CN109167007A - Heat-resisting lithium ion battery coated separator and preparation method thereof - Google Patents
Heat-resisting lithium ion battery coated separator and preparation method thereof Download PDFInfo
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- CN109167007A CN109167007A CN201811030032.0A CN201811030032A CN109167007A CN 109167007 A CN109167007 A CN 109167007A CN 201811030032 A CN201811030032 A CN 201811030032A CN 109167007 A CN109167007 A CN 109167007A
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- heat
- ion battery
- lithium ion
- resisting
- organic polymer
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 144
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 93
- 239000011248 coating agent Substances 0.000 claims abstract description 88
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- -1 polypropylene lithium Polymers 0.000 claims abstract description 57
- 229920000620 organic polymer Polymers 0.000 claims abstract description 55
- 239000005011 phenolic resin Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 18
- 230000002146 bilateral effect Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000008602 contraction Effects 0.000 claims abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 12
- 238000007711 solidification Methods 0.000 claims abstract description 12
- 230000008023 solidification Effects 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 230000008595 infiltration Effects 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 239000004743 Polypropylene Substances 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- UIGQEZZSKOINIE-UHFFFAOYSA-N [Li].CC=C Chemical compound [Li].CC=C UIGQEZZSKOINIE-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M50/449—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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Cell Separators (AREA)
Abstract
The present invention relates to a kind of heat-resisting lithium ion battery coated separator and preparation method thereof, heat-resisting organic polymer coating liquid preparation method: is obtained into heat-resisting lithium ion battery coated separator through solidification, pore-forming and drying after the coating of polypropylene lithium ion battery basement membrane unilateral or bilateral surface；Heat-resisting organic polymer coating liquid is mainly made of heat-resisting organic polymer, pore former and water, and heat-resisting organic polymer is water soluble phenol resin, and pore former is polyvinylpyrrolidone or polyvinyl alcohol.Final longitudinal contraction rate≤3.0% of the product at temperature T obtained, does not shrink laterally, T >=190 DEG C；The micropore that diameter is 30-70 nanometers is distributed in coating, it is not peeling-off in 180 degree folding 100 times or more coatings and basement membrane.The good thermal stability of product is made in preparation method of the invention, simple process and low cost.
Description
Technical field
The invention belongs to field of lithium ion battery, it is related to a kind of heat-resisting lithium ion battery coated separator and preparation method thereof,
In particular to a kind of heat-resisting lithium ion battery coated separator and preparation method thereof with water soluble phenol resin coating.
Background technique
Currently, the diaphragm of commercial Li-ion battery largely uses polypropylene diaphragm.Since polyacrylic fusing point is lower than 165
DEG C, under higher temperature, polypropylene can occur melting and soften, and polypropylene diaphragm can be shunk, so that lithium ion battery is positive and negative
Short circuit thermal occurs for pole, leads to lithium ion battery swelling fracture and burning, seriously affects the safety of lithium ion battery.Also,
More importantly current polypropylene diaphragm once be pierced will constitute positive and negative anodes short circuit, puncture site can be brought rapidly up to
More than the fusing point of polypropylene diaphragm high polymer, further expansion pierces through area, forms larger range of short circuit, in turn results in temperature
Sharply promotion, there are hidden peril of explosion.
In order to improve the heat resistance of polypropylene diaphragm, the way of mainstream is the coated with nano inorganic particle on diaphragm at present
(such as aluminium oxide, zirconium oxide)+polyvinylidene fluoride coating, can make diaphragm keep integrity of shape at a higher temperature, prevent
Lithium ion battery plus-negative plate is in high temperature or is punctured lower short circuit thermal.But one side nano inorganic pellet hardness is high, there are still
The possibility of diaphragm is pierced through, and exacerbates process equipment abrasion, increases production cost；On the other hand, nano inorganic particle is insoluble
In any solution system, it is irregular to will cause coating, influences battery performance；In addition, the specific gravity of inorganic particle is larger, increase weight to diaphragm
Obviously.
Therefore, develop that a kind of heat resistance is good and the great reality meaning of low-cost heat-resisting lithium ion battery coated separator
Justice.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defects of prior art, and it is good, at low cost to provide a kind of heat resistance
Lithium ion battery coated separator honest and clean and with heat-resisting organic polymer coating.
In order to achieve the above object, present invention employs the following technical solutions:
Heat-resisting lithium ion battery coated separator, by polypropylene lithium ion battery basement membrane and one side or the coating group of bilateral
At；
The material of the coating is heat-resisting organic polymer, and the heat-resisting organic polymer is water soluble phenol resin, institute
It states and the micropore that diameter is 30-70 nanometers is distributed in coating；The positive electrode of lithium ion battery in the process of running, will form needle
The crystallization of shape elongated conductive can cause positive and negative anodes short-circuit, and aperture, which is less than or equal to 70 nanometers, can effectively prevent passing through for crystallization, prevent short
Road phenomenon.
Longitudinal contraction rate≤3.0% of the heat-resisting lithium ion battery coated separator at temperature T is not shunk laterally, and T >=
190 DEG C, and longitudinal contraction rate >=38% of the polypropylene lithium ion battery basement membrane at temperature T, it can be seen that coating of the invention
Greatly improve the thermal contraction performance of heat-resisting lithium ion battery coated separator；
Heat-resisting lithium ion battery coated separator 180 degree folding 100 times or more coatings and basement membrane be not peeling-off, explanation
The binding strength of heat-resisting lithium ion battery coated separator floating coat and basement membrane of the invention is high, and durability is good.
As a preferred technical scheme:
Heat-resisting lithium ion battery coated separator as described above, heat resistance on every square metre of polypropylene lithium ion battery basement membrane
The weight of organic polymer is 1-10 grams.The present invention can select the coating of heat resistance organic polymer on basement membrane according to actual needs
Amount, coated weight is directly proportional to the thickness of coating, and coated weight is bigger, and coating layer thickness is bigger, and reliability is better, but overweight coating meeting again
The drawback for bringing battery volume excessive.
Heat-resisting lithium ion battery coated separator as described above, the hole of the coating of the heat-resisting lithium ion battery coated separator
Gap rate is 75-90%.Since micropore can be used as the channel of lithium-ion battery electrolytes, coating needs hole with higher
Rate, porosity is higher, and conductivity is higher, and the internal resistance of battery is smaller.
Heat-resisting lithium ion battery coated separator as described above, after sufficiently being infiltrated with lithium-ion electrolyte, the heat-resisting lithium
The conductivity of ion battery coated separator is more than or equal to the conductivity of the polypropylene lithium ion battery basement membrane, illustrates that the present invention is right
The progress of polypropylene lithium ion battery basement membrane is coating modified can't to reduce its electric conductivity.
Heat-resisting lithium ion battery coated separator as described above, the heat-resisting lithium ion battery coated separator is at temperature T
With automatic shutoff characteristic, this feature is polypropylene diaphragm (unrelated with coating) institute inherent feature, when battery is in high temperature, diaphragm
Hole cavities close, thoroughly break off the positive electrode of lithium ion battery and the connection of negative electrode material, prevent violent electrochemical reaction
Occur.
The present invention also provides a kind of methods for preparing heat-resisting lithium ion battery coated separator as described above, will be heat-resisting organic
Polymer coating liquid is made resistance to through solidification, pore-forming and drying after polypropylene lithium ion battery basement membrane unilateral or bilateral surface is coated with
Hot lithium ion battery coated separator；
The heat-resisting organic polymer coating liquid is mainly made of heat-resisting organic polymer, pore former and water, the pore-forming
Agent is polyvinylpyrrolidone or polyvinyl alcohol.
As a preferred technical scheme:
Method as described above, the specific steps are as follows:
A, heat-resisting organic polymer and pore former are dissolved in the water to obtain heat-resisting organic polymer coating liquid；
B, heat-resisting organic polymer coating liquid is coated on to the unilateral side or two sides of polypropylene lithium ion battery basement membrane, heating is solid
Pore former is cleaned up with water after change, drying obtains finished product.
Solvent of the invention is not limited in water, other can dissolve heat-resisting organic polymer and pore former and facilitate separation
The solvent also applicable present invention.
Method as described above, according to parts by weight, each component content in the heat-resisting organic polymer coating liquid are as follows: resistance to
Hot organic polymer 5-20 parts, 5-20 parts of pore former, 60-90 parts of water.
Method as described above, the cured temperature is 150 DEG C, time 3-10min, in polypropylene when the solidification
The two sides of lithium ion battery basement membrane apply the tension of 200-500cN, to keep smooth, the termination of washing of basement membrane in solidification process
Condition is that pore former removal efficiency is more than or equal to 99.9wt%, and the temperature of the drying is 100 DEG C, time 5-20min.
Invention mechanism:
It, can be significantly after heat-resisting organic polymer (water soluble phenol resin) is coated on polypropylene diaphragm by the present invention
The percent thermal shrinkage of diaphragm is reduced, the heat-resisting organic polymer coating liquor of coating is uniform, and coating layer thickness consistency is good, and can shape
At small and uniform hole.Coating process controllability is higher simultaneously, and water soluble phenol resin has good dissolution in water
Performance can dissolve without adding cosolvent i.e., be conducive to coating solution preparation, pore former recycling and device fabrication, environmentally friendly.
In addition, water soluble phenol resin and pore former are homogeneous system in aqueous solution, pore former and coating segregation in washing process
And remove, being formed has micropore and the higher heat-resisting organic polymer coating of porosity.
The utility model has the advantages that
A, heat-resisting lithium ion battery coated separator of the invention, have good resistance to thermal dimensional stability, at high temperature every
Film contraction is minimum, will not be because there is a phenomenon where inside battery positive and negative anodes short circuit thermals for diaphragm retracts, and then causes lithium ion battery
Swelling fracture and burning are also possible to prevent the expansion of puncture site area when diaphragm pierces through caused positive and negative anodes short circuit heating, prevent
The sharply promotion for only forming larger range of short circuit and temperature, is strict controlled in limited area for temperature rise caused by partial short-circuit
Between, explosion danger is then avoided, safety is good；
B, heat-resisting lithium ion battery coated separator of the invention, wherein heat-resisting organic polymer coating is frivolous, coating weight
Only 1~10 gram/m2；
C, heat-resisting lithium ion battery coated separator of the invention, the micropore uniformity of heat-resisting organic polymer coating is good, applies
Layer porosity is higher；
D, the preparation method of heat-resisting lithium ion battery coated separator of the invention, simple process, it is convenient to operate, at low cost
It is honest and clean, great application prospect.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
The preparation method of heat-resisting lithium ion battery coated separator, the specific steps are as follows:
A, water soluble phenol resin and polyvinylpyrrolidone are dissolved in the water to obtain heat-resisting organic polymer coating liquid,
Wherein, according to parts by weight, each component content in heat-resisting organic polymer coating liquid are as follows: 15 parts of water soluble phenol resin, poly- second
10 parts of alkene pyrrolidone, 75 parts of water；
B, heat-resisting organic polymer coating liquid is coated on to the two sides of polypropylene lithium ion battery basement membrane, is used after being heating and curing
Water cleans up polyvinylpyrrolidone, and drying obtains finished product, wherein cured temperature is 150 DEG C, time 5min, solidification
When polypropylene lithium ion battery basement membrane two sides apply 300cN tension, when pore former removal efficiency be 99.9wt% when wash
It terminates, the temperature of drying is 100 DEG C, time 10min.
Final heat-resisting lithium ion battery coated separator obtained, by polypropylene lithium ion battery basement membrane and its coating of bilateral
Composition；The material of coating is water soluble phenol resin, porosity 78%, and it is 40-60 nanometers micro- that diameter is distributed in coating
Hole, the weight of water soluble phenol resin on every square metre of polypropylene lithium ion battery basement membrane of polypropylene lithium ion battery basement membrane bilateral
It is 4.5 grams；Longitudinal contraction rate of the heat-resisting lithium ion battery coated separator at 190 DEG C is 1.6%, is not shunk laterally；
Folding 102 secondary coating of heat-resisting lithium ion battery coated separator 180 degree and basement membrane be not peeling-off.
After sufficiently being infiltrated with lithium-ion electrolyte, the conductivity of heat-resisting lithium ion battery coated separator be greater than polypropylene lithium from
The conductivity of sub- battery basement membrane.Heat-resisting lithium ion battery coated separator has automatic shutoff characteristic at 190 DEG C.
Embodiment 2
The preparation method of heat-resisting lithium ion battery coated separator, the specific steps are as follows:
A, water soluble phenol resin and polyvinylpyrrolidone are dissolved in the water to obtain heat-resisting organic polymer coating liquid,
Wherein, according to parts by weight, each component content in heat-resisting organic polymer coating liquid are as follows: 20 parts of water soluble phenol resin, poly- second
20 parts of alkene pyrrolidone, 60 parts of water；
B, heat-resisting organic polymer coating liquid is coated on to the two sides of polypropylene lithium ion battery basement membrane, is used after being heating and curing
Water cleans up polyvinylpyrrolidone, and drying obtains finished product, wherein cured temperature is 150 DEG C, time 5min, solidification
When polypropylene lithium ion battery basement membrane two sides apply 300cN tension, when pore former removal efficiency be 99.9wt% when wash
It terminates, the temperature of drying is 100 DEG C, time 10min.
Final heat-resisting lithium ion battery coated separator obtained, by polypropylene lithium ion battery basement membrane and its coating of bilateral
Composition；The material of coating is water soluble phenol resin, porosity 85%, and it is 40-70 nanometers micro- that diameter is distributed in coating
Hole, the weight of water soluble phenol resin is equal on every square metre of polypropylene lithium ion battery basement membrane of propylene lithium ion battery basement membrane bilateral
It is 4 grams；Longitudinal contraction rate of the heat-resisting lithium ion battery coated separator at 190 DEG C is 1.9%, is not shunk laterally；It is heat-resisting
Folding 108 secondary coating of lithium ion battery coated separator 180 degree and basement membrane be not peeling-off.
After sufficiently being infiltrated with lithium-ion electrolyte, the conductivity of heat-resisting lithium ion battery coated separator be greater than polypropylene lithium from
The conductivity of sub- battery basement membrane.Heat-resisting lithium ion battery coated separator has automatic shutoff characteristic at 190 DEG C.
Embodiment 3
The preparation method of heat-resisting lithium ion battery coated separator, the specific steps are as follows:
A, water soluble phenol resin and polyvinylpyrrolidone are dissolved in the water to obtain heat-resisting organic polymer coating liquid,
Wherein, according to parts by weight, each component content in heat-resisting organic polymer coating liquid are as follows: 5 parts of water soluble phenol resin, polyethylene
5 parts of pyrrolidones, 90 parts of water；
B, heat-resisting organic polymer coating liquid is coated on to the two sides of polypropylene lithium ion battery basement membrane, is used after being heating and curing
Water cleans up polyvinylpyrrolidone, and drying obtains finished product, wherein cured temperature is 150 DEG C, time 5min, solidification
When polypropylene lithium ion battery basement membrane two sides apply 300cN tension, when pore former removal efficiency be 100.0wt% when wash
It terminates, the temperature of drying is 100 DEG C, time 10min.
Final heat-resisting lithium ion battery coated separator obtained, by polypropylene lithium ion battery basement membrane and its coating of bilateral
Composition；The material of coating is water soluble phenol resin, porosity 86%, and it is 40-70 nanometers micro- that diameter is distributed in coating
Hole, the weight of water soluble phenol resin is equal on every square metre of polypropylene lithium ion battery basement membrane of propylene lithium ion battery basement membrane bilateral
It is 2.5 grams；Longitudinal contraction rate of the heat-resisting lithium ion battery coated separator at 190 DEG C is 2.9%, is not shunk laterally；It is resistance to
Folding 101 secondary coating of hot lithium ion battery coated separator 180 degree and basement membrane be not peeling-off.
After sufficiently being infiltrated with lithium-ion electrolyte, the conductivity of heat-resisting lithium ion battery coated separator be equal to polypropylene lithium from
The conductivity of sub- battery basement membrane.Heat-resisting lithium ion battery coated separator has automatic shutoff characteristic at 190 DEG C.
Embodiment 4
The preparation method of heat-resisting lithium ion battery coated separator, the specific steps are as follows:
A, water soluble phenol resin and polyvinyl alcohol are dissolved in the water to obtain heat-resisting organic polymer coating liquid, wherein
According to parts by weight, each component content in heat-resisting organic polymer coating liquid are as follows: 10 parts of water soluble phenol resin, polyvinyl alcohol 5
Part, 85 parts of water；
B, heat-resisting organic polymer coating liquid is coated on to the two sides of polypropylene lithium ion battery basement membrane, is used after being heating and curing
Water cleans up polyvinyl alcohol, and drying obtains finished product, wherein cured temperature is 150 DEG C, time 5min, poly- when solidification
The two sides of propylene lithium ion battery basement membrane apply the tension of 300cN, and when pore former removal efficiency is 99.9wt%, washing is terminated, and dry
Dry temperature is 100 DEG C, time 10min.
Final heat-resisting lithium ion battery coated separator obtained, by polypropylene lithium ion battery basement membrane and its coating of bilateral
Composition；The material of coating is water soluble phenol resin, porosity 75%, and it is 30-45 nanometers micro- that diameter is distributed in coating
Hole, the weight of water soluble phenol resin is equal on every square metre of polypropylene lithium ion battery basement membrane of propylene lithium ion battery basement membrane bilateral
It is 5 grams；Longitudinal contraction rate of the heat-resisting lithium ion battery coated separator at 190 DEG C is 1.3%, is not shunk laterally；It is heat-resisting
Folding 110 secondary coating of lithium ion battery coated separator 180 degree and basement membrane be not peeling-off.
After sufficiently being infiltrated with lithium-ion electrolyte, the conductivity of heat-resisting lithium ion battery coated separator be equal to polypropylene lithium from
The conductivity of sub- battery basement membrane.Heat-resisting lithium ion battery coated separator has automatic shutoff characteristic at 190 DEG C.
Embodiment 5
The preparation method of heat-resisting lithium ion battery coated separator, the specific steps are as follows:
A, water soluble phenol resin and polyvinyl alcohol are dissolved in the water to obtain heat-resisting organic polymer coating liquid, wherein
According to parts by weight, each component content in heat-resisting organic polymer coating liquid are as follows: 10 parts of water soluble phenol resin, polyvinyl alcohol 15
Part, 75 parts of water；
B, heat-resisting organic polymer coating liquid is coated on to the two sides of polypropylene lithium ion battery basement membrane, is used after being heating and curing
Water cleans up polyvinyl alcohol, and drying obtains finished product, wherein cured temperature is 150 DEG C, time 5min, poly- when solidification
The two sides of propylene lithium ion battery basement membrane apply the tension of 300cN, and when pore former removal efficiency is 99.9wt%, washing is terminated, and dry
Dry temperature is 100 DEG C, time 10min.
Final heat-resisting lithium ion battery coated separator obtained, by polypropylene lithium ion battery basement membrane and its coating of bilateral
Composition；The material of coating is water soluble phenol resin, porosity 90%, and it is 30-50 nanometers micro- that diameter is distributed in coating
Hole, the weight of water soluble phenol resin is equal on every square metre of polypropylene lithium ion battery basement membrane of propylene lithium ion battery basement membrane bilateral
It is 3 grams；Longitudinal contraction rate of the heat-resisting lithium ion battery coated separator at 190 DEG C is 2.7%, is not shunk laterally；It is heat-resisting
Folding 101 secondary coating of lithium ion battery coated separator 180 degree and basement membrane be not peeling-off.
After sufficiently being infiltrated with lithium-ion electrolyte, the conductivity of heat-resisting lithium ion battery coated separator be greater than polypropylene lithium from
The conductivity of sub- battery basement membrane.Heat-resisting lithium ion battery coated separator has automatic shutoff characteristic at 190 DEG C.
Embodiment 6
The preparation method of heat-resisting lithium ion battery coated separator, the specific steps are as follows:
A, water soluble phenol resin and polyvinyl alcohol are dissolved in the water to obtain heat-resisting organic polymer coating liquid, wherein
According to parts by weight, each component content in heat-resisting organic polymer coating liquid are as follows: 8 parts of water soluble phenol resin, polyvinyl alcohol 11
Part, 80 parts of water；
B, heat-resisting organic polymer coating liquid is coated on to the unilateral side of polypropylene lithium ion battery basement membrane, is used after being heating and curing
Water cleans up polyvinyl alcohol, and drying obtains finished product, wherein cured temperature is 150 DEG C, time 3min, poly- when solidification
The two sides of propylene lithium ion battery basement membrane apply the tension of 500cN, and when pore former removal efficiency is 99.9wt%, washing is terminated, and dry
Dry temperature is 100 DEG C, time 5min.
Final heat-resisting lithium ion battery coated separator obtained, by polypropylene lithium ion battery basement membrane and the coating of one side
Composition；The material of coating is water soluble phenol resin, porosity 80%, and it is 40-60 nanometers micro- that diameter is distributed in coating
Hole, the weight of water soluble phenol resin is 1 gram on every square metre of polypropylene lithium ion battery basement membrane；Heat-resisting lithium ion battery coating
Longitudinal contraction rate of the diaphragm at 200 DEG C is 2.4%, is not shunk laterally；Heat-resisting lithium ion battery coated separator 180 degree is anti-
It is not peeling-off with basement membrane that 110 secondary coatings are folded again.
After sufficiently being infiltrated with lithium-ion electrolyte, the conductivity of heat-resisting lithium ion battery coated separator be greater than polypropylene lithium from
The conductivity of sub- battery basement membrane.Heat-resisting lithium ion battery coated separator has automatic shutoff characteristic at 200 DEG C.
Embodiment 7
The preparation method of heat-resisting lithium ion battery coated separator, the specific steps are as follows:
A, water soluble phenol resin and polyvinylpyrrolidone are dissolved in the water to obtain heat-resisting organic polymer coating liquid,
Wherein, according to parts by weight, each component content in heat-resisting organic polymer coating liquid are as follows: 14 parts of water soluble phenol resin, poly- second
17 parts of alkene pyrrolidone, 69 parts of water；
B, heat-resisting organic polymer coating liquid is coated on to the unilateral side of polypropylene lithium ion battery basement membrane, is used after being heating and curing
Water cleans up polyvinylpyrrolidone, and drying obtains finished product, wherein cured temperature is 150 DEG C, time 10min, Gu
Apply the tension of 200cN, the water when pore former removal efficiency is 99.98wt% when change in the two sides of polypropylene lithium ion battery basement membrane
Termination is washed, the temperature of drying is 100 DEG C, time 20min.
Final heat-resisting lithium ion battery coated separator obtained, by polypropylene lithium ion battery basement membrane and the coating of one side
Composition；The material of coating is water soluble phenol resin, porosity 79%, and it is 50-70 nanometers micro- that diameter is distributed in coating
Hole, the weight of water soluble phenol resin is 10 grams on every square metre of polypropylene lithium ion battery basement membrane；Heat-resisting lithium ion battery applies
Longitudinal contraction rate of the layer diaphragm at 210 DEG C is 3.0%, is not shunk laterally；Heat-resisting lithium ion battery coated separator 180 degree
Folding 105 secondary coating and basement membrane be not peeling-off.
After sufficiently being infiltrated with lithium-ion electrolyte, the conductivity of heat-resisting lithium ion battery coated separator be greater than polypropylene lithium from
The conductivity of sub- battery basement membrane.Heat-resisting lithium ion battery coated separator has automatic shutoff characteristic at 210 DEG C.
Claims (9)
1. heat-resisting lithium ion battery coated separator, it is characterized in that: by polypropylene lithium ion battery basement membrane and one side or bilateral
Coating composition；
The material of the coating is heat-resisting organic polymer, and the heat-resisting organic polymer is water soluble phenol resin, the painting
The micropore that diameter is 30-70 nanometers is distributed in layer；
Longitudinal contraction rate≤3.0% of the heat-resisting lithium ion battery coated separator at temperature T is not shunk laterally, T >=190
℃；
Heat-resisting lithium ion battery coated separator 180 degree folding 100 times or more coatings and basement membrane be not peeling-off.
2. heat-resisting lithium ion battery coated separator according to claim 1, which is characterized in that every square metre of polypropylene lithium from
The weight of heat resistance organic polymer is 1-10 grams on sub- battery basement membrane.
3. heat-resisting lithium ion battery coated separator according to claim 1, which is characterized in that the porosity of the coating is
75-90%.
4. heat-resisting lithium ion battery coated separator according to claim 1, which is characterized in that abundant with lithium-ion electrolyte
After infiltration, the conductivity of the heat-resisting lithium ion battery coated separator is more than or equal to the electricity of the polypropylene lithium ion battery basement membrane
Conductance.
5. heat-resisting lithium ion battery coated separator according to claim 1, which is characterized in that the heat-resisting lithium ion battery
Coated separator has automatic shutoff characteristic at temperature T.
6. the method for preparing heat-resisting lithium ion battery coated separator as claimed in any one of claims 1 to 5, it is characterized in that: will
Heat-resisting organic polymer coating liquid is after polypropylene lithium ion battery basement membrane unilateral or bilateral surface is coated with through solidification, pore-forming and baking
It is drying to obtain heat-resisting lithium ion battery coated separator；
The heat-resisting organic polymer coating liquid is mainly made of heat-resisting organic polymer, pore former and water, and the pore former is
Polyvinylpyrrolidone or polyvinyl alcohol.
7. according to the method described in claim 6, it is characterized in that, specific step is as follows:
A, heat-resisting organic polymer and pore former are dissolved in the water to obtain heat-resisting organic polymer coating liquid；
B, heat-resisting organic polymer coating liquid is coated on to the unilateral side or two sides of polypropylene lithium ion battery basement membrane, after being heating and curing
Pore former is cleaned up with water, drying obtains finished product.
8. the method according to the description of claim 7 is characterized in that according to parts by weight, the heat-resisting organic polymer coating
Each component content in liquid are as follows: heat-resisting organic polymer 5-20 parts, 5-20 parts of pore former, 60-90 parts of water.
9. the method according to the description of claim 7 is characterized in that the cured temperature be 150 DEG C, time 3-10min,
Apply the tension of 200-500cN when the solidification in the two sides of polypropylene lithium ion battery basement membrane, the termination condition of washing be at
Agent removal efficiency in hole is more than or equal to 99.9wt%, and the temperature of the drying is 100 DEG C, time 5-20min.
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