CN116598714A - Battery diaphragm slurry, battery diaphragm, preparation method of battery diaphragm and application of battery diaphragm slurry and battery diaphragm in preparation of battery - Google Patents
Battery diaphragm slurry, battery diaphragm, preparation method of battery diaphragm and application of battery diaphragm slurry and battery diaphragm in preparation of battery Download PDFInfo
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- CN116598714A CN116598714A CN202310783593.2A CN202310783593A CN116598714A CN 116598714 A CN116598714 A CN 116598714A CN 202310783593 A CN202310783593 A CN 202310783593A CN 116598714 A CN116598714 A CN 116598714A
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- battery
- battery diaphragm
- slurry
- hexafluoropropylene
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- 239000002002 slurry Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 19
- 239000002608 ionic liquid Substances 0.000 claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012528 membrane Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000011245 gel electrolyte Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- RZEQQEXIZXEASF-UHFFFAOYSA-N lithium trifluoro(sulfinato)methane Chemical compound [Li+].C(F)(F)(F)[S-](=O)=O RZEQQEXIZXEASF-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- -1 lithium bis (trifluoromethane) sulfonyl imide salt Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
-
- 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 & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses battery diaphragm slurry, a battery diaphragm, a preparation method of the battery diaphragm and application of the battery diaphragm slurry and the battery diaphragm to preparation of a battery. The battery diaphragm slurry at least comprises the following raw materials: polyvinylidene fluoride-hexafluoropropylene porous powder material; electrolyte and solvent for the electrolyte. The invention uses the porous structure which is abundant in the polyvinylidene fluoride-hexafluoropropylene porous powder material and is mutually communicated to bear electrolyte, and directly uses the polyvinylidene fluoride-hexafluoropropylene porous powder bearing the electrolyte as the main raw material of the battery diaphragm, rather than being used as the surface coating only; the battery diaphragm prepared by the method has relatively small impedance, so that the energy consumption of the internal resistance of the battery in the charging and discharging process is reduced, and the performances of the battery, such as the cycle efficiency, specific discharge capacity, coulombic efficiency and the like, are improved; and the polyvinylidene fluoride-hexafluoropropylene porous powder material is not required to be dissolved by using an organic solvent, so that the pollution of the organic solvent to the environment is avoided.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to battery diaphragm slurry, a battery diaphragm, a preparation method of the battery diaphragm and application of the battery diaphragm slurry and the battery diaphragm to battery preparation.
Background
The lithium ion battery diaphragm is a key material related to the performance of the lithium ion battery, is arranged between the positive electrode and the negative electrode of the battery, plays an isolating role in preventing the positive electrode and the negative electrode from being contacted to cause short circuit in the battery, and can also play a role in providing an ion transmission channel in the charge and discharge process; it can be seen that the quality of the separator performance directly affects the capacity, cycle performance, and safety performance of the battery. Proper selection of electrolyte and separator are critical to achieving good cell performance. In particular, the separator must have specific properties such as chemical and electrochemical inertness to all battery elements, mechanical and dimensional stability, and physical strength.
In order to meet these characteristics, various solutions have been intensively studied, including adding nanofillers (i.e., composite separators) in the separator to promote electrochemical and mechanical properties, or mixing different polymers having complementary characteristics. The safety performance of batteries becomes particularly important when the batteries are exposed to mechanical, thermal or electrical abuse conditions, which is typical in high power lithium ion battery applications. In case of using a highly volatile, thermally unstable and toxic organic solvent type electrolyte in the separator, there is a considerable risk of leakage of the battery, which puts greater demands on the safety performance of the battery.
To solve this problem, two solutions exist in the prior art:
one such method is to coat the surface of a polyolefin separator with an alumina ceramic, PVDF gel layer, etc., for example, chinese patent publication No. CN112563664B discloses a separator comprising a substrate and a coating layer formed of a polymer including polyvinylidene fluoride-hexafluoropropylene and polyacrylate on the substrate, and a lithium ion battery.
The disadvantages of this membrane are: after prolonged use, there is a greater risk of peeling between the surface coating and the substrate, resulting in an unstable performance improvement function of the coating to the substrate.
Secondly, the ionic liquid electrolyte is adopted, the ionic liquid has the advantages of low flammability, negligible steam pressure, low toxicity, high ionic conductivity and the like, and can be used as a solvent or an additive for the lithium battery electrolyte, so that the battery capacity can be improved by 10-20%, the working temperature range is widened to-40-120 ℃, the ionic working efficiency of the lithium battery is more stable than that of the common lithium battery in the current market, the service life is longer, the explosion-proof performance and the flame retardant performance are obviously improved, and the safety performance is better.
For example, chinese patent publication No. CN112310476B discloses an ionic liquid electrolyte for lithium ion battery, which comprises lithium salt, ionic liquid, organic solvent and additive.
Another example is that chinese patent application publication No. CN112615047a discloses a gel electrolyte membrane, a method for preparing the same, and a lithium ion battery, wherein the gel electrolyte membrane comprises a high polymer material, bis (trifluoromethanesulfonyl) lithium and guanidine salt ionic liquid; the preparation method of the gel electrolyte membrane comprises the following steps: (1) Mixing a high polymer material with an organic solvent, stirring and heating in a water bath to obtain a mixture; (2) Adding bis (trifluoromethanesulfonyl) lithium and guanidine salt ionic liquid into the mixture, and stirring to obtain a milky gel polymer; (3) Casting the gel polymer on a carrier, and then scraping a film by using a film scraping machine; (4) And (5) placing the carrier in a vacuum drying oven for drying to obtain the gel electrolyte membrane.
The separator has the following defects: the use of specific organic solvents is required, which not only dissolve the high molecular polymer material, but also have good affinity for lithium salts and ionic liquids; the organic solvent can be directly volatilized into the air in the drying process, so that the environment is polluted, and the recycling is not facilitated.
Disclosure of Invention
The invention aims to provide a battery diaphragm slurry, a battery diaphragm, a preparation method thereof and application thereof in preparing a battery, wherein the battery diaphragm is prepared by directly adopting micron-sized porous blocks of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) on the premise of not using an organic solvent, so that the trouble of using the organic solvent is avoided, and the battery diaphragm has excellent performance.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the battery separator slurry comprises the following raw materials in percentage by weight:
polyvinylidene fluoride-hexafluoropropylene porous powder material;
electrolyte and solvent for the electrolyte.
The invention uses the porous structure which is abundant in the polyvinylidene fluoride-hexafluoropropylene porous powder material and is mutually communicated to bear electrolyte, and directly uses the polyvinylidene fluoride-hexafluoropropylene porous powder bearing the electrolyte as the main raw material of the battery diaphragm, rather than being used as the surface coating only; the battery diaphragm prepared by the method has relatively small impedance, so that the energy consumption of the internal resistance of the battery in the charging and discharging process is reduced, and the performances of the battery, such as the cycle efficiency, specific discharge capacity, coulombic efficiency and the like, are improved; and the polyvinylidene fluoride-hexafluoropropylene porous powder material is not required to be dissolved by using an organic solvent, so that the pollution of the organic solvent to the environment is avoided.
Preferably, in the battery separator slurry, the solvent is an ionic liquid. The ionic liquid not only can play a role in dissolving electrolyte, but also has the advantages of low flammability, negligible steam pressure, low toxicity, high ionic conductivity and the like, the capacity of a battery can be improved by 10-20% when the ionic liquid is added into a battery diaphragm as a solvent of the electrolyte, the working temperature range is widened to-40-120 ℃, the ionic liquid has more stable ionic working efficiency and longer service life compared with the common lithium ion battery in the current market, the explosion-proof performance and flame retardant performance are obviously improved, and the safety performance is better.
Preferably, in the battery separator slurry, the ionic liquid is Pyre13TFSI.
The invention also provides a preparation method of the battery diaphragm slurry, which comprises the following steps:
(a) Dissolving electrolyte by adopting the solvent to obtain electrolyte solution;
preferably, the concentration of the electrolyte solution is 0.5-2M;
(b) And mixing the polyvinylidene fluoride-hexafluoropropylene porous powder material with the electrolyte solution, and standing overnight to obtain the battery diaphragm slurry.
Preferably, the mass ratio of the polyvinylidene fluoride-hexafluoropropylene porous powder material to the electrolyte solution is 1: (1-2).
The polyvinylidene fluoride-hexafluoropropylene porous powder material can be prepared by the following method:
and mixing the polyvinylidene fluoride-hexafluoropropylene nano particles into water, aggregating the polyvinylidene fluoride-hexafluoropropylene nano particles in the water under the drive of strong shearing force to form micron-sized fractal porous agglomerates, and drying, ball-milling and screening to obtain the polyvinylidene fluoride-hexafluoropropylene porous powder material with the particle size smaller than 60 mu m.
The invention also provides a battery diaphragm, which is prepared from the battery diaphragm slurry.
The invention also provides a preparation method of the battery diaphragm, which comprises the following steps:
(1) Transferring the battery diaphragm slurry between two forming plates, and hot-pressing for 2-5min at 150-300 ℃ for forming;
the melting temperature of the polyvinylidene fluoride-hexafluoropropylene is about 130 ℃, so that the hot pressing temperature is set between 150 ℃ and 300 ℃ without being excessively high; the hot pressing time is between 2 and 5min, preferably 3min.
(2) And (3) keeping the pressure unchanged, and taking out after the temperature is reduced to room temperature to obtain the battery diaphragm.
The invention also provides application of the battery separator in preparing batteries, including but not limited to lithium ion batteries.
The invention also provides a lithium ion battery, which comprises the battery diaphragm.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses the porous structure which is abundant in the polyvinylidene fluoride-hexafluoropropylene porous powder material and is mutually communicated to bear electrolyte, and directly uses the polyvinylidene fluoride-hexafluoropropylene porous powder bearing the electrolyte as the main raw material of the battery diaphragm, rather than being used as the surface coating only; the battery diaphragm prepared by the method has relatively small impedance, so that the energy consumption of the internal resistance of the battery in the charging and discharging process is reduced, and the performances of the battery, such as the cycle efficiency, specific discharge capacity, coulombic efficiency and the like, are improved; and the polyvinylidene fluoride-hexafluoropropylene porous powder material is not required to be dissolved by using an organic solvent, so that the pollution of the organic solvent to the environment is avoided.
Drawings
FIG. 1 is an electron microscope analysis diagram of a battery separator according to the present invention;
FIG. 2 is a graph showing the results of performance analysis of a lithium ion battery prepared using the battery separator of the present invention;
wherein Specific discharge capacity [ mAh g ] -1 ]Represents specific discharge capacity (milliamp per gram), cycle number [ - ]]Represents the number of cycles, efficiency [%]Coulombic efficiency (percent) is expressed.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the attached drawings and the detailed description.
Example 1
The preparation method of the lithium ion battery diaphragm comprises the following steps:
(1) Transferring the battery diaphragm slurry between two forming plates, and hot-press forming at the melting temperature of polyvinylidene fluoride-hexafluoropropylene;
the battery diaphragm slurry is prepared by the following steps:
(a) Dissolving electrolyte by adopting a solvent to obtain electrolyte solution;
specifically, dry LiTFSI (lithium bis (trifluoromethane) sulfonyl imide salt) is added into ionic liquid Pyr 13TFSI, and after dissolution, electrolyte solution with the concentration of 0.5M is obtained;
(b) Mixing polyvinylidene fluoride-hexafluoropropylene porous powder material with the electrolyte solution, and standing overnight to obtain the battery diaphragm slurry of the embodiment;
specifically, firstly preparing a polyvinylidene fluoride-hexafluoropropylene porous powder material, wherein the polyvinylidene fluoride-hexafluoropropylene porous powder material is prepared by the following steps:
1) A high shear device HC-5000 was prepared, equipped with a microchannel (300 μm wide, 5.26X10-8 square meter in rectangular cross section and 5.8 mm in length) at an operating pressure of 120bar, corresponding to 4.8X10 6 s -1 Is a shear rate of (2);
2) Mixing polyvinylidene fluoride-hexafluoropropylene nano particles into water to obtain a suspension with the volume fraction of 18%; introducing the suspension into the microchannel at the shear rate, wherein a solid-like gel is formed upon passage through the microchannel;
3) The gel obtained was dried in an oven at 60 ℃ and then ball milled at 600rpm for 30min; screening the obtained powder-form agglomerate, and collecting polymer agglomerate (PC) with the size smaller than 63 μm to obtain the polyvinylidene fluoride-hexafluoropropylene porous powder material;
mixing the polyvinylidene fluoride-hexafluoropropylene porous powder material with an electrolyte solution according to the mass ratio of 1:1, stirring for a few seconds by using a magnetic rod, and standing for one night so that the electrolyte solution fully impregnates the pores of the polyvinylidene fluoride-hexafluoropropylene porous powder material, thereby obtaining battery diaphragm slurry (PC/IL slurry);
finally, the battery separator slurry was transferred to an aluminum plate, covered with a second aluminum plate, placed in a preheated hydraulic hand press, and hot-pressed at the melting temperature of polyvinylidene fluoride-hexafluoropropylene (about 130 ℃) for 3min;
(2) Keeping the pressure unchanged, and taking out after the temperature is reduced to room temperature to obtain the battery diaphragm of the embodiment;
namely, after the hot pressing is finished, the hydraulic hand press is cooled, but the pressure is kept unchanged, and the battery diaphragm (PCIL film) can be taken out after the film temperature is reduced to room temperature.
The battery separator was subjected to electron microscopy analysis, and the analysis result was shown in fig. 1.
Example 2
The preparation method of the battery separator of the present embodiment is basically the same as that of embodiment 1, except that: the concentration of the electrolyte solution was 0.5M, and the polyvinylidene fluoride-hexafluoropropylene porous powder material was mixed with the electrolyte solution in a mass ratio of 1:1.
Example 3
The preparation method of the battery separator of the present embodiment is basically the same as that of embodiment 1, except that: the concentration of the electrolyte solution was 0.5M, and the polyvinylidene fluoride-hexafluoropropylene porous powder material was mixed with the electrolyte solution in a mass ratio of 1:1.
Example 4
The preparation method of the battery separator of the present embodiment is basically the same as that of embodiment 1, except that: and adopting absolute ethyl alcohol as solvent to replace the ionic liquid to dissolve electrolyte.
Example 5
The preparation method of the battery separator of the present embodiment is basically the same as that of embodiment 1, except that: the ionic liquid used was Pyre13TFSI.
Comparative example 1
According to the battery diaphragm of the comparative example, the same method as that of CN112563664B is adopted, aqueous emulsion of polyvinylidene fluoride-hexafluoropropylene porous powder material and electrolyte solution are mixed according to the mass ratio of 1:1, and then the aqueous emulsion and the electrolyte solution are coated on two sides of a PE diaphragm in a spraying mode, so that the battery diaphragm is obtained.
Comparative example 2
The comparative example is a battery separator, which is a conventional PE separator.
Comparative example 3
The comparative example is a battery separator, which is a conventional PP separator.
The battery separators of examples 1-5 and comparative examples 1-2 were assembled into corresponding lithium ion batteries, and the performance of each lithium ion battery was tested, and the test results are shown in fig. 2 and table 1.
TABLE 1
As can be seen from fig. 2 and table 1, the battery separators prepared in examples 1 to 5 of the present invention have relatively small impedance compared to comparative examples 1 to 3, thereby reducing the energy consumption of the internal resistance of the battery during the charge and discharge process and improving the cycle efficiency, specific discharge capacity and coulombic efficiency of the battery.
Claims (10)
1. The battery diaphragm slurry is characterized by comprising the following raw materials in percentage by weight:
polyvinylidene fluoride-hexafluoropropylene porous powder material;
electrolyte and solvent for the electrolyte.
2. The battery separator slurry of claim 1 wherein the solvent is an ionic liquid.
3. The battery separator slurry of claim 1 wherein the ionic liquid is Pyre13TFSI.
4. A method for producing the battery separator slurry according to any one of claims 1 to 3, comprising the steps of:
(a) Dissolving electrolyte by adopting the solvent to obtain electrolyte solution;
(b) And mixing the polyvinylidene fluoride-hexafluoropropylene porous powder material with the electrolyte solution, and standing overnight to obtain the battery diaphragm slurry.
5. The method of claim 4, wherein the electrolyte solution has a concentration of 0.5 to 2M.
6. The preparation method according to claim 4, wherein the mass ratio of the polyvinylidene fluoride-hexafluoropropylene porous powder material to the electrolyte solution is 1: (1-2).
7. A battery separator made using the battery separator slurry of any one of claims 1-3.
8. The method for preparing a battery separator according to claim 7, comprising the steps of:
(1) Transferring the battery diaphragm slurry between two forming plates, and hot-pressing for 2-5min at 150-300 ℃ for forming;
(2) And (3) keeping the pressure unchanged, and taking out after the temperature is reduced to room temperature to obtain the battery diaphragm.
9. Use of a battery separator for the preparation of a battery, characterized in that: the battery separator of claim 7 applied between the positive and negative electrodes of a battery.
10. A lithium ion battery comprising the battery separator of claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310783593.2A CN116598714A (en) | 2023-06-29 | 2023-06-29 | Battery diaphragm slurry, battery diaphragm, preparation method of battery diaphragm and application of battery diaphragm slurry and battery diaphragm in preparation of battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310783593.2A CN116598714A (en) | 2023-06-29 | 2023-06-29 | Battery diaphragm slurry, battery diaphragm, preparation method of battery diaphragm and application of battery diaphragm slurry and battery diaphragm in preparation of battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116598714A true CN116598714A (en) | 2023-08-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310783593.2A Pending CN116598714A (en) | 2023-06-29 | 2023-06-29 | Battery diaphragm slurry, battery diaphragm, preparation method of battery diaphragm and application of battery diaphragm slurry and battery diaphragm in preparation of battery |
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| Country | Link |
|---|---|
| CN (1) | CN116598714A (en) |
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2023
- 2023-06-29 CN CN202310783593.2A patent/CN116598714A/en active Pending
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