CN109103395A - Battery separator and preparation method thereof - Google Patents
Battery separator and preparation method thereof Download PDFInfo
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- CN109103395A CN109103395A CN201810967346.7A CN201810967346A CN109103395A CN 109103395 A CN109103395 A CN 109103395A CN 201810967346 A CN201810967346 A CN 201810967346A CN 109103395 A CN109103395 A CN 109103395A
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- baso
- hfp
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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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to battery technology fields more particularly to a kind of battery separator and preparation method thereof.Battery separator in the present invention includes electrostatic spinning basement membrane, and is coated on the PVDF-HFP/BaSO of two sides of electrostatic spinning basement membrane4Composite coating.The preparation method of battery separator, easy to operate in the present invention, scratches PVDF-HFP/BaSO on two sides of electrostatic spinning basement membrane4Composite coating is impregnated after standing in water, then is dried, and obtains battery separator.The battery separator has excellent gas permeability, thermal stability and conductivity, and then battery is made to possess better multiplying power discharging and cycle performance, and battery is long, highly-safe.
Description
Technical field
The present invention relates to battery technology fields, more particularly, to a kind of battery separator and preparation method thereof.
Background technique
Electrostatic spinning is a kind of special fiber fabrication process, and polymer solution or melt carry out injection spinning in strong electrical field
Silk forms one layer of static spinning membrane.Because of the special process of electrostatic spinning, static spinning membrane porosity with higher, but because
Aperture is excessive, cannot directly do diaphragm use, be easy to appear short circuit phenomenon, it usually needs is coated plug-hole on its surface.
In consideration of it, special propose the application.
Summary of the invention
It is an object of the present invention to provide a kind of battery separator, which includes electrostatic spinning basement membrane,
And it is coated on PVDF-HFP (the Poly vinylidenefluoride-hexafluoro of two sides of electrostatic spinning basement membrane
Propylene copolymer, Kynoar-hexafluoropropene)/BaSO4(barium sulfate) composite coating.Battery separator tool
There are preferable gas permeability, thermal stability and conductivity.
It is another object of the present invention to provide a kind of preparation method of battery separator as described above, this method operations
Simply, the battery diaphragm prepared has excellent gas permeability, thermal stability and conductivity, and then possesses better multiplying power discharging
And cycle performance.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of battery separator, the battery separator includes electrostatic spinning basement membrane, and is coated on electrostatic spinning basement membrane
The PVDF-HFP/BaSO of two sides4Composite coating.
Preferably, the electrostatic spinning basement membrane includes aramid fiber electrostatic spinning diaphragm.
Preferably, the PVDF-HFP/BaSO4Composite coating with a thickness of 2-5um.
Preferably, the electrostatic spinning basement membrane with a thickness of 10-25um.
Preferably, the PVDF-HFP/BaSO4Composite coating is mainly prepared by following raw material in parts by weight:
1-8 parts of PVDF-HFP, BaSO41-7 parts and organic solvent 45-60 parts；
Preferably, the PVDF-HFP/BaSO4Composite coating is mainly prepared by following raw material in parts by weight:
2.5-5 parts of PVDF-HFP, BaSO42.5-5 parts and organic solvent 48-55 parts.
Preferably, the organic solvent includes in n,N-Dimethylformamide, glycol ether, cresols and methyl iso-butyl ketone (MIBK)
At least one.
The preparation method of battery separator as described above, comprising the following steps:
PVDF-HFP/BaSO is scratched on two sides of electrostatic spinning basement membrane4Composite coating is soaked in water after standing
Bubble, then be dried, obtain battery separator.
Preferably, the PVDF-HFP/BaSO4The time of repose of composite coating is 50-70s, and soaking time is 25- in water
35min, drying temperature are 30-65 DEG C, drying time 1-4min；
Preferably, the PVDF-HFP/BaSO4The time of repose of composite coating is 55-65s, and soaking time is 28- in water
32min, drying temperature are 50-60 DEG C, drying time 2-3min.
Preferably, the PVDF-HFP/BaSO4The preparation method of the mixed slurry of composite coating, comprising the following steps:
Grind BaSO4, then by BaSO4It is added to progress ultrasonic wave dispersion in organic solvent, adds PVDF-HFP powder simultaneously
Magnetic agitation dispersion is carried out, PVDF-HFP and BaSO are obtained4Mixed slurry.
Preferably, the ultrasonic dispersing time is 0.5-2h, and magnetic agitation jitter time is 2.2-2.7h；
Preferably, the ultrasonic dispersing time is 1-1.5h, and magnetic agitation jitter time is 2.4-2.6h.
Compared with the prior art, the invention has the following beneficial effects:
(1) battery separator in the present invention includes electrostatic spinning basement membrane, and is coated on two sides of electrostatic spinning basement membrane
The PVDF-HFP/BaSO in face4Composite coating.The battery separator is prominent in terms of gas permeability, thermal stability and conductivity, meets
The safe handling demand of battery.
(2) preparation method of the battery separator in the present invention, it is easy to operate, it is scratched on two sides of Electrospun basement membrane
PVDF-HFP/BaSO4Composite coating is impregnated after standing in water, then is dried, and obtains battery separator.The battery with every
Film has excellent gas permeability, thermal stability and conductivity, and then battery is made to possess better multiplying power discharging and cycle performance.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is electrostatic spinning preparation process schematic device of the present invention；
Fig. 2 is the SEM picture of aramid fiber electrostatic spinning diaphragm of the present invention；
Fig. 3 is the SEM picture of the battery separator of the embodiment of the present invention 1；
Fig. 4 is the thermal contraction effect picture of the battery separator of the embodiment of the present invention 3 at different temperatures；
Fig. 5 is following for the battery that the battery of Celgard2325 diaphragm assembling and the diaphragm of embodiment 1 assemble in comparative example 1
Ring the performance test results schematic diagram；
Fig. 6 is times of the battery of the diaphragm assembling of the battery of Celgard2325 diaphragm assembling and embodiment 1 in comparative example 1
Rate discharge performance test result schematic diagram.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to an aspect of the present invention, a kind of battery separator, the battery separator include electrostatic spinning basement membrane, with
And it is coated on the PVDF-HFP/BaSO of two sides of electrostatic spinning basement membrane4Composite coating.
Electrostatic spinning basement membrane has preferable porosity；PVDF-HFP has relatively high relative to other polymers matrix
Ionic conductivity；Blanc fixe quality is fine and smooth, and whiteness is high, and acid and alkali resistance, light, thermally and chemically performance is high.The present invention is in electrostatic
The two sides of spinning basement membrane are coated with PVDF-HFP/BaSO4Composite coating, obtained battery separator have preferable gas permeability, heat
Stability and conductivity meet the safe handling demand of battery.
Preferably, the electrostatic spinning basement membrane includes aramid fiber electrostatic spinning diaphragm.
Aramid fiber material combination electrostatic spinning process makes aramid fiber static spinning membrane itself have higher porosity and good
Thermal contraction performance, safety are more secure.
Preferably, the PVDF-HFP/BaSO4Composite coating with a thickness of 2-5um.
PVDF-HFP/BaSO4The thickness of composite coating it is typical but non-limiting be, for example, 2um, 2.5um, 3um,
3.5um, 4um, 4.5um or 5um.
Preferably, the electrostatic spinning basement membrane with a thickness of 10-25um.
The thickness of electrostatic spinning basement membrane it is typical but non-limiting be, for example, 10um, 11um, 12um, 13um, 14um,
15um, 16um, 17um, 18um, 19um, 20um, 21um, 22um, 23um, 24um or 25um.
Preferably, the PVDF-HFP/BaSO4Composite coating is mainly prepared by following raw material in parts by weight:
1-8 parts of PVDF-HFP, BaSO41-7 parts and organic solvent 45-60 parts；
By using PVDF-HFP/BaSO made from 1-8 parts PVDF-HFP, 1-7 parts BaSO4 and 45-60 parts of organic solvents4
Composite coating has better caking property.
The typical but non-limiting parts by weight of PVDF-HFP are, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5
Part, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts or 8 parts.
BaSO4Parts by weight it is typical but non-limiting be, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4
Part, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts or 7 parts.
The typical but non-limiting parts by weight of organic solvent are, for example, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50
Part, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts or 60 parts.
Preferably, the PVDF-HFP/BaSO4Composite coating is mainly prepared by following raw material in parts by weight:
2.5-5 parts of PVDF-HFP, BaSO42.5-5 parts and organic solvent 48-55 parts.
Pass through further preferred PVDF-HFP, BaSO4With the proportion of organic solvent, obtained PVDF-HFP/BaSO4It is compound
Coating is coated on electrostatic spinning basement membrane, can assign the more excellent air permeability of diaphragm, ionic conductivity and heat resistance.Its
In, heat resistance is as shown in figure 3, battery separator stability obtained in the present invention is preferable.
Preferably, the organic solvent includes in n,N-Dimethylformamide, glycol ether, cresols and methyl iso-butyl ketone (MIBK)
At least one.
The preparation method of battery separator as described above, comprising the following steps:
PVDF-HFP/BaSO is scratched on two sides of electrostatic spinning basement membrane4Composite coating is soaked in water after standing
Bubble, then be dried, obtain battery separator.
The preparation method is easy to operate, and the battery separator as made from this method has excellent gas permeability, thermostabilization
Property and conductivity, and then assign the better multiplying power discharging of battery and cycle performance.
Preferably, the PVDF-HFP/BaSO4The time of repose of composite coating is 50-70s, and soaking time is 25- in water
35min, drying temperature are 30-65 DEG C, drying time 1-4min；
PVDF-HFP/BaSO4The typical but non-limiting for example, 50min, 51min of the time of repose of composite coating,
52min、53min、54min、55min、56min、57min、58min、59min、60min、61min、62min、63min、
64min, 65min, 66min, 67min, 68min, 69min or 70min.
PVDF-HFP/BaSO4Composite coating in water soaking time it is typical but non-limiting be, for example, 25min,
26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min or 35min.
PVDF-HFP/BaSO4Typical but non-limiting composite coating drying temperature is, for example, 30 DEG C, 35 DEG C, 40 DEG C, 45
DEG C, 50 DEG C, 55 DEG C, 60 DEG C or 65 DEG C.
PVDF-HFP/BaSO4Composite coating drying time it is typical but non-limiting be, for example, 1min, 1.5min, 2min,
2.5min, 3min, 3.5min or 4min.
Preferably, the PVDF-HFP/BaSO4The time of repose of composite coating is 55-65s, and soaking time is 28- in water
32min, drying temperature are 50-60 DEG C, drying time 2-3min.
Preferably, the PVDF-HFP/BaSO4The preparation method of the mixed slurry of composite coating, comprising the following steps:
Grind BaSO4, then by BaSO4It is added to progress ultrasonic wave dispersion in organic solvent, adds PVDF-HFP powder simultaneously
Magnetic agitation dispersion is carried out, PVDF-HFP and BaSO are obtained4Mixed slurry.
PVDF-HFP/BaSO in the present invention4The preparation method of the mixed slurry of composite coating is very simple, by by BaSO4Powder
Body, PVDF-HFP powder and organic solvent mixing are dispersed with stirring, and PVDF-HFP/BaSO can be obtained4Mixed slurry.
Wherein, BaSO4Preparation method the following steps are included:
(a) 4-9 parts of BaCl are weighed at room temperature245-55 parts of distilled water are dissolved in, solution A is formed；Weigh 0.04-0.1 parts firmly
Resin acid sodium is dissolved in 35-50 parts of dehydrated alcohols, forms solution B；B is poured into and stirs 12-17min in A, forms solution C；
(b) 3-5 parts of anhydrous Nas are weighed2SO445-55 parts of distilled water are dissolved in, and it is 8.8-9.2 that ammonium hydroxide, which is added dropwise, to adjust pH value,
Form solution D；
(c) under the conditions of magnetic agitation, solution D is slowly dropped in solution C, generates white precipitate；This is sunk with ethyl alcohol
It forms sediment washing 3-5 times, then 60-65 DEG C of vacuum drying 22-25h.
Preferably, the ultrasonic dispersing time is 0.5-2h, and magnetic agitation jitter time is 2.2-2.7h；
Ultrasonic dispersing time it is typical but non-limiting be, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h,
1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h.
Typical but non-limiting magnetic agitation jitter time is, for example, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h or 2.7h.
Preferably, the ultrasonic dispersing time is 1-1.5h, and magnetic agitation jitter time is 2.4-2.6h.
It is preferably carried out in scheme in one kind, the preparation method of battery separator, comprising the following steps:
(a) 4-9 parts of BaCl are weighed at room temperature245-55 parts of distilled water are dissolved in, solution A is formed；Weigh 0.04-0.1 parts firmly
Resin acid sodium is dissolved in 35-50 parts of organic solvents, forms solution B；B is poured into and stirs 12-17min in A, forms solution C；
Weigh 3-5 parts of anhydrous Nas2SO445-55 parts of distilled water are dissolved in, and it is 8.8-9.2, shape that ammonium hydroxide, which is added dropwise, to adjust pH value
At solution D；
Under the conditions of magnetic agitation, solution D is slowly dropped in solution C, generates white precipitate.The precipitating is washed with ethyl alcohol
It washs 3-5 times, then 60-65 DEG C of vacuum drying 22-25h, obtains BaSO4；
(b) obtained 1-8 part BaSO in grinding steps (a)4, then by the BaSO after grinding4Powder is added to 45-60 parts
Ultrasonic wave dispersion is carried out in organic solvent, is added 1-7 parts of PVDF-HFP powders and is carried out magnetic agitation dispersion, obtains PVDF-
HFP and BaSO4Mixed slurry；
(c) at room temperature, use the scraper of 50um by PVDF-HFP and BaSO on clean glass plate4Mixed slurry it is uniform
Be coated in a thickness of 10-25um aramid fiber electrostatic spinning diaphragm two sides, unilateral PVDF-HFP/BaSO4Composite coating with a thickness of
Glass plate is impregnated into 25-35min in deionized water after 2-5um, standing 50-70s.Then in 30-65 DEG C of vacuum oven
It is thoroughly dried, drying time 1-4min obtains battery separator.
Below with reference to specific embodiment, comparative example and attached drawing, the present invention will be further described.
Embodiment 1
A kind of battery separator, including aramid fiber electrostatic spinning basement membrane, and it is coated on two sides of aramid fiber electrostatic spinning basement membrane
The PVDF-HFP/BaSO in face4Composite coating.
The preparation method of the battery separator, comprising the following steps:
(a) 4 parts of BaCl are weighed at room temperature245 parts of distilled water are dissolved in, solution A is formed；It is molten to weigh 0.04 part of odium stearate
Solution forms solution B in 35 parts of dehydrated alcohols；B is poured into and stirs 12min in A, forms solution C；
Weigh 3 parts of anhydrous Nas2SO445 parts of distilled water are dissolved in, and it is 8.8 that ammonium hydroxide, which is added dropwise, to adjust pH value, forms solution D；
Under the conditions of magnetic agitation, solution D is slowly dropped in solution C, generates white precipitate.The precipitating is washed with ethyl alcohol
It washs 3 times, then 60 DEG C of vacuum drying 25h, obtain BaSO4；
(b) 1 part of BaSO in grinding steps (a)4, then by the BaSO after grinding4It is added in 45 parts of glycol ethers and carries out ultrasound
Wavelength-division dissipates, and adds 1 part of PVDF-HFP powder and carries out magnetic agitation dispersion, obtains PVDF-HFP and BaSO4Mixed slurry；
(c) at room temperature, use the scraper of 50um by PVDF-HFP and BaSO on clean glass plate4Mixed slurry it is uniform
The aramid fiber electrostatic spinning diaphragm two sides being coated in a thickness of 10um, One-sided coatings stand glass after 50s with a thickness of 2.5um
Plate impregnates 25min in deionized water.Then it is thoroughly dried in 30 DEG C of vacuum ovens, drying time 4min is obtained
To battery separator.
Embodiment 2
A kind of battery separator, including aramid fiber electrostatic spinning basement membrane, and it is coated on two sides of aramid fiber electrostatic spinning basement membrane
The PVDF-HFP/BaSO in face4Composite coating.
The preparation method of the battery separator, comprising the following steps:
(a) 9 parts of BaCl are weighed at room temperature255 parts of distilled water are dissolved in, solution A is formed；Weigh 0.1 part of odium stearate dissolution
In 50 parts of organic solvents, solution B is formed；B is poured into and stirs 17min in A, forms solution C；
Weigh 5 parts of anhydrous Nas2SO455 parts of distilled water are dissolved in, and it is 9.2 that ammonium hydroxide, which is added dropwise, to adjust pH value, forms solution D；
Under the conditions of magnetic agitation, solution D is slowly dropped in solution C, generates white precipitate.The precipitating is washed with ethyl alcohol
It washs 5 times, then 65 DEG C of vacuum drying 22h, obtain BaSO4；
(b) 8 obtained part BaSO in grinding steps (a)4, then by the BaSO after grinding4It is added to 60 parts of methyl-isobutyls
Ultrasonic wave dispersion is carried out in ketone, is added 7 parts of PVDF-HFP and is carried out magnetic agitation dispersion, obtains PVDF-HFP and BaSO4's
Mixed slurry；
(c) at room temperature, use the scraper of 50um by PVDF-HFP and BaSO on clean glass plate4Mixed slurry it is uniform
The aramid fiber static spinning membrane two sides being coated in a thickness of 25um, One-sided coatings soak glass plate after standing 70s with a thickness of 5um
Steep 35min in deionized water.Then it is thoroughly dried in 65 DEG C of vacuum ovens, drying time 1min obtains electricity
Pond diaphragm.
Embodiment 3
A kind of battery separator, including aramid fiber electrostatic spinning basement membrane, and it is coated on two sides of aramid fiber electrostatic spinning basement membrane
The PVDF-HFP/BaSO in face4Composite coating.
The preparation method of the battery separator, comprising the following steps:
(a) 5 parts of BaCl are weighed at room temperature250 parts of distilled water are dissolved in, solution A is formed；It is molten to weigh 0.06 part of odium stearate
Solution forms solution B in 40 parts of organic solvents；B is poured into and stirs 15min in A, forms solution C；
Weigh 3.4 parts of anhydrous Nas2SO450 parts of distilled water are dissolved in, and it is 9 that ammonium hydroxide, which is added dropwise, to adjust pH value, forms solution D；
Under the conditions of magnetic agitation, solution D is slowly dropped in solution C, generates white precipitate.The precipitating is washed with ethyl alcohol
It washs 4 times, then 65 DEG C of vacuum drying for 24 hours, obtain BaSO4；
(b) 2.5 obtained part BaSO in grinding steps (a)4, then by the BaSO after grinding4It is added to 48 parts of N, N- diformazan
In base formamide carry out ultrasonic wave dispersion, add 2.5 parts of PVDF-HFP and carry out magnetic agitation dispersion, obtain PVDF-HFP and
BaSO4Mixed slurry；
(c) at room temperature, use the scraper of 50um by PVDF-HFP and BaSO on clean glass plate4Mixed slurry it is uniform
Be coated in a thickness of 19um aramid fiber static spinning membrane two sides, One-sided coatings impregnate glass plate after standing 55s with a thickness of 3um
28min in deionized water.Then it is thoroughly dried in 50 DEG C of vacuum ovens, drying time 3min obtains battery
Use diaphragm.
Embodiment 4
A kind of battery separator, including aramid fiber electrostatic spinning basement membrane, and it is coated on two sides of aramid fiber electrostatic spinning basement membrane
The PVDF-HFP/BaSO in face4Composite coating.
The preparation method of the battery separator, comprising the following steps:
(a) BaSO is prepared4, preparation method is same as Example 3；
(b) 5 obtained part BaSO in grinding steps (a)4, then by the BaSO after grinding4It is added in 55 parts of organic solvents
Ultrasonic wave dispersion is carried out, 5 parts of PVDF-HFP is added and carries out magnetic agitation dispersion, obtain PVDF-HFP and BaSO4Mixing
Slurry；
(c) at room temperature, use the scraper of 50um by PVDF-HFP and BaSO on clean glass plate4Mixed slurry it is uniform
The aramid fiber static spinning membrane two sides being coated in a thickness of 18um, One-sided coatings soak glass plate after standing 65s with a thickness of 4um
Steep 32min in deionized water.Then it is thoroughly dried in 60 DEG C of vacuum ovens, drying time 2min obtains electricity
Pond diaphragm.
Embodiment 5
A kind of battery separator removes PVDF-HFP/BaSO4Composite coating is by 2 parts of PVDF-HFP, 2 parts of BaSO4With 47 parts of N,
Dinethylformamide is prepared, unilateral PVDF-HFP/BaSO4Composite coating with a thickness of 2um other than, other operating procedures
It is same as Example 3.
Embodiment 6
A kind of battery separator removes PVDF-HFP/BaSO4Composite coating is by 6 parts of PVDF-HFP, 6 parts of BaSO4With 56 parts of N,
Other than dinethylformamide is prepared, other operating procedures are same as Example 4.
Comparative example 1
A kind of commercial battery diaphragm, model Celgard2325.
Comparative example 2
A kind of battery separator removes PVDF-HFP/BaSO4Composite coating is by 0.5 part of PVDF-HFP, 11 parts of BaSO4With 70 parts
Other than n,N-Dimethylformamide is prepared, other operating procedures are same as Example 4.
Comparative example 2 as different from Example 4, PVDF-HFP/BaSO in this comparative example4Composite coating each component content is not
Within scope of protection of the present invention.
Test example
(1) diaphragm obtained in embodiment and comparative example is tested for the property, test result is as shown in Table 1.
(2)LiCo2It is assembled respectively with the battery separator in embodiment 1 and comparative example 1 for anode using lithium piece as cathode
At button cell, cycle performance and multiplying power discharging property test are carried out, test results are shown in figure 5 for cycle performance, multiplying power discharging
The performance test results are as shown in Figure 6；
Cycle performance test: 0.1C charge and discharge cycles 5 times first, then with 0.5C charging 1C electric discharge until 150 charge and discharge
Loop test terminates.
Multiplying power discharging property test: first 0.1C charge and discharge cycles 5 times, then 0.5C charging, with 1C, 2C, 4C, 8C different multiplying
Discharge mode respectively charge and discharge cycles 5 times until test terminates.
The performance test results of diaphragm in one embodiment and comparative example of table
As shown in Table 1, the battery separator that embodiment 1-6 is obtained have excellent porosity, air permeability, needle thorn intensity,
Tensile strength and heat resistance.Porosity is 50% or more, and it is 2.7-3.2N that needle, which pierces intensity,.By advanced optimizing PVDF-
HFP/BaSO4Composite coating each component matches when preparation process, and obtained battery separator is in porosity, needle thorn intensity, drawing
It is more protruded in terms of stretching intensity and heat resistance.
Comparative example 2 as different from Example 4, PVDF-HFP/BaSO in this comparative example4Composite coating each component content is not
Within scope of protection of the present invention, battery separator that comparative example 2 obtains air permeability, needle thorn intensity, tensile strength and
The effect of the diaphragm all obtained not as good as embodiment 4 in terms of heat resistance is good, it follows that PVDF-HFP/BaSO4Composite coating is each
Constituent content could obtain more excellent performance of battery separator within scope of protection of the present invention.
By attached drawing 5 it is found that the cycle performance of the battery of the battery separator assembling obtained by the embodiment of the present invention 1 better than pair
The battery that Celgard2325 diaphragm assembles in ratio 1, after 10-150 charge and discharge cycles are tested, the assembling of 1 septation of embodiment
The capacity of battery do not change substantially, cycle performance is preferable, and battery is longer；And Celgard2325 in comparative example 1
For the battery of diaphragm assembling in 10-150 charge and discharge cycles test process, the capacity of battery declines more, poor circulation.
By attached drawing 6 it is found that being better than in comparative example by the multiplying power discharging property of the battery of 1 septation of embodiment of the present invention assembling
The battery of Celgard2325 diaphragm assembling, it follows that there is excellent multiplying power using battery made from the diaphragm in the present invention
Discharge performance, battery is longer, highly-safe.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of battery separator, which is characterized in that the battery separator includes electrostatic spinning basement membrane, and is coated on electrostatic
The PVDF-HFP/BaSO of two sides of spinning basement membrane4Composite coating.
2. battery separator according to claim 1, which is characterized in that the electrostatic spinning basement membrane includes aramid fiber Static Spinning
Silk diaphragm.
3. battery separator according to claim 1, which is characterized in that the PVDF-HFP/BaSO4The thickness of composite coating
Degree is 2-5um.
4. battery separator according to claim 1, which is characterized in that the electrostatic spinning basement membrane with a thickness of 10-
25um。
5. battery separator according to claim 1, which is characterized in that the PVDF-HFP/BaSO4Composite coating is main
It is prepared by following raw material in parts by weight:
1-8 parts of PVDF-HFP, BaSO41-7 parts and organic solvent 45-60 parts；
Preferably, the PVDF-HFP/BaSO4Composite coating is mainly prepared by following raw material in parts by weight:
2.5-5 parts of PVDF-HFP, BaSO42.5-5 parts and organic solvent 48-55 parts.
6. battery separator according to claim 5, which is characterized in that the organic solvent includes N, N- dimethyl formyl
At least one of amine, glycol ether, cresols and methyl iso-butyl ketone (MIBK).
7. the preparation method of battery separator according to claim 1-6, which is characterized in that including following step
It is rapid:
PVDF-HFP/BaSO is scratched on two sides of electrostatic spinning basement membrane4Composite coating is impregnated in water after standing, then into
Row drying, obtains battery separator.
8. the preparation method of battery separator according to claim 7, which is characterized in that
The PVDF-HFP/BaSO4The time of repose of composite coating is 50-70s, and soaking time is 25-35min in water, dry temperature
Degree is 30-65 DEG C, drying time 1-4min；
Preferably, the PVDF-HFP/BaSO4The time of repose of composite coating is 55-65s, and soaking time is 28- in water
32min, drying temperature are 50-60 DEG C, drying time 2-3min.
9. the preparation method of battery separator according to claim 7, which is characterized in that the PVDF-HFP/BaSO4It is multiple
Close the preparation method of the mixed slurry of coating, comprising the following steps:
Grind BaSO4, then by BaSO4It is added to progress ultrasonic wave dispersion in organic solvent, PVDF-HFP is added and carries out magnetic force
It is dispersed with stirring, obtains PVDF-HFP and BaSO4Mixed slurry.
10. the preparation method of battery separator according to claim 9, which is characterized in that the ultrasonic dispersing time
For 0.5-2h, magnetic agitation jitter time is 2.2-2.7h；
Preferably, the ultrasonic dispersing time is 1-1.5h, and magnetic agitation jitter time is 2.4-2.6h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810967346.7A CN109103395A (en) | 2018-08-23 | 2018-08-23 | Battery separator and preparation method thereof |
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| CN201810967346.7A CN109103395A (en) | 2018-08-23 | 2018-08-23 | Battery separator and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140205883A1 (en) * | 2012-03-28 | 2014-07-24 | Sharp Laboratories Of America, Inc. | Reactive separator for a metal-ion battery |
| CN105958000A (en) * | 2016-07-11 | 2016-09-21 | 东莞市魔方新能源科技有限公司 | Lithium ion battery composite membrane and preparation method thereof |
-
2018
- 2018-08-23 CN CN201810967346.7A patent/CN109103395A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140205883A1 (en) * | 2012-03-28 | 2014-07-24 | Sharp Laboratories Of America, Inc. | Reactive separator for a metal-ion battery |
| CN105958000A (en) * | 2016-07-11 | 2016-09-21 | 东莞市魔方新能源科技有限公司 | Lithium ion battery composite membrane and preparation method thereof |
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Application publication date: 20181228 |