CN113697789A - Carbon-coated sodium titanium phosphate composite material and preparation method of negative electrode plate - Google Patents
Carbon-coated sodium titanium phosphate composite material and preparation method of negative electrode plate Download PDFInfo
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- CN113697789A CN113697789A CN202110994571.1A CN202110994571A CN113697789A CN 113697789 A CN113697789 A CN 113697789A CN 202110994571 A CN202110994571 A CN 202110994571A CN 113697789 A CN113697789 A CN 113697789A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 111
- MJEPCYMIBBLUCJ-UHFFFAOYSA-K sodium titanium(4+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Na+] MJEPCYMIBBLUCJ-UHFFFAOYSA-K 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 239000011888 foil Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 18
- 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 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000006255 coating slurry Substances 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 239000006258 conductive agent Substances 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003292 glue Substances 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000019265 sodium DL-malate Nutrition 0.000 claims description 4
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 4
- 239000001394 sodium malate Substances 0.000 claims description 4
- 239000001433 sodium tartrate Substances 0.000 claims description 4
- 229960002167 sodium tartrate Drugs 0.000 claims description 4
- 235000011004 sodium tartrates Nutrition 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 235000011083 sodium citrates Nutrition 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005056 compaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010668 complexation reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000011345 viscous material Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229910019441 NaTi2(PO4)3 Inorganic materials 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H01M4/00—Electrodes
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- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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Abstract
The invention discloses a preparation method of a carbon-coated sodium titanium phosphate composite material and a negative pole piece; preparing a carbon-coated sodium titanium phosphate composite material: (1) adding a carbon source, a sodium source, a phosphorus source and a titanium source into a dispersing agent, and stirring to obtain slurry; (2) stirring and refluxing the slurry, removing part of the dispersing agent under reduced pressure, and drying to obtain a powdery precursor; (3) and pressing the precursor into a rough blank, calcining in an inert atmosphere, and cooling to obtain the carbon-coated sodium titanium phosphate composite material. Preparing a carbon-coated sodium titanium phosphate negative pole piece: s1, mixing the water-based conductive slurry, water-based glue and a solvent, adding a conductive agent and a carbon-coated sodium titanium phosphate composite material, and uniformly stirring to obtain water-based coating slurry; s2, coating the water system coating slurry on a hydrophobic carbon-coated aluminum foil, drying, compacting and slitting to obtain the carbon-coated sodium titanium phosphate negative electrode plate. The method of the invention has no emission of any harmful or corrosive gas, is a green and environment-friendly production process, and the used raw materials are common and cheap.
Description
Technical Field
The invention relates to the field of nano material technology and electrochemistry, in particular to a carbon-coated sodium titanium phosphate composite material and a preparation method of a carbon-coated sodium titanium phosphate negative pole piece.
Background
In the process of changing new and old energy forms, and utilizing and developing new energy, secondary batteries play an important role. At present, although lead-acid batteries and lithium-ion batteries are widely used in the fields of mobile power supplies, energy storage and the like, new battery systems are rapidly developed due to respective defects, and new water-based batteries are receiving attention.
Sodium titanium phosphate (NaTi) having NASICON structure2(PO4)3) The polyanion material has the advantages of high ion conductivity and high structural stability due to the three-dimensional polyanion framework. The sodium ion battery or the water system sodium ion battery cathode material can keep stable in the process of charging and discharging, and the volume change is almost zero. At present, the existing laboratory preparation technology such as a hydrothermal method or a sol-gel method is not suitable for large-scale production, and even if some technologies can realize large-scale production, the following problems also exist: firstly, almost all the technologies use decomposable phosphate such as ammonium dihydrogen phosphate or ammonium phosphate as a phosphorus source, so a large amount of corrosive harmful tail gas, namely ammonia gas, is generated, the generation of the ammonia gas not only increases the risk of environmental pollution, but also greatly increases the complexity of equipment and the production cost in the subsequent treatment; secondly, the prior more technologies adopt the processes of wet grinding and dispersing raw materials and then drying in the production process, and the prior spray drying technology needs to consume a large amount of energy; thirdly, although the phosphoric acid is cheap and the byproduct generated by decomposition is only water which is greenThe production concept of color, however, phosphoric acid itself is a viscous liquid, and cannot be prepared into a powdery precursor with other raw materials, so that the large-scale preparation of the titanium sodium phosphate cannot be realized by using phosphoric acid as a phosphorus source at present.
In the manufacturing process of the lithium ion battery pole piece, before coating, polyvinylidene fluoride (PVDF) is generally adopted as a binder, N-methyl pyrrolidone (NMP) is adopted as solvent slurry, N-methyl pyrrolidone is an organic solvent with certain toxicity, and the slurry mixing process and the coating process have extremely high requirements on humidity, so that the production cost is increased. The electrode plate prepared by the common aqueous colloidal solution cannot be applied to a battery taking an aqueous solution as an electrolyte, and when the electrode plate meets aqueous electrolyte again, the electrode plate expands to cause that active substances fall off from a current collector, so that the performance and the cycle life of the battery are influenced. Based on the defects, the invention provides a technical scheme for preparing the sodium titanium phosphate negative pole piece by taking the hydrophobic carbon-coated aluminum foil as a current collector and coating water-based slurry.
Disclosure of Invention
The invention aims to provide an environment-friendly preparation method of a carbon-coated sodium titanium phosphate composite material, and simultaneously provides a method for preparing a sodium titanium phosphate negative electrode plate by taking a hydrophobic carbon-coated aluminum foil as a current collector and coating water system slurry.
The invention is realized by the following technical scheme:
a preparation method of a carbon-coated sodium titanium phosphate composite material is characterized by comprising the following steps:
(1) adding a carbon source, a sodium source, a phosphorus source and a titanium source into a dispersing agent and uniformly stirring to obtain slurry;
(2) stirring and refluxing the slurry, removing part of the dispersing agent under reduced pressure, and then drying to obtain a powdery precursor;
(3) pressing the precursor into a rough blank, calcining in an inert atmosphere, and cooling to obtain the carbon-coated sodium titanium phosphate composite material (NaTi)2(PO4)3/C)。
Specifically, the inert atmosphere in the preparation process of the present invention is nitrogen, argon or argon-hydrogen (hydrogen content 5-10%).
In the preparation method, stirring reflux and decompression are key processes for removing the dispersing agent, reaction raw materials are not mixed and then are not subjected to a reflux process and a decompression process, a powdery precursor cannot be obtained by directly drying, a viscous material is obtained, a pure-phase sodium titanium phosphate product cannot be obtained after the viscous material is sintered, and a hardened ceramic-like solid is obtained. In the preparation process of the invention, if no carbon source is added into the raw materials, the corresponding sodium titanium phosphate (NaTi) can be obtained according to the difference of the used sodium source2(PO4)3) Or carbon-coated sodium titanium phosphate (NaTi)2(PO4)3C) products.
Further, the mass ratio of the carbon source, the sodium source, the phosphorus source and the titanium source in the step (1) is (1-2): (1.5-3): (4-7): (3.5-4); the mass volume ratio of the carbon source to the dispersing agent is 20-40 g/L.
Further, the carbon source in the step (1) is at least one selected from glucose, polyvinyl alcohol and carbon nanotubes; the sodium source is at least one selected from sodium dihydrogen phosphate, sodium carbonate, sodium bicarbonate, sodium citrate, sodium malate, sodium tartrate and disodium ethylene diamine tetraacetate; the phosphorus source is phosphoric acid; the titanium source is nano titanium dioxide or metatitanic acid with hydroxylated surface; the dispersant is pure water. Specifically, if no carbon source is added in the preparation process of the carbon-coated sodium titanium phosphate, the corresponding sodium titanium phosphate or carbon-coated sodium titanium phosphate product can be obtained according to the difference of the sodium source; when no carbon source is added in the preparation process, when the sodium source is inorganic sodium salt such as sodium dihydrogen phosphate, sodium carbonate or sodium bicarbonate and the like, the prepared product is the sodium titanium phosphate; when the sodium source is organic sodium salt such as sodium citrate, sodium malate, sodium tartrate or disodium ethylene diamine tetraacetate, the obtained product is carbon-coated titanium sodium phosphate, and the coating amount of carbon in the material prepared by the method is less.
Further, in the step (2), the slurry is stirred and refluxed for 3 to 12 hours at the temperature of 100 ℃ and 120 ℃, 50 to 70 percent of dispersing agent is removed by reduced pressure distillation, and then the slurry is transferred into a rake type vacuum drying machine and dried to obtain a powdery precursor.
Further, pressing the precursor into a rough blank in the step (3), then placing the rough blank in a tubular atmosphere furnace, introducing inert gas with the gas flow rate of 20-100mL/min, heating to 800-1000 ℃ at the speed of 2-5 ℃/min, calcining for 3-12 hours, cooling to room temperature, and stopping introducing gas to obtain the carbon-coated titanium sodium phosphate composite material.
According to the preparation method of the carbon-coated sodium titanium phosphate composite material, metatitanic acid and phosphoric acid with hydroxyl structures are refluxed at a high temperature, and react by utilizing the complexation of the hydroxyl groups to generate polyphosphoric acid and a polytitanium complex with strong complexation, and the phosphoric acid is sealed in a precursor with a solid structure, so that the large-scale preparation of the sodium titanium phosphate is realized.
A preparation method of a carbon-coated sodium titanium phosphate negative pole piece is characterized in that the carbon-coated sodium titanium phosphate composite material prepared by the preparation method is used as an active material of the negative pole piece, and the preparation method of the negative pole piece comprises the following steps:
s1, mixing the water-based conductive slurry, water-based glue and a solvent, then adding a conductive agent and the carbon-coated sodium titanium phosphate composite material, and uniformly stirring to obtain water-based coating slurry;
s2, coating the water system coating slurry on a hydrophobic carbon-coated aluminum foil, drying, compacting and slitting to obtain the carbon-coated sodium titanium phosphate negative electrode plate.
The carbon-coated sodium titanium phosphate negative electrode plate provided by the invention is prepared by taking a hydrophobic carbon-coated aluminum foil as a current collector and coating water-based slurry.
Further, step S1, adding the aqueous conductive slurry, the aqueous glue and the solvent into a homogenizer, stirring and dispersing for 0.5-4 hours, then adding the conductive agent and the carbon-coated sodium titanium phosphate composite material, stirring and dispersing for 0.5-4 hours, adjusting the solid content to 45-55%, and the viscosity to 4000-7000mPa · S, and obtaining the coating slurry.
Further, the water-based conductive slurry is 5-10 wt% of water-dispersible carbon nanotubes or 5-10 wt% of water-dispersible graphene; the water-based adhesive is at least one selected from water-dispersed polytetrafluoroethylene, water-dispersed acrylonitrile multipolymer and water-dispersed polyvinyl alcohol; the solvent is deionized water.
Further, in step S2, the compacted density is 2.2-2.4g/cm3。
Further, the preparation method of the hydrophobic carbon-coated aluminum foil in the step S2 includes: and uniformly mixing polytetrafluoroethylene, graphene and absolute ethyl alcohol, then coating the mixture on the carbon-coated aluminum foil, and drying to obtain the hydrophobic carbon-coated aluminum foil.
The invention has the beneficial effects that:
(1) the process for preparing the carbon-coated sodium titanium phosphate composite material provided by the invention has no emission of any harmful or corrosive gas, is an environment-friendly production process, and the raw materials used in the invention are common and cheap, and the adopted technical process conditions have simple requirements on equipment and simple process route. Based on the simple process route, the one-step preparation of the carbon-coated sodium titanium phosphate product is easily realized.
(2) The invention not only provides the technical scheme for preparing the cathode pole piece of the sodium titanium phosphate battery by using the low-cost hydrophobic carbon-coated aluminum foil as the current collector, but also is coated by using the water-based slurry, and the process route is green and environment-friendly.
(3) According to the preparation method of the carbon-coated sodium titanium phosphate composite material, metatitanic acid and phosphoric acid with hydroxyl structures are refluxed at a high temperature, and react by utilizing the complexation of the hydroxyl groups to generate polyphosphoric acid and a polytitanium complex with strong complexation, and the phosphoric acid is sealed in a precursor with a solid structure, so that the carbon-coated sodium titanium phosphate is finally prepared on a large scale.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a first-turn charge-discharge curve of a battery assembled in test example 1;
figure 2 is an XRD pattern of the materials prepared in examples 1-3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of sodium titanium phosphate comprises the following steps:
(1) 1450g of sodium dihydrogen phosphate (sodium source), 2250g of phosphoric acid (phosphorus source) and 1940g of metatitanic acid (titanium source) are added into 25L of deionized water (dispersing agent) and stirred uniformly to obtain slurry;
(2) stirring and refluxing the obtained slurry for 5 hours at 100 ℃, removing about 2/3 parts of deionized water under reduced pressure, transferring the slurry into a rake vacuum dryer, and drying to obtain a powdery precursor;
(3) pressing the obtained powdery precursor into a rough blank, then placing the rough blank in a tubular atmosphere furnace, introducing nitrogen, heating to 350 ℃ at the air flow rate of 50mL/min at the speed of 5 ℃/min, calcining for 2 hours, then heating to 800 ℃, preserving heat, calcining for 4 hours, cooling to room temperature, stopping introducing air, and obtaining a white product, namely sodium titanium phosphate (NaTi)2(PO4)3)。
Example 2
A preparation method of a carbon-coated sodium titanium phosphate composite material comprises the following steps:
(1) adding 900g of glucose (carbon source), 1450g of sodium dihydrogen phosphate (sodium source), 2250g of phosphoric acid (phosphorus source) and 1940g of metatitanic acid (titanium source) into 25L of deionized water (dispersing agent) and uniformly stirring to obtain slurry;
(2) stirring and refluxing the obtained slurry for 5 hours at 100 ℃, removing about 2/3 parts of deionized water under reduced pressure, transferring the slurry into a rake vacuum dryer, and drying to obtain a powdery precursor;
(3) pressing the obtained powdery precursor into a rough blank, then placing the rough blank in a tubular atmosphere furnace, introducing nitrogen, heating to 350 ℃ at the air flow rate of 50mL/min at the speed of 5 ℃/min, calcining for 2 hours, then heating to 800 ℃, preserving heat, calcining for 4 hours, cooling to room temperature, stopping introducing air, and obtaining a black powdery product, namely carbon-coated titanium sodium phosphate (NaTi)2(PO4)3/C)。
The above example 2 is different from example 1 in that a carbon source is added to example 2 and the other preparation conditions are the same.
The reaction equation for example 1 above is: NaH2PO4+2H2TiO3+2H3PO4＝NaTi2(PO4)3+6H2O, a first reaction byproduct is seen, and no other harmful waste gas or solid is generated except water, so that the method accords with the concept of atom economy and environmental protection of green chemistry; the carbon-coated sodium titanium phosphate composite material can be obtained by adding a carbon source in the preparation process, as shown in example 2.
Example 3
A preparation method of a carbon-coated sodium titanium phosphate composite material comprises the following steps:
(1) adding 900g of glucose (carbon source), 50g of polyvinyl alcohol (carbon source), 1450g of sodium dihydrogen phosphate (sodium source), 2250g of phosphoric acid (phosphorus source) and 1940g of metatitanic acid (titanium source) into 25L of deionized water (dispersing agent) and uniformly stirring to obtain slurry;
(2) stirring and refluxing the obtained slurry for 5 hours at 100 ℃, removing about 2/3 parts of deionized water under reduced pressure, transferring the slurry into a rake vacuum dryer, and drying to obtain a powdery precursor;
(3) pressing the obtained powdery precursor into a rough blank, then placing the rough blank in a tubular atmosphere furnace, introducing nitrogen, heating to 350 ℃ at the air flow rate of 50mL/min, calcining for 2 hours at the speed of 5 ℃/min, then heating to 800 ℃, and keeping the temperatureCalcining at a warm temperature for 4 hours, cooling to room temperature, stopping ventilation, and obtaining a black powder product of carbon-coated sodium titanium phosphate (NaTi)2(PO4)3and/C). The above example 3 is different from example 2 in the carbon source, and the other preparation conditions are the same.
Example 4
Example 4 is different from example 2 in the carbon source, and the preparation conditions are the same, and the carbon source used in example 4 includes 900g of glucose and 20g of carbon nanotubes.
Example 5
A preparation method of a carbon-coated sodium titanium phosphate composite material comprises the following steps:
(1) adding 500g of glucose (carbon source), 10g of carbon nanotube (carbon source), 970g of sodium tartrate (sodium source), 3460g of phosphoric acid (phosphorus source) and 1980g of metatitanic acid (titanium source) into 25L of deionized water (dispersing agent) and uniformly stirring to obtain slurry;
(2) stirring and refluxing the obtained slurry for 5 hours at 100 ℃, removing about 2/3 parts of deionized water under reduced pressure, transferring the slurry into a rake vacuum dryer, and drying to obtain a powdery precursor;
(3) pressing the obtained powdery precursor into a rough blank, then placing the rough blank in a tubular atmosphere furnace, introducing nitrogen, heating to 350 ℃ at the air flow rate of 50mL/min at the speed of 5 ℃/min, calcining for 2 hours, then heating to 800 ℃, preserving heat, calcining for 4 hours, cooling to room temperature, stopping introducing air, and obtaining a black powdery product, namely carbon-coated titanium sodium phosphate (NaTi)2(PO4)3/C)。
Example 6
Example 6 differs from example 5 in the sodium source, and the preparation conditions are the same, and the sodium source used in example 6 is sodium malate.
Example 7
A preparation method of a carbon-coated sodium titanium phosphate negative pole piece adopts the carbon-coated sodium titanium phosphate composite material prepared in the embodiment 2 as an active material of the negative pole piece, and comprises the following steps:
s1, stirring and dispersing 10 wt% of water-dispersed graphene, water-dispersed polytetrafluoroethylene, water-dispersed polyvinyl alcohol and deionized water for 90 minutes, adding a conductive agent SP and the carbon-coated sodium titanium phosphate composite material prepared in the example 2, continuously stirring and dispersing for 60 minutes, and adjusting the solid content to be 50% and the viscosity to be 5000mPa & S to obtain water-based coating slurry; wherein the mass ratio of the carbon-coated sodium titanium phosphate to the water-dispersible graphene to the conductive agent SP to the water-dispersible polytetrafluoroethylene to the water-dispersible polyvinyl alcohol is 95: 2: 1.5: 1: 0.5;
s2, coating the obtained water system coating slurry on a hydrophobic carbon-coated aluminum foil, drying, compacting and slitting to obtain a carbon-coated sodium titanium phosphate negative electrode plate; wherein the loading of the active material is 55mg/cm2The compacted density is 2.2g/cm3The preparation method of the hydrophobic carbon-coated aluminum foil comprises the following steps: uniformly mixing polytetrafluoroethylene, graphene and absolute ethyl alcohol, then coating the mixture on a carbon-coated aluminum foil to form a coating with the thickness of 2 microns, and drying to obtain the hydrophobic carbon-coated aluminum foil.
Example 8
A preparation method of a carbon-coated sodium titanium phosphate negative pole piece adopts the carbon-coated sodium titanium phosphate composite material prepared in the embodiment 2 as an active material of the negative pole piece, and comprises the following steps:
s1, stirring and dispersing 5 wt% of water-dispersed graphene, 5 wt% of water-dispersed acrylonitrile multipolymer and deionized water for 90 minutes, then adding a conductive agent SP and the carbon-coated titanium sodium phosphate composite material prepared in the embodiment 2, continuously stirring and dispersing for 60 minutes, and adjusting the solid content to be 50% and the viscosity to be 5000mPa & S to obtain water-based coating slurry; wherein the mass ratio of the carbon-coated sodium titanium phosphate to the water-dispersible graphene to the conductive agent SP to the water-dispersible acrylonitrile multipolymer is 95: 2: 1.5: 1.5;
s2, coating the obtained water system coating slurry on a hydrophobic carbon-coated aluminum foil, drying, compacting and slitting to obtain a carbon-coated sodium titanium phosphate negative electrode plate; wherein the loading of the active material is 55mg/cm2The compacted density is 2.2g/cm3The preparation method of the hydrophobic carbon-coated aluminum foil comprises the following steps: mixing polytetrafluoroethylene, graphene and absolute ethyl alcoholAnd uniformly coating the mixture on a carbon-coated aluminum foil to form a coating with the thickness of 3 mu m, and drying to obtain the hydrophobic carbon-coated aluminum foil.
Example 8 differs from example 7 in the ingredients used to prepare the aqueous coating slurry.
Comparative example 1
The difference between the comparative example 1 and the example 8 is that the carbon-coated aluminum foil used in the comparative example 1 is a common carbon-coated aluminum foil, and the rest conditions are the same as those in the example 8, so that the carbon-coated sodium titanium phosphate negative electrode plate is obtained.
Test example 1:
adding a zigzag lamination of a diaphragm between a lithium manganate positive electrode piece and the carbon-coated titanium sodium phosphate negative electrode piece prepared in the embodiment 8 to prepare a battery cell, and then connecting tabs, packaging with an aluminum-plastic film, injecting an aqueous electrolyte, activating, and sealing secondarily to obtain a soft package battery; the electric performance of the battery obtained by the test of the blue battery test system pair is shown in figure 1, and the charge-discharge cut-off voltage is 1.0-2.0V and the battery capacity is 7Ah when the battery is activated can be seen from figure 1. And (3) assembling the carbon-coated sodium titanium phosphate negative pole piece obtained in the comparative example 1 and the lithium manganate positive pole piece into a battery, wherein the battery capacity is 4Ah, and the negative active material is easy to fall off from the carbon-coated aluminum foil current collector.
Test example 2: the X-ray diffraction results of the materials prepared in examples 1, 2 and 3 are shown in fig. 2 (a, b and c in fig. 2 represent the materials prepared in examples 1 to 3, respectively), and it can be seen from fig. 2 that the peak patterns of the materials prepared in examples 1 to 3 match the standard pattern, thus proving that the materials were successfully prepared.
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (10)
1. A preparation method of a carbon-coated sodium titanium phosphate composite material is characterized by comprising the following steps:
(1) adding a carbon source, a sodium source, a phosphorus source and a titanium source into a dispersing agent and uniformly stirring to obtain slurry;
(2) stirring and refluxing the slurry, removing part of the dispersing agent under reduced pressure, and then drying to obtain a powdery precursor;
(3) and pressing the precursor into a rough blank, calcining the rough blank in an inert atmosphere, and cooling to obtain the carbon-coated sodium titanium phosphate composite material.
2. The method for preparing the carbon-coated sodium titanium phosphate composite material according to claim 1, wherein the mass ratio of the carbon source, the sodium source, the phosphorus source and the titanium source in the step (1) is (1-2): (1.5-3): (4-7): (3.5-4); the mass volume ratio of the carbon source to the dispersing agent is 20-40 g/L.
3. The method for preparing the carbon-coated sodium titanium phosphate composite material according to claim 1 or 2, wherein the carbon source in the step (1) is at least one selected from glucose, polyvinyl alcohol and carbon nanotubes; the sodium source is at least one selected from sodium dihydrogen phosphate, sodium carbonate, sodium bicarbonate, sodium citrate, sodium malate, sodium tartrate and disodium ethylene diamine tetraacetate; the phosphorus source is phosphoric acid; the titanium source is nano titanium dioxide or metatitanic acid with hydroxylated surface; the dispersant is pure water.
4. The method for preparing the carbon-coated sodium titanium phosphate composite material as claimed in claim 1, wherein the slurry in the step (2) is stirred and refluxed at 100-120 ℃ for 3-12 hours, 50-70% of the dispersant is removed by reduced pressure distillation, and then the slurry is transferred into a rake vacuum dryer to be dried to obtain a powdery precursor.
5. The method for preparing a carbon-coated sodium titanium phosphate composite material as claimed in claim 1, wherein the precursor is pressed into a rough blank in step (3), then the rough blank is placed in a tubular atmosphere furnace, inert gas is introduced into the furnace at a gas flow rate of 20-100mL/min, the temperature is raised to 800-.
6. A preparation method of a carbon-coated sodium titanium phosphate negative pole piece is characterized in that the carbon-coated sodium titanium phosphate composite material prepared by the preparation method of any one of claims 1 to 5 is used as an active material of the negative pole piece, and the preparation method of the negative pole piece comprises the following steps:
s1, mixing the water-based conductive slurry, water-based glue and a solvent, then adding a conductive agent and the carbon-coated sodium titanium phosphate composite material, and uniformly stirring to obtain water-based coating slurry;
s2, coating the water system coating slurry on a hydrophobic carbon-coated aluminum foil, drying, compacting and slitting to obtain the carbon-coated sodium titanium phosphate negative electrode plate.
7. The preparation method of the carbon-coated sodium titanium phosphate negative electrode plate as claimed in claim 6, wherein the step S1 comprises the steps of adding the aqueous conductive slurry, the aqueous adhesive and the solvent into a homogenizer, stirring and dispersing for 0.5-4 hours, then adding the conductive agent and the carbon-coated sodium titanium phosphate composite material, stirring and dispersing for 0.5-4 hours, and adjusting the solid content to 45-55% and the viscosity to 4000-7000mPa · S to obtain the coating slurry.
8. The preparation method of the carbon-coated sodium titanium phosphate negative electrode plate as claimed in claim 6 or 7, wherein the aqueous conductive slurry is 5-10 wt% of water-dispersible carbon nanotubes or 5-10 wt% of water-dispersible graphene; the water-based adhesive is at least one selected from water-dispersed polytetrafluoroethylene, water-dispersed acrylonitrile multipolymer and water-dispersed polyvinyl alcohol; the solvent is deionized water.
9. The preparation method of the carbon-coated sodium titanium phosphate negative electrode plate as claimed in claim 6, wherein the compaction density in the step S2 is 2.2-2.4g/cm3。
10. The method for preparing the carbon-coated sodium titanium phosphate negative electrode plate as claimed in claim 6, wherein the method for preparing the hydrophobic carbon-coated aluminum foil in step S2 comprises the following steps: and uniformly mixing polytetrafluoroethylene, graphene and absolute ethyl alcohol, then coating the mixture on the carbon-coated aluminum foil, and drying to obtain the hydrophobic carbon-coated aluminum foil.
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