CN106910855B - Lithium ion battery separator and preparation method thereof and lithium ion battery - Google Patents
Lithium ion battery separator and preparation method thereof and lithium ion battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- 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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Abstract
Field of lithium ion battery of the present invention specifically discloses lithium ion battery separator of a kind of heat resistance raising and preparation method thereof and lithium ion battery.It include: that polyethylene, crosslinking agent and cross-linking aid melt blending are obtained mixture A by (1)；(2) the mixture A is shaped to initial diaphragm B, the gel content of the initial diaphragm B is less than 5 weight %；(3) the initial diaphragm B is subjected to high-temperature cross-linking and forms cross linking membrane C, the gel content of the cross linking membrane C is 30-70 weight %；(4) it is stretched the cross linking membrane C to obtain stretched film D；(5) it is made annealing treatment the stretched film D to obtain lithium ion battery separator；Wherein, the melt index MI of the polyethylene is 0.02g/10min~5g/10min；Relative to the polyethylene of 100 parts by weight, the dosage of the crosslinking agent is 0.03~8 parts by weight, and the dosage of the cross-linking aid is 0.03~10 parts by weight.The lithium ion battery separator of heat resistance raising can be made according to the method.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular, to a kind of lithium ion battery separator and preparation method and
Lithium ion battery.
Background technique
Lithium ion battery separator is the important component of lithium ion battery, it is a kind of insulation porous membrane, main to make
With being to separate the positive and negative electrode of battery, free ion is allowed therebetween to pass through, prevent the two poles of the earth from contacting and short-circuit, additionally
Have the function of electrolyte ion capable of being made to pass through.Specifically, which needs certain porosity and pore-size distribution, allow ion just
Often pass through, safety is in addition provided in lithium ion battery use process: on the one hand isolation positive and negative anodes prevent the two from directly contacting
And it is short-circuit；On the other hand in battery because of external fault or internal short-circuit, when inside battery being caused to react thermal runaway, which can be
Normal Self-closed hole under lower temperature, partition battery plus-negative plate reaction, makes battery stop working, and in reaction stopping but internal temperature
When continuously rising to higher temperature, diaphragm still has enough high temperature resistances, remain dimensionally-stable will not holes, that is, have higher
Broken film temperature.Therefore, it is desirable to which obtaining diaphragm i.e. has lower Self-closed hole temperature to have higher holes temperature again.The performance of the diaphragm is very
Capacity, internal resistance and the cycle performance that battery is determined in big degree, are of great significance to the comprehensive performance for improving battery.
Current commercialized lithium ion battery separator is mainly the polyolefine materials such as polyethylene, polypropylene, this is because poly-
Olefin(e) compound can provide good mechanical strength and heat resistance within the scope of relatively reasonable cost, and at high temperature also
Have heat and close performance, to improve the security performance of lithium ion battery separator.
CN102134342A discloses a kind of crosslinking polyolefin microporous membrane, and preparing raw material includes polyolefin, cosolvent, mistake
Oxygen compound, silane and antioxidant.It is initially formed MIcroporous polyolefin film in its disclosed preparation method, then completes to be crosslinked again.
CN103421208B discloses a kind of cross-linking radiation lithium ion battery separator and preparation method thereof.It will gather including (1)
Ethylene porous septum be immersed in the photoinitiator containing 0.01-10 mass %, 0.01-10 mass % crosslinking agent effumability
5 seconds or more in organic solvent, drying at room temperature after taking-up；(2) by diaphragm the hydrophilic monomer of 0-5 mass % aqueous solution liquid level
With irradiation bomb irradiation 2 seconds or more at following 1-50mm, or directly the diaphragm after immersion is placed under inert gas shielding with irradiation
Source irradiation 2 seconds or more, irradiation temperature was room temperature to 110 DEG C, and it is poly- to obtain cross-linking radiation from irradiation bomb distance 3-15cm for membrane surface
Ethylene porous septum.
CN103059375A discloses a kind of Lithium-ion battery diaphragm master batch, including high density polyethylene (HDPE), crosslinking agent, hydrophilic
Modified aluminum oxide nano-powder, the density of high density polyethylene (HDPE) are 0.95-0.96, and average molecular weight is 200,000-50 ten thousand, are handed over
Connection agent is tert-butyl hydroperoxide.Also disclosed preparation method includes by three oxygen of high density polyethylene (HDPE), crosslinking agent and hydrophilic modifying
Change and obtains Lithium-ion battery diaphragm master batch through extruding pelletization after two aluminum nanopowders are uniformly mixed.
CN101345296B discloses a kind of lithium ion battery separator preparation method, including by molecular weight 1,000,000-700 ten thousand
Ultra high molecular polyethylene, polynorbornene crosslinking agent, antioxidant and mineral oil be stirred under the conditions of 40-300rpm；It will
Mixture after stirring is squeezed out to obtain substrate；Substrate is cooled and shaped at 5-40 DEG C；Biaxial tension is carried out into film to substrate；Make
With the mineral oil in high concentration alkane kind of extractants extraction film；It will be heat-treated to obtain lithium-ion electric through film extracted
Pond diaphragm.
In actual production, the lithium ion battery separator of the prior art there are poor heat resistance, processing technology is complicated, technique at
The defects of this is high.
Summary of the invention
It is complicated that the purpose of the present invention is to solve prior art processing technologys, and process costs are high, and product film heat resistance is poor
The problem of, provide a kind of lithium ion battery separator and preparation method and lithium ion battery.
To achieve the goals above, the present invention provides a kind of preparation methods of lithium ion battery separator, comprising: (1) will
Polyethylene, pore former, crosslinking agent and cross-linking aid melt blending obtain mixture A；(2) the mixture A is shaped to initially
Diaphragm B, the gel content of the initial diaphragm B is less than 5 weight %；(3) the initial diaphragm B is subjected to high-temperature cross-linking and forms friendship
Join film C, the gel content of the cross linking membrane C is 30~70 weight %；(4) it is stretched the cross linking membrane C to obtain stretched film
D；(5) it is made annealing treatment the stretched film D to obtain lithium ion battery separator；Wherein, the melt index MI of the polyethylene
For 0.02g/10min~5g/10min；Relative to the polyethylene of 100 parts by weight, the dosage of the crosslinking agent is 0.03~8
Parts by weight, the dosage of the cross-linking aid are 0.03~10 parts by weight.
The present invention also provides a kind of lithium ion battery separators as made from method of the invention.
The present invention also provides a kind of lithium ion batteries, including lithium-ion membrane of the invention.
The present invention in order to realize goal of the invention, selected with polyethylene composition with specific by the lithium ion battery separator provided
The polyethylene of MI is matrix resin, improves melt and is drawn again further combined with specific crosslinking agent and cross-linking aid by being first crosslinked
The preparation method stretched obtains the lithium ion battery separator of heat resistance raising.The diaphragm can have 30% or more hole
Rate, the diaphragm area conservation rate after 120s is kept at 170 DEG C are 80% or more.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is isothermal rheological curve of the mixture A at 150 DEG C in embodiment 1；
Fig. 2 is the surface topography stereoscan photograph of lithium ion battery separator prepared by embodiment 1；
Fig. 3 is the surface topography stereoscan photograph of lithium ion battery separator prepared by comparative example 2.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of preparation methods of lithium ion battery separator, comprising: (1) by polyethylene, pore former, friendship
Connection agent and cross-linking aid melt blending obtain mixture A；(2) the mixture A is shaped to initial diaphragm B, the initial film
The gel content of piece B is less than 5 weight %；(3) the initial diaphragm B is subjected to high-temperature cross-linking and forms cross linking membrane C, the cross linking membrane
The gel content of C is 30~70 weight %；(4) it is stretched the cross linking membrane C to obtain stretched film D；(5) by the stretched film
D is made annealing treatment to obtain lithium ion battery separator；Wherein, the melt index MI of the polyethylene is 0.02g/10min~5g/
10min；Relative to the polyethylene of 100 parts by weight, the dosage of the crosslinking agent is 0.03~8 parts by weight, and the crosslinking helps
The dosage of agent is 0.03~10 parts by weight.
, according to the invention it is preferred to, the melt index MI of the polyethylene is 0.1g/10min~3g/10min.Melting refers to
Number MI can be measured according to ASTM D 1238.
Preferred embodiment according to the present invention, the polyethylene are high density polyethylene (HDPE), the density of the preferably described polyethylene
For 0.945g/cm3~0.962g/cm3, more preferably 0.950g/cm3~0.962g/cm3。
, according to the invention it is preferred to, the crosslinking agent be selected from 2,5- dimethyl -2,5- di-t-butyl peroxy -3- hexin,
Cumyl peroxide, t-butylcumylperoxide, 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, 3,3,5,
One of three oxygen ring in heptan of 7,7- pentamethyl -1,2,4- and 1,4- dual-tert-butyl cumene hydroperoxide are a variety of.
, according to the invention it is preferred to, the cross-linking aid be triallylcyanurate, Triallyl isocyanurate,
One of trimethylol-propane trimethacrylate and trimethylolpropane trimethacrylate are a variety of.
In the preparation method of lithium ion battery separator provided by the invention, from each component for preparing lithium ion battery separator
It being blended into during obtaining diaphragm, control preparation step first crosslinks and then again stretches cross linking membrane, so as to
Preferably matched with polyethylene composition composition formula such as lithium ion battery separator of the invention, obtain lithium that heat resistance improves from
Sub- battery diaphragm.Specifically, can the gel content of the product as made from each step determine whether to control the hair of cross-linking reaction
Raw, the gel content of the product made from step (1) and (2) is low, is only the blending of each component material and is shaped to initial diaphragm.
And control carries out high-temperature cross-linking in step (3), gel content is 30~70 weight % in cross linking membrane obtained.
It in preparation method of the invention, is stretched again on the basis of obtaining cross linking membrane, cooperation can be more advantageous to originally
The lithium ion battery separator of invention obtains the lithium ion battery separator of heat resistance raising with polyethylene composition.
According to the present invention, in step (1), the melt blending is implemented in double screw extruder, the melt blending
Temperature be 140~160 DEG C.
, according to the invention it is preferred to, the gel content of the mixture A is less than 1 weight %.Illustrate that there is no a large amount of
Crosslinking.
, according to the invention it is preferred to, in step (2), the molding temperature is 25~150 DEG C.Mixture A is formed
For initial diaphragm B, casting film-forming can be, be also possible to tabletting film forming.
, according to the invention it is preferred to, in step (3), the hot crosslinked temperature is 180~230 DEG C.
, according to the invention it is preferred to, in step (4), the temperature of the stretching is 90~150 DEG C.The stretching can be with
It is simple tension, is also possible to biaxial tension.
, according to the invention it is preferred to, in step (5), the temperature of the annealing is 110~150 DEG C.The annealing can be with
There is stress relaxation effect.
The present invention also provides a kind of lithium ion battery separators as made from method of the invention.
According to the present invention, the gel content of the diaphragm is 30~70 weight %, preferably 40~65 weight %.
, according to the invention it is preferred to, the porosity of the diaphragm is 30% or more.
, according to the invention it is preferred to, the diaphragm kept at 170 DEG C the diaphragm area conservation rate after 120s be 80% with
On.
The present invention also provides a kind of lithium ion batteries, including lithium-ion membrane of the invention.
The main member of the lithium ion battery may include electrode, isolation film and electrolyte.Electrode and electrolyte can be with
It is repeated no more to be well known in the art.The lithium ion battery can use battery forms well known in the art and structure, wherein
Isolation film be lithium-ion membrane of the invention.
The present invention will be described in detail by way of examples below.
In following embodiment, the measurement of gel content:
It is obtained according to ASTM-D2765 measurement dimethylbenzene insolubles content.A certain amount of polyvinyl resin clast is taken, is wrapped in
In the copper mesh of 120 mesh, it is put into the conical flask with reflux unit, using dimethylbenzene as solvent, after boiling reflux at least 24 hours,
Drying calculates the content of insoluble matter, i.e. gel content to constant weight；
Pore-forming situation is observed by Electronic Speculum in the surface of lithium ion battery separator, and Electronic Speculum is FEI Co. Nova NanoSEM
The scanning electron microscope instrument of 450 models；
The porosity of lithium ion battery separator is tested by hexadecane method:
First by diaphragm samples weighing, it is then immersed in 1h in analytically pure hexadecane, taking-up wipes surface extraction raffinate away with filter paper,
It is calculate by the following formula porosity: ε %=(VHexadecane/VSample) × 100%, VHexadecaneIndicate hexadecane volume；VSampleIndicate sample volume；
The heat resistance of lithium ion battery separator is tested:
Baking oven with form is warming up to testing temperature (170 DEG C), while the both sides of sample to be tested film are fixed on one
Size on rectangular quoit, before writing down sample test.After the temperature of baking oven to be measured stablizes 5min, oven door is opened one
Sample to be tested is put into baking oven rapidly, while pressing manual time-keeping by a crack, observes test specimens by the visual windows of baking oven
The situation of change of product film.After testing time, sample is taken out rapidly out of test oven, is down to room temperature to sample temperature
When, the size of sample is measured, the area conservation rate of diaphragm before and after being put into baking oven is calculated,
Diaphragm area conservation rate %=(area/diaphragm of the diaphragm by baking oven test is put into the initial area before baking oven)
× 100%
If sample fuses during the test or starts to fuse, it is considered as sample film and breaks, no longer need to sample size.
Embodiment 1
(1) lithium ion battery separator polyethylene composition composition formula:
Matrix resin is the HDPE (density=0.960g/cm of MI=0.3g/10min3) 100g, 2,5- dimethyl -2,5-
Two (tert-butyl peroxy base) hexane 0.7g, Triallyl isocyanurate 1.1g.
(2) prepared by lithium ion battery separator:
Double screw extruder (draw ratio 18/1, the revolving speed of screw rod of each component in low sheraing of above-mentioned formula will be formed
Be 100 revs/min) in extruding pelletization obtain mixture A, blending temperature is 140 DEG C, while testing mixture A in 150 DEG C of isothermals
The rheological curve of 30min, as shown in Figure 1.As seen from Figure 1, during melt blending, the viscosity of mixture A is in test-strips
It can be held essentially constant under part, illustrate that the processing heat stability of this compound composition is good, there is no crosslinkings.Mixture A sampling
Measurement gel content is 0.5 weight %；
Mixture A is formed into (forming temperature is 140 DEG C) in a manner of tabletting and obtains initial diaphragm B, initial diaphragm B sampling is surveyed
Determining gel content is 0.5 weight %；
By initial diaphragm B, cross linking membrane C, high-temperature cross-linking, crosslinking at 180 DEG C in tableting processes is made in tabletting in tablet press machine
Gel content is measured by sampling in film C, and the content of diformazan benzene insoluble is 62 weight %；
Cross linking membrane C is subjected to simple tension 550% at 130 DEG C, obtains stretched film D；It is handled again in 130 DEG C of isothermal annealings
5min obtains lithium ion battery separator.
The surface of lithium ion battery separator is subjected to Electronic Speculum observation, photo is as shown in Figure 2.As can be seen from Figure 2, lithium-ion electric
There is the hole of large stretch of even aperture distribution in pond diaphragm.
It is 45% by the porosity of lithium ion battery separator hexadecane method test film.
Lithium ion battery separator is subjected to heat resistance test, keeps at 170 DEG C 120s diaphragm by white bleach, diaphragm
Area conservation rate is 85%.
Embodiment 2
(1) lithium ion battery separator polyethylene composition composition formula:
Matrix resin is the HDPE (density=0.955g/cm of MI=2g/10min3) 100g, 2,5- dimethyl -2,5- bis-
(tert-butyl peroxy base) hexane 0.7g, Triallyl isocyanurate 1.1g.
(2) prepared by lithium ion battery separator:
Double screw extruder (draw ratio 18/1, the revolving speed of screw rod of each component in low sheraing of above-mentioned formula will be formed
Be 100 revs/min) in extruding pelletization obtain mixture A, blending temperature is 150 DEG C, and the rheology for testing mixture A with embodiment 1 is bent
Line, it is same as Example 1 to be held essentially constant, illustrate that the processing heat stability of this compound composition is good, there is no crosslinkings.It is mixed
Closing object A and gel content is measured by sampling is 0.5 weight %；
Mixture A is formed into (forming temperature is 145 DEG C) in a manner of tabletting and obtains initial diaphragm B, initial diaphragm B sampling is surveyed
Determining gel content is 0.5 weight %；
By initial diaphragm B, cross linking membrane C, high-temperature cross-linking, crosslinking at 230 DEG C in tableting processes is made in tabletting in tablet press machine
Gel content is measured by sampling in film C, and the content of diformazan benzene insoluble is 66 weight %；
Cross linking membrane C is subjected to simple tension 400% at 130 DEG C, obtains stretched film D；It is handled again in 110 DEG C of isothermal annealings
5min lithium ion battery separator.
The surface of lithium ion battery separator is subjected to Electronic Speculum observation, big film perforation occurs with the similar lithium ion battery separator of Fig. 2
The hole that diameter is evenly distributed.
It is 41% by the porosity of lithium ion battery separator hexadecane method test film.
Lithium ion battery separator is subjected to heat resistance test, keeps at 170 DEG C 120s diaphragm by white bleach, diaphragm
Area conservation rate is 83%.
Embodiment 3
(1) lithium ion battery separator polyethylene composition composition formula:
Matrix resin is the HDPE (density=0.960g/cm of MI=0.3g/10min3) 100g, 2,5- dimethyl -2,5-
Two (tert-butyl peroxy base) hexane 0.65g, Triallyl isocyanurate 1g.
(2) prepared by lithium ion battery separator:
Double screw extruder (draw ratio 18/1, the revolving speed of screw rod of each component in low sheraing of above-mentioned formula will be formed
Be 100 revs/min) in extruding pelletization obtain mixture A, blending temperature is 150 DEG C, and the rheology for testing mixture A with embodiment 1 is bent
Line, it is same as Example 1 to be held essentially constant, illustrate that the processing heat stability of this compound composition is good, there is no crosslinkings.It is mixed
Closing object A and gel content is measured by sampling is 0.5 weight %；
Mixture A is formed into (forming temperature is 145 DEG C) in a manner of tabletting and obtains initial diaphragm B, initial diaphragm B sampling is surveyed
Determining gel content is 0.5 weight %；
By initial diaphragm B, cross linking membrane C, high-temperature cross-linking, crosslinking at 180 DEG C in tableting processes is made in tabletting in tablet press machine
Gel content is measured by sampling in film C, and the content of diformazan benzene insoluble is 58 weight %；
Cross linking membrane C is subjected to simple tension 620% at 132 DEG C, obtains stretched film D；It is handled again in 132 DEG C of isothermal annealings
5min lithium ion battery separator.
The surface of lithium ion battery separator is subjected to Electronic Speculum observation, big film perforation occurs with the similar lithium ion battery separator of Fig. 2
The hole that diameter is evenly distributed.
It is 48% by the porosity of lithium ion battery separator hexadecane method test film.
Lithium ion battery separator is subjected to heat resistance test, keeps at 170 DEG C 120s diaphragm by white bleach, diaphragm
Area conservation rate is 81%.
Comparative example 1
(1) be formulated: matrix resin is the HDPE (density=0.960g/cm of MI=0.3g/10min3)。
(2) it prepares: being obtained through extruding pelletization in double screw extruder (draw ratio 18/1, the revolving speed of screw rod are 100 revs/min)
Expect that A, extrusion temperature are 140 DEG C；
Material A tabletting is obtained into initial diaphragm B；
Initial diaphragm B is subjected to stretching 330% at 130 DEG C, diaphragm is broken when stretching, and the high temperature tensile strength of diaphragm is non-
It is often poor.
Comparative example 2
(1) be formulated: matrix resin is the HDPE (density=0.948g/cm of MI=8.5g/10min3) 100g, 2,5- diformazans
Base -2,5- bis- (tert-butyl peroxy base) hexane 0.7g, Triallyl isocyanurate 1.1g.
(2) it prepares: according to the method for embodiment 1, lithium ion battery separator is made.
The surface of lithium ion battery separator is subjected to Electronic Speculum observation, photo is as shown in Figure 3.From figure 3, it can be seen that film surface without
Hole.
Comparative example 3
(1) be formulated: matrix resin is the HDPE (density=0.960g/cm of MI=0.3g/10min3) 100g, 2,5- diformazans
Base -2,5- bis- (tert-butyl peroxy base) hexane 0.7g, Triallyl isocyanurate 1.1g.
(2) it prepares: double screw extruder (draw ratio 18/1, spiral shell of each component in low sheraing of above-mentioned formula will be formed
The revolving speed of bar is 100 revs/min) in extruding pelletization obtain mixture A, blending temperature is 140 DEG C；
By mixture A, cross linking membrane C is made in tabletting in tablet press machine, in tableting processes at 240 DEG C high-temperature cross-linking；
By cross linking membrane C at 80 DEG C simple tension 200% or so, stretched film is broken.
Stretched film is subjected to gel content test, the content of diformazan benzene insoluble is 81 weight %.
Comparative example 4
(1) be formulated: matrix resin is the PE (density=0.965g/cm of MI=0.01g/10min3) 100g, 2,5- diformazans
Base -2,5- bis- (tert-butyl peroxy base) hexane 0.7g, Triallyl isocyanurate 1.1g.
(2) it prepares: according to the method for embodiment 1.
Melt blending cannot be completed, cannot get lithium ion battery separator.
The lithium ion battery separator polyethylene composition provided by the invention it can be seen from above embodiments and comparative example
Lithium ion battery separator preparation method through the invention can obtain the lithium ion battery separator of heat resistance raising.It can be with
With 30% or more porosity, the diaphragm area conservation rate after 120s is kept at 170 DEG C is 80% or more.
Claims (12)
1. a kind of preparation method of lithium ion battery separator, comprising:
(1) polyethylene, crosslinking agent and cross-linking aid melt blending are obtained into mixture A；
(2) the mixture A is shaped to initial diaphragm B, the gel content of the initial diaphragm B is less than 5 weight %；
(3) the initial diaphragm B is subjected to high-temperature cross-linking and forms cross linking membrane C, the gel content of the cross linking membrane C is 30~70 weights
Measure %；
(4) it is stretched the cross linking membrane C to obtain stretched film D；
(5) it is made annealing treatment the stretched film D to obtain lithium ion battery separator；
Wherein, the melt index MI of the polyethylene is 0.02g/10min~5g/10min；Relative to described in 100 parts by weight
Polyethylene, the dosage of the crosslinking agent are 0.03~8 parts by weight, and the dosage of the cross-linking aid is 0.03~10 parts by weight；
In step (3), the hot crosslinked temperature is 180~230 DEG C.
2. according to the method described in claim 1, wherein, the polyethylene is high density polyethylene (HDPE).
3. according to the method described in claim 2, wherein, the density of the polyethylene is 0.945g/cm3~0.962g/cm3。
4. according to the method described in claim 1, wherein, the crosslinking agent is selected from 2,5- dimethyl -2,5-, bis- (t-butyl peroxy
Base) -3- hexin, cumyl peroxide, t-butylcumylperoxide, 2,5- dimethyl -2,5- two (t-butylperoxy)
One of hexane, three oxygen ring in heptan of 3,3,5,7,7- pentamethyl -1,2,4- and 1,4- dual-tert-butyl cumene hydroperoxide are more
Kind；
The cross-linking aid is triallylcyanurate, Triallyl isocyanurate, trimethylol propane trimethyl propylene
One of acid esters and trimethylolpropane trimethacrylate are a variety of.
5. according to the method described in claim 1, wherein, in step (1), the melt blending is real in double screw extruder
It applies, the temperature of the melt blending is 140~160 DEG C.
6. method according to claim 1 or 5, wherein in step (1), the gel content of the mixture A is less than 1
Weight %.
7. according to the method described in claim 1, wherein, in step (2), the molding temperature is 25~150 DEG C.
8. according to the method described in claim 1, wherein, in step (4), the temperature of the stretching is 90~150 DEG C.
9. according to the method described in claim 1, wherein, in step (5), the temperature of the annealing is 110~150 DEG C.
10. a kind of lithium ion battery separator as made from method of any of claims 1-9.
11. diaphragm according to claim 10, wherein the gel content of the diaphragm is 30~70 weight %, porosity
It is 30% or more, the diaphragm area conservation rate after 120s is kept at 170 DEG C is 80% or more.
12. a kind of lithium ion battery, including lithium ion battery separator described in claim 10 or 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510977545.2A CN106910855B (en) | 2015-12-23 | 2015-12-23 | Lithium ion battery separator and preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
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| CN111497293B (en) * | 2020-03-31 | 2022-04-05 | 江苏厚生新能源科技有限公司 | Preparation method of high-wettability film, high-wettability film and application thereof |
| CN112768844B (en) * | 2021-01-12 | 2023-03-24 | 天津市捷威动力工业有限公司 | Long-lasting tab and application |
| CN113659289B (en) * | 2021-08-09 | 2023-06-09 | 界首市天鸿新材料股份有限公司 | Three-layer co-extrusion diaphragm capable of reducing closed pore temperature of lithium battery diaphragm |
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| CN104993081A (en) * | 2015-05-22 | 2015-10-21 | 宁波大学 | Production method of cross-linked polyethylene lithium ion battery diaphragm |
| CN104987576A (en) * | 2015-07-09 | 2015-10-21 | 神华集团有限责任公司 | Polyethylene composition, preparing method thereof and high polymer product capable of being painted, high in resistance and resistant to temperature |
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| CN104993081A (en) * | 2015-05-22 | 2015-10-21 | 宁波大学 | Production method of cross-linked polyethylene lithium ion battery diaphragm |
| CN104987576A (en) * | 2015-07-09 | 2015-10-21 | 神华集团有限责任公司 | Polyethylene composition, preparing method thereof and high polymer product capable of being painted, high in resistance and resistant to temperature |
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