CN115101887A - Lithium ion battery diaphragm and preparation method and application thereof - Google Patents
Lithium ion battery diaphragm and preparation method and application thereof Download PDFInfo
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- CN115101887A CN115101887A CN202210866701.8A CN202210866701A CN115101887A CN 115101887 A CN115101887 A CN 115101887A CN 202210866701 A CN202210866701 A CN 202210866701A CN 115101887 A CN115101887 A CN 115101887A
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- polyvinylidene fluoride
- lithium ion
- ion battery
- film layer
- polyethylene
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002033 PVDF binder Substances 0.000 claims abstract description 130
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 130
- -1 polyethylene Polymers 0.000 claims abstract description 105
- 239000004698 Polyethylene Substances 0.000 claims abstract description 97
- 229920000573 polyethylene Polymers 0.000 claims abstract description 96
- 239000004005 microsphere Substances 0.000 claims abstract description 94
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000007590 electrostatic spraying Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000005507 spraying Methods 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 claims description 56
- 239000012528 membrane Substances 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- 239000012466 permeate Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 239000002121 nanofiber Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920007485 Kynar® 761 Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 238000011056 performance test Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- 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
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- 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
- H01M50/491—Porosity
-
- 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)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a lithium ion battery diaphragm and a preparation method and application thereof, wherein the battery diaphragm comprises a first polyvinylidene fluoride film layer, a polyethylene microsphere layer and a second polyvinylidene fluoride film layer which are sequentially arranged; the first polyvinylidene fluoride film layer and the second polyvinylidene fluoride film layer are respectively provided with a microporous structure, the polyethylene microsphere layer is obtained by taking polyethylene microsphere dispersion liquid as a raw material and spraying the polyethylene microsphere dispersion liquid on the first polyvinylidene fluoride film layer or the second polyvinylidene fluoride film layer in an electrostatic spraying mode, and the polyethylene microsphere dispersion liquid comprises polyethylene microspheres, lithium halide and a dispersing solvent; when the diaphragm is prepared, firstly preparing a polyvinylidene fluoride film layer by adopting an electrostatic spinning method, then spraying a polyethylene microsphere layer on the polyvinylidene fluoride film layer by adopting an electrostatic spraying method, and then preparing another polyvinylidene fluoride film layer on the polyethylene microsphere layer by adopting the electrostatic spinning method; the diaphragm has the performances of thermal shutdown, good electrolyte wettability, good thermal dimensional stability, high porosity, high liquid absorption rate and the like.
Description
Technical Field
The invention relates to the technical field of lithium battery diaphragms, in particular to a lithium ion battery diaphragm and a preparation method and application thereof.
Background
The battery separator (battery separator), which is a layer of separator material between the positive electrode and the negative electrode of the battery, is a very critical part in the battery, has direct influence on the safety and cost of the battery, and has the main functions of: the positive electrode and the negative electrode are separated, electrons in the battery cannot freely pass through the battery, and ions in the electrolyte freely pass through the battery between the positive electrode and the negative electrode.
At present, the commercialized membrane material is mainly polyolefin membrane, which has excellent chemical stability, corrosion resistance and better mechanical property, but practice finds that it is still difficult to consider the following problems, and there is a clear concern about the phenomenon of one another: (1) the electrolyte has poor wettability; (2) when the battery is in special use condition and the temperature is increased, the thermal shrinkage is serious, and the battery can be short-circuited; (3) the function of shutting down the battery reaction at high temperature is not possessed, and even if the function is possessed, the temperature of thermal shutdown is difficult to be effectively adjusted, and the diaphragm needs to be improved again, so that the research and development cost is greatly improved.
Disclosure of Invention
It is an object of the present invention to overcome one or more of the deficiencies of the prior art and to provide a novel lithium ion battery separator that addresses the problem of this mismatch in the prior art.
The invention also provides a preparation method of the lithium ion battery diaphragm.
The invention also provides a lithium ion battery containing the lithium ion battery diaphragm.
In order to achieve the purpose, the invention adopts a technical scheme that:
a lithium ion battery diaphragm comprises a first polyvinylidene fluoride film layer, a polyethylene microsphere layer and a second polyvinylidene fluoride film layer which are sequentially arranged; the first polyvinylidene fluoride film layer and the second polyvinylidene fluoride film layer are respectively provided with a microporous structure, the polyethylene microsphere layer is obtained by spraying polyethylene microsphere dispersion liquid serving as a raw material on the first polyvinylidene fluoride film layer or the second polyvinylidene fluoride film layer in an electrostatic spraying mode, and the polyethylene microsphere dispersion liquid comprises polyethylene microspheres, lithium halide and a dispersing solvent.
According to some preferred aspects of the invention, the lithium halide is lithium chloride and/or lithium bromide.
According to the invention, the addition of the lithium halide not only enables the polyethylene microspheres to be suitable for electrostatic spraying, but also basically does not introduce other cations for the later-stage lithium ion battery, thereby being beneficial to ensuring the product quality.
According to some preferred aspects of the present invention, the dispersion solvent is absolute ethanol.
According to some preferred aspects of the present invention, the lithium halide is added in an amount of 0.05% to 0.3% by mass of the polyethylene microsphere dispersion.
According to some preferred aspects of the present invention, the polyethylene microspheres are added in an amount of 8% to 12% by mass of the polyethylene microsphere dispersion.
According to some preferred and specific aspects of the present invention, the polyethylene microspheres have a particle size of 1-5 μm.
In some preferred embodiments of the present invention, the preparation method of the polyethylene microsphere dispersion comprises: respectively adding the polyethylene microspheres, the dispersing solvent and the lithium halide into a mixing container, and then carrying out ultrasonic treatment under ice water for 10-30min to obtain a uniformly dispersed polyethylene microsphere dispersion liquid.
According to some preferred aspects of the present invention, the first polyvinylidene fluoride membrane layer and the second polyvinylidene fluoride membrane layer are respectively spun by using polyvinylidene fluoride spinning solution as a raw material and adopting an electrostatic spinning method.
Further, the polyvinylidene fluoride spinning solution is prepared by dispersing polyvinylidene fluoride in a mixed solvent, wherein the mixed solvent is composed of N, N-dimethylformamide and tetrahydrofuran.
Further, in the mixed solvent, the feeding mass ratio of the N, N-dimethylformamide to the tetrahydrofuran is 8-10: 1.
According to some preferred aspects of the present invention, the mass concentration of the polyvinylidene fluoride spinning solution is 16% to 20%.
In some preferred embodiments of the present invention, the method for preparing the polyvinylidene fluoride spinning solution comprises: and respectively adding polyvinylidene fluoride and a mixed solvent into a mixing container, and then stirring at 50-65 ℃ for 2-8h to obtain the polyvinylidene fluoride spinning solution.
According to some preferred aspects of the present invention, the electrostatic spraying method comprises the following process parameters: the electrostatic spraying voltage is 8-12kV, the spraying propelling speed is 0.8-1.2mL/h, the environmental humidity is 10% -20%, and the rotating speed of the receiver roller is 250-350 r/min.
According to some preferred aspects of the present invention, the electrostatic spinning method comprises the following process parameters: the spinning voltage is 8-12kV, the spinning advancing speed is 1.3-1.8mL/h, the environmental humidity is 10% -20%, and the rotating speed of the receiver roller is 250-350 r/min. In some preferred embodiments of the present invention, in the preparation process of the lithium ion battery separator, the mass concentration of the polyvinylidene fluoride spinning solution is controlled to be 16% to 20%, the addition amount of the polyethylene microspheres in the polyethylene microsphere dispersion is 8% to 12%, when the spinning amount of the polyvinylidene fluoride spinning solution is 4mL to 6mL, the spraying amount of the polyethylene microsphere dispersion is 2mL to 4mL, and the spinning amount of the polyvinylidene fluoride spinning solution is greater than the spraying amount of the polyethylene microsphere dispersion.
According to the invention, the lithium ion battery diaphragm comprises a working state and a thermal shutdown state, when the lithium ion battery diaphragm is in the working state, the polyethylene microsphere layer is provided with a pore channel communicated with the microporous structure, and the lithium ion battery diaphragm can conduct lithium ions;
when the lithium ion battery diaphragm is in a thermal shutdown state, the polyethylene microsphere layer is softened or melted to form a compact structure, part of the polyethylene microsphere layer permeates and is blocked in the microporous structure, namely, the polyvinylidene fluoride film layer is closed, and the lithium ion battery diaphragm can block lithium ions from passing through.
The invention provides another technical scheme that: the preparation method of the lithium ion battery separator comprises the following steps: the method comprises the steps of spinning one of a first polyvinylidene fluoride film layer and a second polyvinylidene fluoride film layer by using a polyvinylidene fluoride spinning solution as a raw material and adopting an electrostatic spinning method, then forming a polyethylene microsphere layer on the spun polyvinylidene fluoride film layer by using a polyethylene microsphere dispersion solution as a raw material and adopting an electrostatic spraying method, and forming the other of the first polyvinylidene fluoride film layer and the second polyvinylidene fluoride film layer on the polyethylene microsphere layer by using the polyvinylidene fluoride spinning solution as a raw material and adopting the electrostatic spinning method.
The invention provides another technical scheme that: a lithium ion battery comprising a positive electrode, a negative electrode, and a separator, wherein: the diaphragm is the lithium ion battery diaphragm.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the novel lithium ion battery diaphragm provided by the invention, polyethylene microspheres are specially designed to form polyethylene microsphere dispersion liquid, so that the polyethylene microsphere dispersion liquid is suitable for electrostatic spraying, and then the polyethylene microspheres and a polyvinylidene fluoride film layer can be mutually attached and assembled without layering without adhesive, particularly after mutual assembly, the battery diaphragm is endowed with a thermal shutdown function, and effective regulation and control of thermal shutdown temperature can be realized by regulating different polyethylene materials adopted by the polyethylene microspheres, the material of the polyethylene microspheres can be selected according to needs on the existing basis without improving the diaphragm again, so that the thermal shutdown temperature is regulated, and the research and development cost is greatly saved; meanwhile, the inventor unexpectedly finds that after the first polyvinylidene fluoride film layer, the polyethylene microsphere layer and the second polyvinylidene fluoride film layer which are sequentially arranged are assembled, the high-temperature thermal dimensional stability can still be kept at high temperature, so that the battery diaphragm can still effectively separate the anode and the cathode at high temperature, and the occurrence of a short circuit condition is avoided (generally, the battery is small in size and small in volume, so that the anode and the cathode are relatively small in distance and mutually adjacent, if the diaphragm generates a relatively obvious thermal shrinkage phenomenon, the anode and the cathode of the battery are easily contacted and are short-circuited); moreover, the polyethylene microsphere layer is positioned in the middle, so that the polyethylene microspheres are not easy to fall off.
In addition, the battery diaphragm also has high porosity and high liquid absorption rate, has good wettability to electrolyte, and can provide sufficient space for the transmission of lithium ions.
Drawings
Fig. 1 is a schematic structural diagram of a lithium ion battery separator prepared in example 1 of the present invention;
fig. 2 is a schematic structural diagram of a lithium ion battery separator prepared in example 1 of the present invention (after thermal shutdown);
FIG. 3 is a schematic diagram of a lithium ion battery separator prepared in example 1 of the present invention, a commercially available Ceguard 2325 separator and a PVDF nanofiber membrane alone (the PVDF nanofiber membrane is prepared in the same manner as in example 1) after heat treatment at 160 ℃ for 20 min;
FIG. 4 is a scanning electron microscope image of a cross section of the lithium ion battery separator prepared in example 1 after being subjected to a heat treatment at 110 ℃;
fig. 5 is a schematic diagram showing the open-circuit voltage variation during heating of a battery assembled by using the lithium ion battery separator prepared in example 1 according to the present invention;
FIG. 6 is a graph showing the charge and discharge curves at room temperature of a battery assembled by using the lithium ion battery separator prepared in example 1 according to the present invention;
fig. 7 is a graph showing the charging and discharging curves at 110 ℃ of a battery assembled by using the lithium ion battery separator prepared in example 1 according to the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art. In the following, polyvinylidene fluoride powder was purchased from arkema, france under the designation Kynar 761; polyethylene microspheres were purchased from Qingdao Sainuo New materials, Inc.
Example 1
The embodiment provides a lithium ion battery diaphragm, which comprises a first polyvinylidene fluoride film layer, a polyethylene microsphere layer and a second polyvinylidene fluoride film layer which are sequentially arranged; the first polyvinylidene fluoride membrane layer and the second polyvinylidene fluoride membrane layer are respectively provided with a micropore structure, the polyethylene microsphere layer is obtained by taking polyethylene microsphere dispersion liquid as a raw material and spraying the polyethylene microsphere layer on the first polyvinylidene fluoride membrane layer in an electrostatic spraying mode, and the first polyvinylidene fluoride membrane layer and the second polyvinylidene fluoride membrane layer are respectively spun by taking polyvinylidene fluoride spinning liquid as a raw material and adopting an electrostatic spinning method.
Specifically, the polyethylene microsphere dispersion is prepared by the following method: 1g of polyethylene microspheres was weighed into a 50mL beaker, 9g of absolute ethanol was added to the beaker, and 0.02g of LiCl was added. And performing ultrasonic treatment for 20min under ice water to obtain uniformly dispersed polyethylene microsphere dispersion.
The polyvinylidene fluoride spinning solution is prepared by the following method: 2.21g of dried polyvinylidene fluoride powder was poured into a three-necked flask, and 9g N, N-dimethylformamide and 1g of tetrahydrofuran were added thereto. And fully stirring the mixture at about 60 ℃ for 6 hours to fully dissolve the polyvinylidene fluoride powder in the mixed solvent to obtain the polyvinylidene fluoride spinning solution.
The preparation method of the battery diaphragm comprises the following steps:
preparing a PVDF nano-fiber membrane (a first polyvinylidene fluoride membrane layer in the example) by using a polyvinylidene fluoride spinning solution through an electrostatic spinning method, wherein the propelling speed is 0.15 mL/h;
replacing polyethylene microsphere dispersion liquid after spinning 5mL of spinning solution, spraying the polyethylene microsphere dispersion liquid on the surface of the first polyvinylidene fluoride membrane layer by an electrostatic spraying method, and adjusting the propelling speed to be 1 mL/h;
spraying 3mL of polyethylene microsphere dispersion liquid, replacing polyvinylidene fluoride spinning liquid, finally spinning a PVDF nanofiber membrane (a second polyvinylidene fluoride membrane layer in the example) at a propelling speed of 0.15mL/h, and stopping spinning after 5mL of spinning liquid is spun;
the voltage of the whole spinning process is about 10kV, the rotating speed of the roller is about 300r/min, and the humidity is controlled to be about 10%.
Example 2
The embodiment provides a lithium ion battery diaphragm, which comprises a first polyvinylidene fluoride film layer, a polyethylene microsphere layer and a second polyvinylidene fluoride film layer which are sequentially arranged; the first polyvinylidene fluoride film layer and the second polyvinylidene fluoride film layer are respectively provided with a microporous structure, the polyethylene microsphere layer is obtained by spraying polyethylene microsphere dispersion liquid serving as a raw material on the first polyvinylidene fluoride film layer in an electrostatic spraying mode, and the first polyvinylidene fluoride film layer and the second polyvinylidene fluoride film layer are respectively spun by taking polyvinylidene fluoride spinning liquid as a raw material and adopting an electrostatic spinning method.
Specifically, the polyethylene microsphere dispersion is prepared by the following method: 1.2g of polyethylene microspheres were weighed into a 50mL beaker, and 9g of absolute ethanol and 0.02g of LiCl were added to the beaker. And performing ultrasonic treatment for 20min under ice water to obtain uniformly dispersed polyethylene microsphere dispersion.
The polyvinylidene fluoride spinning solution is prepared by the following method: 2.5g of dried polyvinylidene fluoride powder was poured into a three-necked flask, and 9g N, N-dimethylformamide and 1g of tetrahydrofuran were added thereto. And fully stirring the mixture at about 60 ℃ for 6 hours to fully dissolve the polyvinylidene fluoride powder in the mixed solvent to obtain the polyvinylidene fluoride spinning solution.
The preparation method of the battery diaphragm comprises the following steps:
preparing a PVDF nano-fiber membrane (a first polyvinylidene fluoride membrane layer in the example) by using a polyvinylidene fluoride spinning solution through an electrostatic spinning method, wherein the propelling speed is 0.15 mL/h;
replacing the polyethylene microsphere dispersion liquid after spinning 5mL of spinning liquid, spraying the polyethylene microsphere dispersion liquid on the surface of the first polyvinylidene fluoride film layer by an electrostatic spraying method, and adjusting the propelling speed to be 1 mL/h;
spraying 3mL of polyethylene microsphere dispersion liquid, replacing polyvinylidene fluoride spinning liquid, finally spinning a PVDF nanofiber membrane (a second polyvinylidene fluoride membrane layer in the example) at a propelling speed of 0.15mL/h, and stopping spinning after 5mL of spinning liquid is spun;
the voltage of the whole spinning process is about 10kV, the rotating speed of the roller is about 300r/min, and the humidity is controlled to be about 10%. The resulting fiber film had a slightly larger fiber diameter than example 1 and a thicker PE intermediate layer at the same time.
Example 3
The embodiment provides a lithium ion battery diaphragm, which comprises a first polyvinylidene fluoride film layer, a polyethylene microsphere layer and a second polyvinylidene fluoride film layer which are sequentially arranged; the first polyvinylidene fluoride film layer and the second polyvinylidene fluoride film layer are respectively provided with a microporous structure, the polyethylene microsphere layer is obtained by spraying polyethylene microsphere dispersion liquid serving as a raw material on the first polyvinylidene fluoride film layer in an electrostatic spraying mode, and the first polyvinylidene fluoride film layer and the second polyvinylidene fluoride film layer are respectively spun by taking polyvinylidene fluoride spinning liquid as a raw material and adopting an electrostatic spinning method.
Specifically, the polyethylene microsphere dispersion is prepared by the following method: 1.1g of polyethylene microspheres were weighed into a 50mL beaker, and 9g of absolute ethanol and 0.02g of LiCl were added to the beaker. And performing ultrasonic treatment for 20min under ice water to obtain uniformly dispersed polyethylene microsphere dispersion.
The polyvinylidene fluoride spinning solution is prepared by the following method: 2.21g of dry polyvinylidene fluoride powder was poured into a three-necked flask, and 9g N, N-dimethylformamide and 1g of tetrahydrofuran were added thereto. And fully stirring the mixture at about 60 ℃ for 6 hours to fully dissolve the polyvinylidene fluoride powder in the mixed solvent to obtain the polyvinylidene fluoride spinning solution.
The preparation method of the battery diaphragm comprises the following steps:
preparing a PVDF nanofiber membrane (a first polyvinylidene fluoride membrane layer in the embodiment) by adopting a polyvinylidene fluoride spinning solution through an electrostatic spinning method, wherein the propelling speed is 0.16 mL/h;
replacing polyethylene microsphere dispersion liquid after spinning 5mL of spinning solution, spraying the polyethylene microsphere dispersion liquid on the surface of the first polyvinylidene fluoride membrane layer by an electrostatic spraying method, and adjusting the propelling speed to be 1 mL/h;
spraying 3mL of polyethylene microsphere dispersion liquid, replacing polyvinylidene fluoride spinning liquid, finally spinning a PVDF nanofiber membrane (a second polyvinylidene fluoride membrane layer in the example) at a propelling speed of 0.16mL/h, and stopping spinning after 5mL of spinning liquid is spun;
the voltage of the whole spinning process is about 10kV, the rotating speed of the roller is about 300r/min, and the humidity is controlled to be about 10%.
The resulting fiber membrane was finer in fiber diameter than example 1.
Performance testing
The lithium ion battery separator prepared in example 1, a commercially available Ceglard2325 separator on the market, and a PVDF-only nanofiber membrane (the PVDF nanofiber membrane was prepared according to the same method as in example 1) were respectively subjected to performance tests.
The lithium ion battery separator structure prepared in embodiment 1 is shown in fig. 1, and includes a first polyvinylidene fluoride film layer 1, a polyethylene microsphere layer 2, and a second polyvinylidene fluoride film layer 3, which are sequentially disposed, at this time, the polyethylene microsphere layer 2 has pore channels respectively communicated with the microporous structures of the first polyvinylidene fluoride film layer 1 and the second polyvinylidene fluoride film layer 3, and the lithium ion battery separator can conduct lithium ions;
when the lithium ion battery diaphragm is in a thermal shutdown state, as shown in fig. 2, the polyethylene microsphere layer 2 ' is softened or melted to form a compact structure, and part of the polyethylene microsphere layer permeates and is blocked in the microporous structures of the first polyvinylidene fluoride film layer 1 ' and the second polyvinylidene fluoride film layer 3 ', namely the polyvinylidene fluoride film layers are sealed, and the lithium ion battery diaphragm can block lithium ions from passing through and realizes thermal shutdown.
Thermal dimensional stability test results referring to fig. 3, Celgard2325, PVDF nanofiber membrane, and the lithium ion battery separator prepared in example 1 were respectively subjected to heat treatment at 160 ℃ for 20min, and then the dimensional stability of the membrane was observed. The thermal dimensional shrinkage of Celgard2325 reaches 57.2%, the thermal dimensional shrinkage of the PVDF nanofiber membrane is 8.3%, and the thermal dimensional shrinkage of the lithium ion battery separator prepared in example 1 is 11.0%, which indicates that the lithium ion battery separator prepared in example 1 has good thermal dimensional stability, and particularly after hot-melt polyethylene microspheres are added on the PVDF nanofiber membrane, the thermal dimensional shrinkage is slightly affected, and the use requirements are met.
Fig. 4 is a scanning electron microscope image of a cross section of the lithium ion battery separator prepared in example 1 after being heat-treated at 110 ℃. The figure shows that the clear three-layer structure has a clear boundary line, and after the polyethylene microspheres in the middle layer are melted, the polyethylene in the middle layer can permeate into the polyvinylidene fluoride film layers on the upper layer and the lower layer, so that the microporous structure of the fiber film can be completely blocked.
And assembling the button full-cell according to the sequence of the positive electrode shell/the positive electrode/the diaphragm/the negative electrode/the steel sheet/the elastic sheet/the negative electrode shell, wherein the positive electrode material is ternary nickel-cobalt-manganese (NCM523), and the negative electrode material is a graphite negative electrode.
Fig. 5 shows the change of the open circuit voltage of the battery assembled by the lithium ion battery separator prepared in example 1 during the heating process, and it can be seen that the open circuit voltage of the battery is maintained at about 3.15V at room temperature, the battery is placed in a constant temperature heating device at 110 ℃, the voltage of the battery drops to a certain extent, and then suddenly drops to 0 within a period of about 16s at a certain stage. This indicates that the lithium ion battery separator prepared in example 1 can rapidly respond thermally during the operation of the battery. When the temperature inside the battery suddenly rises to the melting temperature of the polyethylene microspheres, the polyethylene microsphere layer of the lithium ion battery separator prepared in example 1 can be melted rapidly to block the microporous structure of the fibrous membrane rapidly, so that the effect of preventing lithium ion transmission is achieved, and the voltage is rapidly reduced to 0.
The assembled battery was charged and discharged at room temperature and 100 ℃ respectively, and the test results are shown in fig. 6-7;
setting a holding time of 1min between the charging and discharging steps, after finishing the constant-current constant-voltage charging step, putting the battery into a constant-temperature heating device at 110 ℃ for discharging during the holding period of the battery, and testing the discharge capacity of the battery at 110 ℃;
the battery can be normally charged and discharged at room temperature, and shows good discharge capacity, which is 162.47 mAh/g;
however, when the battery was discharged at 110 ℃, the discharge capacity of the battery decreased to 0.03mAh/g, and normal discharge was not possible. This is because when the temperature inside the battery reaches 110 ℃, the polyethylene microspheres of the polyethylene microsphere layer rapidly melt and form a dense layer, so that the original pores of the separator fail. This indicates that the lithium ion battery separator of the present invention can effectively shut down the reaction of the battery at 110 ℃.
In addition, the porosity and the liquid absorption rate of the lithium ion battery separator prepared in the example 1 are tested, and the result shows that: it has a high porosity of 68.8% and a high liquid uptake of 484%.
Porosity test
The porosity of the membrane was tested using n-butanol imbibition. Making the diaphragm into 2 × 2cm 2 Square of (2). And (3) placing the membrane to be tested in n-butyl alcohol, wherein the membrane needs to be completely soaked in n-butyl alcohol liquid for 4 hours. Sandwiching the soaked membrane between two pieces of filter paper, pressing with a weight of 20g for 10s to absorb n-butanol on the surface of the membrane, weighing, and recording as m 1 . The porosity was calculated according to equation (1).
Porosity (%) ═ m 1 -m 0 )/ρ b V (1)；
Wherein: m is 0 Mass of the diaphragm, m 1 The quality of the diaphragm after soaking in n-butanol, rho b Is the density of n-butanol, V is the diaphragmVolume.
Liquid uptake test
The membranes were tested for liquid pick-up using a gravimetric method. And (3) fully soaking the dried diaphragm to be tested in enough electrolyte, taking out the diaphragm once every 10min, sucking the electrolyte on the surface of the diaphragm by using filter paper, weighing and recording as mi. The mass of the diaphragm is measured to be unchanged, and the liquid absorption rate is calculated according to the formula (2-2).
Liquid absorption rate (%) [ (m) i -m 0 )/m 0 ]×100％ (2-2)；
Wherein: m is a unit of 0 Is the dry weight of the separator, m i Is the wet weight of the separator.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. A lithium ion battery separator, characterized in that: the battery diaphragm comprises a first polyvinylidene fluoride film layer, a polyethylene microsphere layer and a second polyvinylidene fluoride film layer which are sequentially arranged; the first polyvinylidene fluoride film layer and the second polyvinylidene fluoride film layer are respectively provided with a microporous structure, the polyethylene microsphere layer is obtained by spraying polyethylene microsphere dispersion liquid serving as a raw material on the first polyvinylidene fluoride film layer or the second polyvinylidene fluoride film layer in an electrostatic spraying mode, and the polyethylene microsphere dispersion liquid comprises polyethylene microspheres, lithium halide and a dispersing solvent.
2. The lithium ion battery separator according to claim 1, wherein: the lithium halide is lithium chloride and/or lithium bromide; and/or the dispersing solvent is absolute ethyl alcohol.
3. The lithium ion battery separator according to claim 1 or 2, wherein: by mass percentage, the addition amount of the lithium halide accounts for 0.05-0.3% of the polyethylene microsphere dispersion liquid, and the addition amount of the polyethylene microspheres accounts for 8-12% of the polyethylene microsphere dispersion liquid.
4. The lithium ion battery separator according to claim 1, wherein: the particle size of the polyethylene microspheres is 1-5 μm.
5. The lithium ion battery separator according to claim 1, wherein: the first polyvinylidene fluoride membrane layer and the second polyvinylidene fluoride membrane layer are respectively spun by taking polyvinylidene fluoride spinning solution as a raw material and adopting an electrostatic spinning method; the polyvinylidene fluoride spinning solution is prepared by dispersing polyvinylidene fluoride in a mixed solvent, wherein the mixed solvent is composed of N, N-dimethylformamide and tetrahydrofuran.
6. The lithium ion battery separator according to claim 5, wherein: in the mixed solvent, the feeding mass ratio of the N, N-dimethylformamide to the tetrahydrofuran is 8-10: 1, and the mass concentration of the polyvinylidene fluoride spinning solution is 16-20%.
7. The lithium ion battery separator according to claim 5 or 6, wherein: in the electrostatic spraying mode, the process parameters are as follows: the electrostatic spraying voltage is 8-12kV, the spraying propulsion speed is 0.8-1.2mL/h, the environmental humidity is 10% -20%, and the rotating speed of a receiver roller is 250-; in the electrostatic spinning method, the technological parameters are as follows: the spinning voltage is 8-12kV, the spinning advancing speed is 1.3-1.8mL/h, the environmental humidity is 10% -20%, and the rotating speed of a receiver roller is 250-350 r/min.
8. The lithium ion battery separator according to claim 1, wherein: the lithium ion battery diaphragm comprises a working state and a thermal shutdown state, when the lithium ion battery diaphragm is in the working state, the polyethylene microsphere layer is provided with a pore channel communicated with the microporous structure, and the lithium ion battery diaphragm can conduct lithium ions;
when the lithium ion battery diaphragm is in a thermal shutdown state, the polyethylene microsphere layer is in a compact structure, part of the polyethylene microsphere layer permeates and is blocked in the microporous structure, and the lithium ion battery diaphragm can block lithium ions from passing through.
9. A method for preparing the lithium ion battery separator according to any one of claims 1 to 8, wherein: the preparation method comprises the following steps: the method comprises the steps of spinning one of a first polyvinylidene fluoride film layer and a second polyvinylidene fluoride film layer by using a polyvinylidene fluoride spinning solution as a raw material and adopting an electrostatic spinning method, then forming a polyethylene microsphere layer on the spun polyvinylidene fluoride film layer by using a polyethylene microsphere dispersion solution as a raw material and adopting an electrostatic spraying method, and forming the other of the first polyvinylidene fluoride film layer and the second polyvinylidene fluoride film layer on the polyethylene microsphere layer by using the polyvinylidene fluoride spinning solution as a raw material and adopting the electrostatic spinning method.
10. A lithium ion battery comprises a positive electrode, a negative electrode and a diaphragm, and is characterized in that: the separator is the lithium ion battery separator as defined in any one of claims 1 to 8.
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