CN116409801A - Preparation method of polypyrrole coated Prussian blue positive electrode composite material - Google Patents
Preparation method of polypyrrole coated Prussian blue positive electrode composite material Download PDFInfo
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- CN116409801A CN116409801A CN202211719749.2A CN202211719749A CN116409801A CN 116409801 A CN116409801 A CN 116409801A CN 202211719749 A CN202211719749 A CN 202211719749A CN 116409801 A CN116409801 A CN 116409801A
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 85
- 239000013225 prussian blue Substances 0.000 title claims abstract description 85
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000011259 mixed solution Substances 0.000 claims abstract description 74
- 239000000243 solution Substances 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003999 initiator Substances 0.000 claims abstract description 36
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 36
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000008139 complexing agent Substances 0.000 claims abstract description 32
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000264 sodium ferrocyanide Substances 0.000 claims abstract description 31
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims abstract description 31
- 238000000975 co-precipitation Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- -1 transition metal salt Chemical class 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 235000002639 sodium chloride Nutrition 0.000 claims description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011780 sodium chloride Substances 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- 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 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229960004249 sodium acetate Drugs 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 239000000176 sodium gluconate Substances 0.000 claims description 3
- 235000012207 sodium gluconate Nutrition 0.000 claims description 3
- 229940005574 sodium gluconate Drugs 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 61
- 238000003756 stirring Methods 0.000 description 40
- 229910052742 iron Inorganic materials 0.000 description 30
- 238000005406 washing Methods 0.000 description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- 238000001035 drying Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 239000011790 ferrous sulphate Substances 0.000 description 9
- 235000003891 ferrous sulphate Nutrition 0.000 description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 9
- 230000002572 peristaltic effect Effects 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 239000005457 ice water Substances 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 229940077484 ammonium bromide Drugs 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 229940010556 ammonium phosphate Drugs 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000015424 sodium Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a preparation method of a polypyrrole coated Prussian blue positive electrode composite material. Firstly mixing sodium ferrocyanide, first soluble sodium salt and water to obtain a first mixed solution; mixing the soluble divalent transition metal salt, the second soluble sodium salt and water to obtain a second mixed solution; thirdly mixing the first mixed solution, the second mixed solution and the complexing agent, and performing coprecipitation reaction to obtain Prussian blue wet material; fourthly, mixing the Prussian blue wet material, pyrrole, water and an alcohol solvent to obtain a liquid to be treated; fifthly, mixing the solution to be treated with an initiator to obtain the polypyrrole coated Prussian blue positive electrode composite material; neither the first soluble sodium salt nor the second soluble sodium salt includes sodium ferrocyanide. The method provided by the invention can improve the coating uniformity of the polypyrrole layer and improve the cycling stability of the anode material.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a preparation method of a polypyrrole coated Prussian blue positive electrode composite material.
Background
Along with the continuous development of global lithium resources, the cost of the lithium resources is always high, and the lithium ion battery gradually loses competitiveness in the field of large-scale energy storage. Compared with a lithium ion battery, the sodium ion battery has the advantages in cost and has a better application prospect in the field of large-scale energy storage.
Prussian blue compounds are common positive electrode materials of sodium ion batteries, and have a chemical formula of Na x M[Fe(CN) 6 ] y ·zH 2 O (where x has a value of 0<x<2, y has a value of 0<y<1, M is transition metal), has the characteristics of high specific capacity, long cycle life and excellent low-temperature performance, and has low raw material cost and simple synthesis method.
The preparation method of Prussian blue generally adopts a coprecipitation method, the obtained Prussian blue often contains more crystal water and vacancy defects, and during the subsequent drying process, the water in the Prussian blue is dried, so that the structure of the Prussian blue is unstable, the circulation stability of the Prussian blue is influenced, and the Prussian blue is generally improved by adopting a measure of coating the Prussian blue;
the traditional coating method is mainly a solid-phase coating method, but the solid-phase coating method has the problem of uneven coating, thereby influencing the circulation stability of the finally obtained anode material.
Disclosure of Invention
The invention aims to provide a preparation method of a polypyrrole coated Prussian blue positive electrode composite material, which can further improve the uniformity of a polypyrrole coating layer and improve the cycling stability of a positive electrode material.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a polypyrrole coated Prussian blue positive electrode composite material, which comprises the following steps:
firstly mixing sodium ferrocyanide, first soluble sodium salt and water to obtain a first mixed solution;
mixing the soluble divalent transition metal salt, the second soluble sodium salt and water to obtain a second mixed solution;
thirdly mixing the first mixed solution, the second mixed solution and the complexing agent, and performing coprecipitation reaction to obtain Prussian blue wet material;
fourthly, mixing the Prussian blue wet material, pyrrole, water and an alcohol solvent to obtain a liquid to be treated;
fifthly, mixing the solution to be treated with an initiator to obtain the polypyrrole coated Prussian blue positive electrode composite material;
neither the first soluble sodium salt nor the second soluble sodium salt includes sodium ferrocyanide.
Preferably, the first soluble sodium salt and the second soluble sodium salt independently comprise one or more of sodium chloride, sodium citrate, sodium alginate, disodium edetate, sodium oxalate, sodium acetate, sodium gluconate and sodium pyrophosphate.
Preferably, the soluble divalent transition metal salt comprises a soluble divalent manganese salt and a soluble divalent iron salt.
Preferably, the molar ratio of sodium ferrocyanide to the first soluble sodium salt is 1:1 to 1.8;
the concentration of sodium ferrocyanide in the first mixed solution is 0.16-0.64 mol/L.
Preferably, the molar ratio of the soluble divalent transition metal salt to the second soluble sodium salt is 1:2 to 5;
the concentration of the soluble divalent transition metal salt in the second mixed solution is 0.32-0.96 mol/L.
Preferably, the complexing agent comprises a nitrogen-containing complexing agent;
the molar ratio of the sodium ferrocyanide to the complexing agent in the first mixed solution is 0.32:1 to 2.5;
the molar ratio of the sodium ferrocyanide in the first mixed solution to the soluble divalent transition metal salt in the second mixed solution is 0.32:0.4 to 1.
Preferably, the temperature of the coprecipitation reaction is 0 to 30 ℃.
Preferably, the water content of the Prussian blue wet material is 60% -70%;
the dosage ratio of the Prussian blue wet material to the pyrrole is 50g: 1-10 mL.
Preferably, the alcohol solvent comprises one or more of ethanol, methanol and ethylene glycol;
the volume ratio of the water to the alcohol solvent is 1-3: 1, a step of;
the concentration of Prussian blue in the solution to be treated is 0.50.7g/mL.
Preferably, the initiator comprises one or more of ammonium persulfate, hydrogen peroxide, potassium persulfate and sodium persulfate;
the mass ratio of the initiator to the Prussian blue wet material is 1-2: 10.
the invention provides a preparation method of a polypyrrole coated Prussian blue positive electrode composite material, which comprises the following steps: firstly mixing sodium ferrocyanide, first soluble sodium salt and water to obtain a first mixed solution; mixing the soluble divalent transition metal salt, the second soluble sodium salt and water to obtain a second mixed solution; thirdly mixing the first mixed solution, the second mixed solution and the complexing agent, and performing coprecipitation reaction to obtain Prussian blue wet material; fourthly, mixing the Prussian blue wet material, pyrrole, water and an alcohol solvent to obtain a liquid to be treated; fifthly, mixing the solution to be treated with an initiator to obtain the polypyrrole coated Prussian blue positive electrode composite material; neither the first soluble sodium salt nor the second soluble sodium salt includes sodium ferrocyanide. According to the invention, the Prussian blue wet material is obtained by the coprecipitation method, is not subjected to drying treatment, and is coated in the alcohol water solution, so that the activity of water can be reduced, the influence of water on Prussian blue is reduced, and the cycle stability of the anode material is further improved.
Drawings
Fig. 1 is an SEM image of the polypyrrole coated prussian blue positive electrode composite material obtained in example 1;
fig. 2 is an XRD pattern of the polypyrrole-coated prussian blue positive electrode composite material obtained in example 1;
fig. 3 is a first charge-discharge curve of a sodium-ion half-cell assembled by taking the polypyrrole-coated Prussian blue positive electrode composite material obtained in example 1 as a positive electrode material;
fig. 4 is a cycle performance chart of a sodium ion half battery assembled by taking the polypyrrole coated Prussian blue positive electrode composite material obtained in example 1 as a positive electrode material;
fig. 5 is a graph showing the rate performance of a sodium-ion half battery assembled by using the polypyrrole-coated Prussian blue positive electrode composite material obtained in example 1 as a positive electrode material.
Detailed Description
The invention provides a preparation method of a polypyrrole coated Prussian blue positive electrode composite material, which comprises the following steps:
firstly mixing sodium ferrocyanide, first soluble sodium salt and water to obtain a first mixed solution;
mixing the soluble ferrous salt, the second soluble sodium salt and water for the second time to obtain a second mixed solution;
thirdly mixing the first mixed solution, the second mixed solution and the complexing agent, and performing coprecipitation reaction to obtain Prussian blue wet material;
fourthly, mixing the Prussian blue wet material, pyrrole, water and an alcohol solvent to obtain a liquid to be treated;
fifthly, mixing the solution to be treated with an initiator to obtain the polypyrrole coated Prussian blue positive electrode composite material;
neither the first soluble sodium salt nor the second soluble sodium salt includes sodium ferrocyanide.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
The invention mixes sodium ferrocyanide, first soluble sodium salt and water to obtain first mixed solution.
In the present invention, the first soluble sodium salt preferably includes one or more of sodium chloride, sodium citrate, sodium alginate, disodium ethylenediamine tetraacetate, sodium oxalate, sodium acetate, sodium gluconate and sodium pyrophosphate; when the first soluble sodium salt includes two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited in the present invention, and may be mixed in any ratio.
In the present invention, the molar ratio of sodium ferrocyanide to the first soluble sodium salt is preferably 1:1 to 1.8, more preferably 1:1.2 to 1.7, more preferably 1:1.3 to 1.5. In the present invention, the concentration of sodium ferrocyanide in the first mixed solution is preferably 0.16 to 0.64mol/L, more preferably 0.20 to 0.60mol/L, and still more preferably 0.25 to 0.55mol/L.
The process of the first mixing is not particularly limited, and may be performed by a process well known to those skilled in the art.
The invention mixes the soluble bivalent transition metal salt, the second soluble sodium salt and the water for the second time to obtain a second mixed solution.
In the present invention, the soluble divalent transition metal salt preferably includes a soluble divalent manganese salt and a soluble divalent iron salt. In the present invention, the soluble ferrous salt preferably includes one or more of ferrous chloride, ferrous sulfate and ferrous nitrate; when the soluble divalent transition metal salt is preferably two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited in the present invention, and the soluble divalent transition metal salt may be mixed in any ratio.
In the present invention, the second soluble sodium salt is the same as the first soluble sodium salt, and will not be described in detail herein.
In the present invention, the molar ratio of the soluble divalent transition metal salt to the second soluble sodium salt is preferably 1:2 to 5, more preferably 1:3 to 4. In the present invention, the concentration of the soluble divalent transition metal salt in the second mixed solution is preferably 0.32 to 0.96mol/L, more preferably 0.40 to 0.90mol/L, and still more preferably 0.50 to 0.80mol/L.
The second mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
The first mixed solution, the second mixed solution and the complexing agent are mixed for the third time, and coprecipitation reaction is carried out to obtain Prussian blue wet material.
In the present invention, the complexing agent preferably comprises a nitrogen-containing type complexing agent. In the present invention, the nitrogen-containing complexing agent preferably includes one or more of concentrated aqueous ammonia, ammonium chloride, ammonium fluoride, ammonium bromide, ammonium iodide, ammonium acetate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium chloride, ammonium sulfate and ammonium nitrate.
In the present invention, the molar ratio of the sodium ferrocyanide in the first mixed solution and the soluble divalent transition metal salt in the second mixed solution is preferably 0.32:0.4 to 1, more preferably 0.32:0.5 to 0.9, more preferably 0.32:0.6 to 0.8. In the present invention, the molar ratio of sodium ferrocyanide to complexing agent in the first mixed solution is preferably 0.32:1 to 2.5, more preferably 0.32:1.2 to 2.3, more preferably 0.32:1.5 to 2.0.
In the present invention, the complexing agent is preferably added in the form of a complexing agent solution. In the invention, the mass concentration of the complexing agent in the complexing agent solution is preferably 25g/L to 50g/L. In the present invention, the pH of the complexing agent solution is preferably from 6 to 8. The preparation method of the complexing agent solution is not particularly limited, and the complexing agent and water are directly mixed. In the present invention, when the complexing agent is concentrated aqueous ammonia, it is preferable that the pH adjusting agent is added to adjust the pH after mixing the concentrated aqueous ammonia with water. In the present invention, the mass concentration of the concentrated aqueous ammonia is preferably 28%. In the present invention, the pH adjustor preferably includes one or more of ammonium chloride, ammonium fluoride, ammonium bromide, ammonium iodide, ammonium acetate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium chloride, ammonium sulfate and ammonium nitrate. The process of the pH adjustment is not particularly limited, and may be employed as is well known to those skilled in the art.
In the present invention, the third mixing preferably includes:
and dropwise adding the second mixed solution and the complexing agent solution into the first mixed solution under the condition of stirring.
The stirring condition parameters are not particularly limited, and may be performed as known to those skilled in the art.
In the present invention, the dropping rate of the second mixed liquid is preferably 1 to 5mL/min, and more preferably 2 to 4mL/min. In the present invention, the dripping rate of the complexing agent solution is preferably 1-2 mL/min.
In the present invention, the temperature of the coprecipitation reaction is preferably 0 to 30 ℃, more preferably 2 to 25 ℃, and even more preferably 5 to 20 ℃.
In the present invention, the coprecipitation reaction starts to occur when the second mixed liquid and the complexing agent solution are dropped into the first mixed liquid. In the invention, the time of the coprecipitation reaction comprises the dripping time of the second mixed solution and the complexing agent solution and the continuous stirring time after the dripping is finished. In the invention, the dripping time is preferably 1 to 5 hours; the duration of the stirring is preferably 2 to 5 hours.
After the coprecipitation reaction, the present invention also preferably includes sequentially aging and centrifugally washing the obtained product.
In the present invention, the aging time is preferably 4 to 15 hours, and the temperature is preferably 20 to 30 ℃. The centrifugal washing process is not particularly limited, and may be performed by a process known to those skilled in the art.
In the invention, the water content in the Prussian blue wet material is preferably 60% -70%.
After the Prussian blue wet material is obtained, the Prussian blue wet material, pyrrole, water and an alcohol solvent are mixed for the fourth time to obtain a liquid to be treated.
In the invention, the dosage ratio of the Prussian blue wet material to the pyrrole is preferably 50g:1 to 5mL, more preferably 50g:2 to 4mL, more preferably 50g: 2-3 mL. In the present invention, the alcohol solvent preferably includes one or more of ethanol, methanol and ethylene glycol; the volume ratio of the water to the alcohol solvent is preferably 1-3: 1, a step of; the concentration of Prussian blue in the solution to be treated is preferably 0.5 to 0.7g/mL, and more preferably 0.6g/mL.
In the present invention, the fourth mixing is preferably performed under stirring. The stirring condition parameters are not particularly limited in the present invention, and those well known to those skilled in the art may be employed. In the present invention, the temperature of the fourth mixing is preferably 0 to 5 ℃. In a specific embodiment of the invention, said fourth mixing is preferably performed in a cold water bath.
After the solution to be treated is obtained, the solution to be treated and an initiator are mixed in a fifth mode, and the polypyrrole coated Prussian blue positive electrode composite material is obtained.
In the present invention, the initiator preferably includes one or more of ammonium persulfate, hydrogen peroxide, potassium persulfate, and sodium persulfate. In the invention, the mass ratio of the initiator to the Prussian blue wet material is preferably 1-2: 10.
in the present invention, the initiator is preferably added in the form of an initiator solution. In the present invention, the mass concentration of the initiator solution is preferably 0.1 to 0.5g/mL.
In the present invention, the fifth mixing preferably includes:
and adding the initiator solution into the solution to be treated under the condition of stirring. In the present invention, the initiator solution, before addition, further preferably includes performing a pre-cooling treatment; the temperature of the initiator solution after the pre-cooling treatment is preferably 0-8 ℃.
The stirring condition parameters are not particularly limited, and may be performed as known to those skilled in the art. In the present invention, the addition rate of the initiator solution is preferably 0.5 to 2mL/min. In the present invention, the initiator solution is preferably added by pumping with peristaltic pump.
In the present invention, the temperature of the fifth mixing is preferably 0 to 10 ℃.
After the fifth mixing, the present invention also preferably includes sequentially filtering, washing and drying the obtained material. The process of filtering, washing and drying is not particularly limited, and may be performed by a process well known to those skilled in the art.
The preparation method provided by the invention has the advantages of simple process, low cost, short period and low energy consumption, and is suitable for industrial production.
For further explanation of the present invention, the following describes in detail the preparation method of the polypyrrole coated Prussian blue positive electrode composite material provided by the present invention with reference to the accompanying drawings and examples, but they should not be construed as limiting the protection scope of the present invention.
Example 1
15.972g of sodium ferrocyanide, 14.705g of sodium chloride and 100mL of water are mixed to obtain a first mixed solution;
mixing 11.12g of ferrous sulfate, 29.41g of sodium chloride and 100mL of water to obtain a second mixed solution;
mixing 75mL of 28% ammonia water and 100mL of deionized water, and controlling the pH value within the range of 7-7.5 by using an ammonium chloride solution with the concentration of 1mol/L to obtain a complexing agent solution;
dripping the second mixed solution into the first mixed solution at the dripping speed of 2mL/min and the dripping speed of 1mL/min under the condition of stirring at 25 ℃, and continuously stirring for 2 hours after the dripping is finished, so as to perform coprecipitation reaction; after the obtained feed liquid is aged for 12 hours, obtaining an iron-based Prussian blue wet material (the water content is 63 percent) through centrifugal washing;
under the conditions of ice water bath and stirring, adding 50g of iron-based Prussian blue wet material into 100mL of aqueous-alcoholic solution (the volume of water and ethanol is 3:2), and then adding 1mL of pyrrole to obtain a material liquid to be treated;
9.13g of ammonium persulfate is added into 40mL of deionized water for dissolution, and precooling treatment is carried out to obtain an initiator solution with the temperature of 4 ℃;
pumping an initiator solution into the feed liquid to be treated by a peristaltic pump at the adding rate of 1mL/min under the condition of stirring, and sequentially filtering, washing and drying the obtained product to obtain the polypyrrole coated iron-based Prussian blue positive electrode composite material.
Example 2
15.972g of sodium ferrocyanide, 14.705g of sodium chloride and 100mL of water are mixed to obtain a first mixed solution;
mixing 11.12g of ferrous sulfate, 29.41g of sodium chloride and 100mL of water to obtain a second mixed solution;
mixing 75mL of 28% ammonia water and 100mL of deionized water, and controlling the pH value within the range of 7-7.5 by using an ammonium chloride solution with the concentration of 1mol/L to obtain a complexing agent solution;
dripping the second mixed solution into the first mixed solution at the dripping speed of 2mL/min and the dripping speed of 1mL/min under the condition of stirring at 25 ℃, and continuously stirring for 2 hours after the dripping is finished, so as to perform coprecipitation reaction; after the obtained feed liquid is aged for 12 hours, obtaining an iron-based Prussian blue wet material (the water content is 63 percent) through centrifugal washing;
under the conditions of ice water bath and stirring, adding 50g of iron-based Prussian blue wet material into 100mL of aqueous-alcoholic solution (the volume of water and ethanol is 3:2), and adding 3mL of pyrrole to obtain a material liquid to be treated;
adding 13.69g of ammonium persulfate into 40mL of deionized water for dissolution, and performing precooling treatment to obtain an initiator solution with the temperature of 4 ℃;
pumping an initiator solution into the feed liquid to be treated by a peristaltic pump at the adding rate of 1mL/min under the condition of stirring, and sequentially filtering, washing and drying the obtained product to obtain the polypyrrole coated iron-based Prussian blue positive electrode composite material.
Example 3
15.972g of sodium ferrocyanide, 14.705g of sodium chloride and 100mL of water are mixed to obtain a first mixed solution;
mixing 11.12g of ferrous sulfate, 29.41g of sodium chloride and 100mL of water to obtain a second mixed solution;
mixing 75mL of 28% ammonia water and 100mL of deionized water, and controlling the pH value within the range of 7-7.5 by using an ammonium chloride solution with the concentration of 1mol/L to obtain a complexing agent solution;
dripping the second mixed solution into the first mixed solution at the dripping speed of 2mL/min and the dripping speed of 1mL/min under the condition of stirring at 25 ℃, and continuously stirring for 2 hours after the dripping is finished, so as to perform coprecipitation reaction; after the obtained feed liquid is aged for 12 hours, obtaining an iron-based Prussian blue wet material (the water content is 63 percent) through centrifugal washing;
under the conditions of ice water bath and stirring, adding 50g of iron-based Prussian blue wet material into 100mL of aqueous-alcoholic solution (the volume of water and ethanol is 3:2), and then adding 5mL of pyrrole to obtain a material liquid to be treated;
adding 21.3g of ammonium persulfate into 40mL of deionized water for dissolution, and performing precooling treatment to obtain an initiator solution with the temperature of 4 ℃;
pumping an initiator solution into the feed liquid to be treated by a peristaltic pump at the adding rate of 1mL/min under the condition of stirring, and sequentially filtering, washing and drying the obtained product to obtain the polypyrrole coated iron-based Prussian blue positive electrode composite material.
Example 4
15.972g of sodium ferrocyanide, 14.705g of sodium chloride and 100mL of water are mixed to obtain a first mixed solution;
mixing 11.12g of ferrous sulfate, 29.41g of sodium chloride and 100mL of water to obtain a second mixed solution;
mixing 150mL of 28% ammonia water and 100mL of deionized water, and controlling the pH value within the range of 7-7.5 by using 1mol/L ammonium chloride solution to obtain complexing agent solution;
dripping the second mixed solution into the first mixed solution at the dripping speed of 2mL/min and the dripping speed of 1mL/min under the condition of stirring at 25 ℃, and continuously stirring for 2 hours after the dripping is finished, so as to perform coprecipitation reaction; after the obtained feed liquid is aged for 12 hours, obtaining an iron-based Prussian blue wet material (the water content is 63 percent) through centrifugal washing;
under the conditions of ice water bath and stirring, adding 50g of iron-based Prussian blue wet material into 100mL of aqueous-alcoholic solution (the volume of water and ethanol is 3:2), and then adding 5mL of pyrrole to obtain a material liquid to be treated;
adding 21.3g of ammonium persulfate into 40mL of deionized water for dissolution, and performing precooling treatment to obtain an initiator solution with the temperature of 4 ℃;
pumping an initiator solution into the feed liquid to be treated by a peristaltic pump at the adding rate of 1mL/min under the condition of stirring, and sequentially filtering, washing and drying the obtained product to obtain the polypyrrole coated iron-based Prussian blue positive electrode composite material.
Comparative example 1
15.972g of sodium ferrocyanide, 14.705g of sodium chloride and 100mL of water are mixed to obtain a first mixed solution;
mixing 11.12g of ferrous sulfate, 29.41g of sodium chloride and 100mL of water to obtain a second mixed solution;
dripping the second mixed solution into the first mixed solution at the dripping speed of 2mL/min under the condition of stirring at 25 ℃, continuously stirring for 2h after the dripping is finished, and performing coprecipitation reaction; after the obtained feed liquid is aged for 12 hours, obtaining an iron-based Prussian blue wet material (the water content is 63 percent) through centrifugal washing;
under the conditions of ice water bath and stirring, adding 50g of iron-based Prussian blue wet material into 100mL of aqueous-alcoholic solution (the volume of water and ethanol is 3:2), and adding 3mL of pyrrole to obtain a material liquid to be treated;
adding 13.69g of ammonium persulfate into 40mL of deionized water for dissolution, and performing precooling treatment to obtain an initiator solution with the temperature of 4 ℃;
pumping an initiator solution into the feed liquid to be treated by a peristaltic pump at the adding rate of 1mL/min under the condition of stirring, and sequentially filtering, washing and drying the obtained product to obtain the polypyrrole coated iron-based Prussian blue positive electrode composite material.
Comparative example 2
15.972g of sodium ferrocyanide, 14.705g of sodium citrate and 100mL of water are mixed to obtain a first mixed solution;
mixing 11.12g of ferrous sulfate, 29.41g of sodium citrate and 100mL of water to obtain a second mixed solution;
dripping the second mixed solution into the first mixed solution at the dripping speed of 2mL/min under the condition of stirring at 25 ℃, continuously stirring for 2h after the dripping is finished, and performing coprecipitation reaction; after the obtained feed liquid is aged for 12 hours, obtaining an iron-based Prussian blue wet material (the water content is 63 percent) through centrifugal washing;
under the conditions of ice water bath and stirring, adding 50g of iron-based Prussian blue wet material into 100mL of aqueous-alcoholic solution (the volume of water and ethanol is 3:2), and adding 3mL of pyrrole to obtain a material liquid to be treated;
adding 13.69g of ammonium persulfate into 40mL of deionized water for dissolution, and performing precooling treatment to obtain an initiator solution with the temperature of 4 ℃;
pumping an initiator solution into the feed liquid to be treated by a peristaltic pump at the adding rate of 1mL/min under the condition of stirring, and sequentially filtering, washing and drying the obtained product to obtain the polypyrrole coated iron-based Prussian blue positive electrode composite material.
Comparative example 3
15.972g of sodium ferrocyanide, 14.705g of sodium citrate and 100mL of water are mixed to obtain a first mixed solution;
mixing 11.12g of ferrous sulfate, 29.41g of sodium citrate and 100mL of water to obtain a second mixed solution;
dripping the second mixed solution into the first mixed solution at the dripping speed of 2mL/min under the condition of stirring at 25 ℃, continuously stirring for 2h after the dripping is finished, and performing coprecipitation reaction; after the obtained feed liquid is aged for 12 hours, obtaining an iron-based Prussian blue wet material (the water content is 63 percent) through centrifugal washing;
under the conditions of ice water bath and stirring, adding 50g of iron-based Prussian blue wet material into 100mL of aqueous-alcoholic solution (the volume of water and ethanol is 2:3), and adding 3mL of pyrrole to obtain a material liquid to be treated;
adding 13.69g of ammonium persulfate into 40mL of deionized water for dissolution, and performing precooling treatment to obtain an initiator solution with the temperature of 4 ℃;
pumping an initiator solution into the feed liquid to be treated by a peristaltic pump at the adding rate of 1mL/min under the condition of stirring, and sequentially filtering, washing and drying the obtained product to obtain the polypyrrole coated iron-based Prussian blue positive electrode composite material.
Comparative example 4
15.972g of sodium ferrocyanide, 14.705g of sodium citrate and 100mL of water are mixed to obtain a first mixed solution;
mixing 11.12g of ferrous sulfate, 29.41g of sodium citrate and 100mL of water to obtain a second mixed solution;
dripping the second mixed solution into the first mixed solution at the dripping speed of 2mL/min under the condition of stirring at 25 ℃, continuously stirring for 2h after the dripping is finished, and performing coprecipitation reaction; after the obtained feed liquid is aged for 12 hours, obtaining an iron-based Prussian blue wet material (the water content is 63 percent) through centrifugal washing;
under the conditions of ice water bath and stirring, adding 50g of iron-based Prussian blue wet material into 100mL of aqueous-alcoholic solution (the volume of water and ethanol is 1:4), and adding 3mL of pyrrole to obtain a material liquid to be treated;
adding 13.69g of ammonium persulfate into 40mL of deionized water for dissolution, and performing precooling treatment to obtain an initiator solution with the temperature of 4 ℃;
pumping an initiator solution into the feed liquid to be treated by a peristaltic pump at the adding rate of 1mL/min under the condition of stirring, and sequentially filtering, washing and drying the obtained product to obtain the polypyrrole coated iron-based Prussian blue positive electrode composite material.
Performance testing
Test example 1
Scanning electron microscope test is carried out on the polypyrrole coated iron-based Prussian blue positive electrode composite material obtained in the embodiment 1, an obtained SEM image is shown in fig. 1, and as can be seen from fig. 1, the size of the polypyrrole coated iron-based Prussian blue is not greatly changed, and it can be seen that the material surface has a uniform polypyrrole coating layer.
Test example 2
X-ray diffraction test is carried out on the polypyrrole coated iron-based Prussian blue positive electrode composite material obtained in the embodiment 1, the obtained XRD is shown in a figure 2, and as can be seen from the figure 2, the diffraction peak of the polypyrrole coated iron-based Prussian blue positive electrode composite material obtained in the invention is relatively sharp, and no impurity phase peak exists, which indicates that the purity of the product is relatively high.
Test example 3
Taking the polypyrrole coated iron-based Prussian blue positive electrode composite material obtained in the example 1 as a positive electrode material, mixing the positive electrode material, a binder and conductive carbon black in NMP according to the mass ratio of 90:5:5 in a drying room with the dew point lower than-40 ℃ and the humidity lower than 10%, homogenizing, controlling the solid content to be 45%, coating the mixture on an aluminum foil current collector, baking the mixture in vacuum for 4-8 hours at the temperature of 100-110 ℃, and preparing a sodium positive electrode sheet by punching after compression molding;
NaPF with metal sodium sheet as negative electrode and 1mol/L 6 The EC/DMC (Vol 1: 1) of the electrolyte is used for assembling the sodium ion half-cell; carrying out electrochemical performance test on the obtained sodium ion half cell;
the first charge-discharge curve obtained at the current density of 0.1C is shown in FIG. 3, and as can be seen from FIG. 3, the specific discharge capacity of the material reaches 121.43mAh/g;
the cycle performance chart obtained is shown in fig. 4, and it can be seen from fig. 4 that the cycle is 60 times at a current density of 1C, and the capacity retention is 94.89%;
the obtained rate performance graph is shown in fig. 5, and as can be seen from fig. 5, the polypyrrole coated iron-based Prussian blue positive electrode composite material obtained by the invention has very excellent rate performance as a positive electrode of a sodium ion battery.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. The preparation method of the polypyrrole coated Prussian blue positive electrode composite material is characterized by comprising the following steps of:
firstly mixing sodium ferrocyanide, first soluble sodium salt and water to obtain a first mixed solution;
mixing the soluble divalent transition metal salt, the second soluble sodium salt and water to obtain a second mixed solution;
thirdly mixing the first mixed solution, the second mixed solution and the complexing agent, and performing coprecipitation reaction to obtain Prussian blue wet material;
fourthly, mixing the Prussian blue wet material, pyrrole, water and an alcohol solvent to obtain a liquid to be treated;
fifthly, mixing the solution to be treated with an initiator to obtain the polypyrrole coated Prussian blue positive electrode composite material;
neither the first soluble sodium salt nor the second soluble sodium salt includes sodium ferrocyanide.
2. The method according to claim 1, wherein the first soluble sodium salt and the second soluble sodium salt independently comprise one or more of sodium chloride, sodium citrate, sodium alginate, disodium edetate, sodium oxalate, sodium acetate, sodium gluconate, and sodium pyrophosphate.
3. The method of preparation according to claim 1, characterized in that the soluble divalent transition metal salt comprises a soluble divalent manganese salt and/or a soluble divalent iron salt.
4. The process according to claim 1 or 2, characterized in that the molar ratio of sodium ferrocyanide to the first soluble sodium salt is 1:1 to 1.8;
the concentration of sodium ferrocyanide in the first mixed solution is 0.16-0.64 mol/L.
5. A process according to claim 1 or 3, wherein the molar ratio of the soluble divalent transition metal salt to the second soluble sodium salt is 1:2 to 5;
the concentration of the soluble divalent transition metal salt in the second mixed solution is 0.32-0.96 mol/L.
6. A method of preparation according to any one of claims 1 to 3 wherein the complexing agent comprises a nitrogen-containing complexing agent;
the molar ratio of the sodium ferrocyanide to the complexing agent in the first mixed solution is 0.32:1 to 2.5;
the molar ratio of the sodium ferrocyanide in the first mixed solution to the soluble divalent transition metal salt in the second mixed solution is 0.32:0.4 to 1.
7. The method according to claim 6, wherein the temperature of the coprecipitation reaction is 0 to 30 ℃.
8. The preparation method of claim 1, wherein the water content of the Prussian blue wet material is 60% -70%;
the dosage ratio of the Prussian blue wet material to the pyrrole is 50g: 1-10 mL.
9. The method according to claim 8, wherein the alcoholic solvent comprises one or more of ethanol, methanol and ethylene glycol;
the volume ratio of the water to the alcohol solvent is 1-3: 1, a step of;
the concentration of Prussian blue in the solution to be treated is 0.5-0.7 g/mL.
10. The production method according to claim 1 or 8, wherein the initiator comprises one or more of ammonium persulfate, hydrogen peroxide, potassium persulfate, and sodium persulfate;
the mass ratio of the initiator to the Prussian blue wet material is 1-2: 10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117219748A (en) * | 2023-10-08 | 2023-12-12 | 铜陵新地标实业有限公司 | Negative electrode material, negative electrode plate and potassium ion battery with negative electrode plate |
| CN117457902A (en) * | 2023-12-25 | 2024-01-26 | 宁波容百新能源科技股份有限公司 | Prussian blue positive electrode material, preparation method thereof and battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117219748A (en) * | 2023-10-08 | 2023-12-12 | 铜陵新地标实业有限公司 | Negative electrode material, negative electrode plate and potassium ion battery with negative electrode plate |
| CN117219748B (en) * | 2023-10-08 | 2024-05-31 | 铜陵新地标实业有限公司 | Negative electrode material, negative electrode plate and potassium ion battery with negative electrode plate |
| CN117457902A (en) * | 2023-12-25 | 2024-01-26 | 宁波容百新能源科技股份有限公司 | Prussian blue positive electrode material, preparation method thereof and battery |
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