CN104362280A - Blend superfine fiber diaphragm for lithium ion battery - Google Patents
Blend superfine fiber diaphragm for lithium ion battery Download PDFInfo
- Publication number
- CN104362280A CN104362280A CN201410669024.6A CN201410669024A CN104362280A CN 104362280 A CN104362280 A CN 104362280A CN 201410669024 A CN201410669024 A CN 201410669024A CN 104362280 A CN104362280 A CN 104362280A
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- China
- Prior art keywords
- superfine fiber
- lithium ion
- ion battery
- fiber diaphragm
- silsesquioxane
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a blend superfine fiber diaphragm for a lithium ion battery. The blend superfine fiber diaphragm is characterized by comprising polyvinylidene fluoride, cellulose acetate and polyhedral oligomeric silsesquioxane. The polyhedral oligomeric silsesquioxane is one of alkyl silsesquioxane, alkenyl silsesquioxane or aryl silsesquioxane. The blend superfine fiber diaphragm provided by the invention has good hydrophilcity, high strength and excellent thermal size stability; the solution absorbing rate of the blend superfine fiber diaphragm is 300-900 percent, the thermal shrinkage rate of the blend superfine fiber diaphragm is smaller than 5 percent, the specific capacity of a gel polymer lithium ion battery assembled by adopting the blend superfine fiber diaphragm reaches 200-220 mAh.g<-1>, and the lithium intercalation utilization rate of an anode material LiCoO2 can reach above 70 percent.
Description
Technical field
The present invention relates to a kind of diaphragm for lithium ion battery, particularly the blended superfine fibre barrier film of a kind of height ratio capacity lithium ion battery, belong to textile material field.
Technical background
The generation of energy crisis makes people focus is gathered in more and more the reversible energy and material of high-energy-density, light weight, safety non-toxic; this trend is just being complied with in research and the development of lithium ion battery, and is acknowledged as current state-of-the-art commercialization secondary cell in the world.Compared with traditional lead-acid battery, nickel-cadmium cell, Ni-MH battery, the advantage such as lithium ion battery has that voltage is high, specific energy is high, discharge and recharge life-span length, memory-less effect, environmental pollution are little, quick charge, self-discharge rate are low, is applied at numerous high-technology fields such as automobile, mobile communication, Aero-Space, defence and militaries.
Barrier film plays vital effect in lithium ion battery, and it can prevent battery plus-negative plate from contacting and internal short-circuit occurs, and the micropore simultaneously on film is again for the lithium ion fast transferring between positive and negative polarities in electrolyte provides passage.At present, lithium ion battery widely uses the polyolefin based materials that diaphragm material mostly is dry method tension or phase inversion, with Celgard company produce for representative, such film porosity is lower, only about about 40%, the patent relating to TPO battery diaphragm has: US4138495, US3801404, CN101267028A, CN101257106, CN101786332A etc.But the polarity extra-heavy of polyolefine material, extreme difference compatible with electrolyte, this just has influence on capacity in this, as the battery of barrier film and useful life, thus can produce serious obstruction to the fast development of lithium ion battery.
In recent years, the nonwoven cloth-like microporous membrane that meltblown and electro-spinning form for superfine fibre becomes lithium ion battery separator research emphasis.Adopt superfine fibre nonwoven cloth to be used as lithium ion battery separator to have: fibre diameter is little is about that 100 ~ 1000nm, specific area are large, porosity up to 60% ~ 90%, porous nickel and frivolous feature.Especially electrostatic spinning technique can spin out the membrane for polymer such as Kynoar and copolymer, polyethylene glycol oxide, polyacrylonitrile and polymethyl methacrylate that can form gel polymer electrolyte, greatly overcome TPO diaphragm material porosity prepared by existing technique low, the shortcoming that pick up is few, wetting property is poor.Such as US Patent No. 7279251B1 describes a profit and utilizes electrostatic spinning process to prepare the method for superfine fibre barrier film.Korean Patent WO01/9022A1 reports the method with superfine fibre membrane for polymer preparing by electrostatic spinning direct battery lead plate again.The patent relating to Static Spinning lithium ion battery separator also has US671301182, ZL 200610144191.4, CN102013516A etc.But the electro-spinning of existing report is for lithium ion battery superfine fibre barrier film also Shortcomings: 1) output is little, production efficiency is low, in most situation, every hole spinning solution is extruded rate and is less than 10ml/h, is 0.1 ~ 5ml/h under normal circumstances; 2) urgently promote further with the electric-woven super-fine fiber barrier film thermal endurance of Kynoar and blended polymer thereof and mechanical property.
In addition, LiCoO
2as the positive electrode that current lithium ion battery is uniquely practical, its theoretical embedding lithium capacity is 274mAh/g.Then existing report shows, with LiCoO
2for positive electrode, the first discharge specific capacity of the gel polymer lithium ion battery of existing commercially available or bibliographical information diaphragm material assembling is adopted to have 60% of not enough theoretical value, the specific capacity adopting emulsion polymerization synthesis Kynoar/vinyl acetate diaphragm cell as Lu Lei etc. is 130mAh/g (chemical journal, 2007,65 (6): 475-480); The specific capacity that Jeong etc. adopt coating technology to prepare Kynoar-hexafluoropropylene/silica separator battery is 152mAh/g (Journal of Power Sources, 2011,196:6716-6722); Kimb etc. adopt the specific capacity of the Kynoar diaphragm cell of electrostatic spinning technique exploitation to be 135mAh/g (Electrochimica Acta, 2004,50:69-75); The specific capacity of the electrospinning Kynoar/polyacrylonitrile diaphragm cell of the report such as Gopalan is 120mAh/g (Journal of Membrane Science, 2008,325:683-690).
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is, provides a kind of lithium ion battery blended superfine fibre barrier film, and this blended superfine fibre barrier film has excellent thermal stability, significantly can promote the specific capacity of lithium ion battery especially.
The technical scheme that the present invention solve the technical problem is: design the blended superfine fibre barrier film of a kind of lithium ion battery, it is characterized in that, be made up of Kynoar, cellulose acetate and cage-type silsesquioxane, its mass percent component is:
Kynoar 95% ~ 50%;
Cellulose acetate 5% ~ 50%;
Cage-type silsesquioxane 0.5 ~ 3%;
Described cage-type silsesquioxane is the one in alkyl, thiazolinyl or aryl silsesquioxane.
The strong electron group (C-F) that Kynoar macromolecular chain of the present invention contains, for the conventional high polymer material of gel polymer electrolyte, there is good fibre forming property, good chemistry and electrochemical stability, be conducive to lithium salts dissolving in the polymer simultaneously, there is provided higher carrier concentration, Kynoar has higher dielectric constant in addition, and molecular weight is preferably 100,000 ~ 300,000.
Cellulose acetate is the natural high polymer of a kind of chemical modification obtained after hydroxyl acetic acid esterified in cellulosic molecule, there is excellent lyophily performance, in the present invention, its effect improves moisture absorption and the heat resistance of blended superfine fibre barrier film, simultaneously, owing to containing a large amount of O atoms in cellulose acetate, also effectively gel polymer electrolyte can be formed with electrolyte.Described cellulose acetate molecular weight preferably 30,000 ~ 100,000.
Described Kynoar and cellulose acetate mass ratio 100: 0 ~ 60: 40, preferred range is 80: 20 ~ 70: 30.
In the present invention, cage-type silsesquioxane adds object is improve barrier film mechanical property and thermal stability.Described cage-type silsesquioxane is a kind of novel inorganic nano-particle, its Stability Analysis of Structures, and symmetry is very strong, light weight, diameter are 1 ~ 3nm, and hardness is high, and heat resisting temperature is high, can form physics crosslinking points in large molecular matrix, be a kind of effectively nanoreinforcement material.The molecular formula RSiO of cage-type silsesquioxane classics
1.5, be quantitatively " sesquialter " at O: Si=1.5: 1, wherein R can be alkyl, thiazolinyl, the one in aryl, preferred aryl groups cage-type silsesquioxane.With SiO in existing patent and bibliographical information
2, Al
2o
3compare Deng inorganic nano-particle, because the existence of R group in cage-type silsesquioxane gives itself and Kynoar and cellulose acetate intermolecular greatly better compatibility.Described cage-type silsesquioxane addition is diaphragm quality mark preferably 1 ~ 2%.
The preparation method of blended superfine fibre barrier film of the present invention adopts known Static Spinning or air-flow auxiliary wire Static Spinning, and its work flow is short, and technique is simple, is produced on a large scale.The blended superfine fibre barrier film adopting preparation method of the present invention to obtain, in conjunction with Kynoar, cellulose acetate and cage-type silsesquioxane three advantage, there is the thermal dimensional stability of good lyophily, higher intensity and excellence, tool pick up is 300 ~ 900%, at 180 DEG C under process, its percent thermal shrinkage is less than 5%, and the gel polymer lithium ion battery specific capacity prepared with it reaches 200 ~ 220mAhg
-1, positive electrode LiCoO
2embedding lithium utilance can reach more than 70%, greatly improve LiCoO
2embedding lithium utilance.
Accompanying drawing explanation
Fig. 1 is preparation facilities and the embodiment 1 blended superfine fibre barrier film scanning electron microscope (SEM) photograph of the embodiment of the present invention;
Fig. 2 is the specific volume spirogram of the fastening lithium ionic cell charge and discharge cycles 40 times of the embodiment of the present invention 1 blended superfine fibre barrier film assembling.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
(1) by molecular weight 350, the Kynoar parts by weight 80 parts of 000 and molecular weight 60, cellulose acetate 18 parts and the aryl cage-type silsesquioxane 2 parts of 000 are dissolved in the N that Mixing ratio by weight is 3: 7, in the composite organic solvent of dinethylformamide/acetone, make it dissolve completely with high speed agitator stirring and make the spinning solution that gross mass mark is the stable homogeneous of 13% Kynoar/cellulose acetate;
(2) above-mentioned configuration spinning solution 1 is injected micro syringe 2, and extrude with the internal channel 31 of the rate of extrusion of 15ml/h from Metallic Nozzle At The Ingot 3, the high velocity air that spinning solution 1 produces 0.15MPa by air compressor 4 in shower nozzle internal channel 31 exit and outer tunnel 32 meets, Metallic Nozzle At The Ingot 3 is connected with the positive pole 51 of the HV generator 5 applying 20kV simultaneously, spinning solution 1 blows ejection under effect and forms jet and be refined into superfine fibre 6 by further drawing-off electrostatic is molten, the superfine fibre 6 formed is collected in apart from the receiving system 7 of shower nozzle 1 top 20cm through solvent evaporates, the even blended superfine fibre barrier film 8 (see Fig. 1) of non-woven cloth-like can be obtained
The membrane thicknesses of gained is about 26 μm, and porosity is 80.7%, and brute force is 11.1MPa, and elongation at break is 119.6%, and pick up is 768.2%, and percent thermal shrinkage is 1.9%.With LiCoO
2for the blended superfine fibre film of gained is assembled into fastening lithium ionic cell by positive electrode, its initial specific capacities is 204.1mAhg
-1, LiCoO
2embedding lithium utilance up to 74.9%, circulate after 40 times, its specific capacity is still at 175mAhg
-1above (see Fig. 2).
Embodiment 2 ~ 11
Implementation process embodiment 1 is basically identical, just different on processing conditions, concrete condition as shown in Table 1 and Table 2:
The foregoing is only the preferred embodiments of the present invention, not thereby restriction uses the scope of the claims of the present invention.
The concrete the key technical indexes form of table 2 embodiment
* percent thermal shrinkage test oven temperature is at 180 DEG C, free shrink 24h.
Claims (1)
1. the blended superfine fibre barrier film of lithium ion battery, is characterized in that, be made up of Kynoar, cellulose acetate and cage-type silsesquioxane, and its mass percent component is:
Kynoar 95% ~ 50%;
Cellulose acetate 5% ~ 50%;
Cage-type silsesquioxane 0.5 ~ 3%;
Described cage-type silsesquioxane is the one in alkyl, thiazolinyl or aryl silsesquioxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410669024.6A CN104362280A (en) | 2014-11-17 | 2014-11-17 | Blend superfine fiber diaphragm for lithium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410669024.6A CN104362280A (en) | 2014-11-17 | 2014-11-17 | Blend superfine fiber diaphragm for lithium ion battery |
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| CN104362280A true CN104362280A (en) | 2015-02-18 |
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| CN201410669024.6A Pending CN104362280A (en) | 2014-11-17 | 2014-11-17 | Blend superfine fiber diaphragm for lithium ion battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105428578A (en) * | 2015-12-24 | 2016-03-23 | 广东永畅兴精密制造股份有限公司 | Battery production method and fiber diaphragm formed thereby |
| CN108777284A (en) * | 2018-06-11 | 2018-11-09 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of lithium ion battery composite separation membrane |
| CN109786621A (en) * | 2018-12-17 | 2019-05-21 | 中科院广州化学有限公司 | A kind of modified fibre diaphragm and preparation method thereof of silsesquioxane for high-performance lithium battery |
| CN110911612A (en) * | 2019-11-11 | 2020-03-24 | 苏州大学 | Cellulose acetate-based cross-linked composite lithium ion battery diaphragm and preparation method and application thereof |
| CN111430782A (en) * | 2020-05-08 | 2020-07-17 | 曹亚琼 | Silicon aerogel modified lithium ion battery diaphragm and preparation method thereof |
| CN112563669A (en) * | 2019-09-26 | 2021-03-26 | 上海恩捷新材料科技有限公司 | High-wettability diaphragm and preparation method thereof |
| CN115275520A (en) * | 2022-08-29 | 2022-11-01 | 江苏欧力特能源科技有限公司 | Composite diaphragm for lithium battery and preparation method thereof |
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| DE10304735A1 (en) * | 2002-12-18 | 2004-07-08 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Separator used in lithium or other, preferably primary or secondary, battery consists of porous film(s) of polymer matrix containing polyhedral oligomeric silicon-oxygen clusters produced by making nonporous film and providing porosity |
| JP2006092810A (en) * | 2004-09-21 | 2006-04-06 | Aisin Seiki Co Ltd | Electrolyte material, electrolyte film, catalyst paste, film electrode junction and fuel cell |
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| CN102586926A (en) * | 2012-02-23 | 2012-07-18 | 中国科学院合肥物质科学研究院 | Electrostatic spinning preparation method of POSS (Polyhedral Oligomeric Silsesquioxane)-containing polymer composite fiber |
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Patent Citations (6)
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| DE10304735A1 (en) * | 2002-12-18 | 2004-07-08 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Separator used in lithium or other, preferably primary or secondary, battery consists of porous film(s) of polymer matrix containing polyhedral oligomeric silicon-oxygen clusters produced by making nonporous film and providing porosity |
| JP2006092810A (en) * | 2004-09-21 | 2006-04-06 | Aisin Seiki Co Ltd | Electrolyte material, electrolyte film, catalyst paste, film electrode junction and fuel cell |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105428578A (en) * | 2015-12-24 | 2016-03-23 | 广东永畅兴精密制造股份有限公司 | Battery production method and fiber diaphragm formed thereby |
| CN108777284A (en) * | 2018-06-11 | 2018-11-09 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of lithium ion battery composite separation membrane |
| CN109786621A (en) * | 2018-12-17 | 2019-05-21 | 中科院广州化学有限公司 | A kind of modified fibre diaphragm and preparation method thereof of silsesquioxane for high-performance lithium battery |
| CN112563669A (en) * | 2019-09-26 | 2021-03-26 | 上海恩捷新材料科技有限公司 | High-wettability diaphragm and preparation method thereof |
| CN110911612A (en) * | 2019-11-11 | 2020-03-24 | 苏州大学 | Cellulose acetate-based cross-linked composite lithium ion battery diaphragm and preparation method and application thereof |
| CN111430782A (en) * | 2020-05-08 | 2020-07-17 | 曹亚琼 | Silicon aerogel modified lithium ion battery diaphragm and preparation method thereof |
| CN115275520A (en) * | 2022-08-29 | 2022-11-01 | 江苏欧力特能源科技有限公司 | Composite diaphragm for lithium battery and preparation method thereof |
| CN115275520B (en) * | 2022-08-29 | 2023-07-07 | 江苏欧力特能源科技有限公司 | Composite diaphragm for lithium battery and preparation method thereof |
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Application publication date: 20150218 |