaphragm of preparation of the embodiment of the present invention is steady compared with commercially available PE diaphragm
It is qualitative to significantly improve, when the solid content of ceramics is increased to 35% or more, obtained Ceramic Composite diaphragm at 170 DEG C not yet
It can melt, and punctured resistance also significantly improves.Compared with the diaphragm of comparative example 1, the Ceramic Composite of preparation of the embodiment of the present invention
Diaphragm, coating stripping intensity and punctured resistance are higher, this is because using general dispersing agent, ceramic particle in comparative example 1
Dispersion effect it is poor, correspondingly, in obtained Ceramic Composite diaphragm, ceramic particle disperses non-uniform edge in PE basement membrane two sides
Therefore.
It will be seen from figure 1 that the amphipathy macromolecule compound provided by the present invention with comb-type structure is as dispersion
The Ceramic Composite diaphragm of the slurry preparation of agent, Al2O3Even particle distribution, soilless sticking phenomenon, shows Al2O3Particle is in ceramic slurry
It is uniformly dispersed in material.And the diaphragm for using acrylate copolymer ammonium salt to prepare as the slurry of dispersing agent, Al2O3Particle exists
Part is reunited, as shown in Fig. 2, showing Al2O3Particle dispersion effect in ceramic slurry is bad.
The foregoing is merely better embodiments of the invention, are not intended to limit the invention, all of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within spirit and principle.
Claims (10)
1. a kind of ceramic slurry, the slurry includes deionized water, ceramic particle, thickener, binder, dispersing agent and wetting
Agent, which is characterized in that the dispersing agent is the amphipathy macromolecule compound with comb-type structure.
2. ceramic slurry according to claim 1, which is characterized in that the slurry includes the group of following mass percent
Point:
3. ceramic slurry according to claim 1, which is characterized in that the dispersing agent be Tersperse2500,
The combination of one or both of Tersperse2700.
4. ceramic slurry according to claim 1, which is characterized in that the ceramic particle is Al2O3Particle, partial size are
0.1~1 μm.
5. ceramic slurry according to claim 1, which is characterized in that the thickener is methylcellulose, ethoxy fibre
Tie up one of element, hydroxypropyl methyl cellulose, sodium carboxymethylcellulose or more than one combination.
6. ceramic slurry according to claim 1, which is characterized in that the binder is SBR emulsion, polyethylene
One of alcohol, ethylene vinyl acetate, sodium cellulose glycolate, polyvinylpyrrolidone or more than one combination.
7. ceramic slurry according to claim 1, which is characterized in that the wetting agent is octadecyl trimethyl chlorination
The combination of one or both of ammonium, Cetyltrimethylammonium bromide.
8. a kind of preparation method of ceramic slurry described in any one of claims 1 to 7, which is characterized in that the method packet
Include following steps:
Thickener, dispersing agent and wetting agent are added in deionized water and stir to get solution；
Ceramic particle is added in above-mentioned solution, is dispersed with stirring to obtain ceramics dispersion liquid；
Binder is added in above-mentioned ceramics dispersion liquid, is dispersed with stirring, then defoams, filter, obtain ceramic slurry.
9. a kind of Ceramic Composite diaphragm, which is characterized in that the composite diaphragm include basement membrane and be coated on the epilamellar pottery
Porcelain coating, the ceramic coating is by being coated on the basement membrane side for ceramic slurry described in any one of claims 1 to 7
Or two sides, it is dried and is formed.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes Ceramic Composite described in claim 9
Diaphragm.
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| CN201811249684.3A CN109449354A (en) | 2018-10-25 | 2018-10-25 | Ceramic slurry, Ceramic Composite diaphragm and lithium ion battery |
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| CN201811249684.3A CN109449354A (en) | 2018-10-25 | 2018-10-25 | Ceramic slurry, Ceramic Composite diaphragm and lithium ion battery |
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| CN110600660A (en) * | 2019-08-16 | 2019-12-20 | 东莞赣锋电子有限公司 | Preparation method of surface modified alumina ceramic coating diaphragm |
| CN111081947A (en) * | 2019-12-25 | 2020-04-28 | 武汉中兴创新材料技术有限公司 | Preparation method of gel polymer coating diaphragm and diaphragm |
| CN111072317A (en) * | 2019-12-04 | 2020-04-28 | 乐凯胶片股份有限公司 | Ceramic slurry, ceramic diaphragm and lithium ion battery |
| CN111116963A (en) * | 2019-12-27 | 2020-05-08 | 深圳中兴新材技术股份有限公司 | Preparation method of ceramic coating diaphragm, diaphragm and ceramic coating slurry |
| CN111180644A (en) * | 2020-01-06 | 2020-05-19 | 镝普材料(深圳)有限公司 | Lithium ion battery diaphragm with ultrathin coating layer |
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| CN110600660A (en) * | 2019-08-16 | 2019-12-20 | 东莞赣锋电子有限公司 | Preparation method of surface modified alumina ceramic coating diaphragm |
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| CN112038550A (en) * | 2020-08-26 | 2020-12-04 | 东莞市溢兴新材料科技有限公司 | Lithium ion battery ceramic diaphragm and preparation method thereof |
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| CN113629353A (en) * | 2021-08-05 | 2021-11-09 | 中国科学院近代物理研究所 | PET (polyethylene terephthalate) basic weight ion track composite diaphragm for lithium ion battery and preparation method of PET basic weight ion track composite diaphragm |
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Application publication date: 20190308 |