CN111916634A - PTC effect diaphragm for lithium ion battery - Google Patents
PTC effect diaphragm for lithium ion battery Download PDFInfo
- Publication number
- CN111916634A CN111916634A CN202010747453.6A CN202010747453A CN111916634A CN 111916634 A CN111916634 A CN 111916634A CN 202010747453 A CN202010747453 A CN 202010747453A CN 111916634 A CN111916634 A CN 111916634A
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- CN
- China
- Prior art keywords
- lithium ion
- diaphragm
- ptc
- conductor compound
- ion conductor
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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
- 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
Abstract
The invention relates to the technical field of lithium ion battery materials, in particular to a PTC (positive temperature coefficient) effect diaphragm for a lithium ion battery. The composite material consists of a diaphragm base film, a lithium ion conductor compound, PTC matrix resin and an adhesive, wherein the lithium ion conductor compound and the PTC matrix resin are mixed and then are adhered to the diaphragm base film through the adhesive. The composite diaphragm provides an internal channel for lithium ions through a lithium ion conductor compound, and the safety performance of the diaphragm is improved through PTC matrix resin.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a PTC (positive temperature coefficient) effect diaphragm for a lithium ion battery.
Background
The lithium ion battery has high energy density, good cycle performance and high output voltage, can be used in the fields of power, energy storage and the like, but the safety performance of the lithium ion battery needs to be improved urgently. When the lithium ion battery is abused by heat, more side reactions can occur, the reaction activity is accelerated, and the safety problem is easy to occur.
The invention solves the problems of the diaphragm for the lithium ion battery by coating the PTC matrix resin and the lithium ion conductor compound on the diaphragm.
Disclosure of Invention
The invention aims to provide a PTC (positive temperature coefficient) effect diaphragm for a lithium ion battery, which can increase the safety performance of the diaphragm and reduce the reaction activity of the lithium ion battery at high temperature.
In order to achieve the purpose, the invention adopts the following technical scheme:
a PTC effect diaphragm for a lithium ion battery is characterized in that: the diaphragm comprises a diaphragm basal membrane, a lithium ion conductor compound, PTC matrix resin and an adhesive; in which a lithium ion conductor compound is mixed with a PTC matrix resin and then attached to a separator base film via an adhesive.
The diaphragm basement membrane is selected from any one of a dry-method single-drawing diaphragm, a dry-method double-drawing diaphragm and a wet-method diaphragm.
The diaphragm basement membrane is a single-layer or double-layer diaphragm.
The lithium ion conductor compound is Li(1+x)MxTi(2-x)(PO4)3(M ═ Al, Cr, Ga, Fe, Sc, In), x is 0.1 to 0.3, and LiM is2(PO4)3(M ═ Ge, Sn, Hf), perovskite-type compounds, LiMX4Type compounds (M ═ Mg, Mn, Cd, Ti, Cd, Cr, Co, Fe, Zn) or composite type lithium ion conductors Li2SO4-Al2O3，LiAg2SO4-Al2O3，Li(1+x)AlxTi(2-x)(PO4)3-Li2One or more of O; the particle diameter D of the lithium ion conductor compound50The range is 50-3000 nm.
The PTC matrix resin is any one of high-density polyethylene, polyoxyethylene, polystyrene, polyethylene wax, polyaniline and polyphenylene sulfide.
The weight ratio of the lithium ion conductor compound to the PTC matrix resin is 0.1-0.4.
The adhesive comprises one or more of sodium carboxymethylcellulose, polytetrafluoroethylene and polyvinylidene fluoride.
The preparation process of the PTC effect diaphragm for the lithium ion battery comprises the following steps:
(1) adding a lithium ion conductor compound into a solvent with or without a dispersant, and dispersing by ball milling, stirring or ultrasound;
(2) adding PTC matrix resin into the dispersed lithium ion conductor compound dispersion liquid, and dispersing by ball milling, stirring or ultrasound;
(3) adding a binder into the dispersion to prepare coating slurry;
(4) coating the coating slurry on the diaphragm base film by spraying, blade coating, dip-coating or roll coating;
(5) and drying the coated diaphragm to obtain the PTC effect diaphragm for the lithium ion battery.
The adhesive in the step (3) accounts for 1 to 15 weight percent of the total solid content of the coating slurry in the step (3),
the invention has the following beneficial effects:
1. the lithium ion conductor compound coating can conduct lithium ions, and when the lithium ions pass through the pores of the diaphragm, the conduction rate can be increased by using the lithium ion conductor compound, so that the lithium ion conductivity of the diaphragm is increased.
2. When the Curie temperature of the PTC matrix resin is exceeded, the lithium ion conductivity of the PTC matrix resin/lithium ion conductor compound coating is greatly reduced along with the temperature, the reactivity of the lithium ion battery at high temperature is reduced, and the safety performance is improved.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
Example 1
20 parts by mass of a lithium ion conductor compound Li1.3Al0.3Ti1.7(PO4)3Ball milling was performed to make the particle diameter D50 to 100nm, and the ion conductor compound was dispersed in NMP solvent by ultrasonic dispersion.
75 parts by mass of polyethylene wax after ball milling was dispersed in the dispersion of the lithium ion conductor compound, and a suspension was obtained by ultrasonic dispersion.
5 parts by mass of PVDF was added to the above NMP suspension, and after ultrasonic dispersion, a coating film slurry was obtained. And coating the coating slurry on a wet diaphragm (with the thickness of 12 mu m and the air permeability of 200s/100ml) in a blade coating mode, wherein the coating thickness is 2 mu m, and drying to obtain a finished product.
And (3) comparing the finished product with the original diaphragm to prepare a battery core:
example 2
20 parts by mass of a lithium ion conductor compound Li1.3Al0.3Ti1.7(PO4)3-Li2O is ball-milled to a particle size D50 of 200nm, and the ion conductor compound is dispersed in an NMP solvent by ultrasonic dispersion.
75 parts by mass of polyethylene wax after ball milling was dispersed in the dispersion of the lithium ion conductor compound, and a suspension was obtained by ultrasonic dispersion.
5 parts by mass of PVDF was added to the above NMP suspension, and after ultrasonic dispersion, a coating film slurry was obtained. And coating the coating slurry on a wet diaphragm (with the thickness of 12 mu m and the air permeability of 200s/100ml) in a blade coating mode, wherein the coating thickness is 2 mu m, and drying to obtain a finished product.
And (3) comparing the finished product with the original diaphragm to prepare a battery core:
example 3
20 parts by mass of a lithium ion conductor compound LiGe2(PO4)3Ball milling was performed to make the particle diameter D50 to 50nm, and the ion conductor compound was dispersed in NMP solvent by ultrasonic dispersion.
75 parts by mass of polyphenylene sulfide after ball milling was dispersed in the dispersion liquid of the lithium ion conductor compound, and a suspension was obtained by ultrasonic dispersion.
5 parts by mass of PVDF was added to the above NMP suspension, and after ultrasonic dispersion, a coating film slurry was obtained. And coating the coating slurry on a wet diaphragm (with the thickness of 12 mu m and the air permeability of 200s/100ml) in a blade coating mode, wherein the coating thickness is 2 mu m, and drying to obtain a finished product.
And (3) comparing the finished product with the original diaphragm to prepare a battery core:
comparative example
50 parts by mass of a lithium ion conductor compound Li1.3Al0.3Ti1.7(PO4)3Ball milling was performed to make the particle diameter D50 to 100nm, and the ion conductor compound was dispersed in NMP solvent by ultrasonic dispersion.
45 parts by mass of polyethylene wax after ball milling was dispersed in the dispersion of the lithium ion conductor compound, and a suspension was obtained by ultrasonic dispersion.
5 parts by mass of PVDF was added to the above NMP suspension, and after ultrasonic dispersion, a coating film slurry was obtained. And coating the coating slurry on a wet diaphragm (with the thickness of 12 mu m and the air permeability of 200s/100ml) in a blade coating mode, wherein the coating thickness is 2 mu m, and drying to obtain a finished product.
And (3) comparing the finished product with the original diaphragm to prepare the battery cell, wherein the internal resistance of the battery cell rises at 25 ℃:
the above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A PTC effect diaphragm for a lithium ion battery is characterized in that: the diaphragm comprises a diaphragm basal membrane, a lithium ion conductor compound, PTC matrix resin and an adhesive; in which a lithium ion conductor compound is mixed with a PTC matrix resin and then attached to a separator base film via an adhesive.
2. The PTC effect membrane for lithium ion batteries according to claim 1, wherein: the diaphragm basement membrane is selected from any one of a dry-method single-drawing diaphragm, a dry-method double-drawing diaphragm and a wet-method diaphragm.
3. The PTC effect membrane for lithium ion batteries according to claim 1, wherein: the diaphragm basement membrane is a single-layer or double-layer diaphragm.
4. The PTC effect membrane for lithium ion batteries according to claim 1, wherein: the lithium ion conductor compound is Li（1+x）MxTi（2-x）（PO4）3(M = Al, Cr, Ga, Fe, Sc, In), x is 0.1-0.3, LiM2（PO4）3(M = Ge, Sn, Hf), perovskite-type compound, LiMX4Type compounds (M = Mg, Mn, Cd, Ti, Cd, Cr, Co, Fe, Zn) or composite type lithium ion conductors Li2SO4-Al2O3，LiAg2SO4-Al2O3，Li（1+x）AlxTi（2-x）（PO4）3-Li2One or more of O; the particle diameter D of the lithium ion conductor compound50The range is 50-3000 nm.
5. The PTC effect membrane for lithium ion batteries according to claim 1, wherein: the PTC matrix resin is any one of high-density polyethylene, polyoxyethylene, polystyrene, polyethylene wax, polyaniline and polyphenylene sulfide.
6. The PTC effect membrane for lithium ion batteries according to claim 1, wherein: the weight ratio of the lithium ion conductor compound to the PTC matrix resin is 0.1-0.4.
7. The PTC effect membrane for lithium ion batteries according to claim 1, wherein: the adhesive comprises one or more of sodium carboxymethylcellulose, polytetrafluoroethylene and polyvinylidene fluoride.
8. A process for preparing a PTC effect separator for a lithium ion battery according to claim 1, wherein: the method comprises the following steps:
(1) adding a lithium ion conductor compound into a solvent with or without a dispersant, and dispersing by ball milling, stirring or ultrasound;
(2) adding PTC matrix resin into the dispersed lithium ion conductor compound dispersion liquid, and dispersing by ball milling, stirring or ultrasound;
(3) adding a binder into the dispersion to prepare coating slurry;
(4) coating the coating slurry on the diaphragm base film by spraying, blade coating, dip-coating or roll coating;
(5) and drying the coated diaphragm to obtain the PTC effect diaphragm for the lithium ion battery.
9. The process according to claim 8, characterized in that: the adhesive in the step (3) accounts for 1-15 wt% of the total solid content of the coating slurry in the step (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010747453.6A CN111916634A (en) | 2020-07-30 | 2020-07-30 | PTC effect diaphragm for lithium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010747453.6A CN111916634A (en) | 2020-07-30 | 2020-07-30 | PTC effect diaphragm for lithium ion battery |
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| Publication Number | Publication Date |
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| CN111916634A true CN111916634A (en) | 2020-11-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202010747453.6A Pending CN111916634A (en) | 2020-07-30 | 2020-07-30 | PTC effect diaphragm for lithium ion battery |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272977A (en) * | 2008-12-30 | 2011-12-07 | 株式会社Lg化学 | Separator with a porous coating layer, and electrochemical device comprising same |
| US20140322587A1 (en) * | 2013-04-25 | 2014-10-30 | Dongguan Amperex Technology Limited | Separator of lithium-ion-battery preparation and method thereof |
| WO2019090888A1 (en) * | 2017-11-10 | 2019-05-16 | 江苏华富储能新技术股份有限公司 | Organic-inorganic composite separator for lithium battery and preparation method therefor |
| CN110416469A (en) * | 2019-07-22 | 2019-11-05 | 福建巨电新能源股份有限公司 | A kind of lithium ion battery composite zeolite diaphragm and its preparation process |
| CN111403665A (en) * | 2020-03-25 | 2020-07-10 | 石狮申泰新材料科技有限公司 | Ceramic-coated lithium battery diaphragm and preparation method thereof |
-
2020
- 2020-07-30 CN CN202010747453.6A patent/CN111916634A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272977A (en) * | 2008-12-30 | 2011-12-07 | 株式会社Lg化学 | Separator with a porous coating layer, and electrochemical device comprising same |
| US20140322587A1 (en) * | 2013-04-25 | 2014-10-30 | Dongguan Amperex Technology Limited | Separator of lithium-ion-battery preparation and method thereof |
| WO2019090888A1 (en) * | 2017-11-10 | 2019-05-16 | 江苏华富储能新技术股份有限公司 | Organic-inorganic composite separator for lithium battery and preparation method therefor |
| CN110416469A (en) * | 2019-07-22 | 2019-11-05 | 福建巨电新能源股份有限公司 | A kind of lithium ion battery composite zeolite diaphragm and its preparation process |
| CN111403665A (en) * | 2020-03-25 | 2020-07-10 | 石狮申泰新材料科技有限公司 | Ceramic-coated lithium battery diaphragm and preparation method thereof |
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Application publication date: 20201110 |