CN106935769B - A kind of preparation method of the lithium ion battery separator for covering inorganic particulate based on electrostatic self-assembled - Google Patents
A kind of preparation method of the lithium ion battery separator for covering inorganic particulate based on electrostatic self-assembled Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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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- 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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Abstract
The preparation method of the present invention relates to a kind of lithium ion battery separator for covering inorganic particulate based on electrostatic self-assembled, belongs to lithium ion battery material technical field.Polymeric solution is prepared using organic and inorganic self assembly principle, it include the silica sol by negative electrical charge in polymeric solution, one layer of positive polyion is coated in membrane surface again, when polymeric solution is coated on membrane surface, electrostatic self-assembled occurs for positive polyion and silica sol, silicon oxide particle is securely fastened to membrane surface, pass through the auto polymerization process of surface aggregate solution again, further close crosslinking will be formed between silicon oxide particle, realize the assembling process of the inorganic particulate of membrane surface.The present invention provides a kind of novel methods for preparing lithium ion battery separator, have coupled electrostatic self-assembled reaction simultaneously in colloidal sol polymerization process, realize high-bond, the advantages of particle is uniformly dispersed, adhesive-free uses.
Description
Technical field
The preparation method of the present invention relates to a kind of lithium ion battery separator for covering inorganic particulate based on electrostatic self-assembled belongs to
In lithium ion battery material technical field.
Background technique
Battery diaphragm refers to the membrane for polymer among lithium ion cell positive and cathode, is lithium ion battery most critical
Part, have a direct impact to battery security and cost.Its main function has: positive and negative electrode is isolated and makes the electronics in battery
It cannot pass freely through;The ion in electrolyte solution is allowed to pass freely through in positive and negative interpolar.Its lithium ion conduction ability is directly related to
The effect of the overall performance of lithium ion battery, isolation positive and negative anodes makes battery in the case of overcharging or temperature rise can
The raising for limiting electric current, prevents battery short circuit from causing explosion, with microporous self-closing protection, rises to battery user and equipment
To the effect of safeguard protection.The superiority and inferiority of membrane properties determines the interfacial structure and internal resistance of battery, and then influences the capacity of battery, follows
The key characteristics such as ring performance, charging and discharging currents density, it is seen then that the diaphragm haveing excellent performance has the comprehensive performance for improving battery important
Effect.
Existing particles stick not high phenomenon when the lithium ion battery separator surface adhesion ceramic particle of routine, mainly
Be due to this it is physical adherence, is easy to cause intensity low)；In addition, due to directly mixing particle with adhesive, nanoparticle
There are agglomerations, are easy to cause the dispersion of ceramic particle uneven.
Summary of the invention
The purpose of the present invention is: existing particle glues when solving conventional lithium ion battery separator surface adhesion ceramic particle
Connecing property is not high, particle dispersion is uneven, needs the problem big using a large amount of bonding agents, consumption of organic solvent.
The technological means of use is: preparing polymeric solution using organic and inorganic self assembly principle, includes in polymeric solution
Coat one layer of positive polyion by the silica sol of negative electrical charge, then in membrane surface, when by polymeric solution be coated on every
When film surface, electrostatic self-assembled occurs for positive polyion and silica sol, and silicon oxide particle is securely fastened to membrane surface,
Pass through the auto polymerization process of surface aggregate solution again, further will form close crosslinking between silicon oxide particle, realize diaphragm
The assembling process of the inorganic particulate on surface.
Technical solution is:
A kind of preparation method of the lithium ion battery separator for covering inorganic particulate based on electrostatic self-assembled, including walk as follows
It is rapid:
Step 1, the preparation of silica sol: preparing the ethanol solution of the ethyl orthosilicate containing 15~20wt%, then
The mixed solution being made of distilled water, dehydrated alcohol and weak aqua ammonia is slowly added dropwise, heats up and keeps the temperature after being added dropwise, natural cooling
After be aged, obtain silica solution；
Step 2, the preparation of polymeric solution: the silane coupling agent of addition silica solution weight 0.3~1%, 0.5 in silica solution
~0.8% anionic surfactant, 3~5% hydrochloric acid solution, 2~4% crosslinking agent, 0.1~0.5% initiator, mixing
Uniformly, polymeric solution is obtained；
The positive charge of membrane surface: step 3 basement membrane is soaked in the solution containing positive polyion, is taken out, punching
It washes, obtains the basement membrane of positive surface charge；
Step 4 polymerize the coating of colloidal sol: the basement membrane that step 3 is obtained is impregnated in the polymeric solution that step 2 obtains, then
It is slowly promoted, makes surface filming, and the electrostatic interaction of polymeric solution and membrane surface occurs；
Step 5, the polymerization reaction on surface: the basement membrane heating that step 4 is obtained carries out polymerization reaction, generates surface and is covered with nothing
The battery diaphragm of machine particle.
In the step 1, the volume ratio of ethanol solution and mixed solution is 3~5:1, is distilled in mixed solution
The volume ratio range of water, dehydrated alcohol and weak aqua ammonia is 1:6~9:0.05~0.1, the concentration of the weak aqua ammonia is 10~
15wt%。
In the step 1, heating, which refers to, rises to 50~65 DEG C, and soaking time is 1~2h；Digestion time is 10~50h.
In the step 2, silane coupling agent is double-(γ-triethoxy silicon substrate propyl) tetrasulfide (Si69), double
(triethoxy silicon substrate propyl) disulphide (Si75), gamma-mercaptopropyltriethoxysilane (KH-580), three second of γ-aminopropyl
One or more of oxysilane (KH-550), γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH-560).
In the step 2, anionic surfactant is selected from the sodium alkyl sulfate of C10~20, the alkyl benzene sulphonate of C10~20
The mixing of one or more of the alkyl sulfosuccinic disodium of sodium, sodium methylcocoyltaurate or C10~20.
In the step 2, the concentration of hydrochloric acid solution is 5~8wt%.
In the step 2, the crosslinking agent is ethylenediamine, butanediamine, carbodiimides, trihydroxy methyl melamine
Amine, dimethylol urea or aziridine.
In the step 2, the initiator is selected from ammonium sulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, peroxidating
One of di-t-butyl, benzoyl peroxide and suitable azo-initiator or a variety of compoundings.
In the step 3, positive polyion is diallyl dimethyl ammoniumchloride, and positive polyion is in the solution
Concentration is 5~12wt%, and basement membrane is non-woven fabrics, and the non-woven fabrics is selected from polyester non-woven fabric, polypropylene non-woven fabric or polyethylene
Non-woven fabrics.
In the step 4, the rate of promotion is 1~3cm/s.
In the step 5, heating, which refers to, is warming up to 100~115 DEG C.
The present invention also provides the lithium ion battery separators that above-mentioned preparation method directly obtains.
And above-mentioned lithium ion battery separator is improving the application in lithium ion battery cycle charge-discharge capacity retention ratio.
The effect of above step operation: it is prepared in silica solution in step 1, NH3-H2Under O catalytic condition, ethyl orthosilicate
Hydrolysis is the necleophilic reaction of OH-, therefore hydrolysis and polycondensation process are all relatively rapidly, and colloidal particle is easily collected as being relatively large in diameter
Grain, and the quantity of electric charge that surface has is more, is suitable for subsequent electrostatic self-assembled process；In step 2, the work of silane coupling agent
Silica solution can be made surface-hydrophobicized with one side, make to be less likely to occur to reunite during electrostatic self-assembled, it on the other hand can be with
Promote polymerization reaction, keeps inorganic particulate higher in surface binding force；On the one hand the effect of anionic surfactant can promote
Component is uniformly dispersed, and on the other hand, after stirring, the negative electrical charge of silica solution can be made to improve, more conducively electrostatic is from group
The effect of the progress of dress, crosslinking agent and initiator is the raw material of polymerization process；In step 3, positive polyion is carried on
The surface of basement membrane can generate electrostatic interaction with silica solution, particle is carried on basement membrane；In step 4, it on the one hand can make to gather
The surface that solution is overlying on basement membrane is closed, on the other hand, silica solution and positive polyion can be made to generate electrostatic self-assembled, improved inorganic
The combination of particle and basement membrane；It is the polymerization reaction carried out, its effect is further uniformly to cover silicon oxide particle in step 5
The surface for covering and being fixed on basement membrane generates synergistic effect with electrostatic self-assembled.
Beneficial effect
The present invention provides a kind of novel methods for preparing lithium ion battery separator, the coupling simultaneously in colloidal sol polymerization process
Closed electrostatic self-assembled reaction, realize high-bond, particle is uniformly dispersed, adhesive-free use the advantages of.
Detailed description of the invention
Fig. 1 is the surface electron microscope of the diaphragm that is prepared in embodiment 3 after ultrasound destruction；
Fig. 2 is the surface electron microscope of the diaphragm that is prepared in reference examples 1 after ultrasound destruction.
Specific embodiment
Embodiment 1
The preparation of silica sol: step 1 prepares the ethanol solution of the ethyl orthosilicate containing 15wt%, then slowly
It is added dropwise the mixed solution that is made of distilled water, dehydrated alcohol and weak aqua ammonia, the volume ratio of ethanol solution and mixed solution is
3:1, the volume ratio range of distilled water, dehydrated alcohol and weak aqua ammonia is 1:6:0.05 in mixed solution, the weak aqua ammonia it is dense
Degree is 10wt%, and 50 DEG C are warming up to after being added dropwise and keeps the temperature 1h, ageing 10h is carried out after natural cooling, obtains silica solution；
Step 2, the preparation of polymeric solution: in silica solution be added silica solution weight 0.3% silane coupling agent KH580,
0.5% cetyl benzenesulfonic acid sodium, 3% hydrochloric acid solution (5wt%), 2% crosslinking agent ethylenediamine, 0.1% initiator sulfuric acid
Ammonium is uniformly mixed, obtains polymeric solution；
The positive charge of membrane surface: step 3 basement membrane polypropylene non-woven fabric is soaked in containing 5wt% polydiene propyl two
It in the solution of ammonio methacrylate, takes out, rinses, obtain the basement membrane of positive surface charge；
Step 4 polymerize the coating of colloidal sol: the basement membrane that step 3 is obtained is impregnated in the polymeric solution that step 2 obtains, then
It is slowly promoted with 1cm/s rate, makes surface filming, and the electrostatic interaction of polymeric solution and membrane surface occurs；
Step 5, the polymerization reaction on surface: the basement membrane that step 4 is obtained is warming up to 100 DEG C of progress polymerization reactions, generates table
Face is covered with the battery diaphragm of inorganic particulate.
Embodiment 2
The preparation of silica sol: step 1 prepares the ethanol solution of the ethyl orthosilicate containing 20wt%, then slowly
It is added dropwise the mixed solution that is made of distilled water, dehydrated alcohol and weak aqua ammonia, the volume ratio of ethanol solution and mixed solution is
5:1, the volume ratio range of distilled water, dehydrated alcohol and weak aqua ammonia is 1:9:0.1 in mixed solution, the concentration of the weak aqua ammonia
It is 15wt%, 65 DEG C is warming up to after being added dropwise and keeps the temperature 2h, ageing 50h is carried out after natural cooling, obtains silica solution；
Step 2, the preparation of polymeric solution: the silane coupling agent KH560 of addition silica solution weight 1%, 0.8% in silica solution
Cetyl benzenesulfonic acid sodium, 5% hydrochloric acid solution (8wt%), 4% crosslinking agent butanediamine, 0.5% initiator potassium persulfate,
It is uniformly mixed, obtains polymeric solution；
The positive charge of membrane surface: step 3 basement membrane polypropylene non-woven fabric is soaked in containing 12wt% polydiene propyl
It in the solution of alkyl dimethyl ammonium chloride, takes out, rinses, obtain the basement membrane of positive surface charge；
Step 4 polymerize the coating of colloidal sol: the basement membrane that step 3 is obtained is impregnated in the polymeric solution that step 2 obtains, then
It is slowly promoted with 3cm/s rate, makes surface filming, and the electrostatic interaction of polymeric solution and membrane surface occurs；
Step 5, the polymerization reaction on surface: the basement membrane that step 4 is obtained is warming up to 115 DEG C of progress polymerization reactions, generates table
Face is covered with the battery diaphragm of inorganic particulate.
Embodiment 3
The preparation of silica sol: step 1 prepares the ethanol solution of the ethyl orthosilicate containing 18wt%, then slowly
It is added dropwise the mixed solution that is made of distilled water, dehydrated alcohol and weak aqua ammonia, the volume ratio of ethanol solution and mixed solution is
4:1, the volume ratio range of distilled water, dehydrated alcohol and weak aqua ammonia is 1:7:0.08 in mixed solution, the weak aqua ammonia it is dense
Degree is 13wt%, and 55 DEG C are warming up to after being added dropwise and keeps the temperature 2h, ageing 30h is carried out after natural cooling, obtains silica solution；
Step 2, the preparation of polymeric solution: in silica solution be added silica solution weight 0.6% Silane coupling agent KH550,
0.7% cetyl benzenesulfonic acid sodium, 4% hydrochloric acid solution (6wt%), 3% crosslinking agent carbodiimides, 0.2% initiator mistake
Sodium sulphate is uniformly mixed, obtains polymeric solution；
The positive charge of membrane surface: step 3 basement membrane polypropylene non-woven fabric is soaked in containing 7wt% polydiene propyl two
It in the solution of ammonio methacrylate, takes out, rinses, obtain the basement membrane of positive surface charge；
Step 4 polymerize the coating of colloidal sol: the basement membrane that step 3 is obtained is impregnated in the polymeric solution that step 2 obtains, then
It is slowly promoted with 2cm/s rate, makes surface filming, and the electrostatic interaction of polymeric solution and membrane surface occurs；
Step 5, the polymerization reaction on surface: the basement membrane that step 4 is obtained is warming up to 105 DEG C of progress polymerization reactions, generates table
Face is covered with the battery diaphragm of inorganic particulate.
Reference examples 1
Difference with embodiment 3 is: not carrying out the surface coating of the positive polyion of step 3.
The preparation of silica sol: step 1 prepares the ethanol solution of the ethyl orthosilicate containing 18wt%, then slowly
It is added dropwise the mixed solution that is made of distilled water, dehydrated alcohol and weak aqua ammonia, the volume ratio of ethanol solution and mixed solution is
4:1, the volume ratio range of distilled water, dehydrated alcohol and weak aqua ammonia is 1:7:0.08 in mixed solution, the weak aqua ammonia it is dense
Degree is 13wt%, and 55 DEG C are warming up to after being added dropwise and keeps the temperature 2h, ageing 30h is carried out after natural cooling, obtains silica solution；
Step 2, the preparation of polymeric solution: in silica solution be added silica solution weight 0.6% Silane coupling agent KH550,
0.7% cetyl benzenesulfonic acid sodium, 4% hydrochloric acid solution (6wt%), 3% crosslinking agent carbodiimides, 0.2% initiator mistake
Sodium sulphate is uniformly mixed, obtains polymeric solution；
Step 3 polymerize the coating of colloidal sol: basement membrane polypropylene non-woven fabric is impregnated in the polymeric solution that step 2 obtains, then
It is slowly promoted with 2cm/s rate, makes surface filming, and the electrostatic interaction of polymeric solution and membrane surface occurs；
Step 4, the polymerization reaction on surface: the basement membrane that step 4 is obtained is warming up to 105 DEG C of progress polymerization reactions, generates table
Face is covered with the battery diaphragm of inorganic particulate.
Reference examples 2
Difference with embodiment 3 is: silane coupling agent is not added in polymeric solution.
The preparation of silica sol: step 1 prepares the ethanol solution of the ethyl orthosilicate containing 18wt%, then slowly
It is added dropwise the mixed solution that is made of distilled water, dehydrated alcohol and weak aqua ammonia, the volume ratio of ethanol solution and mixed solution is
4:1, the volume ratio range of distilled water, dehydrated alcohol and weak aqua ammonia is 1:7:0.08 in mixed solution, the weak aqua ammonia it is dense
Degree is 13wt%, and 55 DEG C are warming up to after being added dropwise and keeps the temperature 2h, ageing 30h is carried out after natural cooling, obtains silica solution；
Step 2, the preparation of polymeric solution: in silica solution be added silica solution weight 0.7% cetyl benzenesulfonic acid sodium,
4% hydrochloric acid solution (6wt%), 3% crosslinking agent carbodiimides, 0.2% initiator sodium peroxydisulfate, be uniformly mixed, gathered
Close solution；
The positive charge of membrane surface: step 3 basement membrane polypropylene non-woven fabric is soaked in containing 7wt% polydiene propyl two
It in the solution of ammonio methacrylate, takes out, rinses, obtain the basement membrane of positive surface charge；
Step 4 polymerize the coating of colloidal sol: the basement membrane that step 3 is obtained is impregnated in the polymeric solution that step 2 obtains, then
It is slowly promoted with 2cm/s rate, makes surface filming, and the electrostatic interaction of polymeric solution and membrane surface occurs；
Step 5, the polymerization reaction on surface: the basement membrane that step 4 is obtained is warming up to 105 DEG C of progress polymerization reactions, generates table
Face is covered with the battery diaphragm of inorganic particulate.
Reference examples 3
Difference with embodiment 3 is: polymerizeing be added in colloidal sol is cationic surfactant.
The preparation of silica sol: step 1 prepares the ethanol solution of the ethyl orthosilicate containing 18wt%, then slowly
It is added dropwise the mixed solution that is made of distilled water, dehydrated alcohol and weak aqua ammonia, the volume ratio of ethanol solution and mixed solution is
4:1, the volume ratio range of distilled water, dehydrated alcohol and weak aqua ammonia is 1:7:0.08 in mixed solution, the weak aqua ammonia it is dense
Degree is 13wt%, and 55 DEG C are warming up to after being added dropwise and keeps the temperature 2h, ageing 30h is carried out after natural cooling, obtains silica solution；
Step 2, the preparation of polymeric solution: in silica solution be added silica solution weight 0.6% Silane coupling agent KH550,
0.7% trimethyl cetyl ammonium bromide, 4% hydrochloric acid solution (6wt%), 3% crosslinking agent carbodiimides, 0.2% initiation
Agent sodium peroxydisulfate is uniformly mixed, obtains polymeric solution；
The positive charge of membrane surface: step 3 basement membrane polypropylene non-woven fabric is soaked in containing 7wt% polydiene propyl two
It in the solution of ammonio methacrylate, takes out, rinses, obtain the basement membrane of positive surface charge；
Step 4 polymerize the coating of colloidal sol: the basement membrane that step 3 is obtained is impregnated in polymeric solution, then with 2cm/s rate
It is slowly promoted, makes surface filming, and the electrostatic interaction of polymeric solution and membrane surface occurs；
Step 5, the polymerization reaction on surface: the basement membrane that step 4 is obtained is warming up to 105 DEG C of progress polymerization reactions, generates table
Face is covered with the battery diaphragm of inorganic particulate.
The detection of diaphragm physical property
Film thickness is detected according to GB/T6672-2001；
Porosity detection method:
Sampling standard presses GB/T6673-2001 and GB/T6672-2001,
Calculation formula:
ρ1=m/(L×b)
p=(1-ρ1/(d×ρ0))×100
In formula:
ρ1--- the surface density of sample, unit are gram/cm (g/cm2)；
The quality of m --- sample, unit of gram (g)；
The length of L --- sample, unit are centimetre (cm)；
The width of b --- sample, unit are centimetre (cm)；
The porosity of p --- sample, is indicated with %；
The thickness of d --- sample, unit are centimetre (cm)；
The density of ρ 0 --- raw material, unit are gram/cm (g/cm3).
It is detected according to ASTM F316-03 in aperture；
Shrinking percentage is detected according to GB/T12027-2004；
Tensile strength is detected according to GB1040.3-2006；
Being folded without breaking intensity is detected according to ASTM D4833；
Closed pore temperature test method:
Diaphragm is immersed in lithium hexafluorophosphate electrolyte solution, electrolyte is heated, resistance value depending on the temperature, different pushes away
Corresponding closed pore temperature out (maximum value is closed completely).
As a result as follows:
As can be seen from the above table, lithium ion battery separator provided by the invention can be evenly dispersed by inorganic particle and solid
It ties in the surface of basement membrane, while the diaphragm of this method preparation has preferable porosity and thickness.Pass through embodiment 3 and reference examples
1 comparison can be seen that be coated by the surface that positive polyion is added on basement membrane, can be effectively by silicon oxide particle and base
It is formed and is fixed between film, and form stable coated structure by polymerization reaction, improve the being folded without breaking intensity of film；Pass through implementation
Example 3 and reference examples 2 can be seen that can make polymerization reaction more complete by the way that silane coupling agent is added in polymeric solution, improve
The tensile strength of film.
The test of membrane surface coverage strength
Diaphragm is soaked in deionized water, is placed in Vltrasonic device and carries out ultrasonication, supersonic frequency 20kHz, ultrasound
Power 150W, water temperature are room temperature, action time 15min.Diaphragm in embodiment 3 and reference examples 1 Electronic Speculum after ultrasonication is shone
Piece difference is as depicted in figs. 1 and 2, it can be seen from the figure that the surface particles integrality in embodiment 3 is good, and in reference examples 1
Occur falling off.
Cell performance evaluation
Battery preparation: cycle performance and charge-discharge performance in order to measure diaphragm, by diaphragm and cathode graphite, anode
LiCoO2And LiFP6LiFP6 (is dissolved in ethylene carbonate (EC): diethyl carbonate (DEC): dimethyl carbonate by electrolyte
(DMC) solution of 1mol/L is made in volume ratio=1:1:1 mixed liquor), battery is made.
Lithium ion battery separator made from Example 1~3, reference examples 1~3 carries out cycle performance test to it.
Capacity retention ratio: it uses instrument and equipment BS-9300 ability meter with 0.5C rate charge-discharge loop test, uses
Constant-current constant-voltage charging system (CC-CV) and constant-current discharge system, charging/discharging voltage 3.0~4.2V of range, are filled first with 1C constant current
Electricity is then 3.0V with 1C constant-current discharge to final voltage, such as to 4.2V, then to charge to electric current under 4.2V constant pressure less than 20mA
This circulation 500 times, acquires loop-around data.
As a result as follows:
As can be seen from the table, battery diaphragm provided by the invention has preferable performance in being applied to lithium battery, real
Example 3 is applied for reference examples 1, by electrostatic self-assembled, inorganic particle intensity with higher on the diaphragm of generation, warp
After crossing long-run test, it still is able to that battery is made to keep higher easy conservation rate；Embodiment 3 for reference examples 3,
Due to using anionic surfactant addition in polymeric solution, it can also be improved the effect of electrostatic self-assembled, make inorganic
The retentivity of particle is more preferable, is improved the capacity retention ratio of battery operation.
Claims (1)
1. a kind of preparation method of the lithium ion battery separator for covering inorganic particulate based on electrostatic self-assembled, which is characterized in that packet
Include following steps:
The preparation of silica sol: step 1 prepares the ethanol solution of the ethyl orthosilicate containing 15~20wt%, then slowly
The mixed solution being made of distilled water, dehydrated alcohol and weak aqua ammonia is added dropwise, heats up and keeps the temperature after being added dropwise, natural cooling is laggard
Row ageing, obtains silica solution；
Step 2, the preparation of polymeric solution: in silica solution be added silica solution weight 0.3~1% silane coupling agent, 0.5~
0.8% anionic surfactant, 3~5% hydrochloric acid solution, 2~4% crosslinking agent, 0.1~0.5% initiator, mixing is equal
It is even, obtain polymeric solution；
The positive charge of membrane surface: step 3 basement membrane is soaked in the solution containing positive polyion, is taken out, is rinsed, obtain
To the basement membrane of positive surface charge；
Step 4 polymerize the coating of colloidal sol: the basement membrane that step 3 is obtained is impregnated in the polymeric solution that step 2 obtains, then slowly
It is promoted, makes surface filming, and the electrostatic interaction of polymeric solution and membrane surface occurs；
Step 5, the polymerization reaction on surface: the basement membrane heating that step 4 is obtained carries out polymerization reaction, generates surface and is covered with inorganic grain
The battery diaphragm of son；
The volume ratio range of distilled water, dehydrated alcohol and weak aqua ammonia is 1:6~9:0.05~0.1 in mixed solution, and described is dilute
The concentration of ammonium hydroxide is 10~15wt%；
In the step 1, heating, which refers to, rises to 50~65 DEG C, and soaking time is 1~2h；Digestion time is 10~50h；
In the step 2, silane coupling agent is double-(γ-triethoxy silicon substrate propyl) tetrasulfide, bis- (triethoxysilicanes
Base propyl) disulphide, gamma-mercaptopropyltriethoxysilane, gamma-aminopropyl-triethoxy-silane, γ-(2,3- the third oxygen of epoxy)
One or more of propyl trimethoxy silicane；
In the step 2, anionic surfactant be selected from the sodium alkyl sulfate of C10~20, the sodium alkyl benzene sulfonate of C10~20,
The mixing of one or more of sodium methylcocoyltaurate or the alkyl sulfosuccinic disodium of C10~20；Hydrochloric acid solution
Concentration be 5~8wt%；The crosslinking agent is ethylenediamine, butanediamine, carbodiimides, trimethylol melamine, dihydroxy
Methylurea or aziridine；The initiator is selected from ammonium sulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, the tertiary fourth of peroxidating two
One of base, benzoyl peroxide or a variety of compoundings；
In the step 3, positive polyion is diallyl dimethyl ammoniumchloride, the concentration of positive polyion in the solution
It is 5~12wt%, basement membrane is non-woven fabrics, and the non-woven fabrics is selected from polyester non-woven fabric, polypropylene non-woven fabric or polyethylene non-woven
Cloth；
In the step 4, the rate of promotion is 1~3cm/s；
In the step 5, heating, which refers to, is warming up to 100~115 DEG C.
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| CN109232991B (en) * | 2018-08-28 | 2020-09-29 | 武汉轻工大学 | Hydrophobic SiO2Coated halogen-free intumescent flame retardant and preparation method and application thereof |
| CN109585757A (en) * | 2018-10-16 | 2019-04-05 | 上海恩捷新材料科技有限公司 | A kind of lithium ion battery separator slurry and preparation method thereof and lithium ion battery separator |
| CN111834611A (en) * | 2019-04-16 | 2020-10-27 | 南京工业大学 | Preparation method of uniformly dispersed silicon-carbon composite negative electrode material based on magnesiothermic reduction |
| CN111617642B (en) * | 2019-07-01 | 2022-05-06 | 江苏久吾高科技股份有限公司 | Hydrophilic modified hollow fiber membrane and preparation method thereof |
| CN111224047A (en) * | 2019-10-17 | 2020-06-02 | 上海恩捷新材料科技有限公司 | Diaphragm and electrochemical device comprising same |
| CN111092186B (en) * | 2019-12-16 | 2022-07-19 | 天津科技大学 | Method for preparing PE-based lithium ion battery diaphragm based on self-assembly technology and application |
| CN111416088B (en) * | 2020-03-26 | 2021-11-09 | 江苏厚生新能源科技有限公司 | Preparation method of lithium battery ceramic diaphragm |
| CN112201850A (en) * | 2020-10-22 | 2021-01-08 | 江苏厚生新能源科技有限公司 | High-conductivity inorganic solid electrolyte slurry, preparation method thereof, diaphragm and lithium battery |
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| CN104051692A (en) * | 2014-06-09 | 2014-09-17 | 常州大学 | Polyolefin microporous diaphragm for lithium ion battery and preparation method of polyolefin lithium battery diaphragm for lithium ion battery |
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| CN104051692A (en) * | 2014-06-09 | 2014-09-17 | 常州大学 | Polyolefin microporous diaphragm for lithium ion battery and preparation method of polyolefin lithium battery diaphragm for lithium ion battery |
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| "Self-Assembly of PEI/SiO2 on Polyethylene Separators for Li-Ion Batteries with Enhanced Rate Capability";Zhuyi Wang等;《ACS Applied Materials & Interfaces》;20150120;第7卷(第5期);第3314～3322页 * |
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