CN1232577C - Process for preparing polymer diaphragm for lithium ion cell - Google Patents
Process for preparing polymer diaphragm for lithium ion cell Download PDFInfo
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- CN1232577C CN1232577C CNB2003101175077A CN200310117507A CN1232577C CN 1232577 C CN1232577 C CN 1232577C CN B2003101175077 A CNB2003101175077 A CN B2003101175077A CN 200310117507 A CN200310117507 A CN 200310117507A CN 1232577 C CN1232577 C CN 1232577C
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- polyvinylidene difluoride
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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
The present invention belongs to the field of lithium ion batteries, which relates to a preparation method of a polymer membrane used for a lithium ion battery. The preparation method provided by the present invention comprises the following steps: polyolefin is molten and extruded for forming a membrane, heat treatment is carried out, one-way or biaxial tension is carried out to form micropores, and thus, a polymer micropore membrane is made. In one preparation method, the mixture of polyolefin and polyvinylidene difluoride is utilized; In the other preparation method, polyvinylidene difluoride or the copolymer of the polyvinylidene difluoride and hexafluoropropylene is uniformly dissolved by an organic solvent and then coated on the surface of the front body membrane of the polyolefin after heat treatment, and then, one-way or biaxial tension is carried out to form the micropores after the volatilization of the solvent and dryness. The bonding performance between the membrane made by the present invention and electrodes can be obviously improved, the electrical conductivity of batteries and the electrolyte keeping performance of the membrane are enhanced, the membrane has high porosity, the batteries made from the membrane have large capacity and high discharging capability, and the preparation method has the advantages of high operability, simple technology and easy industrial production.
Description
Invention field
The invention belongs to the lithium ion battery field, more particularly, the present invention relates to the preparation method of lithium ion battery with membrane for polymer.
Technical background
Lithium ion battery is a kind of novel lithium cell that grows up on the basis of liquid lithium ionic cell, it had both kept the high-energy-density of traditional lithium cell, the advantage of long circulation life, have good performances such as safe and reliable and fast charging and discharging again, therefore become a new direction of lithium ion battery development, get more and more people's extensive concerning.
In lithium ion battery, membrane for polymer connects and separates positive pole and negative material.Membrane for polymer is the isolator of electronics, but allows ion migration to pass through, and is the important component part of battery.The quality of membrane for polymer performance is determining the interface structure of battery, the internal resistance of battery, and then affect the key characteristics such as capacity, cyclicity, charging and discharging currents density of battery, so the polymers of excellent properties barrier film has important effect for the over-all properties that improves battery.
At present, barrier film commonly used in lithium ion battery is a microporous polyolefin film, and its preparation method mainly contains two kinds of fusion drawn method (MSCS) and thermally induced phase separations (TIPS).The fusion drawn method is the polymeric film that obtains Had Elastic Semi-Crystalline by melt extruding, then it is stretched, in film, produce many micropores, do not need solvent in the manufacturing processed, throughput rate is higher, used macromolecular material is extensive commercial polypropylene (PP), polyethylene (PE), belongs to one of the most cheap mould material.Thermally induced phase separation is the proportioning by telomerized polymer and thinner, controlled temperature, and selection of Extractant, the factors such as time in extraction agent is bathed can be prepared the microporous polymer membranes with different thickness, aperture size, porosity.The technology of thermally induced phase separation need to add and remove thinner, so expense is higher relatively, and may be caused secondary pollution than fusion drawn method complexity.And the fusion drawn method does not comprise any phase separation, and technology is simple, and is pollution-free in the production process.(referring to document 1, Kesting R E, Synthetic Polymer Membranes, Second Edition, 1985; Document 2, Song JY, Wang Y Y, Journal of Power Sources, 1999,77:183; Document 3, Jian K, Pintauro P N, Journa1 of Membrane Science, 1996,117:117; Document 4, US Patent 6 080 507; Document 5, US Patent 5 139 529; Document, US Patent 3 679 538.)
Along with the continuous development of lithium ion battery, battery process is variation progressively.The at present domestic research of related fields that also many patent disclosures arranged is as CN.1 322 019A, CN.1 259 773A, CN.1 423 363A etc.They utilize various physical methods or chemical process in that commercial polypropylene (PP) or polyethylene (PE) porous film surface apply another kind of polymer layer now, or elder generation applies the monomer of these polymeric matrixs at porous film surface, and then polymerization, purpose is in order to promote membranous electrolyte retention, simultaneously certain viscosifying power is arranged, positive pole, negative pole, barrier film are become one with positive and negative electrode.But the method at porous diaphragm surface applied polymeric matrix is wayward aborning, and is blocking microporous easily, makes the battery performance variation.
Summary of the invention
The objective of the invention is in order to overcome the deficiency of above-mentioned technology, a kind of new lithium ion battery preparation method of membrane for polymer is provided, can effectively overcome the shortcoming in the aforesaid method, has the adhesiveproperties that improves barrier film and electrode, advantages such as the conductivity of raising battery and electrolytical maintenance performance.
A kind of lithium ion battery provided by the invention preparation method of membrane for polymer, comprise the steps: polyolefin blend is melt extruded film forming, thermal treatment again, carry out unidirectional or two-way stretch formation micropore, make the polymer micro barrier film, wherein polyolefin blend is the mixture of polyolefine and polyvinylidene difluoride (PVDF) (PVdF).
In above-mentioned method, the polyolefine material that is used for preparing polymer microporous film can be a prior art preparation lithium ion battery with membrane for polymer polyolefine commonly used, as polypropylene (PP), polyethylene (PE), also can be the multipolymer of PP/PE or PP/PE/PP.
Wherein the mass ratio of polyolefine and polyvinylidene difluoride (PVDF) (PVdF) is 10: 1～50: 1, preferred 25: 1～50: 1.
The molecular weight of polyvinylidene difluoride (PVDF) is generally 5～300,000, and preferred 20～280,000.
Melt extrude, thermal treatment temp and unidirectional or two-way stretch adopt preparation lithium ion battery membrane for polymer usual method in the prior art, melt extruding temperature and thermal treatment temp depends on polyolefinic kind usually and decides, polyolefine difference, temperature are also different.
The another kind of lithium ion battery provided by the invention preparation method of membrane for polymer, comprise the steps: polyolefine melt extruded and make precursor film, thermal treatment, carry out unidirectional or two-way stretch formation micropore, wherein with polyvinylidene difluoride (PVDF) or polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer with organic solvent dissolution evenly after, be coated in through heat treated precursor film surface, treat solvent evaporates, carry out unidirectional after the drying again or two-way stretch formation micropore, can make the polymer micro barrier film.
In above-mentioned method, the polyolefine material that is used for preparing polymer microporous film can be a prior art preparation lithium ion battery with membrane for polymer polyolefine commonly used, as polypropylene (PP), polyethylene (PE), also can be the multipolymer of PP/PE or PP/PE/PP.
Wherein polyolefine and polyvinylidene difluoride (PVDF) (PVdF), or with the mass ratio of polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer (PVdF-HFP) be 10: 1～50: 1, preferred 25: 1～50: 1.
The molecular weight of polyvinylidene difluoride (PVDF), polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer is generally 5～300,000, and preferred 20～280,000.
In polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer, the content of R 1216 is generally 15～35wt%, preferred 20～30wt%.
Melt extrude, thermal treatment temp and unidirectional or two-way stretch adopt preparation lithium ion battery membrane for polymer usual method in the prior art, melt extruding temperature and thermal treatment temp depends on polyolefinic kind usually and decides, polyolefine difference, temperature are also different.
Used organic solvent generally is selected from ketone such as acetone, N-Methyl pyrrolidone (NMP) etc. and amides such as dimethyl formamide (DMF) etc.
The inventive method can be adjusted the polymkeric substance proportioning according to actual needs, and then adjusts membranous function, as closed temperature of conductivity, adhesive property, micropore etc.
The advantage of the inventive method is the adhesiveproperties that the barrier film of preparation can significantly improve barrier film and electrode, the conductivity and the membranous ionogen that improve battery keep performance, and membranous porosity is higher, utilizes the capacity of battery of this barrier film preparation big, and the discharge capability of battery is strong.And this preparation method is workable, and technology is simple, is easy to industrialization.
Embodiment
Embodiment is the description of this invention, but the present invention is not limited to this.
Embodiment 1
The preparation of electrode:
With LiCoO
2The DMF solution of powder, carbon black, PVdF-HFP multipolymer mixes, and makes the composite mortar of homogeneous at normal temperatures and pressures, slurry is coated on the aluminium foil as collector uniformly, wherein LiCoO
2Account for the 85wt% that always is coated with application, carbon black accounts for 10wt%, copolymer comprised 5wt%.Aluminium foil is made negative plate after densification and drying.
Middle carbon fiber (MCF) is mixed with the DMF solution of PVdF, make the composite mortar of homogeneous at normal temperatures and pressures, slurry is coated on the Copper Foil as collector uniformly, wherein MCF accounts for the 94wt% that always is coated with application, and PVdF accounts for 6wt%.
Aluminium foil is made negative plate after densification and drying.
Membranous preparation:
After PP and PVdF mixed by mass ratio at 40: 1, melt extruding film forming in 220 ℃ in forcing machine, again 140 ℃ of following thermal treatments 72 hours, is 130 ℃ in temperature then, rate of extension is to carry out the longitudinal stretching pore-forming under the 20m/min, can make polymer microporous film.
The thickness of polymer microporous film is 25 μ m, and pore size is 0.04 μ m, and porosity is 38%, and longitudinal tensile strength is 52N, and transverse tensile strength is 6N, and the closed temperature of micropore is 165 ℃.
The assembling of battery:
Die-cut respectively negative plate and positive plate prepare negative electrode and anode, and barrier film is inserted between negative electrode and the anode, roll the formation electrode device.Electrode device is put into the shell that multilayer film are made, in this shell, inject electrolyte solution, just made a kind of Experimental cell.
Testing method:
Experimental cell discharges and recharges in micro-processor controlled braking and carries out the charge and discharge cycles test on the instrument, and current density is 0.2mA/cm
2, the charging stopping potential is 4.2V, discharge cut-off voltage is 2.5V.
The performance perameter of Experimental cell 1 is seen attached list.
Embodiment 2
PP is melt extruded film forming under 230 ℃ in forcing machine, again 140 ℃ of following thermal treatments 48 hours, to be that 1: 50 PVdF is dissolved in the acetone with the PP mass ratio then, dissolving fully, after stirring, solution is coated in PP precursor film surface, treat that solvent evaporates is complete, drying is 130 ℃ in temperature, rate of extension is to carry out the longitudinal stretching pore-forming under the 20m/min, can make polymer microporous film.
The thickness of polymer microporous film is 25 μ m, and pore size is 0.04 μ m, and porosity is 45%, and longitudinal tensile strength is 47N, and transverse tensile strength is 8N, and the closed temperature of micropore is 165 ℃.
Negative electrode and anodic preparation condition, the assembling of Experimental cell and testing method are with embodiment 1.
The performance perameter of Experimental cell 2 is seen attached list.
Embodiment 3
After PE and PVdF mixed by mass ratio at 1: 30, melt extruding film forming in 210 ℃ in forcing machine, again 118 ℃ of following thermal treatments 72 hours, is 105 ℃ in temperature then, rate of extension is to carry out the longitudinal stretching pore-forming under the 20m/min, can make polymer microporous film.
The performance perameter that makes microporous membrane is: the thickness of film is 23 μ m, and pore size is 0.04 μ m, and porosity is 47%, and longitudinal tensile strength is 50N, and transverse tensile strength is 8N, and the closed temperature of micropore is 132 ℃.
Negative electrode and anodic preparation condition, the assembling of Experimental cell and testing method are with embodiment 1.
The performance perameter of Experimental cell 3 is seen attached list.
Embodiment 4
PE is melt extruded film forming under 190 ℃ in forcing machine, 120 ℃ of following thermal treatments 64 hours, to be that 1: 50 PVdF-HFP multipolymer (HFP content 25wt%) is dissolved in the acetone with the PE mass ratio then, dissolving fully, after stirring, solution is coated in PP precursor film surface, treat that solvent evaporates is intact, drying is 105 ℃ in temperature, rate of extension is to carry out the longitudinal stretching pore-forming under the 20m/min, can make polymer microporous film.
The thickness of polymer microporous film is 25 μ m, and pore size is 0.04 μ m, and porosity is 49%, and longitudinal tensile strength is 59N, and transverse tensile strength is 8N, and the closed temperature of micropore is 132 ℃.
Negative electrode and anodic preparation condition, the assembling of Experimental cell and testing method are with embodiment 1.
The performance perameter of Experimental cell 4 is seen attached list.
Embodiment 5
PP is melt extruded film forming under 210 ℃ in forcing machine, 140 ℃ of following thermal treatments 64 hours, to be that 1: 50 PVdF-HFP multipolymer (HFP content 30wt%) is dissolved in the acetone with the PP mass ratio then, dissolving fully, after stirring, solution is coated in PP precursor film surface, treat that solvent evaporates is intact, drying is 130 ℃ in temperature, rate of extension is to carry out the longitudinal stretching pore-forming under the 20m/min, can make polymer microporous film.
The performance perameter that makes microporous membrane is: the thickness of film is 22 μ m, and pore size is 0.04 μ m, and porosity is 42%, and longitudinal tensile strength is 55N, and transverse tensile strength is 8N, and the closed temperature of micropore is 165 ℃.
Negative electrode and anodic preparation condition, the assembling of Experimental cell and testing method are with embodiment 1.
The performance perameter of Experimental cell 5 is seen attached list.
Embodiment 6
PE is melt extruded film forming under 190 ℃ in forcing machine, 120 ℃ of following thermal treatments 64 hours, to be that 1: 30 PVdF-HFP multipolymer (HFP content 30wt%) is dissolved in the acetone with the PE mass ratio then, dissolving fully, after stirring, solution is coated in PE precursor film surface, treat that solvent evaporates is intact, drying is 105 ℃ in temperature, rate of extension is to carry out the longitudinal stretching pore-forming under the 20m/min, can make polymer microporous film.
The thickness of polymer microporous film is 28 μ m, and pore size is 0.06 μ m, and porosity is 35%, and longitudinal tensile strength is 50N, and transverse tensile strength is 6N, and the closed temperature of micropore is 130 ℃.
Negative electrode and anodic preparation condition, the assembling of Experimental cell and testing method are with embodiment 1.
The performance perameter of Experimental cell 6 is seen attached list.
Subordinate list: the performance perameter of the Experimental cell of forming by the polymer microporous film of embodiment 1 to embodiment 6
| The embodiment numbering | Reversible capacity (mA) | Internal resistance (m Ω) | Cycle life | ||
| The 10th all rates of descent (%) | The 50th all rates of descent (%) | The 200th all rates of descent (%) | |||
| 1 2 3 4 5 6 | 700 500 600 550 700 700 | 50 35 32 28 44 56 | 0.5 1.2 1.0 0.8 1.1 1.6 | 3.2 2.5 2.3 3.0 2.7 3.5 | 10.8 9.6 10.3 9.4 11.1 15.3 |
Claims (8)
1, a kind of lithium ion battery preparation method of membrane for polymer, comprise the steps: polyolefin blend is melt extruded film forming, thermal treatment again, carry out unidirectional or two-way stretch formation micropore, make the polymer micro barrier film, it is characterized in that polyolefin blend is the mixture of polyolefine and polyvinylidene difluoride (PVDF), wherein the mass ratio of polyolefine and polyvinylidene difluoride (PVDF) is 10: 1～50: 1.
2, the process of claim 1 wherein that the mass ratio of polyolefine and polyvinylidene difluoride (PVDF) is 25: 1～50: 1.
3, arbitrary method of claim 1～2, wherein the molecular weight of polyvinylidene difluoride (PVDF) is 5～300,000.
4, the method for claim 3, wherein the molecular weight of polyvinylidene difluoride (PVDF) is 20～280,000.
5, a kind of lithium ion battery preparation method of membrane for polymer, comprise the steps: polyolefine melt extruded and make precursor film, thermal treatment, carry out unidirectional or two-way stretch formation micropore, it is characterized in that with polyvinylidene difluoride (PVDF) or polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer with organic solvent dissolution evenly after, be coated in through heat treated precursor film surface, treat solvent evaporates, carry out unidirectional after the drying again or two-way stretch formation micropore, can make the polymer micro barrier film, wherein polyolefine and polyvinylidene difluoride (PVDF), or with the mass ratio of polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer be 10: 1～50: 1.
6, the method for claim 5, wherein polyolefine and polyvinylidene difluoride (PVDF), or with the mass ratio of polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer be 25: 1～50: 1.
7, arbitrary method of claim 5～6, wherein molecular weight 5～300,000 of polyvinylidene difluoride (PVDF), polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer; In polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer, the content of R 1216 is 15～35wt%.
8, the method for claim 7, wherein molecular weight 20～280,000 of polyvinylidene difluoride (PVDF), polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer; In polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer, the content of R 1216 is 20～30wt%.
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| CNB2003101175077A CN1232577C (en) | 2003-12-24 | 2003-12-24 | Process for preparing polymer diaphragm for lithium ion cell |
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| CNB2003101175077A CN1232577C (en) | 2003-12-24 | 2003-12-24 | Process for preparing polymer diaphragm for lithium ion cell |
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| CN1232577C true CN1232577C (en) | 2005-12-21 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101954738A (en) * | 2010-09-16 | 2011-01-26 | 湖南紫皇冠新能源技术服务有限公司 | Method for preparing polymer microporous membrane for lithium ion battery |
| TWI425700B (en) * | 2010-12-22 | 2014-02-01 | Ind Tech Res Inst | Secondary battery, battery separator and method for manufacturing the same |
| CN102208598B (en) | 2011-05-12 | 2014-03-12 | 中国科学院宁波材料技术与工程研究所 | Electrode plate of graphene coating modified lithium secondary battery and manufacturing method thereof |
| CN105118946B (en) * | 2015-09-13 | 2018-03-20 | 中南大学 | A kind of preparation method of lithium ion battery separator |
| CN105118950A (en) * | 2015-09-13 | 2015-12-02 | 中南大学 | Method for preparing lithium ion battery diaphragm |
| CN105514321A (en) * | 2015-12-14 | 2016-04-20 | 苏州锂盾储能材料技术有限公司 | High efficiency diaphragm material of lithium ion battery and preparation method of diaphragm material |
| CN105542363B (en) * | 2016-01-27 | 2018-01-23 | 燕山大学 | A kind of preparation method of bi-directional synchronization stretching PVDF based coextruded films |
| CN108258169A (en) * | 2016-12-29 | 2018-07-06 | 东莞东阳光科研发有限公司 | A kind of preparation method of lithium battery Kynoar composite diaphragm |
| CN110350131B (en) * | 2018-04-04 | 2020-11-13 | 北京师范大学 | Method for preparing composite polypropylene microporous membrane by phase inversion method, product and application thereof |
| CN111192995A (en) * | 2018-11-15 | 2020-05-22 | 微宏动力系统（湖州）有限公司 | High-cohesiveness battery diaphragm, preparation method thereof and lithium ion battery |
| CN111253679B (en) * | 2020-03-20 | 2021-08-31 | 清华大学 | Composite material and preparation method and application thereof |
| CN113451707A (en) * | 2020-03-26 | 2021-09-28 | 溧阳月泉电能源有限公司 | Polyolefin diaphragm and preparation method thereof |
| CN113471622B (en) * | 2021-06-25 | 2022-08-05 | 湖南中锂新材料有限公司 | Preparation method of lithium battery diaphragm |
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Application publication date: 20041215 Assignee: Henan Huiqiang New Energy Material Technology Co., Ltd. Assignor: Guangzhou Inst. of Chemistry, Chinese Academy of Sciences Contract record no.: 2012990000714 Denomination of invention: Process for preparing polymer diaphragm for lithium ion cell Granted publication date: 20051221 License type: Common License Record date: 20120926 |
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