CN104403195A - Raw material of high-wettability lithium ion battery diaphragm and method for processing high-wettability lithium ion battery diaphragm - Google Patents
Raw material of high-wettability lithium ion battery diaphragm and method for processing high-wettability lithium ion battery diaphragm Download PDFInfo
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- CN104403195A CN104403195A CN201410670346.2A CN201410670346A CN104403195A CN 104403195 A CN104403195 A CN 104403195A CN 201410670346 A CN201410670346 A CN 201410670346A CN 104403195 A CN104403195 A CN 104403195A
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- raw material
- lithium ion
- ion battery
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- maleic anhydride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
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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
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a raw material of a high-wettability lithium ion battery diaphragm, and the raw material is prepared from polyolefin resin and maleic anhydride grafted polypropylene. The invention also discloses a method utilizing the raw material to process a high-wettability lithium ion battery diaphragm, and the method comprises the following steps: 1, polyolefin resin, maleic anhydride grafted polypropylene and other additives are uniformly stirred by a stirring mixer to obtain a mixture I; 2, the mixture I is added into an extrusion casting system to be cast into a sheet to prepare a precursor membrane; 3, the obtained precursor membrane is placed into a constant-temperature oven to be annealed; 4, the annealed precursor membrane is stretched in the longitudinal direction to prepare a diaphragm with a microporous structure. The prepared diaphragm is high in wettability, low in cost and simple in processing procedures.
Description
Technical field
The present invention relates to lithium ion battery, especially relate to a kind of raw material of the high wetting property lithium ion battery separator that barrier film wetting property is high, cost is low and the working method of the simple barrier film of a kind of manufacturing procedure of processing.
Background technology
Have that monomer voltage is high, specific energy is high due to lithium ion battery and the advantage such as self-discharge is little, be therefore widely used in the fields such as digital product, power tool and electromobile.The barrier film overwhelming majority of lithium ion battery adopts polyolefine material to be raw material, is prepared from by unidirectional or two-way stretch.But the hydrophobicity had due to polyolefine material makes it very poor to the electrolytic solution wetting property of polarity, have a strong impact on electrolytic solution pick up, protect electrochemistry and the battery performance such as liquid rate and circulating battery.Therefore improve the wetting property of polyalkene diaphragm to electrolytic solution to have great importance.The infiltrating method of current raising barrier film to electrolytic solution is exactly to improve wetting property and the thermotolerance of barrier film in membrane surface coated ceramic.But the processing units price of the method is high and raw materials cost is also higher, operation is comparatively complicated simultaneously, limits it to a certain extent and uses on a large scale.
Summary of the invention
For overcoming above-mentioned shortcoming, provide the raw material of the high wetting property lithium ion battery separator that a kind of barrier film wetting property of processing is high, cost is low, another object of the present invention is to provide the working method of the simple barrier film of a kind of manufacturing procedure.
The object of the invention is to be realized by following technical measures, a kind of raw material method of high wetting property lithium ion battery separator, is made up of polyolefin resin and maleic anhydride inoculated polypropylene.
As a kind of optimal way, the percentage of grafting of described maleic anhydride inoculated polypropylene is 0.1%-10%.
As a kind of optimal way, also comprise oxidation inhibitor.
As a kind of optimal way, also comprise softening agent.
The invention also discloses a kind of working method of high wetting property lithium ion battery separator, comprise the steps:
Step 1: polyolefin resin, maleic anhydride inoculated polypropylene and other additive are stirred by stir mixing machine, obtains mixture I;
Step 2: mixture I is joined to extrude in casting apparatus and carries out slab, preparation precursor film;
Step 3: gained presoma body film is put into constant temperature oven and carries out anneal;
Step 4: the precursor film after annealing is carried out longitudinal stretching, prepares the barrier film with microvoid structure.
As a kind of optimal way, in described step 1, the stirring velocity of stir mixing machine is 500-6000rpm, and churning time is 10-40min.
As a kind of optimal way, in described step 2, the temperature of forcing machine is 180-240 DEG C, and die head temperature is 185-235 DEG C, and casting roller temperature is 30-120 DEG C, and the precursor film thickness of preparation is 10-40 μm.
As a kind of optimal way, the temperature of described step 3 baking oven is 100-155 DEG C, and annealing time is 10-300 minute.
As a kind of optimal way, in described step 4, draft temperature is 100-155 DEG C, and stretching ratio is 0.5-3.0.
This high wetting property lithium ion battery separator can be applicable to the barrier film preparing lithium ion battery, is particularly useful for lithium-ion power battery dissepiment, is conducive to the usage safety performance and the over-all properties that improve its fast charging and discharging.
The present invention has following advantage and effect relative to prior art:
High by the barrier film wetting property of this Raw material processing, cost is lower, present method has the simple advantage of operation.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
A raw material method for high wetting property lithium ion battery separator, makes primarily of polyolefin resin and maleic anhydride inoculated polypropylene.Wherein the percentage of grafting of maleic anhydride inoculated polypropylene is preferably 0.1%-10%.
Also oxidation inhibitor and/or softening agent can be added in this raw material.
Utilize above-mentioned raw materials to process a method for high wetting property lithium ion battery separator, comprise the steps:
Step 1: polyolefin resin, maleic anhydride inoculated polypropylene and other additive are stirred by stir mixing machine, obtains mixture I; Wherein, the stirring velocity of stir mixing machine is 500-6000rpm, and churning time is 10-40min.
Step 2: mixture I is joined to extrude in casting apparatus and carries out slab, preparation precursor film; Wherein, the temperature of forcing machine is 180-240 DEG C, and die head temperature is 185-235 DEG C, and casting roller temperature is 30-120 DEG C, and the precursor film thickness of preparation is 10-40 μm.
Step 3: gained presoma body film is put into constant temperature oven and carries out anneal; Wherein, the temperature of baking oven is 100-155 DEG C, and annealing time is 10-300 minute.
Step 4: the precursor film after annealing is carried out longitudinal stretching, prepares the barrier film with microvoid structure; Wherein, draft temperature is 100-155 DEG C, and stretching ratio is 0.5-3.0.。
Below in conjunction with specific embodiment and comparative example, such scheme is described further.Should be understood that these embodiments are for illustration of the present invention, be not limited to limit the scope of the invention.The implementation condition adopted in embodiment can do further adjustment as the case may be, and not marked implementation condition is generally the condition in normal experiment.
In following examples, acrylic resin adopts a kind of film-grade height isotatic polypropylene, and melting index is 3.0g/10min (2.16kg), and degree of isotacticity is 98%, density 0.91g/cm3.Other auxiliary agent during preparation casting films, the addition of antioxidant 1010 is 0.2%, and the addition of dioctyl phthalate (DOP) is 2%.
Embodiment 1
Precise polypropylene: 100kg, antioxidant 1010: 0.2kg, maleic anhydride inoculated polypropylene (percentage of grafting 0.9%): 30kg.Precursor film A is prepared, extruder temperature: 230 DEG C, die head temperature: 215 DEG C, casting roller temperature: 90 degrees Celsius, die head aperture: 2.0mm, casting films thickness: 18.5um, rolling length: 1000m by casting apparatus slab.
Precursor film A is put into constant temperature oven heat-treat, thermal treatment temp: 130 DEG C, heat treatment time: 15 hours.
Through heat treated precursor film A, will stretch, prepare lithium ion battery separator, stretch rate: 2.2, draft temperature 120 DEG C, setting temperature 140 DEG C.
Embodiment 2
Precise polypropylene: 98kg, antioxidant 1010: 0.2kg, maleic anhydride inoculated polypropylene (percentage of grafting 1.5%): 10kg.Precursor film B is prepared, extruder temperature: 230 DEG C, die head temperature: 215 DEG C, casting roller temperature: 90 degrees Celsius, die head aperture: 2.0mm, casting films thickness: 18.5um, rolling length: 1000m by casting apparatus slab.
Precursor film B is put into constant temperature oven heat-treat, thermal treatment temp: 130 DEG C, heat treatment time: 15 hours.
Through heat treated precursor film B, will stretch, prepare lithium ion battery separator, stretch rate: 2.2, draft temperature 120 DEG C, setting temperature 140 DEG C.
Comparative example 1
Use acrylic resin, prepare precursor film D by casting apparatus slab, extruder temperature: 230 DEG C, die head temperature: 215 DEG C, casting roller temperature: 90 degrees Celsius, die head aperture: 2.0mm, casting films thickness: 18.5um, rolling length: 1000m.
Precursor film D is put into constant temperature oven heat-treat, thermal treatment temp: 130 DEG C, heat treatment time: 15 hours.
Through heat treated precursor film D, will stretch, prepare lithium ion battery separator, stretch rate: 2.2, draft temperature 120 DEG C, setting temperature 140 DEG C.
Each embodiment and the contact angle situation of comparative example to electrolytic solution as shown in table 1, wherein electrolytic solution is: EC:EMC:DMC=1:1:1.
Table 1
| Time | Embodiment 1 | Embodiment 2 | Comparative example 1 |
| 0s | 37.7776 | 37.679 | 44.476 |
| 30s | 15.365 | 15.284 | 37.776 |
Foregoing description is only set forth section Example of the present invention; the present invention is understood for helping; but embodiments of the present invention are not restricted to the described embodiments; any do not deviate from the principle of the invention under do change, modification, substitute, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a raw material for high wetting property lithium ion battery separator, is characterized in that: be made up of polyolefin resin and maleic anhydride inoculated polypropylene.
2. raw material according to claim 1, is characterized in that: the percentage of grafting of described maleic anhydride inoculated polypropylene is 0.1%-10%.
3. raw material according to claim 1, is characterized in that: also comprise oxidation inhibitor.
4. raw material according to claim 1, is characterized in that: also comprise softening agent.
5. a working method for high wetting property lithium ion battery separator, is characterized in that comprising the steps:
Step 1: polyolefin resin, maleic anhydride inoculated polypropylene and other additive are stirred by stir mixing machine, obtains mixture I;
Step 2: mixture I is joined to extrude in casting apparatus and carries out slab, preparation precursor film;
Step 3: gained presoma body film is put into constant temperature oven and carries out anneal;
Step 4: the precursor film after annealing is carried out longitudinal stretching, prepares the barrier film with microvoid structure.
6. method according to claim 5, is characterized in that: in described step 1, the stirring velocity of stir mixing machine is 500-6000rpm, and churning time is 10-40min.
7. method according to claim 5, is characterized in that: in described step 2, the temperature of forcing machine is 180-240 DEG C, and die head temperature is 185-235 DEG C, and casting roller temperature is 30-120 DEG C, and the precursor film thickness of preparation is 10-40 μm.
8. method according to claim 5, is characterized in that: the temperature of described step 3 baking oven is 100-155 DEG C, and annealing time is 10-300 minute.
9. method according to claim 5, is characterized in that: in described step 4, draft temperature is 100-155 DEG C, and stretching ratio is 0.5-3.0.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410670346.2A CN104403195A (en) | 2014-11-20 | 2014-11-20 | Raw material of high-wettability lithium ion battery diaphragm and method for processing high-wettability lithium ion battery diaphragm |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410670346.2A CN104403195A (en) | 2014-11-20 | 2014-11-20 | Raw material of high-wettability lithium ion battery diaphragm and method for processing high-wettability lithium ion battery diaphragm |
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| CN104403195A true CN104403195A (en) | 2015-03-11 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105479765A (en) * | 2015-11-03 | 2016-04-13 | 深圳市星源材质科技股份有限公司 | Preparation method of high-liquid-absorptivity/high-liquid-maintainability dry one-way stretching diaphragm |
| CN106252564A (en) * | 2016-09-06 | 2016-12-21 | 深圳市星源材质科技股份有限公司 | A kind of preparation method of high puncture strength lithium ion battery separator |
| CN110931691A (en) * | 2019-11-14 | 2020-03-27 | 珠海格力绿色再生资源有限公司 | Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery containing diaphragm |
| CN114188658A (en) * | 2021-11-15 | 2022-03-15 | 深圳中兴新材技术股份有限公司 | Thin film, preparation method thereof and battery |
| CN114243204A (en) * | 2021-11-15 | 2022-03-25 | 四川大学 | Lithium battery diaphragm and preparation method thereof |
| CN114597585A (en) * | 2022-03-28 | 2022-06-07 | 河北金力新能源科技股份有限公司 | Strong-liquid-permeability lithium ion battery diaphragm and preparation method thereof |
| CN114696036A (en) * | 2022-06-02 | 2022-07-01 | 宁德卓高新材料科技有限公司 | Transition metal capture diaphragm and preparation method and application thereof |
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| CN1331725A (en) * | 1998-11-20 | 2002-01-16 | Bba无纺辛普森维尔公司 | Wettable polypropylene compsn. and related method of manufacture |
| CN1362892A (en) * | 2000-01-10 | 2002-08-07 | Lg化学株式会社 | High crystalline polypropylene microporous membrane, multi-component microporous membrane and methods for preparing same |
| JP2002343326A (en) * | 2001-05-16 | 2002-11-29 | Asahi Kasei Corp | Battery separator |
| JP2005112905A (en) * | 2003-10-03 | 2005-04-28 | Nitto Denko Corp | Porous film |
| CN102666687A (en) * | 2009-11-09 | 2012-09-12 | 东丽株式会社 | Porous film and electricity storage device |
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| CN1362892A (en) * | 2000-01-10 | 2002-08-07 | Lg化学株式会社 | High crystalline polypropylene microporous membrane, multi-component microporous membrane and methods for preparing same |
| JP2002343326A (en) * | 2001-05-16 | 2002-11-29 | Asahi Kasei Corp | Battery separator |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105479765A (en) * | 2015-11-03 | 2016-04-13 | 深圳市星源材质科技股份有限公司 | Preparation method of high-liquid-absorptivity/high-liquid-maintainability dry one-way stretching diaphragm |
| CN105479765B (en) * | 2015-11-03 | 2018-12-11 | 深圳市星源材质科技股份有限公司 | A kind of dry method simple tension diaphragm and preparation method thereof |
| CN106252564A (en) * | 2016-09-06 | 2016-12-21 | 深圳市星源材质科技股份有限公司 | A kind of preparation method of high puncture strength lithium ion battery separator |
| CN110931691A (en) * | 2019-11-14 | 2020-03-27 | 珠海格力绿色再生资源有限公司 | Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery containing diaphragm |
| CN110931691B (en) * | 2019-11-14 | 2022-05-13 | 珠海格力绿色再生资源有限公司 | Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery containing diaphragm |
| CN114188658A (en) * | 2021-11-15 | 2022-03-15 | 深圳中兴新材技术股份有限公司 | Thin film, preparation method thereof and battery |
| CN114243204A (en) * | 2021-11-15 | 2022-03-25 | 四川大学 | Lithium battery diaphragm and preparation method thereof |
| CN114597585A (en) * | 2022-03-28 | 2022-06-07 | 河北金力新能源科技股份有限公司 | Strong-liquid-permeability lithium ion battery diaphragm and preparation method thereof |
| CN114696036A (en) * | 2022-06-02 | 2022-07-01 | 宁德卓高新材料科技有限公司 | Transition metal capture diaphragm and preparation method and application thereof |
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Application publication date: 20150311 |