CN100533816C - Battery diaphragm and its preparation method and lithium ion secondary battery containing the diaphragm - Google Patents
Battery diaphragm and its preparation method and lithium ion secondary battery containing the diaphragm Download PDFInfo
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- CN100533816C CN100533816C CNB2006100006111A CN200610000611A CN100533816C CN 100533816 C CN100533816 C CN 100533816C CN B2006100006111 A CNB2006100006111 A CN B2006100006111A CN 200610000611 A CN200610000611 A CN 200610000611A CN 100533816 C CN100533816 C CN 100533816C
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- polyimides
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- forming 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
Abstract
A battery separator includes the substrate and holes distributed on it, in which, the substrate contains polyimide. The battery separator of this invention uses polyimide which is a new material bearing high temperature as substrate, so that it has excellent chemical stability, high temperature, good permeability and high mechanical strength. The lithium-ion rechargeable batteries using this invention don't appear short circuit even in 150 deg. C, thus this battery separator can be used for high-capacity and power batteries.
Description
Technical field
The lithium rechargeable battery that the invention relates to a kind of battery diaphragm and preparation method thereof and contain this barrier film.
Background technology
Lithium rechargeable battery has obtained huge development with advantages such as its high-energy-density, high voltage, little, in light weight, the memoryless property of volume over past ten years, become one of main energy sources of communication class electronic product.But because under abuse conditions, lithium rechargeable battery occurs easily smoldering, catch fire, exploding even causes potential safety hazard such as injury to personnel, makes high power capacity and power lithium-ion battery also not have extensive use.Therefore, improve the key that lithium ion battery security is the research and development lithium ion battery.
Battery diaphragm plays the effect that stops the direct contact short circuit of both positive and negative polarity in lithium ion battery.In order to improve the fail safe of battery, not only require battery diaphragm can stop the direct contact short circuit of both positive and negative polarity at normal temperatures, also requiring at high temperature simultaneously, this battery diaphragm also can stop the direct contact short circuit of both positive and negative polarity.But battery diaphragm commonly used now as polyethylene, the very difficult integrality that guarantees under the high temperature of polypropylene, often occurs in the safety tests such as stove heat shrinking the problem that causes internal short-circuit, initiation thermal runaway because of battery diaphragm.Therefore, the resistance to elevated temperatures of raising battery diaphragm is to improve the key of lithium rechargeable battery high temperature safe performance.
JP-A-63-308866 discloses by lamination and has comprised that low-melting-point polyethylene and the polyacrylic single thin film acquisition of high-melting-point have the method for the microporous membrane of high strength and hot properties.Yet the barrier film internal resistance raises because of lamination, so the gained barrier film is not suitable for the heavy-duty battery of high output.
JP-A-10-298325 discloses a kind of preparation method of porous membrane, and described porous membrane contains low molecular weight polyethylene, low-molecular-weight polypropylene and High molecular weight polyethylene.This porous membrane bad mechanical strength, thermal shock resistance are poor.In addition because the barrier film mechanical strength is low, when the inside battery electrolyte owing to during the very strong pressure of hot gas generation, make film breaks easily.Still dangerous property when the porous membrane that therefore, makes in this way is used for lithium rechargeable battery.
JP-A-2001-59036 has proposed a kind of perforated membrane that has excellent balance between shutdown characteristic (SD characteristic) and thermal endurance, and this perforated membrane will gather bornylene with sheet or lobate being distributed in the matrix polymer.Yet, although this invention has obtained to have the porous membrane of high-fire resistance and high mechanical properties, use polynorbornene not only to increase cost, but also because perforated membrane is synthetic by special reaction, therefore there is byproduct, causes the electrolyte that uses in the battery influenced.In addition, owing to be difficult to fully control reaction condition, make that polynorbornene may be crosslinked with single gelinite, so the thermal endurance of perforated membrane and mechanical strength still may be relatively poor.
CN 1512607A provides a kind of improved perforated membrane on the basis of the perforated membrane that JP-A-2001-59036 proposes, this perforated membrane contains ethylene-propylene-ethylidene norbornene terpolymer, by three's crosslinked action raising intensity and heat resistance.But it is same because used ultra-high molecular weight polyethylene and norborene to improve cost; and be that the traditional thermoplastic PE/PP of employing is main; percent thermal shrinkage is relatively large; can not fundamentally solve the equilibrium relation of shutting down between characteristic and the heat resistance well; from its described content, adopt the super high molecular weight material also can cause so-called " static " phenomenon simultaneously.
Summary of the invention
To the objective of the invention is that perforated membrane heat resistance of the prior art is poor, the shortcoming of bad mechanical strength in order overcoming, a kind of mechanical strength is good, heat resistance is good battery diaphragm and preparation side and lithium rechargeable battery to be provided.
Battery diaphragm provided by the invention comprises base material and the hole that is distributed on the base material, and wherein, described base material contains polyimides.
The preparation method of battery diaphragm provided by the invention comprises and will contain the solution film forming of base material, pore-forming material and solvent, and removes the pore-forming material being lower than under the substrate glass temperature, and wherein, described base material contains polyimides.
Lithium rechargeable battery provided by the invention comprises pole piece and electrolyte, and described pole piece comprises positive pole, negative pole and the battery diaphragm that anodal, negative pole are separated, and wherein, described battery diaphragm is a battery diaphragm provided by the invention.
Battery diaphragm provided by the invention is owing to adopt novel fire resistant material polyimides as base material, thereby has excellent chemical stability, heat-resisting quantity, excellent permeability, high mechanical properties.The battery diaphragm that obtains in the embodiment of the invention is heated to 400 ℃ of high temperature and does not also break; Battery diaphragm less than 0.5%, all is not more than 1.5% at 400 ℃ percent thermal shrinkages, the percent thermal shrinkage much smaller than of the prior art 3% and 5% at 150 ℃ percent thermal shrinkage; Pierce through intensity also in the prior art battery diaphragm pierce through intensity; The average diameter in hole and porosity all satisfy the conductance requirement, and suitable good air permeability is arranged, and percent thermal shrinkage is also much smaller than battery diaphragm of the prior art.Use the lithium rechargeable battery of battery diaphragm provided by the invention, even also be not short-circuited phenomenon under 150 ℃ of high temperature, thereby battery diaphragm provided by the invention can be used in high power capacity and the electrokinetic cell.
Embodiment
The invention provides a kind of battery diaphragm, this battery diaphragm comprises base material and the hole that is distributed on the base material, and wherein, described base material contains polyimides.
Among the present invention, described polyimides can be the polymer that contains imide group in the various repetitives, and under the preferable case, described polyimides is the polyimides with following structural formula:
Wherein, R
1And R
2Identical or different, can be various substituted alkyls, substituted aryl, the feasible hot strength that contains the battery diaphragm of this polyimides of the value of polymerization degree n is that 30-100 MPa, vitrification point are 150-420 ℃.
Under the preferable case, R
1And R
2Be the group that contains aromatic ring, and carbonyl and R
1The direct key of aromatic ring connect; Nitrogen-atoms on the imide and R
2The direct key of aromatic ring connect, the value of n makes that the hot strength of the battery diaphragm that contains this polyimides is that 50-100 MPa, vitrification point are 380-420 ℃, in this case, barrier film has better thermal endurance and bigger hot strength.
Described aromatic ring can be phenyl ring, naphthalene nucleus.More under the preferable case, R
1Be selected from substituted-phenyl, substituted biphenyl base, the substituted diphenylamine ketone group one or more, at least four hydrogen in described substituted-phenyl, substituted biphenyl base, the substituted diphenylamine ketone group on the phenyl ring are by the carbonyl substituted on the imide group, and two carbonyls on the same imide group are positioned at the adjacent position of phenyl ring; R
2Be selected from substituted-phenyl, substituted biphenyl base, the substituted diphenylamine ether one or more, at least two hydrogen in described substituted-phenyl, substituted biphenyl base, the substituted diphenylamine ether on the phenyl ring are replaced by the nitrogen-atoms on the acylimino.
Except that being replaced by carbonyl or imino group, other hydrogen on the phenyl ring also can be replaced by other various functional groups in the above-mentioned phenyl ring, and described functional group can be one or more in halogen, nitro, alkyl, amino, the sulfonic group, is preferably C
4-C
10Straight chain and/or branched alkyl.
Preferred described polyimides is one or more in PMMI, poly-biphenyl tetracarboxylic acid imide, the poly-benzophenone tetramethyl acid imide in the specific embodiment of the invention.Above-mentioned polyimides can be used following structural formula (1), (2) and (3) expression respectively:
In the above-mentioned formula, the feasible hot strength that contains the battery diaphragm of this polyimides of the value of n is that 50-100 MPa, vitrification point are 380-420 ℃, R
3, R
4, R
5, R
6, R
7And R
8Be independently selected from hydrogen, halogen, amino, nitro, the alkyl one or more respectively, described halogen can be fluorine, chlorine, bromine or iodine, and described alkyl is preferably C
4-C
10Straight chained alkyl and/or branched alkyl.
R
2Can be the substituted aryl of following structural formula:
R ' wherein
3, R '
4, R '
5, R '
6, R '
7And R '
8Be independently selected from hydrogen, halogen, amino, nitro, the alkyl one or more respectively, described halogen can be fluorine, chlorine, bromine or iodine, and described alkyl is preferably C
4-C
10Straight chained alkyl and/or branched alkyl.Under the preferable case, R '
3, R '
4, R '
5, R '
6, R '
7And R '
8Be hydrogen, such R
2Low and and the acquisition easily of cost.
In addition, two imide groups on the repetitive also can be positioned on other position of phenyl ring, and for example for structural formula (2), described imide can be positioned on 2,3 and/or 2 ', the 3 ' position of biphenyl (according to the IUPCA nomenclature, two phenyl ring key positions even are 1,1 ' number position).Since the position of imide on phenyl ring do not influence battery diaphragm of the present invention thermal endurance, air permeability, pierce through intensity and thermal contraction performance, therefore polyimides of the present invention is not done requirement to the position of imide, can be said structure formula (1), all places isomers of (2) and (3) described structure or their mixture.
Although it is soluble that the part polyimides is arranged, but,, can't accurately measure the degree of polymerization of polyimides because most of polyimides is an insoluble polymer, therefore, the present invention only characterizes polyimides with battery diaphragm vitrification point and the hot strength that the present invention was concerned about.Among the present invention, be the 30-100 MPa as long as contain the hot strength of the battery diaphragm of polyimides, be preferably the 50-100 MPa, vitrification point is 150-420 ℃, is preferably 380-420 ℃, can reach purpose of the present invention.
There is no particular limitation to the density in the thickness of base material, the size that is distributed in the hole on the base material and hole for battery diaphragm of the present invention, as long as can satisfy the requirement of lithium rechargeable battery to battery diaphragm.Under the preferable case, the average diameter in described hole is preferably the 0.01-5 micron, more preferably the 0.01-1 micron; Described porosity is preferably 20-80 volume %, more preferably 30-60 volume %; The thickness of film is preferably the 5-50 micron, more preferably the 5-30 micron; Hot strength is preferably the 50-100 MPa greater than 50 MPas; Vitrification point is preferably 380-420 ℃.
Polyimides of the present invention can in all sorts of ways and obtain, and for example, can be commercially available, and also can obtain by prepared in various methods.For example, can obtain by the condensation reaction between polynary organic carboxyl acid or derivatives thereof and the organic diamine.Described polynary organic carboxyl acid derivative is selected from binary organic acid acid anhydride, the organic acyl chlorides of quaternary, quaternary organic acid esters.Because quaternary organic carboxyl acid, the organic acyl chlorides of quaternary, quaternary organic acid esters and organic diamine can produce micromolecular compound when reacting, bring inconvenience for the preparation of battery diaphragm, therefore, the preferred described polyimides of the present invention is preferably the product of binary organic acid acid anhydride and organic diamine.Described binary organic acid acid anhydride can be various saturated and/or unsaturated binary organic acid acid anhydrides, and described organic diamine can be the various diamines that contain two secondary amino groups.Contain benzene ring structure in preferred described binary organic acid acid anhydride of the present invention and/or the organic diamine, for example, described binary organic acid acid anhydride can be selected from one or more in BPDA, benzophenone tetracarboxylic dianhydride, the pyromellitic acid anhydride; Described organic diamine can be selected from diaminodiphenyl ether, p-phenylenediamine (PPD), 1, and one or more in 1 '-benzidine or their homologue, described homologue are preferably other locational hydrogen on the phenyl ring by C
4-C
10The above-mentioned organic diamine that alkyl replaces.The mol ratio of described binary organic acid acid anhydride and organic diamine is preferably 0.99-1.03, more preferably 1.00-1.02.
The reaction condition of described binary organic acid acid anhydride and organic diamine and method of operation have been conventionally known to one of skill in the art, do not repeat them here.
The preparation method of battery diaphragm provided by the invention comprises and will contain the solution film forming of base material, pore-forming material and solvent, and removes the pore-forming material being lower than under the substrate glass temperature, and wherein, described base material contains polyimides.
Preferred described polyimides is one or more in the PMMI with said structure formula (1), (2) or (3) described structure, poly-biphenyl tetracarboxylic acid imide, the poly-benzophenone tetramethyl acid imide.Because general polyimides is an insoluble substance, and want to adopt polyimides to make the battery diaphragm of quality homogeneous, polyimides can be mixed with pore-forming material homogeneous, when therefore being the feedstock production battery diaphragm with the polyimides, the preferred described PMMI of the present invention is selected from one or more in the poly-equal diimides of N-alkyl phenyl, the poly-equal diimides of N-alkyl biphenyl base, the poly-equal diimides of N-alkyl diphenyl ether; Described poly-biphenyl tetracarboxylic acid imide is selected from one or more in poly-N-alkyl phenyl biphenyl tetracarboxylic acid imide, poly-N-alkyl biphenyl base biphenyl tetracarboxylic acid imide, the poly-N-alkyl diphenyl ether biphenyl tetracarboxylic acid imide; Described poly-benzophenone tetramethyl acid imide is selected from one or more in poly-N-alkyl phenyl benzophenone tetramethyl acid imide, poly-N-alkyl biphenyl base benzophenone tetramethyl acid imide, the poly-N-alkyl diphenyl ether benzophenone tetramethyl acid imide, and described alkyl is preferably C
4-C
10Straight chain and/or branched alkyl.
Described pore-forming material can be various and base material has excellent compatibility and can be lower than the material of removing under the substrate glass temperature, described pore-forming material can be conventional pore-forming material, as non-volatile organic solvent, as nonane, decane, hendecane, dodecane, atoleine or mineral oil.
Because the pore-forming material of above-mentioned routine is difficult to the size and the distribution in the hole of control battery diaphragm, therefore, the inventor has invented a kind of new pore-forming material.Preferred this new pore-forming material among the present invention, this new pore-forming material is the solid that a kind of decomposition temperature is higher than the boiling point of solvent and is lower than the vitrification point of base material.
Under the preferable case, it is more preferably polycaprolactone, PPOX, polymethylstyrene, the polystyrene of 10000-20000 of 1000-50000 that this new pore-forming material is selected from weight average molecular weight.Above-mentioned pore-forming material can obtain by the whole bag of tricks, for example can be purchased, and also can obtain by prepared in various methods.
In order to increase pore-forming material and base material or to form the compatibility of the material of base material, an end of the more preferred polymeric chain at least of described pore-forming material is by in the above-mentioned polycaprolactone of amino functional, PPOX, polymethylstyrene, the polystyrene one or more.One end of described polymeric chain can be commercially available by the above-mentioned polymer of amino functional, and also can in all sorts of ways prepares.The concrete operation method of described amino functional has been conventionally known to one of skill in the art, does not repeat them here.
Described solvent can be the various solvents that can dissolve base material and pore-forming material simultaneously and be easy to volatilize and remove.Among the present invention, described solvent can be to be various strong polarity nonionic solvent commonly used, be preferably N-2-methyl pyrrolidone (NMP), N, N-dimethylacetylamide (DMAC), N, in dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), m-cresol, oxolane, the methyl alcohol one or more, more preferably one or more among NMP, DMAC, the DMF.
There is no particular limitation to the feeding quantity of base material and pore-forming material in the present invention, specifically according to the required hole density of battery diaphragm and the size decision in hole.Under the preferable case, the weight ratio of described base material and pore-forming material is 0.25-3, more preferably 0.8-2.There is no particular limitation to the addition of described solvent in the present invention, forms uniform solution as long as base material and pore-forming material are dissolved fully, and under the preferable case, described solvent and base material weight are 4.5-10.
Among the present invention, described polyimides can in all sorts of ways and obtain, and for example can be commercially available, and also can obtain by prepared in various methods, for example can obtain by the condensation reaction between quaternary organic carboxyl acid or derivatives thereof and the organic diamine.Preferably adopting binary organic acid acid anhydride such as BPDA, benzophenone tetracarboxylic dianhydride, pyromellitic acid anhydride and organic diamine to carry out condensation reaction as diaminodiphenyl ether, p-phenylenediamine (PPD) in the specific embodiment of the invention makes.
Therefore, the preparation method of battery diaphragm provided by the invention can also realize by following manner: polynary organic carboxyl acid or derivatives thereof, organic diamine, pore-forming material are contacted with solvent, obtain the solution of homogeneous, then with solution film forming, and remove the pore-forming material being lower than under the substrate glass temperature.The mol ratio of described polynary organic carboxyl acid or derivatives thereof and organic diamine is preferably 0.99-1.03,1.00-1.02 more preferably, the weight ratio of the preferred polynary organic carboxyl acid or derivatives thereof of the addition of described pore-forming material and organic diamine total amount and pore-forming material is 0.25-3, more preferably 0.8-2; The feeding quantity preferred solvent of described solvent is 4.5-10 with polynary organic carboxyl acid or derivatives thereof, organic diamine charge weight ratio.The temperature that described polynary organic carboxyl acid or derivatives thereof, organic diamine, pore-forming material contact with solvent is preferably 20-70 ℃, is preferably 1-5 hour time of contact.Described polynary organic carboxyl acid or derivatives thereof is preferably the binary organic acid acid anhydride, and described binary organic acid acid anhydride can be selected from one or more in BPDA, benzophenone tetracarboxylic dianhydride, the pyromellitic acid anhydride; Described organic diamine can be selected from diaminodiphenyl ether, p-phenylenediamine (PPD), 1, one or more in 1 '-benzidine or their homologue.
The method of described film forming can adopt conventional method such as dried film build method and wet film build method.For example, can be by solution be smeared into desired thickness.Described smearing can be realized by the whole bag of tricks, for example can use spreader.The same with conventional film build method, solution smeared into desired thickness after, again solvent is removed, obtain non-porous film, the pore-forming material in the non-porous film is removed promptly got battery diaphragm of the present invention then.Describedly remove the method desolvate and concrete operations for conventionally known to one of skill in the art, the preferred method of heating that adopts is removed solvent, and the temperature of heating is decided on the boiling point of solvent.Among the present invention, removing the temperature of desolvating is the temperature of removing that is lower than the boiling temperature of solvent and is lower than the pore-forming material, more is lower than the vitrification point of base material.
When adopting binary organic acid acid anhydride and organic diamine to be the feedstock production polyimide base material, because binary organic acid acid anhydride, organic diamine be the main polyamic acid that generates under above-mentioned contact conditions, make the polyamic acid dehydration generate polyimides, need to add dehydrating agent or improve reaction temperature.In order to obtain the battery diaphragm of steady quality, function admirable, the present invention preferably adopts the mode that improves reaction temperature to make the polyamic acid dehydration.Therefore, when adopting binary organic acid acid anhydride and organic diamine to be the feedstock production polyimide base material, the preparation method of battery diaphragm of the present invention comprises that also the non-porous film that will remove behind the solvent carried out imidization reaction earlier before removing the pore-forming material, be converted into polyimides with polyamic acid.The reaction temperature of described imidizate is 270-300 ℃, and the reaction time is preferably 3-5 hour.Can directly heat up and also can adopt program mode to heat up to raise the temperature to 270-300 ℃, the present invention preferably adopts with 4-8 ℃/minute heating rate temperature programming to 270-300 ℃, so that the abundant imidizate of polyamic acid generates required polyimides.Can improve amic acid and be converted into imido conversion ratio by raising reaction temperature, prolongation reaction time.Under the above-mentioned condition of the present invention, amic acid is converted into imido conversion ratio greater than 99%, and, therefore allow to exist in the battery diaphragm 2% following amic acid because the existence of a spot of amic acid does not have much affect to thermal endurance, gas permeability and the percent thermal shrinkage of gained battery diaphragm of the present invention.In the specific embodiment of the invention not the amount to amic acid make special requirement.The temperature of imidizate preferably is lower than the decomposition or the volatilization temperature of pore-forming material, to obtain the battery diaphragm of better quality.
Can adopt the whole bag of tricks to remove the pore-forming material, for example can adopt and remove the temperature that the non-porous film that obtains after desolvating is heated to pore-forming substance decomposition or volatilization, make the pore-forming substance decomposition in the non-porous film or vapor away above-mentioned.Since the decomposition of pore-forming material or the vitrification point that volatilization temperature is lower than base material in the non-porous film, like this, by can on base material, staying corresponding hole after pore-forming substance decomposition or the volatilization.Obviously, the size in hole is corresponding to the shared volume of pore-forming material (perhaps content) in the non-porous film.Pore-forming material shared volume in non-porous film is big more, and the hole that stays after the pore-forming material is left away is also big more.
In order to run through the thickness direction of film in the hole that stays after guaranteeing to be left away by the pore-forming material, under the preferable case, the method for preparing battery diaphragm of the present invention also comprises carries out the step of axial tension with removing film that the pore-forming material obtains.Described axial tension can be uniaxial tension or biaxial stretching.The degree of described axial tension is so that the thickness direction of film can be all run through in the hole on the described base material is as the criterion.Under condition of the present invention, described axial tension is preferably twin shaft and stretches to (horizontal and vertical), and the condition of described biaxial stretching is: draft temperature 100-140 ℃, and draw speed 5-15 mm/min, draw ratio is (MD) 2 times vertically, laterally (TD) 2 times.The concrete operations of described axial tension have been conventionally known to one of skill in the art, do not repeat them here.
In order to contain polyimides in the base material of verifying the battery diaphragm that said method of the present invention makes, can carry out qualitative sign according to infrared spectrum.1720cm in the infrared spectrum
-1Near strong peak is a C=O stretching vibration absworption peak, 1380cm
-1Strong peak is a C-N stretching vibration absworption peak in neighbouring.Described infrared spectrum spectrogram adopts the U.S. NEXUS470 of Nicolet company type fourier transform infrared spectroscopy, KBr coating to measure.The said determination method has been conventionally known to one of skill in the art, does not repeat them here.
Can make the battery diaphragm of any thickness as required with said method, the concrete thickness of battery diaphragm depends on the coated weight of film forming solution, under the preferable case, is the 5-50 micron as the thickness of the battery diaphragm of battery diaphragm, more preferably the 5-30 micron.The size in the hole of battery diaphragm depends primarily on the condition of axial tension, and under axial tension condition of the present invention, the diameter in hole can be 0.01-5 micron, more preferably 0.01-1 micron on the gained battery diaphragm.Hole density depends primarily on the ratio of pore-forming material and base material, and the pore-forming amount of substance is big more, and hole density is also big relatively more.The present invention adopts porosity indication window density, and described porosity is the percentage that the cumulative volume of finger-hole accounts for the battery diaphragm volume.Under condition of the present invention, the porosity of gained battery diaphragm can be 20-80 volume %, more preferably 30-60 volume %.The air permeability of battery diaphragm provided by the invention can reach 20-1000 second/100cc, more preferably 20-500 second/100cc; Pierce through intensity and can reach 400gf/18 micron or bigger; 150 ℃ of horizontal thermal contractions are less than 1%, preferably less than 0.5%; 400 ℃ of horizontal thermal contractions are less than 3%.
The invention provides a kind of lithium rechargeable battery, this battery comprises pole piece and electrolyte, and described pole piece comprises positive pole, negative pole and the battery diaphragm that anodal negative pole is separated, and wherein, described battery diaphragm is a battery diaphragm provided by the invention.
Because the present invention only relates to improvement to battery diaphragm, therefore there is no particular limitation to other structure of battery such as electrolyte, positive pole and negative pole, and conventional electrolyte of lithium-ion secondary battery, positive pole, negative pole get final product.Electrolyte is preferably nonaqueous electrolytic solution as described, comprises electrolyte and solvent, and described electrolyte can be lithium hexafluoro phosphate (LiPF
6), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiSbF
6), lithium perchlorate (LiClO
4), lithium perchlorate, fluorocarbon based sulfonic acid lithium (LiCF
3SO
3), Li (CF
3SO
2)
2N, LiC
4F
9SO
3, LiAlO
4, chlorine lithium aluminate (LiAlCl
4), LiN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2) in (x and y are the natural number of 1-10 in the formula), lithium chloride (LiCl) and the lithium iodide (LiI) one or more.Described solvent can be a gamma-butyrolacton, vinyl carbonate (EC), ethyl-methyl carbonic ester (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone, dipropyl carbonate and other are fluorine-containing, various organic acid anhydrides, the N-methyl pyrrolidone, the N-methylformamide, the N-methylacetamide, acetonitrile, N, dinethylformamide (DMF), sulfolane, methyl-sulfoxide, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond.In order to increase the solubility of lithium salts in solvent, the mixed solvent that the present invention preferably uses two or three in the above-mentioned solvent to form, for example usually dimethyl carbonate and diethyl carbonate are mixed with mixed solvent in the ratio of 1:0.9-1:3.0, perhaps dimethyl carbonate, diethyl carbonate and propylene carbonate are mixed with mixed solvent by 1:1:0.2-1:0.5:1.5.It is the 0.1-2.0 mol that the addition of solvent makes lithium salt, is preferably the 0.7-1.6 mol.
Described positive pole comprises collector body and coating and/or is filled in positive electrode on this collector body, and described collector body can be a various collector body known in those skilled in the art, and as aluminium foil, Copper Foil, nickel plated steel strip, the present invention selects for use aluminium foil to make collector body.Described positive electrode can be a various positive electrode known in those skilled in the art, generally includes the conductive agent that positive active material, adhesive and selectivity contain, and described positive active material can be selected from the positive active material of lithium ion battery routine, as Li
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
mMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0), Li
1+aM
bMn
2-bO
4(wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is one or more in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur).
Described negative pole comprises conducting base and coating and/or is filled in negative material on the conducting base.Described conducting base is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil, nickel plated steel strip, the Punching steel strip one or more.Described negative active core-shell material is conventionally known to one of skill in the art, it comprises negative electrode active material and various additive, described negative electrode active material can be selected from the negative electrode active material of lithium ion battery routine, as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more.Described adhesive can be selected from the adhesive of lithium ion battery routine, as in polyvinyl alcohol, polytetrafluoroethylene, CMC (CMC), the butadiene-styrene rubber (SBR) one or more.In general, the content of described adhesive is the 0.5-8 weight % of negative electrode active material, is preferably 2-5 weight %.
The preparation method of described positive pole, negative pole and the assemble method of battery have been conventionally known to one of skill in the art, do not repeat them here.
The following examples will the invention will be further described.
Embodiment 1
Present embodiment is used to illustrate battery diaphragm provided by the invention and preparation method thereof.
5.214 gram pyromellitic acid anhydrides, 4.786 gram diaminodiphenyl ethers, 10.015 gram polymeric chains, one end are contained amino polystyrene, and (weight average molecular weight is 15000, available from Aldrich company) and 100 the gram N-2-methyl pyrrolidones (NMP) at room temperature mix, obtain filming with the I-shaped spreader of filming behind the solution of homogeneous, obtain thickness and be 0.5 millimeter film.This film was removed solvent in 2 hours 120 ℃ of heating, ℃ carried out imidizate 3 hours with 5 ℃ of/minute temperature programmings to 300 then, being warmed up to 350 ℃ again kept 1.5 hours, be cooled to 120 ℃ at last and carry out the biaxial stretching processing simultaneously, draw speed 10 mm/min, draw ratio vertically (MD) is 2 times, and laterally (TD) is 2 times, obtains battery diaphragm of the present invention thus.Wherein there is 1720cm in the fourier-transform infrared spectrogram
-1Near strong peak is C=O stretching vibration absworption peak, 1380cm
-1Strong peak is a C-N stretching vibration absworption peak in neighbouring, and illustrating has imide group in the product, has 1600 centimetres in the spectrogram
-1, 1575 centimetres
-1, 1490 centimetres
-1, 1450 centimetres
-1Absworption peak (phenyl ring characteristic peak), illustrate to have phenyl ring in the product.The thickness that records this battery diaphragm with 1/10000 pair of thickness instrument is 18 microns, and the vitrification point that records barrier film with the DSC method is 380 ℃.
Embodiment 2
Present embodiment is used to illustrate battery diaphragm provided by the invention and preparation method thereof.
8.864 gram bibenzene tetracarboxylic dianhydrides, 3.224 grams are contained amino PPOX to diamino-benzene, 8.032 gram polymeric chains, one end, and (weight average molecular weight is 18000, available from Aldrich company) and 150 the gram DMSO at room temperature mix, obtain filming with the I-shaped spreader of filming behind the solution of homogeneous, obtain thickness and be 0.4 millimeter film.This film was removed solvent in 2 hours 160 ℃ of heating, ℃ carried out imidizate 5 hours with 4 ℃ of/minute temperature programmings to 270 then, being warmed up to 350 ℃ again kept 1.5 hours, be cooled to 120 ℃ at last and carry out the biaxial stretching processing, draw speed 10 mm/min, draw ratio vertically (MD) is 2 times, and laterally (TD) is 2 times, obtains battery diaphragm of the present invention thus.Wherein there is 1720cm in the fourier-transform infrared spectrogram
-1Near strong peak is C=O stretching vibration absworption peak, 1380cm
-1Strong peak is a C-N stretching vibration absworption peak in neighbouring, and illustrating has imide group in the product, has 1600 centimetres in the spectrogram
-1, 1575 centimetres
-1, 1490 centimetres
-1, 1450 centimetres
-1Absworption peak (phenyl ring characteristic peak), illustrate to have phenyl ring in the product.The thickness that records this battery diaphragm with 1/10000 pair of thickness instrument is 18 microns, and the vitrification point that records barrier film with the DSC method is 420 ℃.
Embodiment 3
Present embodiment is used to illustrate battery diaphragm provided by the invention and preparation method thereof.
With 10.693 gram benzophenone tetracarboxylic dianhydrides, 3.516 gram p-phenylenediamine (PPD), 5.982 gram polymethylstyrene (weight average molecular weight 10000, available from Aldrich company) and 150 gram N, dinethylformamide at room temperature mixes, obtain filming with the I-shaped spreader of filming behind the solution of homogeneous, obtain thickness and be 0.5 millimeter film.This film is heated 2 hours removal solvents down at 160 ℃, ℃ carried out imidizate 4 hours with 6 ℃ of/minute temperature programmings to 285 then, being warmed up to 350 ℃ again kept 1.5 hours, be cooled at last and carry out the biaxial stretching processing under 120 ℃ simultaneously, draw speed 10 mm/min, draw ratio vertically (MD) is 2 times, and laterally (TD) is 2 times, obtains battery diaphragm of the present invention thus.Wherein there is 1720cm in the fourier-transform infrared spectrogram
-1Near strong peak is C=O stretching vibration absworption peak, 1380cm
-1Strong peak is a C-N stretching vibration absworption peak in neighbouring, and illustrating has imide group in the product, has 1600 centimetres in the spectrogram
-1, 1575 centimetres
-1, 1490 centimetres
-1, 1450 centimetres
-1Absworption peak (phenyl ring characteristic peak), illustrate to have phenyl ring in the product.The thickness that records this battery diaphragm with 1/10000 pair of thickness instrument is 18 microns, and the vitrification point that records barrier film with the DSC method is 400 ℃.
Embodiment 4
Present embodiment is used to illustrate battery diaphragm provided by the invention and preparation method thereof.
With the poly-equal diimides of the N-amyl group phenyl (average degree of polymerization 200 of 5.031 grams, hot strength 60 MPas, 390 ℃ of vitrification points), 5.893 gram polymeric chains, one end contains amino polystyrene (weight average molecular weight 15000, available from Aldrich company) and 100 the gram N-2-methyl pyrrolidones (NMP) under 70 ℃, mix, obtain filming with the I-shaped spreader of filming behind the solution of homogeneous, obtain thickness and be 0.5 millimeter film.This film is heated 2 hours removal solvents down at 120 ℃, being warmed up to 350 ℃ then kept 1.5 hours, be cooled at last and carry out the biaxial stretching processing under 120 ℃ simultaneously, draw speed 10 mm/min, draw ratio vertically (MD) is 2 times, laterally (TD) is 2 times, obtains battery diaphragm of the present invention thus.Wherein there is 1720cm in the fourier-transform infrared spectrogram
-1Near strong peak is C=O stretching vibration absworption peak, 1380cm
-1Strong peak is a C-N stretching vibration absworption peak in neighbouring, and illustrating has imide group in the product, has 1600 centimetres in the spectrogram
-1, 1575 centimetres
-1, 1490 centimetres
-1, 1450 centimetres
-1Absworption peak (phenyl ring characteristic peak), illustrate to have phenyl ring in the product.The thickness that records this battery diaphragm with 1/10000 pair of thickness instrument is 18 microns, and the vitrification point that records barrier film with the DSC method is 380 ℃.
Embodiment 5
Present embodiment is used to illustrate battery diaphragm provided by the invention and preparation method thereof.
Method by embodiment 3 prepares battery diaphragm of the present invention, and different is to adopt atoleine as the pore-forming material.Wherein there is 1720cm in the fourier-transform infrared spectrogram
-1Near strong peak is C=O stretching vibration absworption peak, 1380cm
-1Strong peak is a C-N stretching vibration absworption peak in neighbouring, and illustrating has imide group in the product, has 1600 centimetres in the spectrogram
-1, 1575 centimetres
-1, 1490 centimetres
-1, 1450 centimetres
-1Absworption peak (phenyl ring characteristic peak), illustrate to have phenyl ring in the product.The thickness that records this battery diaphragm with 1/10000 pair of thickness instrument is 18 microns, and the vitrification point that records barrier film with the DSC method is 380 ℃.
Embodiment 6
Present embodiment is used to illustrate battery diaphragm provided by the invention and preparation method thereof.
5.214 gram pyromellitic acid anhydrides, 4.786 gram diaminodiphenyl ethers, 10.015 gram polymeric chains, one end are contained amino polystyrene, and (weight average molecular weight is 15000, available from Aldrich company) and 100 the gram N-2-methyl pyrrolidones (NMP) at room temperature mix, obtain filming with the I-shaped spreader of filming behind the solution of homogeneous, obtain thickness and be 0.8 millimeter film.This film was removed solvent in 2 hours 120 ℃ of heating, ℃ carried out imidizate 3 hours with 5 ℃ of/minute temperature programmings to 300 then, being warmed up to 350 ℃ again kept 1.5 hours, be cooled to 120 ℃ at last and carry out the biaxial stretching processing simultaneously, draw speed 10 mm/min, draw ratio vertically (MD) is 2 times, and laterally (TD) is 2 times, obtains battery diaphragm of the present invention thus.Wherein there is 1720cm in the fourier-transform infrared spectrogram
-1Near strong peak is C=O stretching vibration absworption peak, 1380cm
-1Strong peak is a C-N stretching vibration absworption peak in neighbouring, and illustrating has imide group in the product, has 1600 centimetres in the spectrogram
-1, 1575 centimetres
-1, 1490 centimetres
-1, 1450 centimetres
-1Absworption peak (phenyl ring characteristic peak), illustrate to have phenyl ring in the product.The thickness that records this battery diaphragm with 1/10000 pair of thickness instrument is 25 microns, and the vitrification point that records barrier film with the DSC method is 380 ℃.The hot strength of barrier film is 110 MPas.
Embodiment 7
Present embodiment is used to illustrate battery diaphragm provided by the invention and preparation method thereof.
8.864 gram bibenzene tetracarboxylic dianhydrides, 3.224 grams are contained amino PPOX to diamino-benzene, 8.032 gram polymeric chains, one end, and (weight average molecular weight is 18000, available from Aldrich company) and 150 the gram DMSO at room temperature mix, obtain filming with the I-shaped spreader of filming behind the solution of homogeneous, obtain thickness and be 0.3 millimeter film.This film was removed solvent in 2 hours 160 ℃ of heating, ℃ carried out imidizate 5 hours with 4 ℃ of/minute temperature programmings to 270 then, being warmed up to 350 ℃ again kept 1.5 hours, be cooled to 120 ℃ at last and carry out the biaxial stretching processing, draw speed 10 mm/min, draw ratio vertically (MD) is 2 times, and laterally (TD) is 2 times, obtains battery diaphragm of the present invention thus.Wherein there is 1720cm in the fourier-transform infrared spectrogram
-1Near strong peak is C=O stretching vibration absworption peak, 1380cm
-1Strong peak is a C-N stretching vibration absworption peak in neighbouring, and illustrating has imide group in the product, has 1600 centimetres in the spectrogram
-1, 1575 centimetres
-1, 1490 centimetres
-1, 1450 centimetres
-1Absworption peak (phenyl ring characteristic peak), illustrate to have phenyl ring in the product.The thickness that records this battery diaphragm with 1/10000 pair of thickness instrument is 5 microns, and the vitrification point that records barrier film with the DSC method is 420 ℃.The hot strength of barrier film is 50 MPas.
Comparative Examples 1
This Comparative Examples is used to illustrate battery diaphragm of the prior art and preparation method thereof.
Prepare battery diaphragm according to CN 1512607A embodiment 1 described method, different is draw ratio vertically (MD) be 2 times, laterally (TD) be 2 times, the thickness of gained barrier film is 18 microns.
The battery diaphragm performance test
Adopt following method to measure average diameter, hot strength, the air permeability in the porosity of the battery diaphragm that embodiment 1-5 and Comparative Examples 1 make, hole, pierce through intensity, thermal endurance and heat-shrinkable respectively, it is as shown in table 1 below to measure structure.
Porosity: adopt the method for testing test of this area routine:, measure its volume (cm from the square sample that microporous barrier downcuts certain-length
3) and weight (g), calculate by following formula: porosity (%)=100 * (1-weight/(resin density * volume))
The average diameter in hole: determine according to the pore diameter distribution curve that the BJH method obtains by the ammonia absorption/desorption type specific area/distribution of pores tester ASAP2010 that makes by Shimadzu Corp.
The distribution in hole: the battery diaphragm that makes with embodiment 1-5 and Comparative Examples 1 is that barrier film is made the LP043450 size battery, above-mentioned battery is carried out 4.3-2.75 volt cycle charge-discharge, circulate and take battery apart after 100 times, observe the distribution of white zinc dendrite on the battery diaphragm, if white zinc dendrite is evenly distributed, the pore size distribution that barrier film is described is even, and vice versa.
Hot strength: the battery diaphragm of 5 mm wides, d millimeters thick is stretched the maximum pull F that tensiometer shows before the record fracture on puller system with 5 mm/second
Max(ox) calculated by following formula: hot strength (MPa)=F
Max/ (5 * d).
Air permeability: measure according to JIS P8117.
Pierce through intensity: the self-contained battery barrier film, with diameter be 1 millimeter, bent at its tip radius be 0.5 millimeter pin with the speed motion of 2 cels, pierce through maximum, force in the battery diaphragm process and count and pierce through intensity.
Heat-shrinkable: with lateral length is L
0The battery diaphragm nature be placed in the baking oven of 150 ℃ and 400 ℃ and kept respectively 1 hour, measure lateral length L then
1, then
Thermal endurance: adopt the thermal endurance of the described heat-pesistant thin film disruption method of CN 1512607A test battery barrier film, the heating rate of different is battery is 10 ℃/minute, is warming up to 400 ℃.
Table 1
The result who from last table 1, provides as can be seen, the battery diaphragm resistance to elevated temperatures excellence that obtains in the embodiment of the invention is heated to 400 ℃ of high temperature and does not also break; Battery diaphragm less than 0.5%, all is not more than 1.5% at 400 ℃ percent thermal shrinkages, the percent thermal shrinkage much smaller than of the prior art 3% and 5% at 150 ℃ percent thermal shrinkage; Pierce through intensity also in the prior art battery diaphragm pierce through intensity; The average diameter in hole and porosity all satisfy the conductance requirement, and suitable good air permeability is arranged, and percent thermal shrinkage is also much smaller than battery diaphragm of the prior art.In addition, the distribution experiment by the hole as can be seen, the battery diaphragm that forms with new pore-forming material provided by the invention compares being more evenly distributed of hole of making the pore-forming material with organic solvent of the prior art.
The test of battery heat-resisting quantity
The individual layer PE material (tonen that battery diaphragm that makes with embodiment 1-5 and Comparative Examples 1 and thickness are 18 microns, outsourcing) and three layers of PP/PE/PP material (celgard, outsourcing) makes the LP043450 size battery for barrier film, above-mentioned battery is carried out the high-temperature behavior test, described high-temperature behavior test is the test of 150 ℃ of stove heat, the method of 150 ℃ of stove heat test is charged to 100% Charging state for above-mentioned battery is carried out 1C, be placed in the baking oven, oven temperature is elevated to 150 ℃ with 5 ℃/minute from room temperature, and wherein cell voltage falls greater than 0.2 volt and is considered as short circuit.Test result is as shown in table 2.
Table 2
| The barrier film source | Short-circuit conditions | The thermal runaway situation |
| Embodiment 1 | Not short circuit | Do not explode, smolder, catch fire, leakage |
| Embodiment 2 | Not short circuit | Do not explode, smolder, catch fire, leakage |
| Embodiment 3 | Not short circuit | Do not explode, smolder, catch fire, leakage |
| Embodiment 4 | Not short circuit | Do not explode, smolder, catch fire, leakage |
| Embodiment 5 | Not short circuit | Do not explode, smolder, catch fire, leakage |
| Comparative Examples 1 | Short circuit | Blast |
| Individual layer PE | Short circuit | Blast |
| Three layers of PP/PE/PP | Short circuit | Blast |
From the result of last table 2 as can be seen, the battery that makes with battery diaphragm provided by the invention has outstanding high temperature resistance, even also do not blast under 150 ℃ of high temperature, smolder, catch fire, dangerous phenomenon such as leakage.
Claims (17)
1, a kind of battery diaphragm, this barrier film comprise base material and the hole that is distributed on the base material, it is characterized in that described base material contains polyimides, and described polyimides is the polyimides with following structural formula:
Wherein, R
1And R
2Identical or different, be various substituted alkyls or substituted aryl, the feasible hot strength that contains the battery diaphragm of this polyimides of the value of polymerization degree n is that 30-100 MPa, vitrification point are 380-420 ℃.
2, battery diaphragm according to claim 1, wherein, described R
1And R
2For containing the group of aromatic ring, and carbonyl and R
1The direct key of aromatic ring connect; Nitrogen-atoms on the imide and R
2The direct key of aromatic ring connect, it is 380-420 ℃ that the value of n makes hot strength 50-100 MPa, the vitrification point of the battery diaphragm that contains this polyimides.
3, battery diaphragm according to claim 2, wherein, described polyimides is selected from the polyimides of have following structural formula (1), (2) or (3):
R in the above-mentioned formula
3, R
4, R
5, R
6, R
7And R
8Be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, C respectively
4-C
10In straight chained alkyl and/or the branched alkyl one or more; R
2Substituted aryl for following structural formula:
R ' wherein
3, R '
4, R '
5, R '
6, R '
7And R '
8Be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, C respectively
4-C
10In straight chained alkyl and/or the branched alkyl one or more.
4, battery diaphragm according to claim 1, wherein, the diameter in described hole is the 0.01-5 micron, and described porosity is 20-80 volume %, and the thickness of film is the 5-50 micron, and the hot strength of film is the 50-100 MPa, vitrification point is 380-420 ℃.
5, a kind of preparation method of battery diaphragm, this method comprises and will contain the solution film forming of base material, pore-forming material and solvent, and remove the pore-forming material under the substrate glass temperature being lower than, it is characterized in that, described base material contains polyimides, and described polyimides is the polyimides with following structural formula:
Wherein, R
1And R
2Identical or different, be various substituted alkyls or substituted aryl, the feasible hot strength that contains the battery diaphragm of this polyimides of the value of polymerization degree n is that 30-100 MPa, vitrification point are 380-420 ℃.
6, method according to claim 5, wherein, the weight ratio of described polyimides and pore-forming material is 0.25-3, the weight ratio of described solvent and polyimides is 4.5-10.
7, according to claim 5 or 6 described methods, wherein, described R
1And R
2For containing the group of aromatic ring, and carbonyl and R
1The direct key of aromatic ring connect; Direct and the R of nitrogen-atoms on the imide
2The direct key of aromatic ring connect, the value of n makes that hot strength 50-100 MPa, the vitrification point of the battery diaphragm that contains this polyimides are 380-420 ℃.
8, method according to claim 7, wherein, described polyimides is selected from the polyimides of have following structural formula (1), (2) or (3):
In the above-mentioned formula; R
3, R
4, R
5, R
6, R
7And R
8Be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, C respectively
4-C
10In straight chained alkyl and/or the branched alkyl one or more; R
2Substituted aryl for following structural formula:
R ' wherein
3, R '
4, R '
5, R '
6, R '
7And R '
8Be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, C respectively
4-C
10In straight chained alkyl and/or the branched alkyl one or more.
9, method according to claim 5, wherein, this method comprises polynary organic carboxyl acid or derivatives thereof, organic diamine, pore-forming material is contacted with solvent, obtain the solution of homogeneous, then with solution film forming, and remove the pore-forming material under the substrate glass temperature being lower than, described polynary organic carboxyl acid or derivatives thereof is quaternary organic carboxyl acid, the organic acyl chlorides of quaternary, quaternary organic acid esters or binary organic acid acid anhydride.
10, method according to claim 9, wherein, the mol ratio of described polynary organic carboxyl acid or derivatives thereof and organic diamine is 0.99-1.03, the total amount of polynary organic carboxyl acid or derivatives thereof and organic diamine and the weight ratio of pore-forming material are 0.25-3, and the weight ratio of described solvent and polynary organic carboxyl acid or derivatives thereof and organic diamine polyimides is 4.5-10.
11, method according to claim 9, wherein, the temperature that polynary organic carboxyl acid or derivatives thereof, organic diamine, pore-forming material are contacted with solvent is 20-70 ℃, the time of contact is 1-5 hour.
12, method according to claim 9, wherein, this method will heat 3-5 hour down at 270-300 ℃ except that the film after desolvating before also being included in and removing the pore-forming material.
13, according to claim 9,10 or 11 described methods, wherein, described polynary organic carboxyl acid or derivatives thereof is selected from one or more in BPDA, benzophenone tetracarboxylic dianhydride, the pyromellitic acid anhydride; Described organic diamine is selected from diaminodiphenyl ether, p-phenylenediamine (PPD), 1, one or more in 1 '-benzidine.
14, according to claim 5,6,9,10 or 11 described methods, wherein, described pore-forming material is that decomposition temperature is higher than the boiling point of solvent and is lower than the solid of the vitrification point of base material.
15, method according to claim 14, wherein, described pore-forming material be selected from weight average molecular weight be 10000-20000 and at least an end of polymeric chain by amidized polycaprolactone, PPOX, polymethylstyrene, polystyrene.
16, according to claim 5,6,9,10 or 11 described methods, wherein, described solvent is selected from N-2-methyl pyrrolidone, N, N-dimethylacetylamide, N, one or more in dinethylformamide, dimethyl sulfoxide (DMSO), m-cresol, oxolane, the methyl alcohol.
17, a kind of lithium rechargeable battery, this battery comprises pole piece and electrolyte, and described pole piece comprises positive pole, negative pole and the battery diaphragm that anodal negative pole is separated, and it is characterized in that, and described battery diaphragm is any described battery diaphragm among the claim 1-4.
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|---|---|---|---|
| CNB2006100006111A CN100533816C (en) | 2006-01-09 | 2006-01-09 | Battery diaphragm and its preparation method and lithium ion secondary battery containing the diaphragm |
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|---|---|---|---|
| CNB2006100006111A CN100533816C (en) | 2006-01-09 | 2006-01-09 | Battery diaphragm and its preparation method and lithium ion secondary battery containing the diaphragm |
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| JP4445537B2 (en) * | 2007-09-26 | 2010-04-07 | 株式会社東芝 | Secondary battery, battery pack and car |
| CN101420018B (en) * | 2007-10-26 | 2011-07-13 | 比亚迪股份有限公司 | Lithium ionic secondary cell barrier and preparation thereof |
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| CN102916150A (en) * | 2012-11-02 | 2013-02-06 | 江苏科技大学 | Preparation method of high-temperature-resisting battery diaphragm |
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Assignee: Huizhou BYD Battery Co., Ltd. Assignor: Biyadi Co., Ltd. Contract record no.: 2010440020081 Denomination of invention: Battery diaphragm and its preparation method and lithium ion secondary battery containing the diaphragm Granted publication date: 20090826 License type: Exclusive License Open date: 20070718 Record date: 20100603 |
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