CN110379983A - A kind of method of modifying of ceramic diaphragm and its application in lithium battery, coating processes - Google Patents
A kind of method of modifying of ceramic diaphragm and its application in lithium battery, coating processes Download PDFInfo
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- CN110379983A CN110379983A CN201910672006.6A CN201910672006A CN110379983A CN 110379983 A CN110379983 A CN 110379983A CN 201910672006 A CN201910672006 A CN 201910672006A CN 110379983 A CN110379983 A CN 110379983A
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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
- H01M50/411—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
- 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
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Abstract
The present invention discloses a kind of method of modifying of ceramic diaphragm and its application in lithium battery, coating processes, belongs to the technical field of battery.Include: step 101, alumina powder be fitted into zirconia ball grinding jar, after alcohol wet ball grinding 12 hours in tube furnace 80 DEG C dry 2 hours, nitrogen protection atmosphere obtains alumina powder；Alumina powder and ceramic powders are uniformly mixed and are put into ball grinder by step 102, and after deionized water mixing and ball milling being added 2 hours, dry 2 hours in 120 DEG C in tube furnace, it is stand-by to obtain mixed-powder.Invention avoids is added some organic binders in ceramic slurry in the prior art, as polyurethane, adhesive easily cause ceramics to fall situations such as dividing due to the consistency problem of ceramic powders and binder.
Description
Technical field
The invention belongs to the technical fields of battery, method of modifying more particularly to a kind of ceramic diaphragm and its in lithium battery
In application, coating processes.
Background technique
Lithium ion battery is as a kind of energy density height, output voltage height, memory-less effect, cycle performance are excellent, environment
Friendly electrochmical power source system has good economic benefit, social benefit and strategic importance, has been widely used in mobile logical
The every field such as news, digital product, and very likely become the most important power-supply system of energy storage and electric car field.
Diaphragm is essential important component in lithium ion battery, on the one hand be isolated positive and negative electrode pole piece to avoid
Between be in contact short circuit, be on the other hand allow lithium ion freely shuttle during battery charging and discharging to meet electric energy
Storage and release.Lithium battery diaphragm superiority and inferiority is very big on the influence of lithium battery performance, such as the internal resistance of cell, discharge capacity, cycle life
And the quality of battery safety.Under normal circumstances, the thickness of diaphragm is thinner, porosity is higher, and the internal resistance of battery is smaller, high
Multiplying power discharging property is also better.
With the popularization of ternary battery and the promotion demand of ferric phosphate lithium cell energy density, ceramic diaphragm replaces common
Diaphragm is the inevitable choice of the following high-energy and high-power big battery and the composite demand in market and science and technology, grasps ceramics
Slurry technology of preparing, diaphragm paint-on technique for promoting the whole competitiveness of independent research lithium ion battery, to improving industrial chain
Structure plays an important role.
Ceramic diaphragm currently on the market is Alumina build-up on basement membrane, to enhance basement membrane high temperature resistance but
It is that ceramic diaphragm generally uses nanoscale aluminum oxide particle, specific surface area easily absorbs water in 4-8m2/g；While in order to
The adhesion effect for enhancing ceramic material and basement membrane, can generally be added some organic binders, such as polyurethane, glue in ceramic slurry
Glutinous agent is easily caused ceramics to fall situations such as dividing, is seriously affected lithium battery due to the consistency problem of ceramic powders and binder
Electrical property and security performance.
Summary of the invention
The present invention is to solve technical problem present in above-mentioned background technique, provide a kind of adhesion effect it is good, to lithium battery
Performance has a kind of method of modifying of ceramic diaphragm of positive effect and its application in lithium battery, coating processes.
The present invention is achieved through the following technical solutions: a kind of method of modifying of ceramic diaphragm, specifically includes the following steps:
Alumina powder is fitted into zirconia ball grinding jar by step 101, after alcohol wet ball grinding 12 hours 80 DEG C in tube furnace
Drying 2 hours, nitrogen protection atmosphere obtains alumina powder；
Alumina powder and ceramic powders are uniformly mixed and are put into ball grinder, and deionized water mixing and ball milling is added by step 102
After 2 hours, is dried 2 hours in 120 DEG C in tube furnace, it is stand-by to obtain mixed-powder；
Mixed-powder is placed in dispersing agent by step 103, and ultrasonic disperse 1 hour, and dispersing agent is enabled to be completely dissolved in mixing
It in powder, is subsequently placed in tube furnace, nitrogen protection atmosphere, room temperature is added in ball grinder ball milling 3 hours after standing 2 hours, obtains
Slurry one；
Step 104 adds binder into slurry one, then proceedes to ball milling 9 hours, obtains ceramic diaphragm slurry.
In a further embodiment, the deionized water in the step 102 and alumina powder and ceramic powders according to
Weight ratio is 2:1, so that the volume of deionized water and alumina powder and ceramic powders is the half of ball grinder.
By using above-mentioned technical proposal, convenient in ball grinder alumina powder and ceramic powders can crush it is thorough
And there are mobile spaces to be enough uniformly mixed alumina powder and ceramic powders.
In a further embodiment, the revolving speed of the ball mill is 360r/min.
In a further embodiment, the ceramic powders include boehmite, fluorophologopite, fluor-apatite, zirconium oxide, oxygen
Change one or more of in magnesium, mullite, cordierite and aluminium titanates.
In a further embodiment, the dispersing agent is polyacrylic acid；The binder includes poly (propylene carbonate), gathers
At least one of ethylene carbonate, polybutylene succinate, poly- 7-oxa-bicyclo[4.1.0 carbonic ester, polystyrene carbonic ester.
A kind of ceramic diaphragm is prepared by method of modifying as described in claim 1.
A kind of coating processes of ceramic diaphragm, comprising: diaphragm, positive plate, negative electrode tab and electrolyte, the diaphragm is by right
It is required that preparation method described in any one of 1 to 5 prepare, the coating processes specifically includes the following steps:
Positive plate and negative electrode tab are carried out sandblasting pretreatment, and pass through acetone ultrasonic cleaning by step 701；
The ceramic diaphragm slurry being prepared is placed in sonic oscillation in ultrasonic wave by step 702, for eliminating ceramic diaphragm slurry
Interior bubble avoids bubble from leading to multimembrane defect.
Positive plate and negative electrode tab are placed on fixture by step 703, are placed in baking oven and are carried out to positive plate and negative electrode tab
Preheating, preheating temperature are 280 DEG C；By on positive plate and negative electrode tab bubble and moisture eliminate.
Step 704 starts to coat in room temperature by coating machine, coating with a thickness of 0.8-6 μm；
Step 705, the drying after the completion of film.
In a further embodiment, the drying includes: cold stage and hot stage；
The cold stage: with the heating rate of 1 DEG C/min from room temperature to 80 DEG C；In drying stage, heating rate is not
Can be fast, the phenomenon that causing film to crack or peel off is prevented, therefore will heat up rate control in 1 DEG C/min.
The hot stage: it is warming up to 120 DEG C from 80 DEG C with the heating rate of 2 DEG C/min, and is kept for 2 hours；By moisture
It is dry thorough.Then with the heating rate of 2 DEG C/min, 700 DEG C are warming up to from 120 DEG C, after being kept for 1 hour, at this time aluminium oxide with
Dispersing agent, binder generate linear contraction between each other, and intensity adhered to one another increases.Cooled to room temperature prevents extremely cold make
At film cracking or peel off.
Beneficial effects of the present invention: during the present invention modifies ceramic diaphragm, first by dispersing agent and mixed powder
The last subsequent ball milling of ultrasonic mixing, adds binder, and such order of addition is then in order to avoid dispersing agent and binder are mixing
It closes and is mutually adsorbed in powder, avoid and some organic binders are added in ceramic slurry in the prior art, such as polyurethane, gluing
Agent easily causes ceramics to fall situations such as dividing due to the consistency problem of ceramic powders and binder.
Detailed description of the invention
Fig. 1 be embodiment 1 to embodiment 3 ceramic diaphragm contact angle figure.
Fig. 2 is the mechanical performance comparison diagram of embodiment 2, embodiment 5 to embodiment 6.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to and limits this hair
Bright protection scope.Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention
It is commercially available or can be prepared by existing method by market.
Through applicants have found that: diaphragm is coated on the positive/negative plate of common lithium battery, which had both been avoided that just
Generation short circuit between negative electrode tab, but can allow for lithium ion during battery charging and discharging free pair of shuttle to meet electricity
The storage and release of energy, but the coating of diaphragm can bring following problems: diaphragm is to need to add during preparation first
Binder and dispersing agent, but since there are consistency problems between dispersing agent and binder, attract each other, cause ceramics every
Film is fallen；Secondly, because the main component of ceramic diaphragm is aluminium oxide, cementation very little between alumina particle, although
Binder is added, but after high temperature sintering, still can reduce the intensity of ceramic diaphragm.Applicant is by adjusting dispersion thus
The addition manner of agent and binder is sintered environment to solve the above problems.
A kind of method of modifying of ceramic diaphragm, specifically includes the following steps:
Alumina powder is fitted into zirconia ball grinding jar by step 101, after alcohol wet ball grinding 12 hours 80 DEG C in tube furnace
Drying 2 hours, nitrogen protection atmosphere obtains alumina powder；
Alumina powder and ceramic powders are uniformly mixed and are put into ball grinder, and deionized water mixing and ball milling is added by step 102
After 2 hours, is dried 2 hours in 120 DEG C in tube furnace, it is stand-by to obtain mixed-powder；
Mixed-powder is placed in dispersing agent by step 103, and ultrasonic disperse 1 hour, and dispersing agent is enabled to be completely dissolved in mixing
It in powder, is subsequently placed in tube furnace, nitrogen protection atmosphere, room temperature is added in ball grinder ball milling 3 hours after standing 2 hours, obtains
Slurry one；
Step 104 adds binder into slurry one, then proceedes to ball milling 9 hours, obtains ceramic diaphragm slurry.
In a further embodiment, the deionized water in the step 102 and alumina powder and ceramic powders according to
Weight ratio is 2:1, so that the volume of deionized water and alumina powder and ceramic powders is the half of ball grinder.
By using above-mentioned technical proposal, convenient in ball grinder alumina powder and ceramic powders can crush it is thorough
And there are mobile spaces to be enough uniformly mixed alumina powder and ceramic powders.
In a further embodiment, the revolving speed of the ball mill is 360r/min.
In a further embodiment, the ceramic powders include boehmite, fluorophologopite, fluor-apatite, zirconium oxide, oxygen
Change one or more of in magnesium, mullite, cordierite and aluminium titanates.
In a further embodiment, the dispersing agent is polyacrylic acid；The binder includes poly (propylene carbonate), gathers
At least one of ethylene carbonate, polybutylene succinate, poly- 7-oxa-bicyclo[4.1.0 carbonic ester, polystyrene carbonic ester.
A kind of ceramic diaphragm is prepared by method of modifying as described in claim 1.
A kind of coating processes of ceramic diaphragm, comprising: diaphragm, positive plate, negative electrode tab and electrolyte, the diaphragm is by right
It is required that preparation method described in any one of 1 to 5 prepare, the coating processes specifically includes the following steps:
Positive plate and negative electrode tab are carried out sandblasting pretreatment, and pass through acetone ultrasonic cleaning by step 701；
The ceramic diaphragm slurry being prepared is placed in sonic oscillation in ultrasonic wave by step 702, for eliminating ceramic diaphragm slurry
Interior bubble avoids bubble from leading to multimembrane defect.
Positive plate and negative electrode tab are placed on fixture by step 703, are placed in baking oven and are carried out to positive plate and negative electrode tab
Preheating, preheating temperature are 280 DEG C；By on positive plate and negative electrode tab bubble and moisture eliminate.
Step 704 starts to coat in room temperature by coating machine, coating with a thickness of 0.8-6 μm；
Step 705, the drying after the completion of film.
In a further embodiment, the drying includes: cold stage and hot stage；
The cold stage: with the heating rate of 1 DEG C/min from room temperature to 80 DEG C；In drying stage, heating rate is not
Can be fast, the phenomenon that causing film to crack or peel off is prevented, therefore will heat up rate control in 1 DEG C/min.
The hot stage: it is warming up to 120 DEG C from 80 DEG C with the heating rate of 2 DEG C/min, and is kept for 2 hours；By moisture
It is dry thorough.Then with the heating rate of 2 DEG C/min, 700 DEG C are warming up to from 120 DEG C, after being kept for 1 hour, at this time aluminium oxide with
Dispersing agent, binder generate linear contraction between each other, and intensity adhered to one another increases.Cooled to room temperature prevents extremely cold make
At film cracking or peel off.
Embodiment 1
A kind of method of modifying of ceramic diaphragm, specifically includes the following steps:
10 parts of alumina powders are fitted into zirconia ball grinding jar by step 101, after alcohol wet ball grinding 12 hours in tube furnace
80 DEG C dry 2 hours, and nitrogen protection atmosphere obtains alumina powder；
Alumina powder and 8 parts of ceramic powders are uniformly mixed and are put into ball grinder by step 102, and 36 parts of deionized waters are added
After mixing and ball milling 2 hours, is dried 2 hours in 120 DEG C in tube furnace, it is stand-by to obtain mixed-powder；
Mixed-powder is placed in 1.5 parts of polyacrylic acid by step 103, and ultrasonic disperse 1 hour, is placed in tube furnace, nitrogen
Protective atmosphere, room temperature are added in ball grinder ball milling 3 hours after standing 2 hours, obtain slurry one；
Step 104 adds 1 part of binder into slurry one, then proceedes to ball milling 9 hours, obtains ceramic diaphragm slurry.It is described viscous
Tying agent includes poly (propylene carbonate), polyethylencarbonate, polybutylene succinate, poly- 7-oxa-bicyclo[4.1.0 carbonic ester, polystyrene
At least one of carbonic ester.The ceramic powders include boehmite, fluorophologopite, fluor-apatite, zirconium oxide, magnesia, not
Come one or more of in stone, cordierite and aluminium titanates.
The revolving speed of above-mentioned ball mill is 360r/min.
In spraying, intensity can reduce ceramic diaphragm after sintering in order to prevent, and the coating processes specifically include following step
It is rapid:
Positive plate and negative electrode tab are carried out sandblasting pretreatment, and pass through acetone ultrasonic cleaning by step 701；
The ceramic diaphragm slurry being prepared is placed in sonic oscillation in ultrasonic wave by step 702；
Positive plate and negative electrode tab are placed on fixture by step 703, are placed in baking oven and are carried out in advance to positive plate and negative electrode tab
Heat, preheating temperature are 280 DEG C；
Step 704 starts to coat in room temperature by coating machine, coating with a thickness of 0.8-6 μm；
Step 705, the drying after the completion of film.
Wherein, the drying includes: cold stage and hot stage；The cold stage: with the heating rate of 1 DEG C/min
From room temperature to 80 DEG C；The hot stage: 120 DEG C are warming up to from 80 DEG C with the heating rate of 2 DEG C/min, and holding 2 is small
When；Then with the heating rate of 2 DEG C/min, 700 DEG C are warming up to from 120 DEG C, after being kept for 1 hour, cooled to room temperature.
Embodiment 2
Embodiment 2 and the difference of embodiment are: 15 parts of alumina powders are fitted into zirconia ball grinding jar by step 101, through alcohol
After wet ball grinding 12 hours in tube furnace 80 DEG C dry 2 hours, nitrogen protection atmosphere obtains alumina powder；
Alumina powder and 5 parts of ceramic powders are uniformly mixed and are put into ball grinder by step 102, and 40 parts of deionized waters are added
After mixing and ball milling 2 hours, is dried 2 hours in 120 DEG C in tube furnace, it is stand-by to obtain mixed-powder；
Mixed-powder is placed in 1 part of polyacrylic acid by step 103, and ultrasonic disperse 1 hour, is placed in tube furnace, and nitrogen is protected
Atmosphere is protected, room temperature is added in ball grinder ball milling 3 hours after standing 2 hours, obtains slurry one；
Step 104 adds 0.8 part of binder into slurry one, then proceedes to ball milling 9 hours, obtains ceramic diaphragm slurry.Other
Step is same as Example 1.
Embodiment 3
Embodiment 3 the difference from embodiment 1 is that: 20 parts of alumina powders are fitted into zirconia ball grinding jar by step 101, through wine
Smart wet ball grinding 80 DEG C drying 2 hours in tube furnace after 12 hours, nitrogen protection atmosphere obtains alumina powder；
Alumina powder and 2 parts of ceramic powders are uniformly mixed and are put into ball grinder by step 102, and 44 parts of deionized waters are added
After mixing and ball milling 2 hours, is dried 2 hours in 120 DEG C in tube furnace, it is stand-by to obtain mixed-powder.
Mixed-powder is placed in 1.2 parts of polyacrylic acid by step 103, and ultrasonic disperse 1 hour, is placed in tube furnace,
Nitrogen protection atmosphere, room temperature are added in ball grinder ball milling 3 hours after standing 2 hours, obtain slurry one；
Step 104 adds 0.6 part of binder into slurry one, then proceedes to ball milling 9 hours, obtains ceramic diaphragm slurry.Other
Step is same as Example 1.
Other steps are same as Example 1.
The performance of ceramic diaphragm is influenced in order to study the addition manner of dispersing agent and binder, does embodiment 4.
Embodiment 4
With embodiment 2 the difference is that: mixed-powder is placed in 1 part of polyacrylic acid and 0.8 part of binder by step 103
In, and ultrasonic disperse 1 hour, it is placed in tube furnace, nitrogen protection atmosphere, ball milling 9 in ball grinder is added after standing 2 hours in room temperature
Hour, obtain ceramic diaphragm slurry.Other steps are same as Example 1.
Influence of the environment being sintered when in order to study spraying process to the intensity of ceramic diaphragm, does embodiment 5 and embodiment
6。
Embodiment 5
With embodiment 2 the difference is that: it is step 705, dry after the completion of the film.Wherein, the drying include: with 5 DEG C/
The heating rate of min is from room temperature to 120 DEG C, after being kept for 3 hours, cooled to room temperature.Other steps and 2 phase of embodiment
Together.
Embodiment 6
With embodiment 2 the difference is that: where the drying includes: cold stage and hot stage；The low temperature rank
Section: with the heating rate of 1 DEG C/min from room temperature to 80 DEG C；The hot stage: with the heating rate of 2 DEG C/min from 80 DEG C
120 DEG C are warming up to, and is kept for 2 hours；Then with the heating rate of 2 DEG C/min, it is warming up to 700 DEG C from 120 DEG C, is kept for 1 hour
Afterwards, cooling rapidly.
Influence for the ratio between studying alumina powder, ceramic powders, binder and dispersing agent to ceramic diaphragm, because
This ceramic diaphragm for preparing embodiment 1 to embodiment 6 carries out contact angle test, ionic conductivity, electrochemical impedance and surveys
Examination and mechanical performance detection.
Firstly, contact angle test be for measuring mutually soak between liquid and the surface of solids characteristic index, it is right
The the contact angle of water the low just to illustrate that hydrophily is stronger, and hydrophily shows that more by force imbibition rate is higher.To sample contact angle tester
Detect its hydrophily.Using high purity water to a process for preparing the diaphragms come to carry out contact angle test at 25 DEG C, by high purity water
It is fitted into contact angle tester, drop drop is automatically formed in film surface, on diaphragm sample extremely at a distance of 6 ㎜ of spacing by machine
Few three points measure, and at least totally 6 times, finally remove arithmetic average.
Fig. 1 is the contact angle picture of the ceramic diaphragm of embodiment 1 to embodiment 6, as seen from Figure 1 the proportion in embodiment 2
For optimum proportioning, and by the way that a process for preparing the contact angles come to be respectively less than 65 °, contact angle is decreased below from 115.63 °
65 °, illustrate that a process for preparing the ceramic diaphragms come to have better wetability.
Ionic conductivity: it for the diffusion phenomena of reactive ion in the electric field, respectively prepared by embodiment 1 to embodiment 5
Ceramic diaphragm out is soaked for a period of time in electrolyte, so that diaphragm adsorption electrolyte is reached saturation state, is then sandwiched in two
Between a stainless steel electrode, ac impedance measurement is carried out on the CHI760D electrochemical workstation of occasion magnificent, measures its ionic conductivity,
According to formula:, R is membrane electrical resistance, and S is real contact area, and L is membrane thicknesses.
The results are shown in Table 1 for it.
Table 1 be embodiment 1 to embodiment 5 ceramic diaphragm resistance and ionic conductivity
As shown in Table 1, the resistance for the ceramic diaphragm that the present invention prepares is small and corresponding ionic conductivity is high, and and contact angle
It is corresponding, thus it is visible a process for preparing come ceramic diaphragm have significant improvement really from the point of view of electrical point.
In order to verify this method drying ceramic diaphragm with the intensity that is come out using prior art preparation with the presence or absence of changing
Kind effect, therefore mechanical performance detection is carried out to embodiment 2, embodiment 5 to embodiment 6.
Fig. 2 is the evaluation tensile strength and Young's modulus of embodiment 2, embodiment 5 to embodiment 6, in terms of result, embodiment
The mechanical performance of 2 samples prepared is substantially better than embodiment 5 and embodiment 6.
Illustrate, if rapidly heating is dry or sharply cools down, ceramic diaphragm cracking can all be caused even to peel off, therefore
Heating rate must be controlled when dry, and answers natural cooling in cooling.
In conclusion dispersing agent and the subsequent ball milling of mixed-powder ultrasonic mixing are added binder, such addition is suitable
Sequence is then in order to avoid dispersing agent and binder mutually adsorb in mixed-powder.
And after coating using heating up stage by stage drying, and heating rate control 1-2 DEG C/min, Hu Zhengyao be for
It prevents heating rate fast, the phenomenon that causing film to crack or peel off, and cooled to room temperature occur, also for anti-
Film cracking caused by only extremely cold peels off.
Simultaneously during heating up at a slow speed, aluminium oxide and dispersing agent, binder generate linear contraction between each other, mutually
Adhesion strength increases, and mechanical performance increases.
It is provided for the embodiments of the invention technical solution above to be described in detail, specific case used herein
The principle and embodiment of the embodiment of the present invention are expounded, the explanation of above embodiments is only applicable to help to understand this
The principle of inventive embodiments；At the same time, for those skilled in the art, according to an embodiment of the present invention, in specific embodiment party
There will be changes in formula and application range, in conclusion the contents of this specification are not to be construed as limiting the invention.
Claims (8)
1. a kind of method of modifying of ceramic diaphragm, which is characterized in that specifically includes the following steps:
Alumina powder is fitted into zirconia ball grinding jar by step 101, after alcohol wet ball grinding 12 hours 80 DEG C in tube furnace
Drying 2 hours, nitrogen protection atmosphere obtains alumina powder；
Alumina powder and ceramic powders are uniformly mixed and are put into ball grinder, and deionized water mixing and ball milling is added by step 102
After 2 hours, is dried 2 hours in 120 DEG C in tube furnace, it is stand-by to obtain mixed-powder；
Mixed-powder is placed in dispersing agent by step 103, and ultrasonic disperse 1 hour, is placed in tube furnace, nitrogen protection atmosphere,
Room temperature is added in ball grinder ball milling 3 hours after standing 2 hours, obtains slurry one；
Step 104 adds binder into slurry one, then proceedes to ball milling 9 hours, obtains ceramic diaphragm slurry.
2. a kind of method of modifying of ceramic diaphragm according to claim 1, which is characterized in that gone in the step 102
Ionized water is 2:1 according to weight ratio with alumina powder and ceramic powders, so that deionized water and alumina powder and ceramic powder
The volume at end is the half of ball grinder.
3. a kind of method of modifying of ceramic diaphragm according to claim 1, which is characterized in that the revolving speed of the ball mill is
360r/min。
4. a kind of method of modifying of ceramic diaphragm according to claim 1, which is characterized in that the ceramic powders include vigorous
It is one or more of in nurse stone, fluorophologopite, fluor-apatite, zirconium oxide, magnesia, mullite, cordierite and aluminium titanates.
5. a kind of method of modifying of ceramic diaphragm according to claim 1, which is characterized in that the dispersing agent is polypropylene
Acid；The binder include poly (propylene carbonate), polyethylencarbonate, polybutylene succinate, poly- 7-oxa-bicyclo[4.1.0 carbonic ester,
At least one of polystyrene carbonic ester.
6. a kind of ceramic diaphragm is prepared by method of modifying as described in claim 1.
7. a kind of coating processes of ceramic diaphragm, comprising: diaphragm, positive plate, negative electrode tab and electrolyte, the diaphragm are wanted by right
Preparation method described in asking any one of 1 to 5 preparation, which is characterized in that the coating processes specifically includes the following steps:
Positive plate and negative electrode tab are carried out sandblasting pretreatment, and pass through acetone ultrasonic cleaning by step 701；
The ceramic diaphragm slurry being prepared is placed in sonic oscillation in ultrasonic wave by step 702；
Positive plate and negative electrode tab are placed on fixture by step 703, are placed in baking oven and are carried out in advance to positive plate and negative electrode tab
Heat, preheating temperature are 280 DEG C；
Step 704 starts to coat in room temperature by coating machine, coating with a thickness of 0.8-6 μm；
Step 705, the drying after the completion of film.
8. a kind of coating processes of ceramic diaphragm according to claim 7, which is characterized in that the drying includes: low temperature
Stage and hot stage；
The cold stage: with the heating rate of 1 DEG C/min from room temperature to 80 DEG C；
The hot stage: it is warming up to 120 DEG C from 80 DEG C with the heating rate of 2 DEG C/min, and is kept for 2 hours；Then with 2 DEG C/
The heating rate of min is warming up to 700 DEG C from 120 DEG C, after being kept for 1 hour, cooled to room temperature.
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| CN104126240A (en) * | 2011-12-09 | 2014-10-29 | 公立大学法人首都大学东京 | Lithium secondary battery separator and method of manufacturing same |
| CN106328869A (en) * | 2015-06-30 | 2017-01-11 | 比亚迪股份有限公司 | Ceramic separator for lithium ion battery and lithium ion battery |
| WO2018213484A1 (en) * | 2017-05-16 | 2018-11-22 | Cornell University | Hybrid separators and the manufacture thereof |
| CN109524601A (en) * | 2018-10-16 | 2019-03-26 | 上海恩捷新材料科技有限公司 | A kind of diaphragm of power lithium ion battery and preparation method thereof |
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