CN104140502A - Binder for lithium ion battery diaphragm, preparation method and diaphragm using the same - Google Patents
Binder for lithium ion battery diaphragm, preparation method and diaphragm using the same Download PDFInfo
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- CN104140502A CN104140502A CN201310571644.1A CN201310571644A CN104140502A CN 104140502 A CN104140502 A CN 104140502A CN 201310571644 A CN201310571644 A CN 201310571644A CN 104140502 A CN104140502 A CN 104140502A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a binder for a lithium ion battery diaphragm, a preparation method and a diaphragm using the same. The binder comprises the following raw materials by weight: 0.5-1 part of a water-soluble polymer, 1-10 parts of a flexible segment monomer, 1-10 parts of a rigid segment monomer, 0.01-0.05 part of an initiator, and 1-10 parts of a plasticizer. The binder for the lithium ion battery diaphragm provided by the invention can be mixed with an inorganic matter to serve as a coating material of the lithium ion battery diaphragm, and the thermal stability and anti-thermal shrinkage performance of the diaphragm can be improved, so that the likely internal short circuit problem caused by poor thermal stability of the existing lithium ion battery diaphragms can be solved, and the diaphragm can have good safety and overcharge tolerance. At the same time, the binder contains polar groups, which can closely bonds with the inorganic matter to improve the wettability and liquid retention of the diaphragm. The flexible segment is introduced while the rigid segment exists, thereby improving the mechanical properties of the binder and guaranteeing the bonding force and the flexibility of the diaphragm.
Description
Technical field
The invention belongs to lithium ion battery separator technical field, be specifically related to a kind of lithium ion battery separator binding agent, also relate to a kind of lithium ion battery separator by the preparation method of binding agent simultaneously and use the barrier film of this binding agent.
Background technology
Lithium ion battery, owing to having higher specific energy density, has become the focus of current electrochemical industry research.At the negative electrode of this type of battery, include the transition metal oxides such as manganese, cobalt, vanadium or nickel, according to the simplest stoichiometry situation, can be described as LiMn
2o
4, LiCoO
2, LiV
2o
5or LiNiO
2, also include and developed in recent years transition metal phosphate, the silicate etc. such as iron, manganese, cobalt, vanadium or nickel rapidly.There is reversible reaction with the compound (as graphite) that can be incorporated into lithium ion in lattice in these compounds, shifts out lithium ion from lattice; In this process, ferrimanganic cobalt nickel is oxidized, and this reaction may be used in chemical cell in order to store electrical energy.Wherein, the compound (anode material) that can accept lithium ion with ionogen is separated from each other with the compound (cathode material) containing lithium, the lithium ion of lithium-containing compound by electrolyte in anode material.
Between battery charge period, along with lithium ion through ionogen by cathode system anode, electronics flows to negative electrode by external circuit by anode.For avoiding chemical cell to occur short circuit, between anode and cathode, need to place the material there is insulativity and to allow lithium ion to pass through, Here it is so-called battery diaphragm.
Battery diaphragm refers to the porous material that the one deck between anode and negative pole is thin, is part very crucial in battery, and the security of battery and cost are had a direct impact.Battery diaphragm should have the physical strength that macroion rate of permeation is become reconciled, and chemical substance used and solvent in system (as the electrolytic solution of battery) are had to permanent stability.In battery, barrier film must make negative electrode and anode electrode isolate completely, but makes electrolytic solution see through simultaneously; Must there is lasting elasticity, and in charging and discharging process, follow system (for example electrode assemblie) mobile.
Battery diaphragm is to determine the lithium ion battery key factor in work-ing life, and therefore, the development of lithium ion battery has been subject to the impact of diaphragm material development.At present, traditional battery diaphragm is mainly the organic polymer films of porous.Typical organic polymer films is microporous polyolefin film, as polyethene microporous membrane, microporous polypropylene membrane.The chemical constitution of polyolefine self, structure and moulding process, determined its physics and chemistry performance, caused it in lithium-ion power battery dissepiment application aspect, to have some defects.
The problem that microporous polyolefin film mainly exists for battery diaphragm has: (1) polyolefine is as non-polar material, poor with the electrolytic solution affinity of strong polarity, has caused its liquid-keeping property poor; (2) microporous polyolefin film adopts organic solvent extraction pore after mechanical stretching pore or mechanical stretching more, by heat setting type, make again, this preparation method causes microporous polyolefin film to have shape memory effect: when temperature is higher, barrier film trends towards recovering the shape of stretching cephacoria, causes larger thermal contraction; (3) polyolefinic temperature of fusion is lower, and base material easily produces fusing when temperature surpasses 165 ℃, and micropore is disappeared, blocking-up ionic conduction (being so-called hot blackout effect); While there is fusing due to microporous polyolefin film, be also accompanied by volumetric shrinkage, membrane area dwindles, and makes barrier film lose the iris action between positive and negative electrode, thereby causes inside battery positive and negative electrode to be short-circuited, and causes even blast of battery burning, produces potential safety hazard.
The security that how to improve lithium ion battery is the important topic of the industry, is also an extremely urgent key problem in technology difficult problem.The major cause that causes lithium ion battery generation potential safety hazard is that battery occurs due to thermal runaway that irreversible electrochemistry side reaction produces.Therefore, the thermostability of raising barrier film is the important leverage of lithium ion battery security.
Summary of the invention
The object of this invention is to provide a kind of lithium ion battery separator binding agent, it mixes as barrier film coating with inorganics, solves the easy generation internal short-circuit problem that existing lithium ion battery separator causes due to poor heat stability.
Second object of the present invention is to provide the preparation method of binding agent for a kind of lithium ion battery separator.
The 3rd object of the present invention is to provide a kind of lithium ion battery separator that uses above-mentioned binding agent.
In order to realize above object, the technical solution adopted in the present invention is: a kind of lithium ion battery separator binding agent, the raw material that comprises following parts by weight: 10 parts of 0.5～1 part of water-soluble polymers, 1～10 part of soft segment monomer, 1～10 part of rigid chain segment monomer, 0.01～0.05 part of initiator, 1～10 part, softening agent, deionized water or distilled water.
Described water-soluble polymers is any one or its combination in polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP).
Described soft segment monomer is any one or a few in vinylformic acid fourth diester, methacrylic acid diethylene glycol dimethyl ether ester, vinyl acetate, ethylene-vinyl acetate; Described rigid chain segment monomer is any one or a few in vinyl cyanide, vinylbenzene, polyaramide, poly-biphenyl.
Described initiator is any one or two kinds in hydrogen peroxide, ammonium persulphate, Potassium Persulphate.
Described softening agent is any one or its combination in adipic acid ester, azelate, SA ester, phosphoric acid aliphatic alcohol ester, Vanay, glycol ether benzoic ether, trioctyl trimellitate, the own ester of tri trimellitate, triethyl citrate, diethyl carbonate, propionic acid tri-n-butyl, triethyl phosphate, tributyl citrate, epoxyoleic acid butyl ester, glycol phthalate, clorafin.
A preparation method for binding agent for above-mentioned lithium ion battery separator, comprises the following steps:
1) water-soluble polymers of getting 0.5～1 weight part is placed in deionized water or the distilled water of 10 weight parts, is warming up to 50～100 ℃, stirs it is dissolved completely, obtains solution A;
2) getting the soft segment monomer of 1～10 weight part and the rigid chain segment monomer of 1～10 weight part adds in step 1) gained solution A successively, under protection of inert gas, the initiator that adds again 0.01～0.05 weight part, under 50～100 ℃ of conditions, polyreaction is carried out in stirring, reaction times is 5～12h, obtains milk sap after reaction;
3) to step 2) gained milk sap stirs, and adds the softening agent of 1～10 weight part and stirs, obtain.
A kind of lithium ion battery separator that uses above-mentioned binding agent, it is characterized in that: comprise basement membrane, the one or both sides of described basement membrane are coated with coating, described coating is the mixture of inorganics and binding agent, in described mixture, the weight fraction of binding agent is 1%～99%.
Described inorganics is any one or its combination in the oxide compound, nitrate, vitriol, silicate, carbonate, phosphoric acid salt, nitride, amide, imide, carbide of main group I, II in the periodic table of elements, III, IV, transition state IV family metal; Described inorganics is particulate state, and granularity is 0.1～10 μ m.
Described basement membrane is any one unitary film in polyolefin film, polyethylene terephthalate (PET) film, polystyrene (PS) film, polyamide (PA) film, polyacrylonitrile (PAN) film, polyimide (PI) film or several composite multilayer membranes; The thickness of described basement membrane is 15～30 μ m.
Described basement membrane had carried out pre-treatment before applying coating, and described pre-treatment is other common barrier film pretreatment processs such as corona, Cement Composite Treated by Plasma, photo-irradiation treatment, high-energy radiation processing.
Described coating can be by printing, coating, absorption, roll-in, dipping, spray or the mode of toppling over is prepared at the one or both sides of basement membrane.
Lithium ion battery separator binding agent of the present invention, adopt water-soluble polymers and the polymkeric substance being generated by soft segment monomer, rigid chain segment monomer copolymerization to carry out composite, and be aided with softening agent, the mixture of gained binding agent and inorganics, as the coating of barrier film, has following beneficial effect:
1) coating that gained binding agent and inorganics are mixed to form, has good resistance to elevated temperatures, makes barrier film guarantee, on the basis of hot blackout effect, to have high heat resistance energy; Improve thermostability and the heat resistanceheat resistant shrinkage of barrier film, thereby solve existing lithium ion battery separator due to the easy generation internal short-circuit problem that poor heat stability causes, make barrier film there is good overcharging resisting performance;
2) gained binding agent contains polar group (CN-,-OH-,-O-etc.), can with inorganics close adhesion, and can be soaked rapidly by electrolytic solution, improve the wettability of barrier film and protect fluidity, make barrier film keep wetting regime; Make the swelling ratio of barrier film lower than 1%, dimensional stability is better, guarantees that battery production is more efficient;
3) gained binding agent and polymer microporous film close adhesion, thus the tight bond of inorganics and polymer microporous film guaranteed; Make basement membrane and coating bonding closely, avoid occurring shedding phenomenon in vibration, bending or folding process, ensure the homogeneity of electric current in battery charge and discharge process;
4) bonding force between film depends on the molecular structure of tackiness agent, and the polarity of molecule is larger, and cementability is stronger, but meanwhile, intermolecular reactive force is also stronger, the rotation difficulty of molecular chain strengthens, distortion ability declines, and the elasticity of barrier film will decline, and can cause film forming rear film harder; Binding agent of the present invention is introduced soft segment when having rigid chain segment, thereby improves its mechanical property, when guaranteeing its cohesive force, improves again its snappiness, thereby guarantees the snappiness of barrier film.
5) gained binding agent contains polar group, and they can be scattered in soft segment by hydrogen bond association together, have played the effect of physical crosslinking point and increased activity filler, thus the physical strength of enhanced film and security;
6) gained binding agent is in barrier film drying course, without unwanted volatile; Whole production process safety and environmental protection, does not have " three wastes " discharge, does not have burning, blast and the potential safety hazard such as poisoning yet.
The lithium ion battery separator of the above-mentioned binding agent of use of the present invention, adopts the mixture of described binding agent and inorganics as coated material, has good resistance to high-heat performance, improves the heat resistanceheat resistant shrinkage of barrier film; Guarantee barrier film when temperature is higher or piercing orientation (short-circuit current flows through and causes heating up), can not cause internal short-circuit problem because there is fusing, improve the thermostability of barrier film, thereby when meeting the requirement of safety cut-off mechanism, the security and the overcharging resisting performance that have improved greatly lithium ion battery, meet the service requirements of high-power battery.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
The lithium ion battery separator binding agent of the present embodiment, the raw material that comprises following weight: polyethylene oxide 1g, vinyl cyanide 1g, vinylformic acid fourth diester 2g, Potassium Persulphate 0.02g, epoxyoleic acid butyl ester 10g, deionized water 10g.
The preparation method of binding agent for the lithium ion battery separator of the present embodiment, comprises the following steps:
1) polyethylene oxide of getting 1g is placed in the deionized water of 10g, is warming up to 100 ℃, stirs it is dissolved completely, obtains solution A;
2) after the cooling of step 1) gained solution A, get the vinyl cyanide (rigid chain segment monomer) of 1g and the vinylformic acid fourth diester (soft segment monomer) of 2g adds in solution A successively, under nitrogen protection, the Potassium Persulphate initiated polymerization that adds again 0.02g, under 100 ℃ of conditions, polyreaction is carried out in stirring, and the reaction times is 6h, obtains white milk sap after reaction;
3) to step 2) gained milk sap stirs, and adds the epoxyoleic acid butyl ester of 10g and stirs, and obtains described binding agent.
The lithium ion battery separator of the above-mentioned binding agent of use of the present embodiment, is characterized in that: comprise basement membrane, the one side of described basement membrane is coated with coating, and described coating is the mixture of titanium dioxide and binding agent.
The preparation method of above-mentioned lithium ion battery separator, comprises the following steps:
A) get the surface-treated titania powder of 1g, be added in described tackiness agent, temperature is controlled at 100 ℃, makes it generate colloidal sol completely, thereby obtains mixture colloidal sol;
B) by thickness, be that the microporous polypropylene membrane of 25 μ m carries out corona pre-treatment, machine walking speed is 30m/min, and corona discharge power is 500w, corona voltage 2kV, thus make basement membrane;
C) mixture colloidal sol is coated in to basement membrane through pretreated one side through coating machine, controls single spreading layer thickness 4 μ m left and right, obtain wet thin-film material;
D) the wet thin-film material of gained is transferred in vacuum drying oven, the temperature that keeps dry is 90 ℃, dry 6h, and obtaining thickness is the composite modified porous polyolefin film of the lithium ion battery separator done of 29 μ m.
Embodiment 2
The lithium ion battery separator binding agent of the present embodiment, the raw material that comprises following weight: polyvinyl alcohol 1g, vinyl cyanide 1g, methacrylic acid diethylene glycol dimethyl ether ester 2g, ammonium persulphate 0.01g, triethyl phosphate 10g, deionized water 10g.
The preparation method of binding agent for the lithium ion battery separator of the present embodiment, comprises the following steps:
1) polyvinyl alcohol of getting 1g is placed in the deionized water of 10g, is warming up to 70 ℃, stirs it is dissolved completely, obtains solution A;
2) after the cooling of step 1) gained solution A, get the vinyl cyanide (rigid chain segment monomer) of 1g and the methacrylic acid diethylene glycol dimethyl ether ester (soft segment monomer) of 2g adds in solution A successively, under nitrogen protection, the ammonium persulphate initiated polymerization that adds again 0.01g, under 70 ℃ of conditions, polyreaction is carried out in stirring, and the reaction times is 10h, obtains white milk sap after reaction;
3) to step 2) gained milk sap stirs, and adds the triethyl phosphate of 10g and stirs, and obtains described binding agent.
The lithium ion battery separator of the above-mentioned binding agent of use of the present embodiment, is characterized in that: comprise basement membrane, the one side of described basement membrane is coated with coating, and described coating is the mixture of zirconium dioxide and binding agent.
The preparation method of above-mentioned lithium ion battery separator, comprises the following steps:
A) get the surface-treated Zirconium dioxide powder of 1g, be dispersed in described tackiness agent, temperature is controlled at 70 ℃, makes it generate colloidal sol completely, thereby obtains mixture colloidal sol;
B) by thickness, be that the polyethene microporous membrane of 20 μ m carries out corona pre-treatment, machine walking speed is 30m/min, and corona discharge power is 500w, corona voltage 10kV, thus make basement membrane;
C) mixture colloidal sol is coated in to basement membrane through pretreated one side through coating machine, controls single spreading layer thickness 4 μ m left and right, obtain wet thin-film material;
D) the wet thin-film material of gained is transferred in vacuum drying oven, the temperature that keeps dry is 50 ℃, dry 10h, and obtaining thickness is the composite modified porous polyolefin film of the lithium ion battery separator done of 24 μ m.
Embodiment 3
The lithium ion battery separator binding agent of the present embodiment, the raw material that comprises following weight: Polyvinylpyrolidone (PVP) 0.5g, vinyl acetate 2g, vinylbenzene 1g, Potassium Persulphate 0.01g, glycol ether benzoic ether 10g, deionized water 10g.
The preparation method of binding agent for the lithium ion battery separator of the present embodiment, comprises the following steps:
1) Polyvinylpyrolidone (PVP) of getting 1g is placed in the deionized water of 10g, is warming up to 90 ℃, stirs it is dissolved completely, obtains solution A;
2) after the cooling of step 1) gained solution A, get the vinyl acetate (soft segment monomer) of 2g and the vinylbenzene (rigid chain segment monomer) of 1g adds in solution A successively, under nitrogen protection, the Potassium Persulphate initiated polymerization that adds again 0.01g, under 70 ℃ of conditions, polyreaction is carried out in stirring, and the reaction times is 10h, obtains white milk sap after reaction;
3) to step 2) gained milk sap stirs, and adds the glycol ether benzoic ether of 10g and stirs, and obtains described binding agent.
The lithium ion battery separator of the above-mentioned binding agent of use of the present embodiment, is characterized in that: comprise basement membrane, the one side of described basement membrane is coated with coating, and described coating is the mixture of zirconium dioxide and binding agent.
The preparation method of above-mentioned lithium ion battery separator, comprises the following steps:
A) get the surface-treated aluminium sesquioxide powder of 1g, be dispersed in described tackiness agent, temperature is controlled at 100 ℃, makes it generate colloidal sol completely, thereby obtains mixture colloidal sol;
B) by thickness, be that the microporous polypropylene membrane of 25 μ m carries out corona pre-treatment, machine walking speed is 30m/min, and corona discharge power is 500w, corona voltage 6kV, thus make basement membrane;
C) mixture colloidal sol is coated in to basement membrane through pretreated one side through coating machine, controls single spreading layer thickness 5 μ m left and right, obtain wet thin-film material;
D) the wet thin-film material of gained is transferred in vacuum drying oven, the temperature that keeps dry is 80 ℃, dry 7h, and obtaining thickness is the composite modified porous polyolefin film of the lithium ion battery separator done of 30 μ m.
Experimental example 1
This experimental example is got the composite modified film of embodiment 1～3 gained as lithium ion battery separator, tests respectively its thermal contraction performance under free state.In comparative example, PP, PE thickness are respectively 25 μ m, 20 μ m left and right.Experimental result is as shown in table 1.
Test method: barrier film sample is cut into the sample of 120mm * 120mm, draws the midperpendicular of 100mm * 100mm along opposite side center line; Barrier film is placed in to each temperature spot lower 2 hours, and sample is taken out after baking oven, measures after placing 10min in laboratory environment again; The length L of midperpendicular after measurement thermal contraction
fand W
f, calculate the operating direction (β of the barrier film under this condition
mD) and horizontal (β
tD) shrinking percentage; Parallel testing 3 times, gets arithmetical av.Calculation formula is as follows:
The thermal contraction performance test result of table 1 embodiment 1～3 gained barrier film
As can be seen from Table 1, more traditional simple PP, the PE film of embodiment 1～3 gained barrier film has better temperature profile; Solved the large problem that conventional membrane is at high temperature shunk, improved the integrity of high temperature lower diaphragm plate, the raising of battery security has been had to crucial meaning.
Experimental example 2
This experimental example is got the composite modified film of embodiment 1,2,3 gained as lithium ion battery separator, tests respectively its stripping strength.Experimental result is as shown in table 2.
Test method: intercept wide 25mm along barrier film operating direction (MD), long 180mm sample; Sample is had to laminated the adhering on steel bar of painting, gently press adhesive surface, effectively bond length is 60mm.Requirement adhesive surface is smooth, and dynamics is even.Sample one end and steel bar one end are fixed on universal testing machine, and draw speed is 100mm/min.This project parallel testing 3 times, gets arithmetical av.
The peel strength test result of table 2 embodiment 1～3 gained barrier film
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Stripping strength, N/m | 123 | 159 | 147 |
As can be seen from Table 2, between the coating of embodiment 1～3 gained barrier film and basement membrane, bonding closely, has been avoided, in vibration, bending or folding process, occurring shedding phenomenon, can ensure the homogeneity of electric current in battery charge and discharge process.
Experimental example 3
This experimental example is got the composite modified film of embodiment 1,2,3 gained as lithium ion battery separator, tests respectively its ventilation property.Experimental result is as shown in table 3.
Test method: use Gurley testing tool to measure the ventilation property (Gurley number) of barrier film.Gurley number refers to that a certain amount of test gas sees through 1in. under 1.22KPa pressure
2the needed time of sample, unit: second (s).In this test, (model: Gurley4110N) test gas is air, and the amount of gas is 100mL, need be with stopwatch timing simultaneously during test to use Gurley instrument.This project parallel testing 3 times, gets arithmetical av.
The ventilation property test result of table 3 embodiment 1～3 gained barrier film
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Basement membrane thickness, μ m | 25 | 20 | 25 |
| Basement membrane air penetrability, sec/100ml | 432 | 484 | 432 |
| Finished product thickness, μ m | 29 | 24 | 30 |
| Finished product air penetrability, sec/100ml | 481 | 535 | 498 |
As can be seen from Table 3, the resulting laminated film of embodiment 1～3, every increase by the 1 μ m of thickness, air penetrability numerical value only increased about 13 seconds, on the conductivity impact of barrier film little.
Claims (10)
1. a lithium ion battery separator binding agent, is characterized in that: the raw material that comprises following parts by weight: 10 parts of 0.5～1 part of water-soluble polymers, 1～10 part of soft segment monomer, 1～10 part of rigid chain segment monomer, 0.01～0.05 part of initiator, 1～10 part, softening agent, deionized water or distilled water.
2. lithium ion battery separator binding agent according to claim 1, is characterized in that: described water-soluble polymers is any one or its combination in polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone.
3. lithium ion battery separator binding agent according to claim 1, is characterized in that: described soft segment monomer is any one or a few in vinylformic acid fourth diester, methacrylic acid diethylene glycol dimethyl ether ester, vinyl acetate, ethylene-vinyl acetate; Described rigid chain segment monomer is any one or a few in vinyl cyanide, vinylbenzene, polyaramide, poly-biphenyl.
4. lithium ion battery separator binding agent according to claim 1, is characterized in that: described initiator is any one or two kinds in hydrogen peroxide, ammonium persulphate, Potassium Persulphate.
5. lithium ion battery separator binding agent according to claim 1, is characterized in that: described softening agent is any one or its combination in adipic acid ester, azelate, SA ester, phosphoric acid aliphatic alcohol ester, Vanay, glycol ether benzoic ether, trioctyl trimellitate, the own ester of tri trimellitate, triethyl citrate, diethyl carbonate, propionic acid tri-n-butyl, triethyl phosphate, tributyl citrate, epoxyoleic acid butyl ester, glycol phthalate, clorafin.
6. a preparation method for binding agent for lithium ion battery separator as claimed in claim 1, is characterized in that: comprise the following steps:
1) water-soluble polymers of getting 0.5～1 weight part is placed in deionized water or the distilled water of 10 weight parts, is warming up to 50～100 ℃, stirs it is dissolved completely, obtains solution A;
2) getting the soft segment monomer of 1～10 weight part and the rigid chain segment monomer of 1～10 weight part adds in step 1) gained solution A successively, under protection of inert gas, the initiator that adds again 0.01～0.05 weight part, under 50～100 ℃ of conditions, polyreaction is carried out in stirring, reaction times is 5～12h, obtains milk sap after reaction;
3) to step 2) gained milk sap stirs, and adds the softening agent of 1～10 weight part and stirs, obtain.
7. a lithium ion battery separator that uses binding agent as claimed in claim 1, it is characterized in that: comprise basement membrane, the one or both sides of described basement membrane are coated with coating, described coating is the mixture of inorganics and binding agent, in described mixture, the weight fraction of binding agent is 1%～99%.
8. lithium ion battery separator according to claim 7, is characterized in that: described inorganics is any one or its combination in the oxide compound, nitrate, vitriol, silicate, carbonate, phosphoric acid salt, nitride, amide, imide, carbide of main group I, II in the periodic table of elements, III, IV, transition state IV family metal; Described inorganics is particulate state, and granularity is 0.1～10 μ m.
9. lithium ion battery separator according to claim 7, is characterized in that: described basement membrane is any one unitary film in polyolefin film, polyethylene terephthalate film, Polystyrene Film, polyamide membrane, polyacrylonitrile film, polyimide film or several composite multilayer membranes; The thickness of described basement membrane is 15～30 μ m.
10. lithium ion battery separator according to claim 9, is characterized in that: described basement membrane had carried out pre-treatment before applying coating, and described pre-treatment is that corona treatment, Cement Composite Treated by Plasma, photo-irradiation treatment or high-energy radiation are processed.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986585A (en) * | 2006-12-01 | 2007-06-27 | 华南师范大学 | Preparing method and application of polymer gel electrolyte for lithium ion cell |
| CN101226994A (en) * | 2007-12-21 | 2008-07-23 | 成都中科来方能源科技有限公司 | Non-woven cloth increasing micropore polymer diaphragm and usage as well as preparation method thereof |
| CN101434708A (en) * | 2008-12-19 | 2009-05-20 | 成都中科来方能源科技有限公司 | Aqueous polymer modified micropore polyolefin barrier diaphragm, and preparation and use thereof |
-
2013
- 2013-11-14 CN CN201310571644.1A patent/CN104140502B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986585A (en) * | 2006-12-01 | 2007-06-27 | 华南师范大学 | Preparing method and application of polymer gel electrolyte for lithium ion cell |
| CN101226994A (en) * | 2007-12-21 | 2008-07-23 | 成都中科来方能源科技有限公司 | Non-woven cloth increasing micropore polymer diaphragm and usage as well as preparation method thereof |
| CN101434708A (en) * | 2008-12-19 | 2009-05-20 | 成都中科来方能源科技有限公司 | Aqueous polymer modified micropore polyolefin barrier diaphragm, and preparation and use thereof |
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