CN106356487B - A kind of painting cloth diaphragm for high-energy density charged lithium cells - Google Patents
A kind of painting cloth diaphragm for high-energy density charged lithium cells Download PDFInfo
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- CN106356487B CN106356487B CN201610761707.3A CN201610761707A CN106356487B CN 106356487 B CN106356487 B CN 106356487B CN 201610761707 A CN201610761707 A CN 201610761707A CN 106356487 B CN106356487 B CN 106356487B
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- 239000004744 fabric Substances 0.000 title claims abstract description 23
- 238000010422 painting Methods 0.000 title claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 51
- 238000000576 coating method Methods 0.000 claims abstract description 51
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 39
- 238000009826 distribution Methods 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 239000002033 PVDF binder Substances 0.000 claims abstract description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000004840 adhesive resin Substances 0.000 claims abstract description 5
- 229920006223 adhesive resin Polymers 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 70
- -1 polypropylene Polymers 0.000 claims description 64
- 239000004743 Polypropylene Substances 0.000 claims description 48
- 229920001155 polypropylene Polymers 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 24
- 239000004698 Polyethylene Substances 0.000 claims description 20
- 239000012530 fluid Substances 0.000 claims description 20
- 229920000573 polyethylene Polymers 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000009825 accumulation Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 230000009977 dual effect Effects 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000010220 ion permeability Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 210000004379 membrane Anatomy 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000005192 partition Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
A kind of painting cloth diaphragm for high-energy density charged lithium cells belongs to battery diaphragm technical field, including a porous basement membrane, and the coating positioned at basement membrane one or both sides；For the size distribution in the aperture of the basement membrane at 0.02 micron to 0.1 micron, pore size distribution range value Delta is 0.5 or smaller；The coating is using polyvinylidene fluoride resin as adhesive resin.This diaphragm improves ion transmission, and enhances cycle characteristics, has good adhesiveness with electrode.
Description
Technical field
The invention belongs to battery diaphragm technical fields, and in particular to be a kind of painting for high-energy density charged lithium cells
Cloth diaphragm.
Background technique
Nonaqueous electrolytic solution rechargeable battery, such as lithium ion secondary battery, have been widely used as power supply, set for portable electronic
Standby such as laptop, mobile phone, digital camera and video camera.In addition, these batteries are characterized by having that high-energy is close
Degree, thus extensive research and application have also been carried out in electric car field in recent years.
Since portable electronic device requires to gradually reduce in size and weight, the shell of nonaqueous electrolyte battery by
Gradually simplify.As exterior member, what earliest battery can was made of stainless steel, then replaced by aluminum-shell battery tank.Present quilt again
Plastic-aluminum Soft Roll replaces.In the case where this Soft Roll housing battery `, since shell is soft, charge and discharge between an electrode and a separator
When electric, it is easy to form air layer, diaphragm and electrode separation, battery cycle life is caused to reduce, and cause cell safety problem.
In terms of solving this problem, electrode is closely bonded with diaphragm together with technology just become most important.
When making basement membrane using MIcroporous polyolefin film, the technology for introducing the porous coating of polyvinylidene fluoride resin will be bonded
Agent is coated in the side or two sides of basement membrane.After assembling battery, the Soft Roll for filling electrolyte is placed in a hot-press arrangement
Hot pressing, electrode and diaphragm can bond together well, and wherein described adhesive porous coating can play adhesive effect.Cause
This, the cycle life of soft-package battery can be significantly improved.
Summary of the invention
It is an object of the invention to overcome defect and deficiency mentioned above, and provide a kind of for high-energy density charging
The painting cloth diaphragm of lithium battery.
The present invention realizes its purpose, and the technical solutions adopted are as follows.
A kind of painting cloth diaphragm for high-energy density charged lithium cells, including a porous basement membrane, and it is located at base
The coating of film one or both sides；The size distribution in the aperture of the basement membrane is at 0.02 micron to 0.1 micron, pore size distribution range value
Delta is 0.5 or smaller；The coating is using polyvinylidene fluoride resin as adhesive resin.
A kind of painting cloth diaphragm for high-energy density charged lithium cells, is made by following steps:
Step 1. plasticizing: PP GRANULES is added to after being plasticized in extruder and is squeezed out, wound, obtain after then cooling down pressure roller
To polypropylene laminar film；
The configuration of step 2. composite fibre solution: polypropylene fibre and polyethylene fibre are added in water, compound fibre is made
Solution is tieed up, is stirred evenly；
Step 3. is compound: in the composite fibre solution of polypropylene laminar film dual coating polypropylene fibre and polyethylene fibre
Obtain coating laminar film；
Step 4. annealing: coating laminar film being rapidly heated to 125 DEG C and keeps the temperature 3 hours, and then air-cooled to 75 DEG C, heat preservation
It is air-cooled to room temperature after 5 hours, obtains slab；
Step 5. simple tension: sending slab into one-way stretcher, obtains the basement membrane that Lapie is 3 ~ 6 times；
The configuration of step 6. coating fluid: dissolution polyvinylidene fluoride resin, ethyl alcohol are in a solvent to prepare coating fluid；Wherein,
The mass ratio of polyvinylidene fluoride resin, ethyl alcohol and solvent is 1:1:3 ~ 5, and the solvent is polar amide series solvent；
Step 7: coating: by coating fluid double spread in basement membrane, wherein the mass ratio of basement membrane and coating fluid is 9 ~ 10:1；
It stands and air-dries；The volatilization of second alcohol and solvent, forms the blank diaphragm with porous coating layers；
Step 8: irradiation grafting: blank diaphragm being placed in grafting equipment, inert gas is passed through, is through total amount
After 10KGY irradiation, this painting cloth diaphragm is obtained.
In step 1, extrusion temperature is set in 162 DEG C ~ 175 DEG C, and the polypropylene is poly- using the isotactic of isotacticity >=90%
Propylene, average molecular weight are 1 × 106, melt index 1.0g/10min.
In step 2, the fibre length of polypropylene fibre is 2~10mm；The fibre length of polyethylene fibre is 2~10mm,
According to mass ratio, water: polypropylene fibre: polyethylene fibre=10:1:1.
In step 3, the mass ratio of polypropylene laminar film and composite fibre solution is 13 ~ 16:2.
In step 5, the preheating temperature before stretching is 105 DEG C ~ 115 DEG C, 120 DEG C ~ 130 DEG C of draft temperature.
In step 6, the solvent is N-Methyl pyrrolidone, dimethyl acetamide or dimethylformamide.
Conventional membrane, the aperture being distributed on the surface of adhesive porous layer are dispersed in 0.05 ~ 10 micron.When surface has
There is such pore structure heterogeneous, ion is seldom through the amount in adhesive resin, and adhesiveness is poor.
This diaphragm improves ion transmission, and enhances cycle characteristics, has good adhesiveness with electrode.
Specific embodiment
Invention is further described in detail below.
A kind of painting cloth diaphragm for high-energy density charged lithium cells, including a porous basement membrane, and it is located at base
The coating of film one or both sides.
For the size distribution in the aperture of the basement membrane at 0.02 micron to 0.1 micron, pore size distribution range value Delta is 0.5
Or it is smaller.Pore size distribution range value Delta is the aperture D95 by following equation from the accumulation pore-size distribution for corresponding to 95%,
Corresponding to the aperture D05 of 5% accumulation pore-size distribution, and the aperture D50 corresponding to 50% accumulation pore-size distribution calculated
Value: Delta=(D95-D05)/D50.Pore size distribution range value Delta can be true by semidry method (ASTM E1294-89)
It is fixed.
The coating is using polyvinylidene fluoride resin as adhesive resin.The polyvinylidene fluoride resin has weight
Average molecular weight is distributed in 200000 or more 550000 or less.
Therefore, in the present invention, basement membrane pore size distribution range value Delta is 0.5 or smaller.Pore-size uniformity in this way
It improves, ion infiltration becomes uniform.The partial deterioration of partition can be suppressed.Therefore, in the battery of recharge, (circulation is special
Property) and electric discharge battery capacity retention performance can be improved.The pore size distribution range value Delta of basement membrane be preferably 0.3 or
Hereinafter, more preferably 0.25 or less.Although most ideal aperture distribution range Delta is 0, such aperture is single.But
In view of the actual production efficiency of basement membrane.Preferably 0.05 or more, more preferably 0.1 or more.
In the case where basement membrane aperture is big, ion permeability can improve.However, in this case, adhesive is porous
Bonding area between layer and electrode reduces, and therefore, the bonding force between diaphragm and electrode can also reduce.In the aperture ratio of basement membrane
In lesser situation, although the adhesion strength between partition and electrode improves, ion permeability is reduced.That is,
There is a kind of trade-off relation between ion permeability and adhesiveness.
Therefore, in the present invention, the pore size of basement membrane is controlled in 0.02 micron to 0.1 micron within the scope of one.
As a result, ion permeability and adhesion strength just reach good balance.The aperture lower limit value of basement membrane is preferably 0.025 micron
Or more, more preferably 0.03 micron or more.In addition, the upper limit of the pore size of the basement membrane be preferably 0.05 micron or with
Under, more preferably 0.04 micron or less.
The Gurley value of diaphragm is between 50 seconds and 400 seconds.Diaphragm porosity ranges are 30% or more, 60% or less.
In order to which mechanical strength and energy density consider, it is preferred that partition with a thickness of 5 microns to 30 microns.
The basement membrane is combined by one layer of microporous barrier and one or more layers porous sheet.Porous sheet is set to micro-
Pore membrane one or both sides.Due to all containing a large amount of micropore inside microporous barrier and porous sheet, and these micropores are mutually to interconnect
Logical, such gas or liquid can be transmitted to the other side from side.
Embodiment 1.
Cloth diaphragm is applied to be made of following methods:
Step 1. plasticizing: PP GRANULES being added to after being plasticized in extruder and squeezed out, and extrusion temperature is set in 170 DEG C,
Then it is wound after cooling down pressure roller, obtains polypropylene laminar film；The polypropylene uses the isotactic polypropylene of isotacticity >=90%, puts down
Average molecular weight is 1 × 106, melt index 1.0g/10min.
The configuration of step 2. composite fibre solution: polypropylene fibre and polyethylene fibre are added in water, compound fibre is made
Solution is tieed up, is stirred evenly；Wherein, the fibre length of polypropylene fibre is 2~10mm；The fibre length of polyethylene fibre be 2~
10mm, according to mass ratio, water: polypropylene fibre: polyethylene fibre=10:1:1；
Step 3. is compound: in the composite fibre solution of polypropylene laminar film dual coating polypropylene fibre and polyethylene fibre
Coating laminar film is obtained, the mass ratio of polypropylene laminar film and composite fibre solution is 16:2；
Step 4. annealing: coating laminar film being rapidly heated to 125 DEG C and keeps the temperature 3 hours, and then air-cooled to 75 DEG C, heat preservation
It is air-cooled to room temperature after 5 hours, obtains slab；
Step 5. simple tension: sending slab into one-way stretcher, and the preheating temperature before stretching is 105 DEG C ~ 115 DEG C, stretches
120 DEG C ~ 130 DEG C of temperature, obtain the basement membrane that Lapie is 3 times；
The configuration of step 6. coating fluid: dissolution polyvinylidene fluoride resin, ethyl alcohol are in a solvent to prepare coating fluid；Wherein,
The mass ratio of polyvinylidene fluoride resin, ethyl alcohol and solvent is 1:1:5, and the solvent is N-Methyl pyrrolidone；
Step 7: coating: by coating fluid double spread in basement membrane, wherein the mass ratio of basement membrane and coating fluid is 9 ~ 10:1；
It stands and air-dries；The volatilization of second alcohol and solvent, forms the blank diaphragm with porous coating layers；
Step 8: irradiation grafting: blank diaphragm being placed in grafting equipment, inert gas is passed through, is through total amount
After 10KGY irradiation, this painting cloth diaphragm is obtained.
Embodiment 2.
Cloth diaphragm is applied to be made of following methods:
Step 1. plasticizing: PP GRANULES being added to after being plasticized in extruder and squeezed out, and extrusion temperature is set in 162 DEG C,
Then it is wound after cooling down pressure roller, obtains polypropylene laminar film；The polypropylene uses the isotactic polypropylene of isotacticity >=90%, puts down
Average molecular weight is 1 × 106, melt index 1.0g/10min.
The configuration of step 2. composite fibre solution: polypropylene fibre and polyethylene fibre are added in water, compound fibre is made
Solution is tieed up, is stirred evenly；Wherein, the fibre length of polypropylene fibre is 2~10mm；The fibre length of polyethylene fibre be 2~
10mm, according to mass ratio, water: polypropylene fibre: polyethylene fibre=10:1:1；
Step 3. is compound: in the composite fibre solution of polypropylene laminar film dual coating polypropylene fibre and polyethylene fibre
Coating laminar film is obtained, the mass ratio of polypropylene laminar film and composite fibre solution is 14:2；
Step 4. annealing: coating laminar film being rapidly heated to 125 DEG C and keeps the temperature 3 hours, and then air-cooled to 75 DEG C, heat preservation
It is air-cooled to room temperature after 5 hours, obtains slab；
Step 5. simple tension: sending slab into one-way stretcher, and the preheating temperature before stretching is 105 DEG C ~ 115 DEG C, stretches
120 DEG C ~ 130 DEG C of temperature, obtain the basement membrane that Lapie is 5 times；
The configuration of step 6. coating fluid: dissolution polyvinylidene fluoride resin, ethyl alcohol are in a solvent to prepare coating fluid；Wherein,
The mass ratio of polyvinylidene fluoride resin, ethyl alcohol and solvent is 1:1:4, and the solvent is dimethyl acetamide；
Step 7: coating: by coating fluid double spread in basement membrane, wherein the mass ratio of basement membrane and coating fluid is 9 ~ 10:1；
It stands and air-dries；The volatilization of second alcohol and solvent, forms the blank diaphragm with porous coating layers；
Step 8: irradiation grafting: blank diaphragm being placed in grafting equipment, inert gas is passed through, is through total amount
After 10KGY irradiation, this painting cloth diaphragm is obtained.
Embodiment 3.
Cloth diaphragm is applied to be made of following methods:
Step 1. plasticizing: PP GRANULES being added to after being plasticized in extruder and squeezed out, and extrusion temperature is set in 175 DEG C,
Then it is wound after cooling down pressure roller, obtains polypropylene laminar film；The polypropylene uses the isotactic polypropylene of isotacticity >=90%, puts down
Average molecular weight is 1 × 106, melt index 1.0g/10min.
The configuration of step 2. composite fibre solution: polypropylene fibre and polyethylene fibre are added in water, compound fibre is made
Solution is tieed up, is stirred evenly；Wherein, the fibre length of polypropylene fibre is 2~10mm；The fibre length of polyethylene fibre be 2~
10mm, according to mass ratio, water: polypropylene fibre: polyethylene fibre=10:1:1；
Step 3. is compound: in the composite fibre solution of polypropylene laminar film dual coating polypropylene fibre and polyethylene fibre
Coating laminar film is obtained, the mass ratio of polypropylene laminar film and composite fibre solution is 13:2；
Step 4. annealing: coating laminar film being rapidly heated to 125 DEG C and keeps the temperature 3 hours, and then air-cooled to 75 DEG C, heat preservation
It is air-cooled to room temperature after 5 hours, obtains slab；
Step 5. simple tension: sending slab into one-way stretcher, and the preheating temperature before stretching is 105 DEG C ~ 115 DEG C, stretches
120 DEG C ~ 130 DEG C of temperature, obtain the basement membrane that Lapie is 6 times；
The configuration of step 6. coating fluid: dissolution polyvinylidene fluoride resin, ethyl alcohol are in a solvent to prepare coating fluid；Wherein,
The mass ratio of polyvinylidene fluoride resin, ethyl alcohol and solvent is 1:1:3, and the solvent is dimethylformamide or dimethyl formyl
Amine；
Step 7: coating: by coating fluid double spread in basement membrane, wherein the mass ratio of basement membrane and coating fluid is 9 ~ 10:1；
It stands and air-dries；The volatilization of second alcohol and solvent, forms the blank diaphragm with porous coating layers；
Step 8: irradiation grafting: blank diaphragm being placed in grafting equipment, inert gas is passed through, is through total amount
After 10KGY irradiation, this painting cloth diaphragm is obtained.
The aperture of the obtained basement membrane of embodiment 1,2,3 aperture size distribution at 0.02 micron to 0.1 micron, aperture point
Cloth value range Delta is 0.5 or smaller.
Multiple functions can be incorporated in one by the way that basement membrane and coating to be compounded to form by fibrous material by the technical program
It rises, on the one hand, ensure that the ion permeability of diaphragm, the Gurley value of diaphragm has excellent between 195 seconds to 320 seconds
Dynamic characteristic, another convenience improve the puncture strength of diaphragm, and puncture strength is greater than 300g.
Table 1, the Delta value and Gurley value of each embodiment
Table 2: the adhesiveness table of diaphragm and electrode
The adhesiveness of porous septum and electrode is dismantled and checked to battery after charge and discharge cycles are tested.As a result it is shown in table
In 2.
It is stripped down from electrode surface adhesive porous coating, this adhesion strength is to measure as follows: using typical
An angle of 90 degrees peeling tester, using cupping machine (RTC- 1225A is produced by A & D company), relative to diaphragm, at 90 degree
It is stretched on direction.By this disbonded test, required load measurement is removed to determine peel strength.
From Table 2, it can be seen that embodiment 1 ~ 3 is relatively high in adhesive strength value between diaphragm and electrode.Here it is by
The influence of bonded areas area between diaphragm and electrode.It can thus be seen that the aperture on the surface of porous layer is smaller, with
Electrode adhesion is higher.However, the surface apertures in comparative example 2 be it is very big, so adhesive strength is slightly worse.From above
In discussion, it is highly advantageous that pore diameter range of the invention, which is in terms of the adhesiveness to electrode,.
In the uniformity of caking property, when membrane surface pore-size distribution is more uniform, caking property is also more uniform.Tradition every
Membrane aperture distribution be it is very big, although certain part adhesiveness are high, other parts bonding force is very weak.Therefore, they bond uniform
Property is wanting in.
From the discussion above, it is considered herein that basement membrane pore size distribution range Delta 0.5 hereinafter, to diaphragm and electrode
It is vital in terms of adhesion strength and bonding uniformity.
The present invention is illustrated according to embodiment, under the premise of not departing from present principles, if the present apparatus can also make
Dry modification and improvement.It should be pointed out that it is all using modes technical solutions obtained such as equivalent substitution or equivalent transformations, all fall within this
In the protection scope of invention.
Claims (6)
1. a kind of painting cloth diaphragm for high-energy density charged lithium cells, including a porous basement membrane, and it is located at basement membrane
The coating of one or both sides；The size distribution in the aperture of the basement membrane is at 0.02 micron to 0.1 micron, pore size distribution range value
Delta is 0.5 or smaller；The coating using polyvinylidene fluoride resin as adhesive resin, which is characterized in that its by with
Lower step is made:
Step 1. plasticizing: PP GRANULES is added to after being plasticized in extruder and is squeezed out, wound, gathered after then cooling down pressure roller
Propylene laminar film；
The configuration of step 2. composite fibre solution: being added polypropylene fibre and polyethylene fibre in water, and it is molten that composite fibre is made
Liquid stirs evenly；
Step 3. is compound: obtaining in the composite fibre solution of polypropylene laminar film dual coating polypropylene fibre and polyethylene fibre
Coat laminar film；
Step 4. annealing: coating laminar film being rapidly heated to 125 DEG C and keeps the temperature 3 hours, and then air-cooled to 75 DEG C, heat preservation 5 is small
When after be air-cooled to room temperature, obtain slab；
Step 5. simple tension: sending slab into one-way stretcher, obtains the basement membrane that Lapie is 3 ~ 6 times；
The configuration of step 6. coating fluid: dissolution polyvinylidene fluoride resin, ethyl alcohol are in a solvent to prepare coating fluid；Wherein, gather inclined
The mass ratio of fluoroethylene resin, ethyl alcohol and solvent is 1:1:3 ~ 5, and the solvent is polar amide series solvent；
Step 7: coating: by coating fluid double spread in basement membrane, wherein the mass ratio of basement membrane and coating fluid is 9 ~ 10:1；It stands
It air-dries；The volatilization of second alcohol and solvent, forms the blank diaphragm with porous coating layers；
Step 8: irradiation grafting: blank diaphragm being placed in grafting equipment, inert gas is passed through, and is 10KGY spoke through total amount
According to rear, this painting cloth diaphragm is obtained；
Pore size distribution range value Delta is the aperture D95 by following equation from the accumulation pore-size distribution for corresponding to 95%, right
Should in 5% accumulation pore-size distribution aperture D05, and corresponding to 50% accumulation pore-size distribution the calculated value of aperture D50:
Delta=(D95-D05)/D50.
2. a kind of painting cloth diaphragm for high-energy density charged lithium cells as described in claim 1, which is characterized in that step
In 1, extrusion temperature is set in 162 DEG C ~ 175 DEG C, and the polypropylene uses the isotactic polypropylene of isotacticity >=90%, mean molecule
Amount is 1 × 106, melt index 1.0g/10min.
3. a kind of painting cloth diaphragm for high-energy density charged lithium cells as described in claim 1, which is characterized in that step
In 2, the fibre length of polypropylene fibre is 2~10mm；The fibre length of polyethylene fibre is 2~10mm；According to mass ratio,
Water: polypropylene fibre: polyethylene fibre=10:1:1.
4. a kind of painting cloth diaphragm for high-energy density charged lithium cells as described in claim 1, which is characterized in that step
In 3, the mass ratio of polypropylene laminar film and composite fibre solution is 13 ~ 16:2.
5. a kind of painting cloth diaphragm for high-energy density charged lithium cells as described in claim 1, which is characterized in that step
In 5, the preheating temperature before stretching is 105 DEG C ~ 115 DEG C, 120 DEG C ~ 130 DEG C of draft temperature.
6. a kind of painting cloth diaphragm for high-energy density charged lithium cells as described in claim 1, which is characterized in that step
In 6, the solvent is N-Methyl pyrrolidone, dimethyl acetamide or dimethylformamide.
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| CN104362276A (en) * | 2014-10-27 | 2015-02-18 | 中国乐凯集团有限公司 | Polyethylene microporous membrane, preparation method and lithium ion battery |
| CN104508863A (en) * | 2012-07-30 | 2015-04-08 | 帝人株式会社 | Nonaqueous electrolyte battery separator and nonaqueous electrolyte battery |
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| CN104508863A (en) * | 2012-07-30 | 2015-04-08 | 帝人株式会社 | Nonaqueous electrolyte battery separator and nonaqueous electrolyte battery |
| CN104362276A (en) * | 2014-10-27 | 2015-02-18 | 中国乐凯集团有限公司 | Polyethylene microporous membrane, preparation method and lithium ion battery |
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