CN117977115A - Battery diaphragm capable of inhibiting growth of sodium dendrite and preparation method and application thereof - Google Patents
Battery diaphragm capable of inhibiting growth of sodium dendrite and preparation method and application thereof Download PDFInfo
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- CN117977115A CN117977115A CN202410366065.1A CN202410366065A CN117977115A CN 117977115 A CN117977115 A CN 117977115A CN 202410366065 A CN202410366065 A CN 202410366065A CN 117977115 A CN117977115 A CN 117977115A
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 28
- 210000001787 dendrite Anatomy 0.000 title claims abstract description 28
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 28
- 239000011734 sodium Substances 0.000 title claims abstract description 28
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 45
- 238000000576 coating method Methods 0.000 claims abstract description 45
- 238000005524 ceramic coating Methods 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 17
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002033 PVDF binder Substances 0.000 claims abstract description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 6
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 3
- 239000001913 cellulose Substances 0.000 claims abstract description 3
- 229920002678 cellulose Polymers 0.000 claims abstract description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peroxyacetic acid Substances CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 3
- 239000000919 ceramic Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 18
- 239000011888 foil Substances 0.000 abstract description 18
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 11
- 230000002829 reductive effect Effects 0.000 abstract description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of diaphragms for sodium ion batteries, in particular to a battery diaphragm capable of inhibiting sodium dendrite growth, and a preparation method and application thereof, wherein the battery diaphragm comprises a base film, a ceramic coating coated on the surface of the base film and a polymer coating coated on the surface of the ceramic coating; wherein the base film is one of PE, PP, PET, PI and cellulose base film; the ceramic coating comprises a ceramic material and a solvent I; the high polymer coating comprises a binder and a solvent II, wherein the binder comprises one or more of sodium carboxymethyl cellulose and PAA, PMMA, PVDF. By adopting the technical scheme, the mechanical strength of the diaphragm and the interfacial stability of the aluminum foil can be effectively improved, the growth of sodium dendrite is inhibited, the interfacial impedance of the diaphragm and the aluminum foil of the battery is reduced, the cycle life of the negative-electrode-free sodium metal battery is prolonged, the safety performance and the electrochemical performance of the diaphragm are excellent, and the preparation method is simple and can be used for industrial production.
Description
Technical Field
The invention relates to the technical field of diaphragms for sodium ion batteries, in particular to a battery diaphragm capable of inhibiting growth of sodium dendrites, and a preparation method and application thereof.
Background
Sodium ion batteries have the advantages of large reserves and low cost, and meanwhile, have a similar working principle to lithium ion batteries and are valued. However, in practical use, it is found that uneven deposition of sodium ions on the negative electrode side of a sodium ion battery during charge-discharge cycles can cause rapid growth of sodium dendrites, and finally, the potential safety hazard is caused by puncturing a diaphragm. In addition, as sodium ions are more easily irreversibly reduced in the electrolyte than sodium ions in the deposition process of the aluminum foil surface, the limited electrolyte in the cell system is continuously consumed, and the cell capacity is rapidly reduced. In the winding process of the anode and the cathode of the battery and the diaphragm, due to the existence of winding tension, the PE diaphragm is easy to misplace or wrinkle with the pole piece after being stretched, so that the interface impedance between the pole piece and the diaphragm in the battery core is increased, the internal resistance of the battery core is increased, and the cycle life of the metal battery is influenced.
Disclosure of Invention
The invention aims to provide a battery diaphragm capable of inhibiting the growth of sodium dendrites, and a preparation method and application thereof, so that the problems are solved, the mechanical strength and the interfacial stability of an aluminum foil of the diaphragm can be effectively improved, the growth of the sodium dendrites is inhibited, the interfacial impedance of the diaphragm and the aluminum foil of the battery is reduced, the cycle life of a non-negative-electrode sodium metal battery is prolonged, the safety performance and the electrochemical performance of the diaphragm are excellent, and the preparation method is simple and can be used for industrial production.
In order to achieve the above purpose, the invention provides a battery separator capable of inhibiting the growth of sodium dendrites, which comprises a base film, a ceramic coating coated on the surface of the base film and a polymer coating coated on the surface of the ceramic coating;
Wherein the base film is one of PE, PP, PET, PI and cellulose base film; the ceramic coating comprises a ceramic material and a solvent I; the high polymer coating comprises a binder and a solvent II, wherein the binder comprises one or more of sodium carboxymethyl cellulose and PAA, PMMA, PVDF. The adhesive is used as a polymer coating on the surface of the ceramic coating, so that the aluminum foil and the diaphragm of the battery can be effectively bonded, and the situation that the electrolyte is continuously consumed due to irreversible reduction of solvent molecules in the electrolyte in the deposition process of sodium ions on the surface of the aluminum foil, so that the capacity of the battery core is rapidly reduced is avoided. Is critical to the capacity retention of the ceramic coating in the cell.
Preferably, the base film is a PE film.
Preferably, the thickness of the base film is 5-25 μm, the thickness of the ceramic coating is 0.1-4 μm, and the thickness of the polymer coating is 0.1-4 μm. The thickness of the ceramic coating is in the range, so that the ceramic coating has better puncture strength, and the puncture strength of the negative-electrode-free sodium metal battery diaphragm is improved.
Preferably, the base film has a vapor permeation value of 70-200sec/100cc.
Preferably, the ceramic material comprises one or more of montmorillonite, boehmite, kaolin, hydroxyapatite.
Preferably, the ceramic material comprises ceramic powder A and ceramic powder B, and the mass ratio of the ceramic powder A to the ceramic powder B is preferably 1-99: 1 to 99, more preferably 1 to 20: 50-90.
Preferably, the ceramic material has a particle size D50 < 2 μm, more preferably 500nm < D50 < 1 μm. The particle size of the ceramic material adopted by the invention is in the range, so that the ceramic material has better covering power when being coated on the surface of the base film, and the puncture strength of the diaphragm of the non-negative sodium metal battery is further improved.
Preferably, the first solvent comprises one or more of pure water and absolute ethyl alcohol, more preferably pure water, and the mass ratio of the ceramic material to the first solvent is 1-50: 1 to 100, more preferably 1:3. the invention controls the mass ratio of the ceramic material to the solvent I in the range, can better form a film on the surface of the base film, and further improves the puncture strength of the diaphragm of the non-negative sodium metal battery.
Preferably, the molecular mass of the binder is more than 5 ten thousand, more preferably 20 ten thousand to 100 ten thousand.
Preferably, the binder comprises a binder A and a binder B, and the mass ratio of the binder A to the binder B is 1-99: 1 to 99, more preferably 1 to 20: 50-90.
Preferably, the second solvent comprises pure water, and the mass ratio of the binder to the second solvent is 1-100: 1 to 100, more preferably 1:10. the invention controls the mass ratio of the binder to the solvent I in the range, can better form a film on the surface of the ceramic coating, and further improves the adhesion between the negative electrode-free sodium metal battery diaphragm and the aluminum foil.
A method for preparing a battery separator capable of inhibiting the growth of sodium dendrites, comprising the following steps:
s1, uniformly mixing a ceramic material and a solvent I to obtain a ceramic solution, completely coating the ceramic solution on the surface of a base film, and vacuum drying to obtain a ceramic coating;
S2, mixing the binder and the solvent II to obtain a polymer solution, coating the polymer solution on the surface of the ceramic coating, and vacuum drying to obtain the polymer coating.
Preferably, the ceramic material in S1 is ground to obtain ground powder, and the ground powder and the solvent I are mixed and stirred to obtain a ceramic solution;
More preferably, the stirring is mechanical stirring, and the rotation speed of the mechanical stirring is 500-1000 r/min; the stirring time is 1-10 hours, more preferably 2-3 hours.
Preferably, the coating in S1 is gravure roll coating. The coating equipment is gravure knife coating equipment; the gravure roll coating scale of the gravure roll is 0.5-4 mu m, more preferably 2 mu m; the speed of gravure roll coating is 1-50 m/min, more preferably 20m/min. According to the invention, the paste is uniformly coated on the surface of the base film through the gravure roller coating, so that the defect or non-uniformity of an interface layer is prevented, and the diaphragm with good comprehensive performance is obtained.
Preferably, the vacuum drying temperature in S1 and S2 is 30-60 ℃.
Preferably, the ceramic coating in S1 is uniformly applied on one side of the base film.
Preferably, the mixing mode in the step S2 is mechanical stirring, and the stirring rotating speed is 1000-2000 r/min; the stirring time is 1-10 hours, more preferably 2-3 hours.
Preferably, the coating mode in the step S2 is gravure roll coating, the coating equipment is gravure knife coating equipment, and the gravure roll scale of the gravure roll coating is 0.5-4 mu m, more preferably 2 mu m; the speed of gravure roll coating is 1-50 m/min, more preferably 20m/min. According to the invention, the slurry is uniformly coated on the surface of the base film through the ultra-gravure roller coating, so that the defect or non-uniformity of an interface layer is prevented, and the diaphragm with good comprehensive performance is obtained.
The application of the battery diaphragm capable of inhibiting the growth of sodium dendrites is that the battery diaphragm is applied to a battery diaphragm without negative electrode sodium metal.
The beneficial effects of the invention are that
The battery diaphragm capable of inhibiting the growth of sodium dendrites comprises a base film, a ceramic coating and a high polymer coating, wherein the ceramic coating and the high polymer coating are arranged on the surface of the base film; the ceramic coating and the polymer coating are respectively and completely covered on the same side surface of the base film, and the ceramic coating is uniformly covered on the surface of the base film, so that the surface strength of the diaphragm can be remarkably improved, and the ceramic coating can bear larger puncture force when a puncture experiment is carried out on the diaphragm, so that the puncture strength of the diaphragm of the non-negative sodium metal battery can be improved by the ceramic coating. The high polymer coating on the surface of the ceramic coating can bond the aluminum foil in the battery with the diaphragm, so that the situation that the deposition speed of sodium ions on the surface of the aluminum foil is too high due to irreversible reduction of solvent molecules in electrolyte, sodium dendrites are generated, the internal resistance of the battery cell is increased, and the capacity of the battery cell is rapidly reduced is prevented. According to the invention, the base film, the ceramic coating and the polymer coating are synergistic, so that the mechanical strength of the diaphragm and the interface stability of the aluminum foil can be effectively improved, the growth of sodium dendrite is inhibited, the interface impedance of the diaphragm and the aluminum foil of the battery is reduced, and the cycle life of the negative-electrode-free sodium metal battery is prolonged.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is an SEM image of a separator of the invention prepared according to example 2;
FIG. 2 is an SEM image of a separator of comparative example 1 of the present invention;
FIG. 3 is a polarization current diagram of a separator made in example 2 of the present invention;
FIG. 4 is a polarization current diagram of a conventional PE separator according to comparative example 1 of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and examples. Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The above-mentioned features of the invention or the features mentioned in the specific examples can be combined in any desired manner, and these specific examples are only intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
A battery diaphragm capable of inhibiting sodium dendrite growth comprises a PE base film, a ceramic coating coated on the surface of the base film and a high polymer coating coated on the surface of the ceramic coating; the ceramic coating comprises montmorillonite and pure water; the polymer coating comprises a binder PVDF and deionized water. The thickness of the base film was 12. Mu.m, the thickness of the ceramic coating was 2. Mu.m, and the thickness of the polymer coating was 1.5. Mu.m. The breathable value of the base film was 84sec/100cc.
Example 2
The invention provides a preparation method of a battery diaphragm capable of inhibiting growth of sodium dendrites, which comprises the following steps:
S1, grinding montmorillonite to obtain ground powder; mixing the ground powder with deionized water according to a ratio of 1:3, wherein the mixing mode is mechanical stirring, the rotating speed of the mechanical stirring is 1000r/min, stirring is carried out for 3 hours to obtain ceramic solution, the ceramic solution is coated on the surface of one side of the PE base film, and after the coating is finished, the coated product is dried in vacuum to obtain the ceramic coating. The coating mode is gravure roll coating;
S2, mixing the binder PVDF and deionized water according to a ratio of 1:10, wherein the mixing mode is mechanical stirring, the rotation speed of the mechanical stirring is 2000r/min, stirring is carried out for 3 hours, a high polymer solution is obtained, the high polymer solution is coated on the surface of the ceramic coating, and after the coating is finished, the coated product is dried in vacuum, so that the high polymer coating is obtained, and the membrane capable of enhancing the interface stability of the non-negative sodium metal battery is obtained. The coating mode is gravure roll coating.
Example 3
Based on example 2, the difference from example 2 is that the ceramic material in S1 is montmorillonite and boehmite mixed according to a ratio of 1:1 and then ground.
Example 4
Based on example 2, the difference from example 2 is that the ceramic material in S1 is boehmite.
Example 5
Based on example 2, the difference from example 2 is that the base film in S1 is a PP separator.
Example 6
Based on example 2, the difference from example 2 is that the binder in S2 is PAA.
Comparative example 1
Is a common PE separator.
Performance testing
The SEM images of the diaphragms prepared in the embodiment 2 and the comparative example 1 are shot by using a scanning electron microscope, wherein fig. 1 is the SEM image of the diaphragms prepared in the embodiment 2, fig. 2 is the SEM image of the diaphragms prepared in the comparative example 1, as shown in fig. 1-2, the ordinary diaphragms are uneven in stress on the surfaces of the diaphragms due to uneven pulling force in the preparation process, a large number of cracks are generated, the cracks seriously affect the puncture strength and the tensile strength of the diaphragms, after the ceramic coating and the polymer coating are modified on the surfaces of the ordinary PE diaphragms in the embodiment 2, the cracks on the surfaces of the base films are covered by the ceramic particles and the polymer particles, the tensile strength and the puncture strength of the diaphragms are obviously improved, and as can be seen from fig. 1, the ceramic particles and the polymer pellets are uniformly distributed on the surfaces of the base films, and the ceramic solution and the adhesive layer solution on the surfaces of the diaphragms are uniformly coated.
The separators of example 2 and comparative example 1 of the present invention were assembled into a metal battery by the following specific assembly method:
According to the positive electrode active material (sodium vanadium phosphate): conductive carbon black: mixing the binder PVDF=8:1:1 in a mass ratio, mixing slurry by using NMP as a solvent, coating the slurry on an aluminum foil, and carrying out vacuum drying at 90 ℃ to obtain a positive electrode plate;
and then the negative electrode current collector (aluminum foil), the positive electrode plate, the electrolyte (1 mol/L NaPF 6) and the obtained separator are assembled into a battery.
The obtained battery is subjected to impedance test at 25+/-2 ℃ with a charge-discharge current of 1 ℃ for 2 hours in a single step and circulated for 2000 weeks, and the electrochemical properties of the battery are respectively tested. The test results are shown in fig. 3-4.
Fig. 3 is a polarization current diagram of a membrane prepared in example 2 of the present invention, and fig. 4 is a polarization current diagram of a common PE membrane in comparative example 1 of the present invention, as shown in fig. 3 to 4, the polarization current of the membrane prepared in example 2 is 5.75 μa, and the polarization current of the common PE membrane in comparative example 1 is 6.4 μa, and the polarization current of example 2 is significantly smaller than that of the common PE membrane, because the polymer coating on the surface of the membrane prepared in example 2 has cohesiveness, the aluminum foil in the battery can be bonded with the membrane, so that the solvent molecules in the electrolyte are prevented from being irreversibly reduced, resulting in excessively high deposition rate of sodium ions on the surface of the aluminum foil, generating sodium dendrites, and increasing the internal resistance of the cell, so that the membrane for enhancing the interface stability of the negative-electrode-free sodium metal battery in example 2 is significantly higher than that of the common PE membrane.
In conclusion, the coating is arranged on the surface of the base film of the battery diaphragm capable of inhibiting the growth of the sodium dendrite, and the mechanical strength of the diaphragm and the deposition stability of sodium ions on the surface of the aluminum foil can be effectively improved through the combined action of the base film, the ceramic coating and the high polymer coating, so that the adhesion effect of the diaphragm and the aluminum foil is improved, the service performance of the diaphragm is improved, the internal resistance of the battery is reduced, and the cycle performance is improved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (10)
1. A battery separator capable of inhibiting sodium dendrite growth, characterized by: the ceramic coating comprises a base film, a ceramic coating coated on the surface of the base film and a high polymer coating coated on the surface of the ceramic coating;
Wherein the base film is one of PE, PP, PET, PI and cellulose base film; the ceramic coating comprises a ceramic material and a solvent I; the high polymer coating comprises a binder and a solvent II, wherein the binder comprises one or more of sodium carboxymethyl cellulose and PAA, PMMA, PVDF.
2. A battery separator capable of inhibiting sodium dendrite growth as recited in claim 1, wherein: the thickness of the base film is 5-25 mu m, the thickness of the ceramic coating is 0.1-4 mu m, and the thickness of the polymer coating is 0.1-4 mu m.
3. A battery separator capable of inhibiting sodium dendrite growth as recited in claim 1, wherein: the base film has a breathable value of 70-200sec/100cc.
4. A battery separator capable of inhibiting sodium dendrite growth as recited in claim 1, wherein: the ceramic material comprises one or more of montmorillonite, boehmite, kaolin and hydroxyapatite.
5. A battery separator capable of inhibiting sodium dendrite growth as recited in claim 1, wherein: the solvent I comprises one or more of pure water and absolute ethyl alcohol, and the mass ratio of the ceramic material to the solvent I is 1-50: 1-100.
6. A battery separator capable of inhibiting sodium dendrite growth as recited in claim 1, wherein: the second solvent comprises pure water, and the mass ratio of the binder to the second solvent is 1-100: 1-100.
7. A method for preparing the battery separator capable of inhibiting the growth of sodium dendrites according to any one of claims 1 to 6, comprising the following steps:
s1, uniformly mixing a ceramic material and a solvent I to obtain a ceramic solution, completely coating the ceramic solution on the surface of a base film, and vacuum drying to obtain a ceramic coating;
S2, mixing the binder and the solvent II to obtain a polymer solution, coating the polymer solution on the surface of the ceramic coating, and vacuum drying to obtain the polymer coating.
8. The method for preparing a battery separator capable of inhibiting the growth of sodium dendrites according to claim 7, wherein the method comprises the steps of: the vacuum drying temperature in S1 and S2 is 30-60 ℃.
9. The method for preparing a battery separator capable of inhibiting the growth of sodium dendrites according to claim 7, wherein the method comprises the steps of: in S1, the ceramic coating is uniformly coated on one side of the base film.
10. Use of a battery separator according to any one of claims 1 to 6 for inhibiting the growth of sodium dendrites, characterized in that: the method is applied to the separator of the non-negative sodium metal battery.
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| CN202410366065.1A CN117977115A (en) | 2024-03-28 | 2024-03-28 | Battery diaphragm capable of inhibiting growth of sodium dendrite and preparation method and application thereof |
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| CN116031467A (en) * | 2023-02-21 | 2023-04-28 | 中国科学院长春应用化学研究所 | Pole-simple high specific energy battery without negative electrode |
| CN117747845A (en) * | 2023-12-08 | 2024-03-22 | 深圳珈钠能源科技有限公司 | Sodium metal battery |
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| CN207611805U (en) * | 2017-12-27 | 2018-07-13 | 株洲市海达新特材料有限公司 | A kind of lithium manganate battery diaphragm |
| KR20190110288A (en) * | 2018-03-20 | 2019-09-30 | 주식회사 제라브리드 | Manufacturing method of separator for secondary battery |
| WO2020094090A1 (en) * | 2018-11-09 | 2020-05-14 | 苏州迪思伏新能源科技有限公司 | Ion-selective composite separator, method for preparing same, and application of same |
| CN115863920A (en) * | 2022-12-30 | 2023-03-28 | 湖州南木纳米科技有限公司 | Composite coating diaphragm and preparation method thereof |
| CN116031467A (en) * | 2023-02-21 | 2023-04-28 | 中国科学院长春应用化学研究所 | Pole-simple high specific energy battery without negative electrode |
| CN117747845A (en) * | 2023-12-08 | 2024-03-22 | 深圳珈钠能源科技有限公司 | Sodium metal battery |
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