CN103840108A - Polypropylene power lithium ion battery diaphragm with enhanced mechanical strength and preparation method thereof - Google Patents
Polypropylene power lithium ion battery diaphragm with enhanced mechanical strength and preparation method thereof Download PDFInfo
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- CN103840108A CN103840108A CN201210472283.0A CN201210472283A CN103840108A CN 103840108 A CN103840108 A CN 103840108A CN 201210472283 A CN201210472283 A CN 201210472283A CN 103840108 A CN103840108 A CN 103840108A
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- Prior art keywords
- battery diaphragm
- power lithium
- polypropylene
- lithium battery
- strengthens
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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
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- 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
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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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a power lithium ion battery diaphragm containing polypropylene resin and a modified agent and a preparation method thereof. The modified agent comprises an inorganic nanoparticle and a nucleating agent, wherein the weight percentage of the polypropylene resin is 85%-95%, the weight percentage of the inorganic nanoparticle is 5%-10%, and the weight percentage of the nucleating agent is 1%-3%. The polypropylene power lithium ion battery diaphragm has high mechanical strength.
Description
Technical field
The present invention relates to a kind of diaphragm of power lithium ion battery that comprises acrylic resin and modifier and preparation method thereof, the preparation method of the modified polypropene power lithium battery diaphragm that particularly a kind of mechanical strength strengthens.
Background technology
Lithium ion battery with its high-energy-density, long circulation life, memory-less effect, safe and reliable and can fast charging and discharging etc. advantage and become the focus of novel power supply technical research, except being widely used in the daily mobile phone of knowing, notebook computer and other digital electronic goods, the development of electric motor car also will drive the larger demand of lithium ion battery, and in the fields such as Aero-Space, navigation, artificial satellite, small-sized medical treatment, military communications equipment, also obtain application, progressively replaced conventional batteries.
Battery diaphragm refers to the membrane for polymer in the middle of lithium ion cell positive and negative pole, is the part of lithium ion battery most critical, and battery security and cost are had a direct impact.Along with the further expansion of lithium ion battery applications scope, the demand of diaphragm material will further increase.And only have in the world a few countries such as Japan, the U.S. to have production technology and the corresponding large-scale production of lithium ion battery polymer barrier film; China is starting late aspect the research and development of lithium ion battery separator; still main dependence on import; therefore; realize the production domesticization of barrier film; the production domesticization barrier film of production high-quality, can be expected to reduce the market price of whole barrier film and even lithium ion battery.
Polyethylene (PE), polypropylene (PP) microporous barrier have higher porosity, lower resistance, higher tearing toughness, good antiacid alkali ability, good elasticity and the retention to aprotic solvent, therefore Study on Li-ion batteries using initial stage of development with it as diaphragm material.Lithium ion battery separator can be divided into dry method and the large class of wet method two by preparation technology's difference:
Dry method is that vistanex melting, extruding, blown film are made to crystalline polymer film, after crystallization processing, annealing, obtains height-oriented sandwich construction, at high temperature further stretch, crystalizing interface is peeled off, formed loose structure, can increase the aperture of film.Dry method can be divided into dry method simple tension and biaxial tension by draw direction difference.
Wet method claims again phase separation method or thermally induced phase separation, liquid hydrocarbon or some small-molecule substances are mixed with vistanex, after heating and melting, form uniform mixture, then cooling is separated, suppress to obtain diaphragm, then diaphragm is heated to approach melting temperature, carry out biaxial tension and make molecular chain orientation, finally be incubated certain hour, with the residual solvent of volatile substances wash-out, can prepare the microporous membrane material of mutual perforation, the applicable material ranges of the method is wide.
Summary of the invention
The technical problem to be solved in the present invention is: for the existing preparation method of current battery barrier film and performance, provide power lithium battery diaphragm of a kind of mechanical strength enhancing and preparation method thereof.
The present invention solves the technical scheme that its technical problem is taked: the acrylic resin that percentage by weight is 85%-95%, the inorganic nano-particle that percentage by weight is 5%-10%, the nucleator that percentage by weight is 1%-3%.
Described inorganic nano-particle is calcium carbonate and titanium dioxide.
Described nucleator is nucleating agent.
The preparation method of the power lithium battery diaphragm that mechanical strength of the present invention strengthens comprises following steps:
(1) by polypropylene and nucleating agent through melt extruding granulation, making nucleator percentage by weight is the masterbatch 1 of 1%-3%;
(2) polypropylene is mixed with the inorganic nano-particle of crossing through surface modification, through melt extruding granulation, making inorganic nano-particle percentage by weight is the masterbatch 2 of 5%-10%;
(3) by masterbatch 1 with masterbatch 2 by weight percentage for 1:1 mixes, make masterbatch 3, through melt extruding, stretching, finally make the power lithium battery diaphragm of three kinds of specifications.
Described surface modification is coupling agent modified, and described coupling agent is KH550.
What step (3) was described melt extrude, drawing process adopts existing dry method stretch processes, and preferred process conditions are as follows: melt extrude temperature and be respectively: 230 ℃, 230 ℃, 230 ℃, 235 ℃, 230 ℃, and pressure position 15, power of motor is 45; The temperature of drawing process is divided into: longitudinal stretching temperature, preheat temperature and cross directional stretch temperature, be respectively 165 ℃, 170 ℃, 175 ℃, and stretching ratio is respectively 5*7,4*6,3.5*5.
Test through universal tensile testing machine, the mechanical strength of finding the power lithium battery diaphragm of gained is respectively 95MPa, 81 MPa, 75 MPa, and be only 50 MPa, 49 MPa, 49 MPa without the hot strength of the polypropylene diaphragm material of inorganic nano-particle and nucleater modified mistake, visible, the mechanical strength of the prepared lithium battery diaphragm of this method obviously strengthens.
Embodiment
embodiment mono-:
(1) by polypropylene and nucleating agent through melt extruding granulation, make nucleating agent percentage by weight and be 3% masterbatch 1;
(2) polypropylene is mixed with calcium carbonate and the titanium dioxide crossed through coupling agent KH550 surface modification, through melt extruding granulation, make inorganic nano-particle percentage by weight and be 5% masterbatch 2;
(3) by masterbatch 1 with masterbatch 2 by weight percentage for 1:1 mixes, make masterbatch 3;
(4)by masterbatch 3 through twin-screws melt extrude, temperature is respectively: 230 ℃, 230 ℃, 230 ℃, 235 ℃, 230 ℃, pressure position 15, power of motor is 45; Carry out biaxial tension through film stretching experimental machine again, finally make the power lithium battery diaphragm of three kinds of specifications, its stretching condition is as described below: draft temperature is respectively: longitudinal stretching temperature, preheat temperature and cross directional stretch temperature, be respectively 165 ℃, 170 ℃, 175 ℃, stretching ratio is 5*7.
The average thickness 13 μ m of the power lithium battery diaphragm of the modification making by above method, hot strength is 95 Mpa.
embodiment bis-:
(1) by polypropylene and nucleating agent through melt extruding granulation, make nucleating agent percentage by weight and be 3% masterbatch 1;
(2) polypropylene is mixed with calcium carbonate and the titanium dioxide crossed through coupling agent KH550 surface modification, through melt extruding granulation, make inorganic nano-particle percentage by weight and be 5% masterbatch 2;
(3) by masterbatch 1 with masterbatch 2 by weight percentage for 1:1 mixes, make masterbatch 3;
(4)by masterbatch 3 through twin-screws melt extrude, temperature is respectively: 230 ℃, 230 ℃, 230 ℃, 235 ℃, 230 ℃, pressure position 15, power of motor is 45; Carry out biaxial tension through film stretching experimental machine again, finally make the power lithium battery diaphragm of three kinds of specifications, its stretching condition is as described below: draft temperature is respectively: longitudinal stretching temperature, preheat temperature and cross directional stretch temperature, be respectively 165 ℃, 170 ℃, 175 ℃, stretching ratio is 4*6.
The average thickness of the power lithium battery diaphragm of the modification making by above method is 20 μ m, and hot strength is 81MPa.
embodiment tri-:
(1) by polypropylene and nucleating agent through melt extruding granulation, make nucleating agent percentage by weight and be 3% masterbatch 1;
(2) polypropylene is mixed with calcium carbonate and the titanium dioxide crossed through coupling agent KH550 surface modification, through melt extruding granulation, make inorganic nano-particle percentage by weight and be 5% masterbatch 2;
(3) by masterbatch 1 with masterbatch 2 by weight percentage for 1:1 mixes, make masterbatch 3;
(4) by masterbatch 3 through twin-screws melt extrude, temperature is respectively: 230 ℃, 230 ℃, 230 ℃, 235 ℃, 230 ℃, pressure position 15, power of motor is 45; Carry out biaxial tension through film stretching experimental machine again, finally make the power lithium battery diaphragm of three kinds of specifications, its stretching condition is as described below: draft temperature is respectively: longitudinal stretching temperature, preheat temperature and cross directional stretch temperature, be respectively 165 ℃, 170 ℃, 175 ℃, stretching ratio is 3.5*5.
The average thickness of the power lithium battery diaphragm of the modification making by above method is 25 μ m, and hot strength is 75MPa.
Claims (7)
1. the polypropylene power lithium battery diaphragm that mechanical property strengthens, is characterized in that, comprises the acrylic resin that percentage by weight is 85%-95%, the inorganic nano-particle that percentage by weight is 5%-10%, the nucleator that percentage by weight is 1%-3%.
2. the polypropylene power lithium battery diaphragm that mechanical property as claimed in claim 1 strengthens, is characterized in that, the thickness of the power lithium battery diaphragm that described mechanical property strengthens is 10 – 30 μ m, and hot strength is 80-100 Mpa.
3. the polypropylene power lithium battery diaphragm that mechanical property as claimed in claim 1 strengthens, is characterized in that, described inorganic nano-particle is calcium carbonate and titanium dioxide.
4. the polypropylene power lithium battery diaphragm that mechanical property as claimed in claim 1 strengthens, is characterized in that, described nucleator is nucleating agent.
5. the polypropylene power lithium battery diaphragm that the mechanical property described in claim 1-4 any one strengthens, is characterized in that, its preparation method comprises following steps:
(1) by polypropylene and nucleating agent through melt extruding granulation, making nucleator percentage by weight is the masterbatch 1 of 1%-3%;
(2) polypropylene is mixed with the inorganic nano-particle of crossing through surface modification, through melt extruding granulation, making inorganic nano-particle percentage by weight is the masterbatch 2 of 5%-10%;
(3) by masterbatch 1 with masterbatch 2 by weight percentage for 1:1 mixes, make masterbatch 3, through melt extruding, stretching, finally make the power lithium battery diaphragm of three kinds of specifications.
6. the polypropylene power lithium battery diaphragm that mechanical property claimed in claim 5 strengthens, is characterized in that, described surface modification is through coupling agent modified, and described coupling agent is KH550.
7. the polypropylene power lithium battery diaphragm that mechanical property claimed in claim 5 strengthens, it is characterized in that, melting that step (3) is described extruded, drawing process adopts existing dry method stretch processes, preferred process conditions are as follows: melt extrude temperature and be respectively: 230 ℃, 230 ℃, 230 ℃, 235 ℃, 230 ℃, pressure position 15, power of motor is 45; The temperature of drawing process is divided into: longitudinal stretching temperature, preheat temperature and cross directional stretch temperature, be respectively 165 ℃, 170 ℃, 175 ℃; Stretching ratio is respectively 5*7,4*6,3.5*5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210472283.0A CN103840108A (en) | 2012-11-21 | 2012-11-21 | Polypropylene power lithium ion battery diaphragm with enhanced mechanical strength and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210472283.0A CN103840108A (en) | 2012-11-21 | 2012-11-21 | Polypropylene power lithium ion battery diaphragm with enhanced mechanical strength and preparation method thereof |
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| CN103840108A true CN103840108A (en) | 2014-06-04 |
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| CN201210472283.0A Pending CN103840108A (en) | 2012-11-21 | 2012-11-21 | Polypropylene power lithium ion battery diaphragm with enhanced mechanical strength and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784528A (en) * | 2016-12-27 | 2017-05-31 | 深圳市星源材质科技股份有限公司 | A kind of preparation method of lithium battery diaphragm |
| CN108400272A (en) * | 2018-03-05 | 2018-08-14 | 陈颖婷 | A kind of lithium battery polypropylene diaphragm being compounded with kenyaite-aerosil |
| CN111497293A (en) * | 2020-03-31 | 2020-08-07 | 江苏厚生新能源科技有限公司 | Preparation method of high-wettability film, high-wettability film and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1825666A (en) * | 2005-12-23 | 2006-08-30 | 范亢俊 | Lithium cell, safety diaphragm of lithium ion cell and mfg. method |
| CN101710614A (en) * | 2009-12-16 | 2010-05-19 | 南京大学 | Diaphragm of modified lithium battery with medium hole nano particles |
| CN102367172A (en) * | 2011-10-17 | 2012-03-07 | 中科院广州化学有限公司 | Modified silicon dioxide and high-property lithium ion battery diaphragm and application thereof |
| CN102403478A (en) * | 2010-09-16 | 2012-04-04 | 铜陵晶能电子股份有限公司 | Production method of high-permeability low-density lithium battery polyolefin diaphragm |
-
2012
- 2012-11-21 CN CN201210472283.0A patent/CN103840108A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1825666A (en) * | 2005-12-23 | 2006-08-30 | 范亢俊 | Lithium cell, safety diaphragm of lithium ion cell and mfg. method |
| CN101710614A (en) * | 2009-12-16 | 2010-05-19 | 南京大学 | Diaphragm of modified lithium battery with medium hole nano particles |
| CN102403478A (en) * | 2010-09-16 | 2012-04-04 | 铜陵晶能电子股份有限公司 | Production method of high-permeability low-density lithium battery polyolefin diaphragm |
| CN102367172A (en) * | 2011-10-17 | 2012-03-07 | 中科院广州化学有限公司 | Modified silicon dioxide and high-property lithium ion battery diaphragm and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784528A (en) * | 2016-12-27 | 2017-05-31 | 深圳市星源材质科技股份有限公司 | A kind of preparation method of lithium battery diaphragm |
| CN108400272A (en) * | 2018-03-05 | 2018-08-14 | 陈颖婷 | A kind of lithium battery polypropylene diaphragm being compounded with kenyaite-aerosil |
| CN108400272B (en) * | 2018-03-05 | 2021-09-17 | 义乌市坤玥玩具有限公司 | Lithium battery polypropylene diaphragm compounded with kenyaite-silicon dioxide aerogel |
| CN111497293A (en) * | 2020-03-31 | 2020-08-07 | 江苏厚生新能源科技有限公司 | Preparation method of high-wettability film, high-wettability film and application thereof |
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Application publication date: 20140604 |