CN117175141A - Lithium battery diaphragm and preparation method and application thereof - Google Patents
Lithium battery diaphragm and preparation method and application thereof Download PDFInfo
- Publication number
- CN117175141A CN117175141A CN202310963293.2A CN202310963293A CN117175141A CN 117175141 A CN117175141 A CN 117175141A CN 202310963293 A CN202310963293 A CN 202310963293A CN 117175141 A CN117175141 A CN 117175141A
- Authority
- CN
- China
- Prior art keywords
- lithium battery
- lithium
- cyanoethyl
- diaphragm
- separator
- Prior art date
- 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.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 6
- -1 polyethylene Polymers 0.000 claims abstract description 22
- 239000004698 Polyethylene Substances 0.000 claims abstract description 20
- 229920000573 polyethylene Polymers 0.000 claims abstract description 20
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims abstract description 18
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000004743 Polypropylene Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 239000012528 membrane Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Cell Separators (AREA)
Abstract
The application discloses a lithium battery diaphragm and a preparation method and application thereof. The cyanoethyl etherified vinyl polyethylene has excellent mechanical properties, and the cyanoethyl etherified vinyl polyethylene is adopted as a pore-forming agent through electrostatic spinning, and can be compounded with a polymer to obtain a structure with high porosity and uniform and compact pore diameter, and the structure endows the diaphragm with higher electrolyte absorption efficiency. The nitrogen-containing groups of the separator can also promote the conduction of lithium ions and control the uniform deposition of lithium dendrites.
Description
Technical Field
The application relates to a lithium battery diaphragm, a preparation method and application thereof, and belongs to the field of lithium battery materials.
Background
The separator is a core component in a lithium battery, and its main function is to prevent direct contact between positive and negative electrode materials while allowing ion transport, and the separator cost is about 10% of the lithium battery production cost.
The quality of the lithium battery diaphragm performance can directly influence the charge and discharge capacity, the charge and discharge efficiency, the service life and the cycle performance of the battery. At present, though the commercial separator such as Polyethylene (PE) and polypropylene (PP) has good ion conductivity, the mechanical properties of the battery separator are influenced by the excessively high porosity and the excessively low thickness, so that the development of the lithium ion battery separator material with the electrochemical properties and the mechanical properties plays a very important role in improving the comprehensive properties of the lithium battery.
Disclosure of Invention
The cyanoethyl etherified vinyl polyethylene has excellent mechanical properties, and the cyanoethyl etherified vinyl polyethylene is adopted as a pore-forming agent through electrostatic spinning, and can be compounded with a polymer to obtain a structure with high porosity and uniform and compact pore diameter, and the structure endows the diaphragm with higher electrolyte absorption efficiency. The nitrogen-containing groups of the separator can also promote the conduction of lithium ions and control the uniform deposition of lithium dendrites.
According to one aspect of the present application, there is provided a lithium battery separator composed of a cyanoethyl etherified vinyl polyethylene copolymer;
wherein, in the lithium battery diaphragm, the content of the cyanoethyl etherified vinyl polyethylene copolymer is 1-20wt%;
the thickness of the lithium battery diaphragm is 10-30 mu m;
the porosity of the lithium battery diaphragm is 70-85%;
the aperture of the lithium battery diaphragm is 0.8-1.2 mu m.
The lithium battery separator also contains a polymer;
the polymer is at least one selected from polyvinylidene fluoride and polytetrafluoroethylene;
in the lithium battery separator, the content of the polymer is 0.1-10wt%.
According to another aspect of the present application, there is provided a method for preparing the above lithium battery separator, comprising the steps of:
and mixing raw materials containing cyanoethyl etherified vinyl polyethylene copolymer and N, N-dimethylformamide to obtain spinning solution, carrying out electrostatic spinning, and drying to obtain the lithium battery diaphragm.
In the spinning solution, the proportion of the cyanoethyl etherified vinyl polyethylene copolymer to the N, N-dimethylformamide is 5-20: 100.
the spinning solution also contains a polymer;
the ratio of the polymer to the N, N-dimethylformamide is 0.01-20: 100.
the voltage of the electrostatic spinning is 10 KV to 30KV;
the temperature of the electrostatic spinning is 20-50 ℃;
the flow rate of the electrostatic spinning is 0.1-0.3 ml/min.
The drying temperature is 50-80 ℃.
The cyanoethyl etherified vinyl polyethylene is prepared by an in-situ polymerization method.
According to another aspect of the present application, there is provided the use of the above-mentioned lithium battery separator, characterized in that,
the lithium ion battery and the lithium metal battery are used.
The application has the advantages that:
the application provides a novel lithium battery diaphragm and a preparation method thereof, wherein the preparation process is simple, and the diaphragm has high mechanical strength; the addition of cyanoethyl etherified vinyl polyethylene can obtain a structure with high porosity and uniform and compact pore diameter after being compounded with a polymer, and the structure endows the diaphragm with higher electrolyte absorption efficiency. The nitrogen-containing groups of the separator can also promote the conduction of lithium ions and control the uniform deposition of lithium dendrites. The diaphragm is used in a lithium ion battery, and can improve the first-cycle charge and discharge performance; the intermediate is used in lithium-sulfur batteries, so that the shuttle of the intermediate can be slowed down, and the battery performance is improved. Improving the mobility of lithium ions, thereby improving the first coulombic efficiency and cycle performance of the battery
Drawings
Fig. 1 is a scanning electron microscope picture of a lithium battery separator prepared in example 1 of the present application.
Fig. 2 is a graph showing the battery performance of the lithium battery separator prepared in example 1 according to the present application in a lithium ion battery.
Fig. 3 is a graph showing the battery performance of the lithium battery separator prepared in example 2 of the present application in a lithium ion battery.
Fig. 4 is a diagram of a lithium sheet scanning electron microscope after the lithium battery of example 2 of the present application is cycled using a PP separator.
Fig. 5 is a scanning electron microscope image of a lithium sheet of the lithium battery separator prepared in example 2 of the present application after cycling in a lithium ion battery.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Example 1:
a lithium battery separator, prepared by the steps of:
(1) Preparing a solution precursor by taking polyvinyl acetate and acrylonitrile as raw materials through a phase transfer and electrocatalytic method, and further preparing cyanoethyl etherified vinyl polyethylene powder through a spray drying method;
(2) Adding 1.0g of cyanoethyl etherified vinyl polyethylene powder into 10mL of DMF solution, and stirring for 12h to obtain an electrostatic spinning solution;
(3) Injecting the solution obtained in the step (2) into an electrostatic spinning injector for electrostatic spinning, wherein the voltage is 21KV, the spinning temperature is 25 ℃, the flow rate is 0.2mL/min, the film obtained by spinning is dried at 60 ℃, and the diaphragm for the lithium battery is obtained, and the uniform and compact structure is characterized by a scanning electron microscope, as shown in figure 1; thanks to the compact structure, the tensile strength of the tested diaphragm can reach 22Mpa (reference standard GB 13022-91), and the tensile strength of the common PP diaphragm is only 18Mpa; the porosity of the membrane is 47.1% (reference standard GB/T33052-2016), and the PP membrane porosity is only 36.2%. The membrane prepared by the electrostatic spinning method has the liquid absorption rate reaching 305.06 percent (refer to standard QB/T2303.11-2008), and the PP membrane is only 71.81 percent.
The separator was used in a lithium ion battery, with NCM811 as the positive electrode, a lithium metal sheet as the negative electrode, and a 2025 button cell was assembled, and the electrical properties at 0.3C were measured, as shown in fig. 2, to be excellent as compared with the ordinary PP separator.
Example 2:
a lithium battery separator, prepared by the steps of:
(1) Preparing a solution precursor by taking polyvinyl acetate and acrylonitrile as raw materials through a phase transfer and electrocatalytic method, and further preparing cyanoethyl etherified vinyl polyethylene powder through a spray drying method;
(2) After mixing 1.5g of cyanoethyl etherified vinyl polyethylene powder with 0.5g of PVDF, adding the mixture into 10mL of DMF solution, and stirring for 24h to obtain an electrostatic spinning solution;
(3) And (3) injecting the solution obtained in the step (2) into an electrostatic spinning injector for electrostatic spinning, wherein the voltage is 22KV, the spinning temperature is 45 ℃, the flow rate is 0.1mL/min, and the membrane obtained by spinning is dried at 60 ℃ to obtain the membrane for the lithium battery.
Fig. 3 is a graph showing the battery performance of the lithium battery separator prepared in example 2 of the present application in a lithium ion battery.
Fig. 4 is a diagram of a lithium sheet scanning electron microscope after the lithium battery of example 2 of the present application is cycled using a PP separator.
Fig. 5 is a scanning electron microscope image of a lithium sheet of the lithium battery separator prepared in example 2 of the present application after cycling in a lithium ion battery.
When the separator was used in a lithium sulfur battery, SC was used as a positive electrode, a lithium metal sheet was used as a negative electrode, and 2025 button cell was assembled, and the battery performance of 0.1C was measured, as shown in fig. 3, and the specific capacity was greatly increased as compared with a general PP separator. The lithium sheet after circulation is subjected to scanning electron microscope characterization, and compared with the PP diaphragm (figure 4), the deposition of lithium dendrite after circulation of the electrostatic spinning diaphragm (figure 5) is more uniform.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (8)
1. A lithium battery diaphragm is characterized in that,
the lithium battery diaphragm consists of cyanoethyl etherified vinyl polyethylene copolymer;
wherein, in the lithium battery diaphragm, the content of the cyanoethyl etherified vinyl polyethylene copolymer is 1-20wt%;
the thickness of the lithium battery diaphragm is 10-30 mu m;
the porosity of the lithium battery diaphragm is 70-85%;
the aperture of the lithium battery diaphragm is 0.8-1.2 mu m.
2. The lithium battery separator as in claim 1, wherein,
the lithium battery separator also contains a polymer;
the polymer is at least one selected from polyvinylidene fluoride and polytetrafluoroethylene;
in the lithium battery separator, the content of the polymer is 0.1-10wt%.
3. A method for producing a lithium battery separator according to any one of claim 1 or 2, characterized in that,
the method comprises the following steps:
and mixing raw materials containing cyanoethyl etherified vinyl polyethylene copolymer and N, N-dimethylformamide to obtain spinning solution, carrying out electrostatic spinning, and drying to obtain the lithium battery diaphragm.
4. A process according to claim 3, wherein,
in the spinning solution, the proportion of the cyanoethyl etherified vinyl polyethylene copolymer to the N, N-dimethylformamide is 5-20: 100.
5. a process according to claim 3, wherein,
the spinning solution also contains a polymer;
the ratio of the polymer to the N, N-dimethylformamide is 0.01-20: 100.
6. a process according to claim 3, wherein,
the voltage of the electrostatic spinning is 10 KV to 30KV;
the temperature of the electrostatic spinning is 20-50 ℃;
the flow rate of the electrostatic spinning is 0.1-0.3 ml/min.
7. A process according to claim 3, wherein,
the drying temperature is 50-80 ℃.
8. The use of a lithium battery separator according to claim 1 or 2, characterized in that,
the lithium ion battery and the lithium metal battery are used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310963293.2A CN117175141B (en) | 2023-07-31 | 2023-07-31 | Lithium battery diaphragm and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310963293.2A CN117175141B (en) | 2023-07-31 | 2023-07-31 | Lithium battery diaphragm and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117175141A true CN117175141A (en) | 2023-12-05 |
| CN117175141B CN117175141B (en) | 2024-03-19 |
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|---|---|---|---|
| CN202310963293.2A Active CN117175141B (en) | 2023-07-31 | 2023-07-31 | Lithium battery diaphragm and preparation method and application thereof |
Country Status (1)
| Country | Link |
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| Publication number | Publication date |
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| CN117175141B (en) | 2024-03-19 |
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