CN111370630A - High-adsorption electrolyte diaphragm, preparation method thereof and lithium battery - Google Patents
High-adsorption electrolyte diaphragm, preparation method thereof and lithium battery Download PDFInfo
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- CN111370630A CN111370630A CN202010175272.0A CN202010175272A CN111370630A CN 111370630 A CN111370630 A CN 111370630A CN 202010175272 A CN202010175272 A CN 202010175272A CN 111370630 A CN111370630 A CN 111370630A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
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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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Abstract
The invention belongs to the technical field of lithium batteries, and particularly relates to a high-adsorption electrolyte diaphragm, a preparation method of the high-adsorption electrolyte diaphragm and a lithium battery. The high-adsorption electrolyte diaphragm comprises the following raw materials: the lithium ion battery comprises a porous lithium battery diaphragm, a high polymer crosslinking agent and a high polymer material containing oleophylic groups; and under the catalytic action, the polymer material is subjected to a crosslinking reaction with the porous lithium battery diaphragm through a polymer crosslinking agent so as to insert lipophilic groups into the surface of the porous lithium battery diaphragm, and further improve the electrolyte adsorption capacity of the PE/PP diaphragm.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a high-adsorption electrolyte diaphragm, a preparation method of the high-adsorption electrolyte diaphragm and a lithium battery.
Background
The traditional PE/PP diaphragm has the problem of poor electrolyte adsorption capacity in the use process of a lithium battery, and the inside of the gap of the electrolyte diaphragm is not sufficient, so that the defects of high internal resistance, low capacity and the like of the battery are caused; in order to solve the problem of poor adsorption capacity of the PE/PP diaphragm electrolyte, the invention grafts an oleophilic group on the surface of the PE/PP diaphragm, thereby improving the adsorption capacity of the PE/PP diaphragm electrolyte.
Disclosure of Invention
The invention provides a high-adsorption electrolyte diaphragm, a preparation method thereof and a lithium battery.
In order to solve the technical problem, the invention provides a high-adsorption electrolyte diaphragm which comprises the following raw materials: the lithium ion battery comprises a porous lithium battery diaphragm, a high polymer crosslinking agent and a high polymer material containing oleophylic groups; and under the catalytic action, the polymer material and the porous lithium battery diaphragm are subjected to a crosslinking reaction through a polymer crosslinking agent so as to insert lipophilic groups into the surface of the porous lithium battery diaphragm.
In a second aspect, the invention further provides a preparation method of the high-adsorption electrolyte membrane, which comprises the following steps: spraying a high-molecular cross-linking agent on the surface of the porous lithium battery diaphragm; then spraying a high polymer material with oleophilic groups; and (3) catalyzing, so that the polymer material and the porous lithium battery diaphragm are subjected to a crosslinking reaction through a polymer crosslinking agent, and lipophilic groups are grafted to the surface of the porous lithium battery diaphragm.
In a third aspect, the present invention further provides a lithium battery, including: a diaphragm; the diaphragm adopts the diaphragm with high adsorption electrolyte as described above.
The high-adsorption electrolyte diaphragm and the preparation method thereof and the lithium battery have the beneficial effects that under the catalytic action, a high polymer material and the porous lithium battery diaphragm are subjected to a crosslinking reaction through a high polymer crosslinking agent, so that oleophilic groups are grafted to the surface of the porous lithium battery diaphragm, and the adsorption capacity of the electrolyte of the diaphragm is improved.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of a process for preparing a high sorption electrolyte membrane of the present invention;
FIG. 2 is a schematic structural view of a highly absorbent electrolyte separator of the present invention;
FIG. 3 is a graph comparing imbibition times of a high sorption electrolyte membrane with a conventional electrolyte membrane;
in fig. 2: the porous lithium battery diaphragm 1 and the macromolecular cross-linking agent 2 contain lipophilic groups 3.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A first part:
the traditional PE/PP diaphragm has the problem of poor electrolyte adsorption capacity in the use process of a lithium battery, and the inside of a gap of the electrolyte diaphragm is not sufficient, so that the defects of high internal resistance, low capacity and the like of the battery are caused; in order to solve the problem of poor adsorption capacity of PE/PP diaphragm electrolyte, the invention provides a high-adsorption electrolyte diaphragm which comprises the following raw materials: the lithium battery comprises a porous lithium battery diaphragm 1, a high polymer cross-linking agent 2 and a high polymer material containing oleophylic groups 3; and under the catalytic action, the polymer material and the porous lithium battery diaphragm are subjected to a crosslinking reaction through a polymer crosslinking agent, so that lipophilic groups are grafted to the surface of the porous lithium battery diaphragm (as shown in fig. 2).
Optionally, the porous lithium battery separator includes any one of a PE film, a PP film, a PI film, and a PEI film, or a composite separator of a plurality thereof. And the catalysis comprises illumination with a wavelength of 50-500nm, optionally 200nm, 400 nm.
Specifically, when the porous lithium battery diaphragm adopts a PP film, the reaction formula of the crosslinking reaction is as follows:
wherein the structural formula of the high polymer material is
R is a hydrocarbon chain;
the structural formula of the oleophilic group is as follows:
the structural formula of the macromolecular crosslinking agent is as follows:
and
the structural formula of the PP film is as follows:
the structural formula of the finally generated high-adsorption electrolyte diaphragm is shown as
According to the reaction formula, under the illumination catalysis, the polymer material and the porous lithium battery diaphragm are subjected to a crosslinking reaction through the polymer crosslinking agent, the oleophylic group is connected to the porous lithium battery diaphragm, and then the adsorption capacity of the porous lithium battery diaphragm on the electrolyte is improved through the oleophylic group.
As described above, referring to fig. 1, the present invention also provides a method for preparing a high adsorption electrolyte membrane, including: spraying a high-molecular cross-linking agent on the surface of the porous lithium battery diaphragm; then spraying a high polymer material with oleophilic groups; and (3) catalyzing, so that the polymer material and the porous lithium battery diaphragm are subjected to a crosslinking reaction through a polymer crosslinking agent, and lipophilic groups are grafted to the surface of the porous lithium battery diaphragm.
Optionally, the spraying thickness of the polymer material is 0.01-11 μm, and can be selected from 0.5 μm, 3 μm and 8 μm.
Optionally, the spraying thickness of the macromolecular crosslinking agent is 0.01-10 μm, and can be selected from 0.2 μm, 1 μm and 3 μm.
As described above, the present invention also provides a lithium battery including: a diaphragm; the diaphragm adopts the diaphragm with high adsorption electrolyte as described above.
A second part:
example 1
Selecting a PP film with the thickness of 20 micrometers as a PP porous lithium battery diaphragm, and spraying a high-molecular cross-linking agent with the thickness of 0.1 micrometer on the surface of the PP porous lithium battery diaphragm; then spraying a high polymer material with oleophylic groups and the thickness of 0.3 mu m; then, light with the wavelength of 350nm is adopted for illumination, so that the macromolecular material with oleophylic groups and the surface of the PP porous lithium battery diaphragm are subjected to a crosslinking reaction through a macromolecular crosslinking agent, and the oleophylic groups are connected to the surface of the PP porous lithium battery diaphragm; and finally, rolling to obtain the high-adsorption electrolyte diaphragm.
Example 2
Selecting a PI film with the thickness of 20 microns as a PI porous lithium battery diaphragm, and spraying a polymer cross-linking agent with the thickness of 0.01 micron on the surface of the PI porous lithium battery diaphragm; then spraying a high polymer material with oleophilic groups with the thickness of 0.01 mu m; then, light with the wavelength of 500nm is adopted for illumination, so that the polymer material with oleophylic groups and the surface of the PI porous lithium battery diaphragm are subjected to a crosslinking reaction through a polymer crosslinking agent, and the oleophylic groups are connected to the surface of the PI porous lithium battery diaphragm; and finally, rolling to obtain the high-adsorption electrolyte diaphragm.
Example 3
Selecting a PE film with the thickness of 20 micrometers as a PE porous lithium battery diaphragm, and spraying a polymer cross-linking agent with the thickness of 10 micrometers on the surface of the PE porous lithium battery diaphragm; then spraying a high polymer material with oleophylic groups and the thickness of 11 mu m; then, light with the wavelength of 50nm is adopted for illumination, so that the macromolecular material with oleophylic groups and the surface of the PE porous lithium battery diaphragm are subjected to a crosslinking reaction through a macromolecular crosslinking agent, and the oleophylic groups are connected to the surface of the PE porous lithium battery diaphragm; and finally, rolling to obtain the high-adsorption electrolyte diaphragm.
Example 4
Selecting a PE film with the thickness of 20 micrometers as a PE porous lithium battery diaphragm, and spraying a macromolecular cross-linking agent with the thickness of 1 micrometer on the surface of the PE porous lithium battery diaphragm; then spraying a 1-micron-thickness high polymer material with oleophylic groups; then, light with the wavelength of 200nm is adopted for illumination, so that the macromolecular material with oleophylic groups and the surface of the PE porous lithium battery diaphragm are subjected to a crosslinking reaction through a macromolecular crosslinking agent, and the oleophylic groups are connected to the surface of the PE porous lithium battery diaphragm; and finally, rolling to obtain the high-adsorption electrolyte diaphragm.
Example 5
Selecting a PEI film with the thickness of 20 micrometers as a PEI porous lithium battery diaphragm, and spraying a macromolecular cross-linking agent with the thickness of 5 micrometers on the surface of the PEI porous lithium battery diaphragm; then spraying a high polymer material with oleophylic groups and the thickness of 8 mu m; then, light with the wavelength of 400nm is adopted for illumination, so that the polymer material with oleophylic groups and the surface of the PEI porous lithium battery diaphragm are subjected to cross-linking reaction through a polymer cross-linking agent, and the oleophylic groups are connected to the surface of the PEI porous lithium battery diaphragm; and finally, rolling to obtain the high-adsorption electrolyte diaphragm.
Example 6
Referring to fig. 3, this example 6 performed the imbibing time test for the highly absorbent electrolyte separator (corresponding to the new type in fig. 3) prepared in example 1 and the conventional electrolyte separator (corresponding to the conventional type in fig. 3). It can be seen that the liquid absorption time of the high-adsorption electrolyte diaphragm is 10 seconds, while the liquid absorption time of the traditional electrolyte diaphragm is 100 seconds, so that the liquid absorption time of the high-adsorption electrolyte diaphragm is greatly shortened, which indicates that the liquid absorption capacity of the high-adsorption electrolyte diaphragm to the electrolyte is greatly improved. Meanwhile, through the combination of chemical reaction and chemical bonds, the stability and the overall consistency of the high-adsorption electrolyte diaphragm are superior to those of the traditional electrolyte diaphragm.
In summary, according to the high-adsorption electrolyte diaphragm, the preparation method thereof and the lithium battery, the polymer material and the porous lithium battery diaphragm are subjected to a crosslinking reaction through the polymer crosslinking agent under the catalytic action, so that lipophilic groups are grafted to the surface of the porous lithium battery diaphragm, and the electrolyte adsorption capacity of the diaphragm is improved; meanwhile, through the combination of chemical reaction and chemical bonds, the stability and the overall consistency of the high-adsorption electrolyte diaphragm are superior to those of the traditional electrolyte diaphragm, so that the high-adsorption electrolyte diaphragm is more suitable for being applied to lithium batteries.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The high-adsorption electrolyte diaphragm is characterized by comprising the following raw materials:
the lithium ion battery comprises a porous lithium battery diaphragm, a high polymer crosslinking agent and a high polymer material containing oleophylic groups; and
under the catalytic action, the polymer material and the porous lithium battery diaphragm are subjected to a crosslinking reaction through a polymer crosslinking agent, so that lipophilic groups are connected to the surface of the porous lithium battery diaphragm.
2. The high adsorption electrolyte membrane according to claim 1,
the structural formula of the high polymer material is shown as
Wherein R is a hydrocarbon chain;
the structural formula of the oleophilic group is
3. The high adsorption electrolyte membrane according to claim 1,
the structural formula of the macromolecular crosslinking agent is as follows:
4. the high adsorption electrolyte membrane according to claim 1,
the catalysis includes illumination with a wavelength of 50-500 nm.
5. The high adsorption electrolyte membrane according to claim 1,
the porous lithium battery diaphragm comprises any one of a PE (polyethylene) film, a PP (polypropylene) film, a PI (polyimide) film and a PEI (polyetherimide) film or a composite diaphragm of a plurality of PE films, PP films, PI films and PEI films.
6. The high-adsorption electrolyte membrane according to claim 5,
when the porous lithium battery diaphragm adopts a PP film, the reaction formula of the crosslinking reaction is as follows:
7. a preparation method of a high-adsorption electrolyte diaphragm is characterized by comprising the following steps:
spraying a high-molecular cross-linking agent on the surface of the porous lithium battery diaphragm;
then spraying a high polymer material with oleophilic groups;
and (3) catalyzing, so that the polymer material and the porous lithium battery diaphragm are subjected to a crosslinking reaction through a polymer crosslinking agent, and lipophilic groups are grafted to the surface of the porous lithium battery diaphragm.
8. The production method according to claim 7,
the spraying thickness of the high polymer material is 0.01-11 mu m.
9. The production method according to claim 7,
the spraying thickness of the macromolecular cross-linking agent is 0.01-10 mu m.
10. A lithium battery, comprising:
a diaphragm;
the separator adopts the high-adsorption electrolyte separator as claimed in claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010175272.0A CN111370630B (en) | 2020-03-13 | 2020-03-13 | High-adsorption electrolyte diaphragm, preparation method thereof and lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010175272.0A CN111370630B (en) | 2020-03-13 | 2020-03-13 | High-adsorption electrolyte diaphragm, preparation method thereof and lithium battery |
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| CN111370630A true CN111370630A (en) | 2020-07-03 |
| CN111370630B CN111370630B (en) | 2022-06-17 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107492620A (en) * | 2017-08-16 | 2017-12-19 | 广州鹏辉能源科技股份有限公司 | A kind of high-temperature-reslithium lithium battery barrier film and preparation method thereof |
| CN107623099A (en) * | 2017-09-19 | 2018-01-23 | 武汉惠强新能源材料科技有限公司 | A kind of compound multi-layer polyolefin lithium electric separator and preparation method thereof |
| CN109346653A (en) * | 2018-10-31 | 2019-02-15 | 河北金力新能源科技股份有限公司 | A kind of lithium electric separator and preparation method thereof containing composite coating |
| CN208596741U (en) * | 2018-06-11 | 2019-03-12 | 江西星盈科技有限公司 | A kind of lithium electric separator with gas absorption function |
-
2020
- 2020-03-13 CN CN202010175272.0A patent/CN111370630B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107492620A (en) * | 2017-08-16 | 2017-12-19 | 广州鹏辉能源科技股份有限公司 | A kind of high-temperature-reslithium lithium battery barrier film and preparation method thereof |
| CN107623099A (en) * | 2017-09-19 | 2018-01-23 | 武汉惠强新能源材料科技有限公司 | A kind of compound multi-layer polyolefin lithium electric separator and preparation method thereof |
| CN208596741U (en) * | 2018-06-11 | 2019-03-12 | 江西星盈科技有限公司 | A kind of lithium electric separator with gas absorption function |
| CN109346653A (en) * | 2018-10-31 | 2019-02-15 | 河北金力新能源科技股份有限公司 | A kind of lithium electric separator and preparation method thereof containing composite coating |
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