CN114914628A - Flame-retardant battery diaphragm coating material capable of inhibiting dendritic crystal growth, preparation method and application of flame-retardant battery diaphragm coating material in double-layer composite diaphragm - Google Patents
Flame-retardant battery diaphragm coating material capable of inhibiting dendritic crystal growth, preparation method and application of flame-retardant battery diaphragm coating material in double-layer composite diaphragm Download PDFInfo
- Publication number
- CN114914628A CN114914628A CN202210228606.5A CN202210228606A CN114914628A CN 114914628 A CN114914628 A CN 114914628A CN 202210228606 A CN202210228606 A CN 202210228606A CN 114914628 A CN114914628 A CN 114914628A
- Authority
- CN
- China
- Prior art keywords
- coating material
- phosphonic acid
- flame
- battery
- layer composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 65
- 238000000576 coating method Methods 0.000 title claims abstract description 55
- 239000011248 coating agent Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 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 title claims abstract description 21
- 239000003063 flame retardant Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000013078 crystal Substances 0.000 title claims abstract description 10
- 230000012010 growth Effects 0.000 title claims abstract description 10
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 9
- -1 triazine organic compound Chemical class 0.000 claims abstract description 22
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000002033 PVDF binder Substances 0.000 claims description 18
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- ROBVLQBZPQQRTQ-UHFFFAOYSA-N [N].C1=CN=NN=C1 Chemical compound [N].C1=CN=NN=C1 ROBVLQBZPQQRTQ-UHFFFAOYSA-N 0.000 claims description 10
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 8
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 7
- 229940120146 EDTMP Drugs 0.000 claims description 6
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 3
- 229940068041 phytic acid Drugs 0.000 claims description 3
- 235000002949 phytic acid Nutrition 0.000 claims description 3
- 239000000467 phytic acid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 14
- 238000000151 deposition Methods 0.000 abstract description 12
- 230000008021 deposition Effects 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 239000012528 membrane Substances 0.000 abstract description 9
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 230000000149 penetrating effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- 239000010410 layer Substances 0.000 description 23
- WJXSXWBOZMVFPJ-NENRSDFPSA-N N-[(2R,3R,4R,5S,6R)-4,5-dihydroxy-6-methoxy-2,4-dimethyloxan-3-yl]-N-methylacetamide Chemical compound CO[C@@H]1O[C@H](C)[C@@H](N(C)C(C)=O)[C@@](C)(O)[C@@H]1O WJXSXWBOZMVFPJ-NENRSDFPSA-N 0.000 description 16
- 241000718541 Tetragastris balsamifera Species 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 210000004379 membrane Anatomy 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- XXONZJKORUUFIZ-UHFFFAOYSA-N 3-sulfanylpyridine-2-sulfonamide Chemical compound NS(=O)(=O)C1=NC=CC=C1S XXONZJKORUUFIZ-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 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 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000755 effect on ion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004222 uncontrolled growth Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
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
-
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a flame-retardant battery diaphragm coating material capable of inhibiting dendritic crystal growth, a preparation method and application of the flame-retardant battery diaphragm coating material for a double-layer composite diaphragm, wherein the flame-retardant battery diaphragm coating material is used for the double-layer composite diaphragm according to a polar group-NH 2 and-H 2 PO 3 Weighing triazine organic compound containing nitrogen heterocycle and organic phosphonic acid respectively according to the molar ratio of 1:1 or 2:1, completely dissolving the triazine organic compound containing nitrogen heterocycle and the organic phosphonic acid in deionized water, dropwise mixing the triazine organic compound containing nitrogen heterocycle and the organic phosphonic acid, stirring the mixture in the whole process, filtering, cleaning, drying and grinding the generated white precipitate to obtain the triazine organic phosphonic acid compound containing nitrogen heterocycleAnd (4) coating the material. The prize cover coating material is coated on PP and other base films to form a double-layer composite diaphragm. The polar group in the separator can react with Li + The lithium ion composite material is combined and can be used as a lithium ion membrane penetrating channel, so that the uniform deposition of lithium ions on the surface of lithium metal is promoted, dendrites are inhibited, and excellent electrical properties are represented. The flame retardancy is also improved.
Description
Technical Field
The invention belongs to the field of preparation of materials related to battery diaphragms, and particularly relates to a diaphragm coating material, a preparation method and preparation application of a corresponding double-layer composite diaphragm.
Background
The development of power batteries prompts the increasing demand of the industry on batteries with high energy density, and the development trend of lithium ion batteries is to face the directions of high specific capacity, higher power, high charge and discharge efficiency, high cycle performance, lower cost and the like. But at the same time the safety problem of the battery with high energy density has been troubling the industry development. In particular, the spontaneous combustion event of the new energy automobile is frequently reported. Data show that the safety problem of new energy automobile is most relevant with the battery, and battery ageing or short circuit are one of the cause of danger, because the high flammability of the inside electrolyte of battery, when the battery takes place the short circuit, and the electrolyte burns and causes danger.
The separator serves as one of the most important components of the battery, and serves to isolate the positive and negative electrodes and prevent short circuits, and has only ionic conductivity but no electronic conductivity. The safety of the battery is greatly dependent on the stability and safety of the separator. At present, most of the widely used separators are prepared by drawing polyolefin resins (PP, PE and the like) through a wet method or a dry method, although the separators have the advantages of high strength and high porosity, the application of the separators is limited by the defects of low liquid absorption rate and poor thermal stability (the melting point is less than or equal to 160 ℃) which are easy to thermally lose control, and lithium ion batteries are mostly exploded due to short circuit caused by poor heat resistance of the separators.
In summary, in lithium ion batteries or lithium metal batteries, for example, the graphite negative electrode or the metal negative electrode surface is used in repeated or high-power charging and discharging applications due to Li + The non-uniform deposition and the increasingly strong tip effect influence, the dendrite can gradually grow and finally pierce through the diaphragm, the metal lithium reacts with various substances in the electrolyte to generate a brittle SEI film, after long circulation, the SEI film can be repeatedly cracked and formed to cause irreversible loss of anode metal, the CE is obviously reduced, the practical application of the lithium metal anode is limited to a great extent, and meanwhile, the dendrite pierces through the diaphragm to generate potential safety hazards. Taking into account Li + Has a high electronegativity, the present invention is directed to coating a surface of a commercial separator with a coatingSelf-assembled supramolecular materials with Li regulation by polar groups contained in the molecules + While the material has significant flame retardant properties, the high flame retardancy of the separator reduces the risk and severity of the accident when short-circuited by puncture.
Disclosure of Invention
Based on the background technology, the invention provides a flame-retardant battery diaphragm coating material capable of inhibiting dendritic crystal growth, a preparation method and an application of the flame-retardant battery diaphragm coating material in a double-layer composite diaphragm, wherein the battery diaphragm coating material can influence the uniform deposition of metal ions and has flame retardance; the method is applied to inhibiting the uncontrolled growth of dendritic crystals on the surface of a negative electrode material in various batteries during charge-discharge circulation, so that the service life of the battery is prolonged, and meanwhile, the self flame retardant property of the diaphragm can be improved when the battery is out of control due to heat, so that the overall safety of the battery is improved.
The preparation method of the flame-retardant battery diaphragm coating material capable of inhibiting dendritic crystal growth is characterized by comprising the following steps of:
according to the polar group-NH 2 and-H 2 PO 3 Weighing triazine nitrogen-containing heterocyclic organic compounds and organic phosphonic acid according to a molar ratio of 1:1 or 2:1 respectively, completely dissolving the triazine nitrogen-containing heterocyclic organic compounds and the organic phosphonic acid in deionized water to obtain a solution A, B, then mixing the triazine nitrogen-containing heterocyclic organic compounds and the organic phosphonic acid drop by drop and stirring the two solutions in the whole process, generating white precipitates immediately in the solution, standing, filtering, washing, drying, cooling and grinding into powder.
Further, the organic phosphonic acid is one of aminotrimethylene phosphonic acid, phytic acid, ethylene diamine tetra methylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid and diethylene triamine pentamethylene phosphonic acid.
Further, the triazine nitrogen-containing heterocyclic organic compound is melamine.
Further, the drying temperature is 50-80 ℃.
Further, graphene oxide is added into the solution A, the solution A is subjected to full ultrasonic dispersion, and then the solution A is mixed with the solution B, and the graphene oxide and the generated white precipitate are deposited together.
Furthermore, the mass ratio of the added amount of the graphene oxide to the triazine nitrogen-containing heterocyclic organic compound is 1: 25.
The flame-retardant battery diaphragm coating material capable of inhibiting dendritic crystal growth is prepared by the preparation method.
The flame-retardant battery diaphragm coating material capable of inhibiting dendritic crystal growth is applied to a double-layer composite diaphragm and is characterized in that battery diaphragm coating material powder is weighed, polyvinylidene fluoride (PVDF) adhesive solution with N-methyl pyrrolidone as a solvent is dripped into the battery diaphragm coating material powder, the mass ratio of the battery diaphragm coating material powder to the PVDF is 8:2, the battery diaphragm coating material powder and the PVDF are magnetically stirred for more than 2 hours, the battery diaphragm coating material powder and the PVDF are coated on one side of a base film by a wet film preparation device, and the base film is dried in vacuum.
Further, the basement membrane is a PP, PE or sodium electric glass fiber diaphragm.
The double-layer composite diaphragm made of the battery diaphragm coating material is characterized in that the diaphragm coating material is coated on a base film, and the thickness of the diaphragm coating material is 30-100 mu m.
The doping of hetero atoms will affect the ion transfer deposition effectively, for example, the negative electrode of lithium metal battery, and the action mode is two: forming electronegative sites (doping atoms or adjacent carbon atoms) to interact with Lewis acid Li +; secondly, a strong local dipole is formed, a strong ion dipole force is generated, Li + is absorbed, an induced dipole is generated, and the binding energy is further increased. B. N, O single doping and O-B/S/P co-doping have three key factors of excellent lithium affinity: electronegativity, local dipole and charge transfer, while lithium affinity will directly affect ion deposition.
Triazine nitrogen heterocyclic ring-containing organic compounds and organic phosphonic acid are common industrial raw materials, molecules of the triazine nitrogen heterocyclic ring-containing organic compounds and organic phosphonic acid respectively contain-H2 PO3 in-NH 2, and most of the triazine nitrogen heterocyclic ring-containing organic compounds and the organic phosphonic acid can interact to form an ionic bond structure in a normal-temperature aqueous solution to generate an insoluble self-assembled supramolecular material. The coating material for the synthetic battery diaphragm is uniformly distributed with more polar group structures, the polar groups contain a large amount of N, O, P, C and other elements, the electronegativity of heteroatoms can be combined with Li < + > with smaller electronegativity (0.98V), and the heteroatoms can be used as a lithium ion film penetrating channel, so that lithium ions are promoted to be uniformly deposited on the surface of lithium metal, the growth of dendrites is inhibited, a stable lithium metal interface is constructed, positive response is generated, and the serious influence of the dendrites on the battery performance is avoided.
The functional porous double-layer composite membrane is coated on the surface of a commercial membrane, such as PP, PE and the like, so as to form the functional porous double-layer composite membrane. The interaction between the polar groups and Li + can guide the uniform deposition of Li + on the surface of the lithium metal cathode, the homogeneous and rapid lithium ion flux at the molecular level is realized on the surface of the electrode through the porous double-layer composite diaphragm, and the gaps among the stacked 2D molecular brushes provide rapid channels for the diffusion of electrolyte, so that the effects of prolonging the service life of the electrode at higher current density, improving the coulomb efficiency of the battery and the like are achieved. And the prepared coating material is of a sheet structure and has a large specific surface area, which is beneficial to exposing a large amount of polar groups in material molecules and achieving the effect of regulating and controlling Li < + > ordered deposition. Meanwhile, an N-P ionic bond is formed in the battery diaphragm coating material, and an N-P compound has a good flame-retardant and good flame-retardant effect, is small in smoke amount, can be self-extinguished, and does not generate harmful gas, so that the flame-retardant property of the battery diaphragm coating material is improved; compared with PP, the thermal stability of the double-layer composite diaphragm is improved. In addition, the addition of graphene oxide will improve the mechanical strength of the material.
The preparation method is simple, easy to control and low in cost, and test results show that compared with a blank control group, the preparation method can effectively regulate and control the uniform deposition of lithium ions through self polar groups, and the diaphragm coated by the material has excellent performance no matter impedance and polarization potential. In terms of flame retardant performance, the diaphragm does not burn or smoke, has small thermal shrinkage and high flame retardance, and can be considered to be applied to high-energy-density batteries such as lithium metal batteries.
Drawings
FIG. 1 is an X-ray diffraction pattern of MASA, GO-MASA powders prepared according to examples 1 and 2 of the present invention.
FIG. 2 is SEM images of a two-layer composite membrane prepared from (a) MASA powder and (b) MASA powder and PP prepared in example 1 of the present invention.
In fig. 3, (a), (b), and (c) are SEM images of PP, a bi-layer composite separator formed by coating the GO-MASA powder prepared in example 2 on the surface of a battery separator prepared in PP, and a bonding interface of the GO-MASA coating layer and PP, respectively.
FIG. 4 is a TG and DSC plots of PP, and a two-layer composite separator made of MASA, GO-MASA powder prepared in examples 1 and 2 and PP.
FIG. 5 (a), (b) and (c) are combustion process diagrams of PP, MASA prepared in example 1 and example 2, GO-MASA powder and PP prepared two-layer composite separator.
FIG. 6 shows the contact angle test of the electrolyte and the double-layer composite separator made of PP, MASA and GO-MASA powder prepared in example 1 and example 2 and PP.
FIG. 7 is a diagram of the polarization potential of a symmetrical cell for PP, MASA prepared in examples 1 and 2, GO-MASA powder and PP made double layer composite separator.
FIG. 8 is an SEM image of MESA, GO-MESA powders prepared in examples 3 and 4.
FIG. 9 is an EIS map of MESA, GO-MESA powders prepared in example 3, example 4.
Fig. 10 is an XRD pattern of the MESA, GO-MESA powders prepared in examples 5, 6.
FIG. 11 is an SEM image of MESA, GO-MESA powders prepared in example 5 and example 6.
FIG. 12 is a graph comparing EIS of MESA, GO-MESA powders prepared in example 5 and example 6 with PP.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings and specific embodiments.
Example 1
0.5046g of melamine was weighed at room temperature and dissolved in 100ml of deionized water, and the solution was stirred magnetically until completely dissolved to give solution A. 0.5981g of aminotrimethylene phosphonic Acid (ATMP) were weighed out and dissolved in 100ml of deionized water to give solution B.
A, B and stirring the two solutions in the whole process, immediately generating white precipitate after mixing, stirring for about 30min, filtering the generated precipitate, respectively washing with deionized water and ethanol, drying at 70 ℃, cooling and grinding into powder to obtain the high-flame-retardancy battery diaphragm coating material, referred to as MASA for short.
Example 2
Weighing 0.5046g of melamine at normal temperature, dissolving in 100ml of deionized water, and magnetically stirring until the melamine is completely dissolved to obtain a solution A; and weighing 20mg of high-purity graphene oxide, adding the high-purity graphene oxide into the solution A, and performing ultrasonic dispersion. 0.5981g of aminotrimethylene phosphonic Acid (ATMP) were weighed out and dissolved in 100ml of deionized water to give solution B.
A, B the two solutions were mixed drop by drop with stirring all the way, and a white precipitate formed immediately after mixing, and was stirred for about 30 min. And filtering the generated precipitate, washing with deionized water and ethanol respectively, drying at 70 ℃, cooling and grinding into powder to obtain the high-flame-retardancy battery diaphragm coating material of the graphite framework material, namely GO-MASA.
FIG. 1 shows the XRD patterns of MASA and GO-MASA prepared in examples 1 and 2, and it can be seen that the characteristic MASA peaks do not overlap with melamine and amino trimethylene phosphonic Acid (ATMP) obviously, and the patterns are not simply added but react with each other to form chemical bonds, and the XRD patterns show unique characteristic peak patterns. And the addition of the graphene oxide has no obvious influence on the formation of a new phase.
The MASA prepared in example 1 and example 2 and the GO-MASA are weighed respectively to prepare the double-layer composite diaphragm, and the specific method is as follows:
80mg of the battery separator coating material powder was weighed, a polyvinylidene fluoride (PVDF) binder solution (containing 20mg of PVDF powder) using N-methylpyrrolidone as a solvent was dropped in the battery separator coating material powder, and the amount of the polyvinylidene fluoride (PVDF) binder solution added was 8:2 in terms of the mass ratio of the battery separator coating material powder to the polyvinylidene fluoride (PVDF). Magnetically stirring for more than 2h, coating on one side of a PP diaphragm by using a wet film preparation device, wherein the coating thickness is 50 mu m, and finally drying in vacuum.
In FIG. 2, (a) and (b) are SEM images of MASA powder prepared in example 1 and a two-layer composite separator prepared by using the MASA powder and PP, respectively. In FIG. 3, (a), (b) and (c) are PP and examples2 coating the GO-MASA powder on the surface of a battery diaphragm prepared from PP to form a double-layer composite diaphragm, and taking an SEM image of the combination interface of the GO-MASA coating layer and the PP. FIG. 4 is a TG and DSC plots of PP, and a two-layer composite separator made of MASA, GO-MASA powder prepared in examples 1 and 2 and PP. The sheet-shaped micro-morphology of MASA and GO-MASA enables the material to have a larger specific surface area, which is beneficial to exposing a large amount of polar groups in material molecules to achieve regulation and control of Li + Ordered deposition. Compared with PP, the thermal stability of the double-layer composite diaphragm is improved.
From the combustion experiment shown in fig. 5, it can be seen that the MASA @ PP double-layer composite membrane has the best flame retardant performance compared with the PP membrane, and is self-generated and non-combustible, and is not fuming like the GO-MASA @ PP double-layer composite membrane, and the thermal deformation time is relatively long, and the mechanical strength of the membrane is high due to the existence of a small amount of graphite in the latter.
Meanwhile, FIG. 6 shows that the MASA and GO-MASA coatings enhance the wettability of the electrolyte and the diaphragm and make a positive response for rapid battery wetting and reduction of ion conduction resistance. As shown in FIG. 7, the prepared sample is coated on one side of a commercial PP diaphragm, a symmetrical battery which uses a lithium metal sheet as an auxiliary electrode and a reference electrode at the same time is assembled, and the charge and discharge test result shows that the polarization potential of the battery after being stabilized is only 20mV at least, and the battery can be stably cycled for 1500h without being damaged.
Example 3
According to the proportion of 1:1 of amino and phosphonic acid groups, 0.5046g of melamine, namely 0.004mol, and 1.31g of ethylenediamine tetramethylene phosphonic acid (EDTMPA), namely 0.003mol, are respectively dissolved in 100ml of deionized water to obtain corresponding solutions, the two solutions are mixed and stirred vigorously for about 30min, filter residues are obtained by filtration, the filter residues are washed by deionized water and ethanol for 2-3 times respectively, and the new sample MESA can be obtained by drying at 70 ℃.
Example 4
0.5046g of melamine, namely 0.004mol, and 1.31g of ethylene diamine tetramethylene phosphonic acid (EDTMPA), namely 0.003mol, are weighed according to the proportion of 1:1 of amino groups and phosphonic acid groups and are respectively dissolved in 100ml of deionized water to obtain corresponding solutions, meanwhile, graphene oxide is added into the melamine solution according to the mass proportion of 25:1 of solute and is fully ultrasonically dispersed, then the two solutions are mixed and are vigorously stirred for about 30min, filter residues are obtained by filtration and are filtered, then the two solutions are respectively washed for 2-3 times by deionized water and ethanol, and the new sample GO-MESA can be obtained by drying at 70 ℃.
From the SEM images of the MESA and GO-MESA powders prepared in the embodiments 3 and 4 in the (a) and (b) in the figure 8, respectively, the flaky micro-morphology enables the material to have a larger specific surface area, which is beneficial to exposing a large amount of polar groups in the material molecules, so as to regulate and control Li + Ordered deposition. The prepared sample is coated on one side of a commercial PP diaphragm to be used as a double-layer composite diaphragm, a symmetric battery which uses a lithium metal sheet as an auxiliary electrode and a reference electrode at the same time is assembled, and fig. 9 is an impedance test curve of the sample assembled battery.
Example 5
At normal temperature, 0.5046g of melamine, namely 0.004mol, is weighed according to the proportion of 1:1 of amino groups and phosphonic acid groups and dissolved in 100ml of deionized water to obtain clear and transparent solution, 2.06ml of 50 wt.% phytic acid solution, namely 0.002mol, is weighed at the same time, the solution is continuously stirred, the phytic acid solution is dripped into the melamine solution drop by drop, a large amount of whitish precipitate is generated in the solution, the solution is continuously stirred for about 30min, then the solution is filtered, filter residues are respectively washed for 2-3 times by deionized water and ethanol, and the MPSA powder is obtained by drying at 70 ℃.
Example 6
Weighing 0.5046g of melamine, namely 0.004mol, according to the proportion of 1:1 of amino groups and phosphonic acid groups at normal temperature, dissolving the melamine in 200ml of deionized water, simultaneously weighing 20mg of graphene oxide, ultrasonically dispersing the graphene oxide in the solution, weighing 2.06ml of 50 w% phytic acid solution, namely 0.002mol, continuously stirring the solution, dropwise adding the phytic acid solution into the melamine solution, stirring for 30min to generate a whitish precipitate in the solution, co-depositing the precipitate and the graphene in a beaker, filtering the generated precipitate, washing the precipitate with deionized water and ethanol respectively, and drying at 70 ℃ to obtain the GO-MPSA based on the graphite framework material.
FIG. 10 is an XRD diagram of MPSA and GO-MPSA prepared in examples 5 and 6, which also shows that precipitates in the solution are not simple addition of melamine and phytic acid molecules but generate new phases, FIG. 11 is an SEM micro-morphology diagram of MPSA and GO-MPSA prepared in examples 5 and 6, the two-dimensional sheet material has large specific surface area, and the function of the two-dimensional sheet material is greatly influenced by the large exposure of polar groups, so that the two-dimensional sheet material has the function of resisting Li + Micro-regulation of transport and deposition, inhibition of lithium dendrite overgrowth, and the like. The impedance plot of fig. 12 also shows its effect on ion transport resistance.
The test result shows that the self-assembled supermolecule material not only can effectively inhibit dendritic crystal growth and greatly prolong the service life of the battery, but also has obvious advantages in the aspect of flame retardant property.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. The preparation method of the flame-retardant battery diaphragm coating material capable of inhibiting dendritic crystal growth is characterized by comprising the following steps of:
according to the polar group-NH 2 and-H 2 PO 3 Weighing triazine nitrogen-containing heterocyclic organic compounds and organic phosphonic acid according to a molar ratio of 1:1 or 2:1 respectively, completely dissolving the triazine nitrogen-containing heterocyclic organic compounds and the organic phosphonic acid in deionized water to obtain a solution A, B, then mixing the triazine nitrogen-containing heterocyclic organic compounds and the organic phosphonic acid drop by drop and stirring the two solutions in the whole process, generating white precipitates immediately in the solution, standing, filtering, washing, drying, cooling and grinding into powder.
2. The method for preparing a battery separator coating material according to claim 1, wherein the organic phosphonic acid is one of aminotrimethylene phosphonic acid, phytic acid, ethylenediamine tetramethylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid.
3. The method for preparing the battery separator coating material according to claim 1, wherein the triazine nitrogen-containing heterocyclic organic compound is melamine.
4. The method for preparing a battery separator coating material according to claim 1, wherein the drying temperature is 50-80 ℃.
5. The method for preparing a battery separator coating material according to any one of claims 1 to 4, wherein graphene oxide is added to the solution A, sufficiently dispersed by ultrasonic waves, and then mixed with the solution B, and the graphene oxide is deposited together with the generated white precipitate.
6. The preparation method of the battery separator coating material according to claim 5, wherein the mass ratio of the added amount of graphene oxide to the triazine nitrogen-containing heterocyclic ring organic compound is 1: 25.
7. A battery separator coating material prepared according to the preparation method of any one of claims 1 to 6.
8. The application of the battery diaphragm coating material in a double-layer composite diaphragm as claimed in claim 7, characterized in that the battery diaphragm coating material powder is weighed, a polyvinylidene fluoride (PVDF) adhesive solution using N-methyl pyrrolidone as a solvent is dropped in, wherein the mass ratio of the battery diaphragm coating material powder to the polyvinylidene fluoride (PVDF) is 8:2, the battery diaphragm coating material powder and the polyvinylidene fluoride (PVDF) are magnetically stirred for more than 2 hours, and the battery diaphragm coating material is coated on one side of a base film by using a coating device and dried in vacuum.
9. The use of the battery separator coating material according to claim 8 for a two-layer composite separator, wherein the base film is a PP, PE or soda-glass fiber-based separator.
10. The two-layer composite separator made of the battery separator coating material according to claim 7, wherein the separator coating material is coated on the base film to a thickness of 30 to 100 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210228606.5A CN114914628B (en) | 2022-02-11 | Flame-retardant battery diaphragm coating material capable of inhibiting dendrite growth, preparation method and application of flame-retardant battery diaphragm coating material to double-layer composite diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210228606.5A CN114914628B (en) | 2022-02-11 | Flame-retardant battery diaphragm coating material capable of inhibiting dendrite growth, preparation method and application of flame-retardant battery diaphragm coating material to double-layer composite diaphragm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114914628A true CN114914628A (en) | 2022-08-16 |
| CN114914628B CN114914628B (en) | 2024-06-07 |
Family
ID=
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497041A (en) * | 2014-12-09 | 2015-04-08 | 东华大学 | Melamine aminotrimethylene phosphonate and preparation method thereof |
| CN105576173A (en) * | 2015-12-16 | 2016-05-11 | 安徽壹石通材料科技股份有限公司 | Preparation method and application of ceramic coating material |
| CN110922518A (en) * | 2019-11-30 | 2020-03-27 | 华东理工大学 | Water-resistant intumescent flame retardant and preparation method and application thereof |
| CN111697188A (en) * | 2020-06-23 | 2020-09-22 | 南京理工大学 | Lithium-sulfur battery interlayer with flame retardant property and preparation method thereof |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497041A (en) * | 2014-12-09 | 2015-04-08 | 东华大学 | Melamine aminotrimethylene phosphonate and preparation method thereof |
| CN105576173A (en) * | 2015-12-16 | 2016-05-11 | 安徽壹石通材料科技股份有限公司 | Preparation method and application of ceramic coating material |
| CN110922518A (en) * | 2019-11-30 | 2020-03-27 | 华东理工大学 | Water-resistant intumescent flame retardant and preparation method and application thereof |
| CN111697188A (en) * | 2020-06-23 | 2020-09-22 | 南京理工大学 | Lithium-sulfur battery interlayer with flame retardant property and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108281705B (en) | Modified nano SiO2Particles, method of preparing the same, and nanofiber membrane, gel electrolyte and lithium metal battery comprising the same | |
| CN111403693B (en) | Negative active material, and negative electrode sheet, electrochemical device, and electronic device using same | |
| KR20140014189A (en) | Manufacturing of high capacity prismatic lithium-ion alloy anodes | |
| KR20100129471A (en) | Organic/inorganic composite separator for electrochemical cell and electrochemical cell including the same | |
| CN112670543B (en) | Composite solid electrolyte membrane based on hollow MOF (metal organic framework) and preparation method and application thereof | |
| CN112635698B (en) | Negative pole piece of zinc secondary battery and preparation method and application thereof | |
| CN112670450A (en) | Negative pole piece for solid-state battery and preparation method and application thereof | |
| WO2014065082A1 (en) | Carbon material for positive electrode of lithium air battery and lithium air battery | |
| CN114171786A (en) | Garnet type solid electrolyte with three-dimensional cross-linking modification layer and preparation method and application thereof | |
| JP5474596B2 (en) | Power storage device | |
| CN116190633B (en) | Layered oxide positive electrode material, preparation method thereof, positive electrode composition, sodium ion secondary battery and application | |
| Ju et al. | Robust zinc anode modification layer with hydrophobic-cation selectivity for stabilized aqueous zinc ion batteries | |
| CN116231067B (en) | Preparation method of flame-retardant ultrathin PEO-based solid electrolyte | |
| CN114270564A (en) | Lithium secondary battery | |
| Tang et al. | Dendrite‐Free Lithium Metal Batteries Enabled by Coordination Chemistry in Polymer‐Ceramic Modified Separators | |
| CN114914628B (en) | Flame-retardant battery diaphragm coating material capable of inhibiting dendrite growth, preparation method and application of flame-retardant battery diaphragm coating material to double-layer composite diaphragm | |
| CN114914628A (en) | Flame-retardant battery diaphragm coating material capable of inhibiting dendritic crystal growth, preparation method and application of flame-retardant battery diaphragm coating material in double-layer composite diaphragm | |
| US20220311044A1 (en) | Method of making composite polymer electrolyte for all solid-state lithium-ion battery | |
| CN113113723B (en) | Coating diaphragm and preparation method and application thereof | |
| JP5461463B2 (en) | Electrode active material, positive electrode for secondary battery equipped with the same, and secondary battery | |
| CN114262447A (en) | Two-dimensional covalent organic framework material with cation framework, preparation method and application thereof, and lithium metal battery electrode | |
| US20120044613A1 (en) | Electrolyte for lithium ion capacitor and lithium ion capacitor including the same | |
| CN108987803B (en) | Lithium metal negative electrode film-forming electrolyte for lithium-sulfur battery and additive thereof | |
| CN111499995A (en) | Polymer composite membrane and preparation method thereof, composite electrode plate and preparation method thereof, and lithium metal secondary battery | |
| WO2023012993A1 (en) | Paste-type electrode for proton conductive secondary battery and proton conductive secondary battery provided with same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |