CN116487545A - Carbon composite ferric sodium pyrophosphate composite material, preparation method thereof and application thereof in sodium ion battery - Google Patents
Carbon composite ferric sodium pyrophosphate composite material, preparation method thereof and application thereof in sodium ion battery Download PDFInfo
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- CN116487545A CN116487545A CN202211190999.1A CN202211190999A CN116487545A CN 116487545 A CN116487545 A CN 116487545A CN 202211190999 A CN202211190999 A CN 202211190999A CN 116487545 A CN116487545 A CN 116487545A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 106
- 239000002131 composite material Substances 0.000 title claims abstract description 101
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 title claims abstract description 36
- 239000011645 ferric sodium diphosphate Substances 0.000 title claims abstract description 29
- 235000019851 ferric sodium diphosphate Nutrition 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011734 sodium Substances 0.000 claims abstract description 20
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 19
- 239000005011 phenolic resin Substances 0.000 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 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 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 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 13
- 239000008103 glucose Substances 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 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 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 235000019820 disodium diphosphate Nutrition 0.000 claims description 2
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 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 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 14
- 239000012535 impurity Substances 0.000 abstract description 7
- 239000010405 anode material Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 14
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 5
- -1 sodium iron pyrophosphate phosphate Chemical compound 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of sodium ion battery anode materials, and particularly discloses a preparation method of a carbon composite ferric sodium pyrophosphate composite material, which comprises the steps of roasting a mixture containing a sodium source, an iron source, a phosphorus source and a composite carbon source in a reducing atmosphere at a temperature of 450-650 ℃ to prepare the carbon composite ferric sodium pyrophosphate composite material; the composite carbon source comprises a small molecular carbon source, PEG and phenolic resin. The invention also comprises the material prepared by the preparation method and application of the material in sodium ion batteries. The preparation method can solve the problems of impurity phase preparation, uniformity of carbon coating and non-ideal tap density, and can effectively improve the electrochemical performance of the material.
Description
Technical field:
the invention belongs to the technical field of battery materials, and particularly relates to the technical field of sodium ion battery anode materials.
The background technology is as follows:
the use of fossil fuels brings about serious environmental pollution problems, and high energy costs, further increases the operating pressure of enterprises, and green sustainable energy represented by solar energy is greatly developed, but solar energy has intermittent characteristics, so that large-scale energy storage is proposed to solve the problems. Among them, chemical energy storage represented by sodium ion batteries is widely paid attention to, and research is rapidly being conducted worldwide due to its wide resource distribution and low price.
As an important component of sodium ion batteries, the capacity of the positive electrode material limits the increase in energy density thereof, and thus becomes a critical part of sodium ion battery business. In the prior transition metal, the iron-based phosphate is beneficial to the good structural stability and the large abundance of resources, and becomes the sodium ion battery anode material with wide application prospect.
Kim et al (Journal of the American Chemical Society 2012,134,10369.) originally proposed a sodium iron pyrophosphate material having a relatively high theoretical specific capacity (129 mAh g) -1 ) High discharge voltage (3.2V vs Na/Na + ) And small volume change<4 percent) is the sodium ion battery anode material with the most commercialized prospect. However, the material has a thermodynamically stable phase marisite-NaFePO during the synthesis process 4 The impurities are not electrochemically active, which limits the practical application. In addition, the electron conductivity of the material is low, so that the multiplying power and the cycle performance of the material are poor, and the exertion of the electrochemical performance of the material is seriously influenced. In general, carbon coating can improve the conductivity of a material, but the uniformity of the carbon coating directly affects the capacity exertion, and nanocrystallization can shorten the ion transmission distance and improve the specific capacity, but can reduce the tap density of the material and deteriorate the processability. In order to achieve higher processing performance while improving the specific capacity of the material, the preparation process of the material needs to be further optimized to realize industryAnd (5) comprehensively improving chemical preparation.
The invention comprises the following steps:
aiming at the problems that the carbon composite sodium iron phosphate composite material is easy to have impurity phases, carbon coating uniformity and tap density are not ideal, the first aim of the invention is to provide a preparation method of the carbon composite sodium iron phosphate composite material (also called as sodium iron phosphate/C composite material in the invention), which aims to reduce the preparation impurity phases, improve the carbon coating uniformity and tap density and improve the electrochemical performance of the prepared material.
The second aim of the invention is to provide the carbon composite ferric sodium pyrophosphate composite material prepared by the preparation method and the application thereof.
The third object of the present invention is to provide a sodium ion battery comprising the carbon-composite ferric sodium pyrophosphate composite material, and a positive electrode material thereof.
The marisite-NaFePO easily appears in the preparation process of the carbon composite ferric sodium pyrophosphate 4 The heterogeneous phase, the uniformity of carbon coating and tap density are not ideal, and the material with high electrochemical performance is difficult to prepare. In view of this problem, the present invention provides the following solutions:
the preparation method of the carbon composite ferric sodium pyrophosphate composite material comprises the steps of roasting a mixture containing a sodium source, an iron source, a phosphorus source and a composite carbon source in a reducing atmosphere at the temperature of 450-650 ℃ to obtain the carbon composite ferric sodium pyrophosphate composite material;
the composite carbon source comprises a small molecular carbon source, PEG and phenolic resin.
The special ternary combination composite carbon source, the reduction roasting process and the temperature combination are innovatively adopted, so that the heterogeneous problem in the preparation process of the sodium ferric pyrophosphate is reduced synergistically, the uniformity of carbon coating is improved, the tap density is improved, and the capacity, multiplying power and other electrochemical properties of the prepared material are improved.
The sodium source is at least one of carbon source sodium, sodium bicarbonate, sodium acetate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydroxide, sodium citrate, sodium nitrate and sodium pyrophosphate;
preferably, the iron source is at least one of ferric nitrate, ferrous oxalate, ferrous acetate, ferrous sulfate, ferric oxide, ferrous oxide and ferric oxide;
preferably, the phosphorus source is at least one of ammonium dihydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, disodium dihydrogen pyrophosphate and diammonium hydrogen phosphate;
preferably, in the sodium source, the iron source and the phosphorus source, the element proportion of Na, fe and P is 3.96-4.04:3:3.96-4.04; preferably 4:3:4.
In the invention, the combination of the components of the composite carbon source is the synergistic reduction of marisite-NaFePO 4 Impurity phase, improving uniformity of carbon coating and tap density, and improving electrochemical performance of the material. According to the invention, the components of the composite carbon source are controlled, so that the coupling coordination of special thermal behaviors among different carbon sources can be facilitated, the coordination can be realized accidentally, the uniformity and tap density of carbon coating are improved, and the key of the electrochemical performance of the material is improved.
In the invention, the small molecular carbon source is at least one of sucrose, glucose, citric acid and malic acid;
preferably, the molecular weight of the PEG is 2000 to 20000, and further preferably 3000 to 6000 in view of preparation cost and material effect;
preferably, in the composite carbon source, the small molecular carbon source, PEG and phenolic resin are 5-7: 2 to 4:0.5 to 3; preferably 6:3:0.5 to 2, preferably 6:3:1 to 1.5.
Preferably, the total mass of the composite carbon source is 5 to 30% of the mass of the sodium iron pyrophosphate theoretically synthesized, more preferably 10 to 20%, still more preferably 15 to 20%.
In the invention, the mixture is particles obtained by spraying mixed slurry of a sodium source, an iron source, a phosphorus source and a composite carbon source;
preferably, the mixed slurry is prepared by wet ball milling and sand milling of a sodium source, an iron source, a phosphorus source and a composite carbon source;
preferably, the medium in the wet ball milling stage is an organic solvent, preferably at least one of methanol, ethanol and acetone;
preferably, the solid content of the ball milling stage is 30-60%, and the ball-material ratio is 5-20:1;
preferably, the ball milling speed is 100-1000rpm, preferably 500-800rmp;
preferably, the ball milling time is 20-60 min;
preferably, the particle size in the slurry after ball milling is D50<2 μm and D100<4 μm.
Preferably, the rotational speed of the sanding stage is 1200-2500rpm, preferably 1600-2300rmp;
preferably, the sanding time is 5-40 min;
preferably, the slurry particle size after sanding is D50<600nm, D100<1.5 μm.
In the invention, the inlet temperature of the spray drying stage is 180-270 ℃, the spray rate is 20-50L/h, and the carrier gas is nitrogen or argon.
In the invention, under the innovation of the innovative synergistic composite carbon source, the marisite-NaFePO can be further controlled synergistically by further matching with the reduction roasting mode and the temperature 4 Impurity phase, improving uniformity of carbon coating and tap density, and improving electrochemical performance of the material.
Preferably, the reducing atmosphere contains at least one of hydrogen, CO, methane and acetylene;
preferably, the reducing atmosphere is further allowed to contain a diluent gas, and the diluent gas is at least one of nitrogen and inert gas;
preferably, in the reducing atmosphere, the content of the reducing gas is 1% or more, preferably 5 to 10%;
the baking temperature is preferably 480 to 580 ℃, more preferably 500 to 530 ℃.
In the invention, the temperature rising rate of the roasting stage is 1-10 ℃/min.
Preferably, the calcination stage is preceded by a reaction of V 1 Is heated to the preheating temperature T at the heating rate of a Then at V 2 Heating to the roasting temperature at the heating rate, and carrying out heat preservation roasting. Preferably T a The temperature of (2) is 350-400 ℃. V (V) 1 The temperature rising rate of the catalyst is 3-6 ℃/min; v (V) 2 The temperature rising rate of (2) is 1-2 ℃/min. The research of the invention also finds that under the composite carbon source, the control of the temperature rising gradient is further matched, so that the synergy can be further realized, and the electrochemical performance of the prepared material, such as multiplying power and circulation stability, can be further synergistically improved.
Preferably, the calcination time is 6 to 18 hours, more preferably 10 to 14 hours.
The preparation method of the carbon composite ferric sodium pyrophosphate composite material comprises the following steps:
carrying out wet ball milling and mixing on a sodium source, an iron source, a phosphorus source and a composite carbon source uniformly, and carrying out secondary sand milling treatment to prepare nanoscale slurry; and then carrying out spray drying-reduction roasting treatment on the slurry to obtain the carbon composite ferric sodium pyrophosphate composite material. The molar ratio of Na, fe and P elements is 4:3: and 4, weighing. The medium of wet ball milling is organic solvent such as methanol, ethanol, acetone, etc. The composite carbon source is a mixture of a small molecular carbon source, polyethylene glycol and phenolic resin, preferably the small molecular carbon source is at least one of sucrose, glucose, citric acid and malic acid, wherein the mass ratio of the small molecular carbon source to the polyethylene glycol to the phenolic resin is 6:3:0.5-1.5, and the total mass of the composite carbon source is 10-20% of the mass of sodium ferric pyrophosphate synthesized theoretically. The atmosphere during calcination was hydrogen-nitrogen (hydrogen ratio 5 to 10%).
The invention also provides the carbon composite ferric sodium pyrophosphate composite material prepared by the preparation method.
In the invention, the special microscopic physical and chemical properties of the material can be endowed by the special control of the preparation method. More importantly, the material prepared by the preparation method disclosed by the invention has excellent phase purity, excellent carbon coating uniformity and high tap density characteristics, and has excellent electrochemical performance, in particular excellent multiplying power performance.
The invention relates to a carbon composite ferric sodium pyrophosphate composite material, which comprises ferric sodium pyrophosphate active particles and a carbon coating layer coated on the surface of the active particles; the carbon coating comprises amorphous carbon and an uncarbonated composite carbon source such as phenolic resin.
The preparation method can endow the material with special microstructure and property, the composite carbon source can assist in improving the phase of sodium ferric pyrophosphate, reduce impurity phase and reduce particle agglomeration, and in addition, the amorphous carbon in the shell layer is combined with the non-carbonized composite carbon source, so that the suitability of particles is improved, the tap density of the material is improved, and the processability is improved. The material prepared by the preparation method can effectively improve electrochemical and electrochemical properties.
In the carbon composite ferric sodium pyrophosphate composite material, the weight of the active nano particles is 90-98%; preferably, the thickness of the carbon coating layer is 1-10 nm; preferably, the size of the active nano particles is 100-600 nm. The tap density is 1.1-1.6 g/cc.
The invention also provides application of the carbon composite ferric sodium pyrophosphate composite material, which is used for preparing sodium ion batteries;
preferably used as a positive electrode active material for preparing sodium ion batteries.
The invention also provides a sodium ion battery anode material, which comprises the active material of the carbon composite ferric sodium pyrophosphate composite material.
Preferably, the positive electrode material further comprises a binder and a conductive agent. The binder and the conductive agent may be materials known in the industry, for example, the binder may be PVDF and the conductive agent may be acetylene black. The content of each component can also be adjusted based on the existing means, for example, the content of the binder is, for example, 5 to 15wt%; the content of the conductive agent is, for example, 5 to 15wt%, and the balance is the active material.
The invention also provides a composite positive electrode of the sodium ion battery, which comprises a current collector and a positive electrode material composited on the current collector, wherein the positive electrode material comprises the positive electrode material.
The invention also provides a sodium ion battery comprising the positive electrode.
The invention has the following remarkable characteristics:
(1) The invention adopts a carbon source combined by a small molecular carbon source, PEG and phenolic resin for preparing the carbon composite ferric sodium pyrophosphate. The invention discovers that the combination of the micromolecular carbon source, PEG and phenolic resin can realize the synergy and can unexpectedly inhibit marisite-NaFePO in ferric sodium pyrophosphate 4 The heterogeneous phase is beneficial to improving the uniformity of carbon coating, the suitability of particle surfaces and tap density, and is beneficial to improving the capacity and the multiplying power performance of the prepared material.
(2) Based on the composite carbon source, the method can further cooperate with the reduction roasting mode and the temperature combination to further realize the synergy and help to synergistically inhibit marisite-NaFePO 4 The heterogeneous problem is helpful for improving the uniformity and tap density of carbon coating and improving the capacity and rate capability of the prepared material.
(3) The method has the advantages of low cost, simple operation and short flow, can realize large-scale production, and has excellent industrial application prospect.
Drawings
FIG. 1 is an XRD pattern of a sodium iron pyrophosphate phosphate material prepared in example 1 of the present invention.
FIG. 2 is an SEM image of a sodium iron pyrophosphate material prepared according to example 1 of the invention.
FIG. 3 is an XRD pattern of the sodium iron pyrophosphate phosphate material prepared in comparative example 1 of the present invention.
FIG. 4 is an SEM image of a sodium iron pyrophosphate phosphate material prepared according to comparative example 1 of the invention.
Detailed Description
Example 1
(1) Ferrous oxalate and sodium dihydrogen phosphate are prepared according to Na: fe: p molar ratio 4:3:4, namely weighing 20kg of the total weight of the composite carbon source, wherein the total weight of the composite carbon source is 15wt.% of theoretical ferric sodium pyrophosphate, the mass ratio of glucose to polyethylene glycol 4000 to 2130 type phenolic resin in the composite carbon source is 6:3:0.5, adding 30kg of ethanol as a solvent, and performing ball milling for 40min at the rotating speed of 800rmp, wherein the particle size D50 of the slurry is less than 1.8 mu m, and the particle size D100 of the slurry is less than 3 mu m;
(2) Transferring the slurry obtained in the step (1) into a sand mill, wherein the rotation speed of the sand mill is 1800rmp, the time is 20min, the particle size D50 of the slurry is less than 500nm, D100 is less than 1.2 mu m, then transferring into a spray drying process, and the inlet temperature is 230 ℃ and the spray rate is 25L/h, so as to prepare precursor powder;
(3) And (3) placing the precursor powder in the step (2) in a box furnace to perform high-temperature roasting under the protection of 5% hydrogen/nitrogen, wherein the roasting temperature is 500 ℃, the time is 10 hours, and the heating rate is 2 ℃/min, so that the sodium ferric pyrophosphate with high specific capacity and high tap density can be obtained.
Example 2
The difference compared with example 1 is that the mass ratio of glucose, polyethylene glycol and phenolic resin in the composite carbon source in the step (1) is 6:3:1, and other steps and parameters are unchanged.
Example 3
The only difference compared to example 1 is that glucose in the complex carbon source in step (1) is changed to sucrose, and other steps and parameters are unchanged.
Example 4
The difference from example 1 is only that the amount of the complex carbon source in step (1) is adjusted to the theoretical amount of sodium iron pyrophosphate, a:10wt.%; b:20wt.%, other steps are unchanged.
Example 5
The difference compared to example 1 is only that the firing temperature in step (3) was adjusted to 550℃and the other steps were unchanged.
Example 6
The difference from example 1 is that the sintering schedule in step (3) was adjusted to a temperature rise rate of 5℃per minute at room temperature to 400℃and a temperature rise rate of 1℃per minute at 400 to 500℃with the other steps unchanged.
Comparative example 1
The difference from example 1 is that the complex carbon source in step (1) was adjusted to glucose alone, and the amount of glucose was the same as that of the complex carbon source, and the other steps were unchanged.
Comparative example 2
The difference from example 1 is that the amount of the polyethylene glycol used in the step (1) is the same as that of the composite carbon source, and the other steps are not changed, except that the composite carbon source in the step (1) is adjusted to be a single polyethylene glycol 4000.
Comparative example 3
The difference from example 1 is that the composite carbon source in step (1) is adjusted to a single phenolic resin, and the amount of phenolic resin is the same as that of the composite carbon source, and the other steps are unchanged.
Comparative example 4
The difference compared with example 1 is that the composite carbon source in step (1) is adjusted to glucose and polyethylene glycol, phenolic resin is absent, and the ratio and total amount of the two are the same as those of example 1, and other steps are unchanged.
Comparative example 5
The difference compared with example 1 is that the composite carbon source in step (1) is adjusted to glucose and phenolic resin, polyethylene glycol is absent, and the ratio and total amount of the two are the same as those of example 1, and other steps are unchanged.
Comparative example 6
The difference from example 1 is that the composite carbon source in step (1) is modified to polyethylene glycol and phenolic resin, glucose is absent, and the ratio and total amount of the two are the same as those of example 1, and the other steps are unchanged.
Comparative example 7
The only difference compared with example 1 is that the phenolic resin in the composite carbon source is replaced with an equal weight of epoxy resin, for example, the composite carbon source in step (1) is adjusted to glucose and polyethylene glycol and epoxy resin, and the ratio and total amount of the two are the same as the composite carbon source of example 1, and the other steps are unchanged.
Comparative example 8
The only difference compared to example 1 is that the PEG4000 is replaced with an equal weight of polypropylene, other operations and parameters are the same as in example 1, for example, the composite carbon source in step (1) is adjusted to glucose and polypropylene and phenolic resin, and the ratio and total amount of the two are the same as in example 1, and the other steps are unchanged.
Comparative example 9
The difference from example 1 is only that the firing atmosphere in step (3) is changed to a non-reducing atmosphere of nitrogen, and the other steps are unchanged.
Comparative example 10
The difference compared to example 1 is only that the firing temperature in step (3) was adjusted to 650℃and the other steps were unchanged.
The sodium ferric pyrophosphate phosphate prepared in each example and comparative example was subjected to electrical property test:
the main testing steps are as follows:
(1) The battery shell with the model 2032 is utilized, the positive electrode is a pole piece of the prepared sodium ferrous fluorophosphate, the current collector is aluminum foil, and the active substances (materials prepared in the examples and the comparative examples) are as follows: conductive carbon (acetylene black): pvdf=7: 2:1, the negative electrode is sodium metal, and a fiber diaphragm (model Whatman GradeGF/D) is used for filling a battery with electrolyte of 1MNaClO4 (pure PC+5% FEC);
(2) Setting standing time to be 10h, setting a multiplying power charging and discharging program, setting multiplying power to be 2C (1 C=129 mA/g), setting voltage interval to be 1.7V-4.3V, and circulating for 500 circles;
(3) The theoretical specific capacity of the sodium ferric pyrophosphate is 129mAh/g;
the test results are shown in table 1:
TABLE 1
On the whole, the composite carbon source is adopted to optimize the raw material proportion, and the ball milling, sanding and spray drying means are combined, so that the compatibility of particle nanocrystallization and high tap density can be realized, the cycling stability of the material is improved, on the basis, the combination of proportion optimization, content, sanding process and roasting process parameters of the composite carbon source is further controlled, and the electrochemical performance of the material under high multiplying power can be further synergistically improved.
Claims (10)
1. The preparation method of the carbon composite ferric sodium pyrophosphate composite material is characterized in that a mixture containing a sodium source, an iron source, a phosphorus source and a composite carbon source is roasted in a reducing atmosphere at the temperature of 450-650 ℃ to prepare the carbon composite ferric sodium pyrophosphate composite material;
the composite carbon source comprises a small molecular carbon source, PEG and phenolic resin.
2. The method for preparing a carbon composite ferric sodium pyrophosphate composite material according to claim 1, wherein the sodium source is at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydroxide, sodium citrate, sodium nitrate and sodium pyrophosphate;
preferably, the iron source is at least one of ferric nitrate, ferrous oxalate, ferrous acetate, ferrous sulfate, ferric oxide, ferrous oxide and ferric oxide;
preferably, the phosphorus source is at least one of ammonium dihydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, disodium dihydrogen pyrophosphate and diammonium hydrogen phosphate;
preferably, in the sodium source, the iron source and the phosphorus source, the element ratio of Na, fe and P is 3.96-4.04:3:3.96-4.04, preferably 4:3:4.
3. The method for preparing the carbon composite ferric sodium pyrophosphate composite material of claim 1, wherein the small molecular carbon source is at least one of sucrose, glucose, citric acid and malic acid;
preferably, the molecular weight of the PEG is 2000-20000.
4. The method for preparing the carbon composite ferric sodium pyrophosphate composite material of claim 1, wherein the mass ratio of the small molecular carbon source, the PEG and the phenolic resin in the composite carbon source is 5-7: 2 to 4:0.5 to 3; preferably 6:3:0.5-2;
preferably, the total mass of the composite carbon source is 5-30% of the mass of the sodium ferric pyrophosphate which is synthesized theoretically.
5. The method for preparing the carbon composite ferric sodium pyrophosphate composite material according to claim 1, wherein the mixture is particles obtained by spraying a mixed slurry of a sodium source, an iron source, a phosphorus source and a composite carbon source;
preferably, the mixed slurry is prepared by wet ball milling and sand milling of a sodium source, an iron source, a phosphorus source and a composite carbon source;
preferably, the medium in the wet ball milling stage is an organic solvent, preferably at least one of methanol, ethanol and acetone;
preferably, the solid content of the ball milling stage is 30-60%, and the ball-material ratio is 5-20:1;
preferably, the ball milling speed is 100-1000rpm, preferably 500-800rmp;
preferably, the ball milling time is 20-60 min;
preferably, the particle size requirement in the precursor slurry after ball milling is D50<2 μm and D100<4 μm;
preferably, the rotational speed of the sanding stage is 1200-2500rpm, preferably 1600-2300rmp;
preferably, the sanding time is 5-40 min;
preferably, the particle size of the precursor after sanding is required to be D50<600nm, D100<1.5 μm;
in the invention, the inlet temperature of the spray drying stage is 180-270 ℃, the spray rate is 20-50L/h, and the carrier gas is nitrogen or argon.
6. The method for producing a carbon composite ferric sodium pyrophosphate composite material according to claim 1, wherein said reducing atmosphere contains at least one of hydrogen, CO, methane, and acetylene;
preferably, the reducing atmosphere is further allowed to contain a diluent gas, and the diluent gas is at least one of nitrogen and inert gas;
preferably, in the reducing atmosphere, the content of the reducing gas is 1% or more, preferably 5 to 10%;
preferably, the roasting temperature is 480-580 ℃;
preferably, the calcination stage is preceded by a reaction of V 1 Is heated to the preheating temperature T at the heating rate of a Then at V 2 Heating to the roasting temperature at the heating rate, and carrying out heat preservation roasting; t (T) a The temperature of (2) is 350-400 ℃; v (V) 1 The temperature rising rate of the catalyst is 3-6 ℃/min; v (V) 2 The temperature rising rate of the catalyst is 1-2 ℃/min;
preferably, the calcination time is 6 to 18 hours, more preferably 10 to 14 hours.
7. A carbon composite ferric sodium pyrophosphate composite material prepared by the preparation method of any one of claims 1 to 6.
8. A composite positive electrode material of a sodium ion battery, comprising a positive electrode active material, a conductive agent and a binder, wherein the positive electrode active material comprises the carbon composite ferric sodium pyrophosphate composite material prepared by the preparation method of any one of claims 1 to 6.
9. A composite positive electrode of a sodium ion battery, comprising a current collector and a positive electrode material composited on the current collector, wherein the positive electrode material comprises the positive electrode material of claim 8.
10. A sodium ion battery comprising the positive electrode of claim 9.
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| CN116675207A (en) * | 2023-07-28 | 2023-09-01 | 赣州立探新能源科技有限公司 | Iron-based pyrophosphoric acid salt material, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116675207A (en) * | 2023-07-28 | 2023-09-01 | 赣州立探新能源科技有限公司 | Iron-based pyrophosphoric acid salt material, and preparation method and application thereof |
| CN116675207B (en) * | 2023-07-28 | 2023-10-20 | 赣州立探新能源科技有限公司 | Iron-based pyrophosphoric acid salt material, and preparation method and application thereof |
| CN116741988A (en) * | 2023-08-11 | 2023-09-12 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
| CN116779847A (en) * | 2023-08-11 | 2023-09-19 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
| CN116779847B (en) * | 2023-08-11 | 2024-01-23 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
| CN118373401A (en) * | 2024-06-25 | 2024-07-23 | 江苏中兴派能电池有限公司 | Hollow porous composite ferric sodium pyrophosphate positive electrode material, preparation method thereof, positive electrode and sodium ion battery |
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