CN104993084A - Biomass nanocrystal coated polyolefin lithium ion battery diaphragm and production method thereof - Google Patents
Biomass nanocrystal coated polyolefin lithium ion battery diaphragm and production method thereof Download PDFInfo
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- CN104993084A CN104993084A CN201510263980.9A CN201510263980A CN104993084A CN 104993084 A CN104993084 A CN 104993084A CN 201510263980 A CN201510263980 A CN 201510263980A CN 104993084 A CN104993084 A CN 104993084A
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- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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 invention relates to the technical filed of polymer materials, and concretely relates to a biomass nanocrystal coated polyolefin lithium ion battery diaphragm and a production method thereof. The diaphragm comprises a polyolefin porous membrane and a biomass nanocrystal coating layer coated at one side or two sides of the polyolefin porous membrane, so the diaphragm greatly improves the melt fracture temperature and improves the safety of lithium ion batteries.
Description
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery and preparation method thereof.
Background technology
Operating voltage is high, energy density is high because having for lithium ion battery, have extended cycle life, quality is light, volume is little and the excellent characteristic such as pollution-free is developed rapidly, become main force's power supply of each electronic product, be widely used in the electronics field such as mobile phone, portable computer, camera, video camera at present, also can be used as the electrical source of power of electric automobile and hybrid electric vehicle etc.In the structure of lithium battery, barrier film is one of interior layer assembly of key, and the performance of barrier film directly affects the characteristics such as the capacity of battery, cycle performance and security performance, and the barrier film of excellent performance has very important effect to the combination property improving battery.Because microporous polyolefin film has higher porosity, lower resistance, higher tearing toughness, good antiacid alkali ability, good elasticity and the retention to aprotic solvent, therefore microporous polyolefin film becomes topmost lithium ion battery separator material.
Along with lithium ion battery applications is more and more extensive, and development trend is that volume is more and more less, quality is more and more lighter, so the thickness of the lithium battery diaphragm needed is also more and more thinner, fail safe also becomes more and more important, and wherein how to prevent from battery short circuit from internal temperature of battery is raised reaching the fusing point of lithium or the point of ignition of electrolyte and the subject matter becoming barrier film development that causes fire incident.The heat formed due to lithium ion battery short circuit makes internal temperature of battery raise, when battery diaphragm temperature arrives closed pore temperature, micropore can pass through by inaccessible blocking-up electric current, but thermal inertia can make temperature rise further, likely reach melt fracture temperature and cause membrane ruptures, cause battery last to be heated and burning or explosion accident occur, therefore lithium battery diaphragm needs larger closed pore temperature and melt fracture temperature difference.Difference between usual polyethylene diagrams break temperature and closed pore temperature also only has 15 DEG C of (closed pore temperatures-130 DEG C, barrier film melt fracture temperature ~ 145 DEG C), the melt fracture temperature of polypropylene lithium battery diaphragm reaches more than 160 DEG C, but closed pore temperature is also high than polyethylene, Celgard company of the U.S. develops polypropylene, polyethylene/polypropylene composite materials barrier film, the difference of its closed pore temperature and melt fracture temperature reaches more than 30 DEG C, but these polyalkene diaphragms are because of its break temperature lower (generally lower than 170 DEG C), if there is safety issue for power lithium battery pool environments such as batteries of electric automobile barrier films, , and polyethylene, the wettability of polypropylene diaphragm and electrolyte is poor, therefore, need the thermal endurance improving battery diaphragm badly, wettability, stable composition, prepare the resistant to elevated temperatures high performance lithium ion battery barrier film that can be used for dynamic lithium battery.
The Separion barrier film of Degussa (Degussa) company of Germany has prepared pottery/composite plastic film by compound Al2O3 on nonwoven fabrics or other inorganic matter nano particles, this film has higher thermal stability, be heated not yielding, do not shrink and melting phenomenon at 200 DEG C, the fail safe of electrokinetic cell can be improved.But polymer and inorganic material make its combined strength bination inadequate due to the difference of intrinsic property, easy dry linting, and barrier film can increase considerably weight after coating inorganic nano particle.In order to increase combined strength bination, there is the method adding various binding agent between inorganic nanoparticles and barrier film, but due to the inorganic material mainly alumina ceramic grain used in the industry at present, because its intrinsic high rigidity frictional dissipation to plant equipment is large, make alkene barrier film thickness of ceramic coating more and more thinner because equipment attrition is poly-in process of production, the consistent uniformity of coating layer thickness is difficult to control, and is unfavorable for large-scale continuous production.
Summary of the invention
The object of the invention is, in order to solve not high, bad to the electrolyte wettability problem of existing polyolefin diaphragm of lithium ion battery melt fracture temperature, to provide a kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery and preparation method thereof.
In order to reach foregoing invention object, the present invention by the following technical solutions:
A kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery, described barrier film comprises polyolefin porous membrane and is overlying on the brilliant coat of biomass nano of polyolefin porous membrane one or both sides.
If at polyalkene diaphragm floating coat a kind of electronic isolation, dystectic organic nanofibers, the melt fracture temperature of polyalkene diaphragm can not only be improved, also can improve the wettability of barrier film.Biomass nano crystalline substance is a kind of novel poly-polysaccharide nano-crystalline, belongs to organic nanofibers, has following advantage in actual use: (1) electronic isolation, and fusing point is greater than 250 DEG C; (2) raw material sources is extensive, cheap, renewable; (3) there is lower density, after filling, excessively can not increase material weight; (4) have rigidity characteristic, demonstrate high strength and modulus, the modulus as Cellulose nanocrystal can reach 145GPa; (5) rich surface hydroxyl, more easily realizes dispersion stabilization in different environments, has higher wettability to electrolyte.So, nanocrystalline by coating biology matter on polyalkene diaphragm, the melt fracture temperature of barrier film can be significantly improved, improve the wettability to battery electrolyte, promote the fail safe of lithium ion battery.
Preferably, described polyolefin porous membrane is polyethylene diagrams, polypropylene diaphragm or polyethylene and polyacrylic composite diaphragm, and the thickness of barrier film is 4-40 μm, and porosity is 35-70%.
Preferably, the thickness of the brilliant coat of described biomass nano is 1-8 μm.
Preferably, in the brilliant coat of described biomass nano, the diameter of biomass nano crystalline substance is 2-80 nanometer, and length is 20-200 nanometer.
Preferably, biomass nano crystalline substance is that Cellulose nanocrystal or chitin are nanocrystalline.
A preparation method for biomass nano crystal coating polyolefin diaphragm of lithium ion battery, specifically comprises the following steps:
(1) biomass nano is brilliant and water joins in agitator tank and stirs, and obtains biomass nano magma material; Wherein, 30-200 gram of biomass nano crystalline substance is added in every kg water;
(2) biomass nano magma material is coated the one or both sides of polyalkene diaphragm;
(3) will be coated with barrier film heat drying at 65-75 DEG C of biomass nano crystalline substance, to the water content of coating lower than after 20wt%, then carry out roll compacting to coating, the intensity of roll compacting is 10N/cm
2, bone dry at then continuing at 80 DEG C, obtains biomass nano crystal coating polyolefin diaphragm of lithium ion battery.
Preferably, the coating process in step (2) comprises dip coating, rolling method, spraying process or die head and is coated with method.
Compared with prior art, beneficial effect is in the present invention:
(1) the present invention is by the brilliant layer of polyalkene diaphragm surface-coated biomass nano, significantly improves the melt fracture temperature of barrier film, improves the fail safe of lithium ion battery;
(2) inorganic material such as the brilliant hardness ratio aluminium oxide of the biomass nano that the present invention is used are little, little to the loss of plant equipment in process of production, and uniform coating thickness consistency controls easily, to be conducive to serialization, large-scale production;
(3) because the brilliant density of biomass nano is much smaller than inorganic nanoparticles such as potteries, the weight ratio polyolefin ceramic diaphragm increased when coating layer thickness is identical is few, and the lithium ion battery energy density of assembling under the same terms is higher;
(4) the biomass nano crystalline substance adopted makes the compatibility of lithium ion battery separator and electrolyte be better than polyolefin ceramic diaphragm, and interface impedance is less, and the lithium ion battery internal resistance assembled under the same terms is less, is conducive to the performance promoting lithium ion battery;
(5) because biomass nano crystalline substance is easy to be dispersed in water, preparation method of the present invention adopts water to make solvent, has the feature of safety and environmental protection;
(6) biomass nano is brilliant large with the intermolecular forces of polyolefin film, and in preparation, add roll compacting operation, in the assembling use procedure of the manufacture production of biomass nano crystal coating lithium ion battery separator and lithium ion battery, there is not dry linting phenomenon.
Embodiment
Below by specific embodiment, explanation is further described to technical scheme of the present invention, but the present invention is not limited to described embodiment.
If without specified otherwise, the raw material adopted in embodiments of the invention is the conventional raw material in this area, and the method adopted in embodiment, is the conventional method of this area.
Embodiment 1:
A kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery, described barrier film comprises polyolefin porous membrane and is overlying on the brilliant coat of biomass nano of polyolefin porous membrane one or both sides;
Polyolefin porous membrane is polyethylene diagrams, polypropylene diaphragm or polyethylene and polyacrylic composite diaphragm, and the thickness of barrier film is 4 μm, and porosity is 35%;
Biomass nano crystalline substance is that Cellulose nanocrystal or chitin are nanocrystalline, and the thickness of the brilliant coat of biomass nano is 1-2 μm.In the brilliant coat of biomass nano, the diameter of biomass nano crystalline substance is 2-10 nanometer, and length is 20-50 nanometer.
Concrete preparation method is as follows for this MULTILAYER COMPOSITE polyolefin diaphragm of lithium ion battery:
(1) biomass nano is brilliant and water joins in agitator tank and stirs, and obtains biomass nano magma material; Wherein, 30 grams of biomass nano crystalline substances are added in every kg water;
(2) biomass nano magma material is coated the one or both sides of polyalkene diaphragm; Coating process comprises dip coating, rolling method, spraying process or die head and is coated with method;
(3) will be coated with barrier film heat drying at 65-75 DEG C of biomass nano crystalline substance, to the water content of coating lower than after 20wt%, then carry out roll compacting to coating, the intensity of roll compacting is 10N/cm
2, bone dry at then continuing at 80 DEG C, obtains biomass nano crystal coating polyolefin diaphragm of lithium ion battery.
Embodiment 2:
A kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery, described barrier film comprises polyolefin porous membrane and is overlying on the brilliant coat of biomass nano of polyolefin porous membrane one or both sides;
Polyolefin porous membrane is polyethylene diagrams, polypropylene diaphragm or polyethylene and polyacrylic composite diaphragm, and the thickness of barrier film is 10 μm, and porosity is 70%;
Biomass nano crystalline substance is that Cellulose nanocrystal or chitin are nanocrystalline, and the thickness of the brilliant coat of biomass nano is 5-8 μm.In the brilliant coat of biomass nano, the diameter of biomass nano crystalline substance is 50-80 nanometer, and length is 150-200 nanometer.
Concrete preparation method is as follows for this MULTILAYER COMPOSITE polyolefin diaphragm of lithium ion battery:
(1) biomass nano is brilliant and water joins in agitator tank and stirs, and obtains biomass nano magma material; Wherein, 30-200 gram of biomass nano crystalline substance is added in every kg water;
(2) biomass nano magma material is coated the one or both sides of polyalkene diaphragm; Coating process comprises dip coating, rolling method, spraying process or die head and is coated with method;
(3) will be coated with barrier film heat drying at 65-75 DEG C of biomass nano crystalline substance, to the water content of coating lower than after 20wt%, then carry out roll compacting to coating, the intensity of roll compacting is 10N/cm
2, bone dry at then continuing at 80 DEG C, obtains biomass nano crystal coating polyolefin diaphragm of lithium ion battery.
Embodiment 3:
A kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery, described barrier film comprises polyolefin porous membrane and is overlying on the brilliant coat of biomass nano of polyolefin porous membrane one or both sides;
Polyolefin porous membrane is polyethylene diagrams, polypropylene diaphragm or polyethylene and polyacrylic composite diaphragm, and the thickness of barrier film is 40 μm, and porosity is 60%;
Biomass nano crystalline substance is that Cellulose nanocrystal or chitin are nanocrystalline, and the thickness of the brilliant coat of biomass nano is 3-5 μm.In the brilliant coat of biomass nano, the diameter of biomass nano crystalline substance is 20-40 nanometer, and length is 50-100 nanometer.
Concrete preparation method is as follows for this MULTILAYER COMPOSITE polyolefin diaphragm of lithium ion battery:
(1) biomass nano is brilliant and water joins in agitator tank and stirs, and obtains biomass nano magma material; Wherein, 30-200 gram of biomass nano crystalline substance is added in every kg water;
(2) biomass nano magma material is coated the one or both sides of polyalkene diaphragm; Coating process comprises dip coating, rolling method, spraying process or die head and is coated with method;
(3) will be coated with barrier film heat drying at 65-75 DEG C of biomass nano crystalline substance, to the water content of coating lower than after 20wt%, then carry out roll compacting to coating, the intensity of roll compacting is 10N/cm
2, bone dry at then continuing at 80 DEG C, obtains biomass nano crystal coating polyolefin diaphragm of lithium ion battery.
Claims (7)
1. a biomass nano crystal coating polyolefin diaphragm of lithium ion battery, is characterized in that, described barrier film comprises polyolefin porous membrane and is overlying on the brilliant coat of biomass nano of polyolefin porous membrane one or both sides.
2. a kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery according to claim 1, it is characterized in that, described polyolefin porous membrane is polyethylene diagrams, polypropylene diaphragm or polyethylene and polyacrylic composite diaphragm, and the thickness of barrier film is 4-40 μm, and porosity is 35-70%.
3. a kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery according to claim 1, is characterized in that, the thickness of the brilliant coat of described biomass nano is 1-8 μm.
4. a kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery according to claim 1, is characterized in that, in the brilliant coat of described biomass nano, the diameter of biomass nano crystalline substance is 2-80 nanometer, and length is 20-200 nanometer.
5. a kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery according to claim 1, is characterized in that, biomass nano crystalline substance is that Cellulose nanocrystal or chitin are nanocrystalline.
6. the preparation method of a kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery according to claim 1, is characterized in that, specifically comprise the following steps:
(1) biomass nano is brilliant and water joins in agitator tank and stirs, and obtains biomass nano magma material; Wherein, 30-200 gram of biomass nano crystalline substance is added in every kg water;
(2) biomass nano magma material is coated the one or both sides of polyalkene diaphragm;
(3) will be coated with barrier film heat drying at 65-75 DEG C of biomass nano crystalline substance, to the water content of coating lower than after 20wt%, then carry out roll compacting to coating, the intensity of roll compacting is 10N/cm
2, bone dry at then continuing at 80 DEG C, obtains biomass nano crystal coating polyolefin diaphragm of lithium ion battery.
7. the preparation method of a kind of biomass nano crystal coating polyolefin diaphragm of lithium ion battery according to claim 6, is characterized in that, the coating process in step (2) comprises dip coating, rolling method, spraying process or die head and is coated with method.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105185940A (en) * | 2015-10-23 | 2015-12-23 | 旭成（福建）科技股份有限公司 | Preparation method and application of polyolefin/nanocrystal cellulose composite diaphragm |
| CN107799702A (en) * | 2016-08-29 | 2018-03-13 | 比亚迪股份有限公司 | A kind of ceramic diaphragm and lithium ion battery and preparation method thereof |
| CN108258171A (en) * | 2017-12-29 | 2018-07-06 | 深圳中兴创新材料技术有限公司 | A kind of high-temperaure coating composite diaphragm and its preparation method and application |
| CN108305973A (en) * | 2017-12-29 | 2018-07-20 | 深圳中兴创新材料技术有限公司 | It is a kind of to have cated composite diaphragm and preparation method and application |
| CN109390532A (en) * | 2017-08-07 | 2019-02-26 | 上海凯矜新材料科技有限公司 | Lithium battery basement membrane coating slurry and preparation method thereof |
| CN112928385A (en) * | 2021-03-23 | 2021-06-08 | 华中科技大学 | Diaphragm coating for lithium metal negative electrode protection and preparation method and application thereof |
| CN113140867A (en) * | 2021-04-14 | 2021-07-20 | 合肥利夫生物科技有限公司 | Lithium battery diaphragm based on biomass furan-based polymer and preparation method thereof |
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| CN107799702A (en) * | 2016-08-29 | 2018-03-13 | 比亚迪股份有限公司 | A kind of ceramic diaphragm and lithium ion battery and preparation method thereof |
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| CN108258171A (en) * | 2017-12-29 | 2018-07-06 | 深圳中兴创新材料技术有限公司 | A kind of high-temperaure coating composite diaphragm and its preparation method and application |
| CN108305973A (en) * | 2017-12-29 | 2018-07-20 | 深圳中兴创新材料技术有限公司 | It is a kind of to have cated composite diaphragm and preparation method and application |
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| CN112928385A (en) * | 2021-03-23 | 2021-06-08 | 华中科技大学 | Diaphragm coating for lithium metal negative electrode protection and preparation method and application thereof |
| CN113140867A (en) * | 2021-04-14 | 2021-07-20 | 合肥利夫生物科技有限公司 | Lithium battery diaphragm based on biomass furan-based polymer and preparation method thereof |
| CN113140867B (en) * | 2021-04-14 | 2022-08-02 | 合肥利夫生物科技有限公司 | Lithium battery diaphragm based on biomass furan-based polymer and preparation method thereof |
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Application publication date: 20151021 |