CN114068906A - Deposition type sodium iron phosphate cathode material and preparation method and application thereof - Google Patents
Deposition type sodium iron phosphate cathode material and preparation method and application thereof Download PDFInfo
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- CN114068906A CN114068906A CN202111201841.5A CN202111201841A CN114068906A CN 114068906 A CN114068906 A CN 114068906A CN 202111201841 A CN202111201841 A CN 202111201841A CN 114068906 A CN114068906 A CN 114068906A
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- Prior art keywords
- sodium
- iron phosphate
- phosphate
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- ferrous
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- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 title claims abstract description 45
- 230000008021 deposition Effects 0.000 title claims abstract description 31
- 239000010406 cathode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 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 description 20
- 239000011734 sodium Substances 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 229940062993 ferrous oxalate Drugs 0.000 claims description 8
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000005955 Ferric phosphate Substances 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- 229940032958 ferric phosphate Drugs 0.000 claims description 5
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 229940116007 ferrous phosphate Drugs 0.000 claims description 4
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 4
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 4
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 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 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000004280 Sodium formate Substances 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
- 235000015165 citric acid Nutrition 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
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims 1
- 235000019838 diammonium phosphate Nutrition 0.000 claims 1
- DDSZSJDMRGXEKQ-UHFFFAOYSA-N iron(3+);borate Chemical compound [Fe+3].[O-]B([O-])[O-] DDSZSJDMRGXEKQ-UHFFFAOYSA-N 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 15
- 239000010405 anode material Substances 0.000 abstract description 10
- 238000007599 discharging Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 28
- 239000012298 atmosphere Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021312 NaFePO4 Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1027—Oxides
-
- 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
- H01M4/36—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Abstract
The invention belongs to the technical field of sodium ion batteries, and discloses a deposition type sodium iron phosphate positive electrode material, a preparation method and application thereof, wherein the chemical formula of the material is NaFePO4‑xB2O3@ A, x ═ 0.001-0.3; a is at least one of nano oxides of Zn, Fe, Cu, Ni, Mn, Co, Cr, Ti, Al, Mo, Zr or Ag elements. The battery prepared from the deposition type sodium iron phosphate cathode material has short diffusion distance of sodium ions and faster transmission rate during charging and discharging; boron oxide and nano oxide in the deposition type sodium iron phosphate anode material; the boron oxide can reduce the structural change degree in the charge-discharge process, improve the conductivity of the sodium iron phosphate anode material and improve the electrochemical performance; the nanometer oxide can effectively inhibit shuttle effect existing in the sodium iron phosphate anode material, and correspondingly improves the recycling performance of the sodium iron phosphate anode material.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a deposition type sodium iron phosphate positive electrode material, and a preparation method and application thereof.
Background
The materials of the sodium ion battery and the lithium ion battery have similar structures, and compared with the lithium ion battery, the sodium ion battery has unique advantages in the aspects of resources, safety, cycle life and the like, so the sodium ion battery is a reasonable alternative scheme of the lithium ion battery, particularly in the application direction of non-mobile batteries, such as battery storage power stations, service area charging stations and the like, but the replacement of lithium ions by the sodium ion battery is not a small problem.
Because the mass and the radius of the sodium ions are larger, the standard potential is higher, and the electronegativity is lower, the voltage of the sodium ion battery is lower than that of corresponding lithium ions, so that the mass and the energy density of the sodium ion battery are not as good as those of the lithium ion battery, and the sodium ion battery is restricted to become a main factor capable of replacing the lithium ion battery. One of the key parts for improving the performance of the sodium-ion battery is in the aspect of positive electrode materials, and the positive electrode materials are core elements which directly influence the electrochemical performance of the sodium-ion battery.
At present, in the electrode materials of the sodium ion battery, the structure of the sodium iron phosphate anode material is not easy to change, so that the influence of the limitation of the lattice structure and the expansion and collapse of the lattice in the process of sodium ion deintercalation is small during charging and discharging, and the stability and the cycle performance of the battery are higher; meanwhile, the sodium iron phosphate cathode material has a specific regular space shape, so that the effect of improving the energy density by depositing an oxide is more obvious.
Therefore, it is highly desirable to provide a method for preparing a deposition-type sodium iron phosphate cathode material, which provides a foundation and a technical support for the preparation of a high-performance sodium ion battery and the practical application of the sodium ion battery.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a deposition type sodium iron phosphate cathode material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a deposited sodium iron phosphate cathode material with a chemical formula of NaFePO4-xB2O3@ A, x ═ 0.001-0.3; a is at least one of nano oxides of Zn, Fe, Cu, Ni, Mn, Co, Cr, Ti, Al, Mo, Zr or Ag elements.
A preparation method of a deposition type sodium iron phosphate cathode material comprises the following steps:
(1) mixing a sodium source, a phosphorus source, a ferrous iron source, a boron source and a complexing agent, reacting, adding alkali to adjust the pH value, carrying out solid-liquid separation, taking a liquid phase, and concentrating to obtain a gel;
(2) carrying out heat treatment and ball milling on the gel to obtain sodium ferric phosphate NaFePO4-xB2O3，x＝0.001-0.3；
(3) Purging A in gas form with the sodium iron phosphate NaFePO4-xB2O3Obtaining deposition type sodium iron phosphate; a is at least one of nano oxides of Zn, Fe, Cu, Ni, Mn, Co, Cr, Ti, Al, Mo, Zr or Ag elements.
Preferably, in step (1), the sodium source is at least one of sodium hydroxide, sodium formate, sodium acetate, sodium oxalate, sodium phosphate, sodium borate or sodium citrate.
Preferably, in the step (1), the phosphorus source is at least one of phosphoric acid, sodium phosphate, iron phosphate, ferrous phosphate, ammonium dihydrogen phosphate, iron phosphate or ammonium hydrogen phosphate.
Preferably, in step (1), the boron source is at least one of boron oxide, boric acid, sodium borate or ferric borate.
Preferably, in the step (1), the ferrous source is at least one of ferrous hydroxide, ferrous phosphate, ferrous oxalate or ferrous acetate.
Preferably, in the step (1), the complex in the complexing agent is at least one of citric acid, oxalic acid or lactic acid.
Preferably, in the step (1), the molar ratio of sodium, phosphate, iron and boron in the sodium source, the phosphorus source, the ferrous iron source and the boron source is (0.01-110): (0.01-120): (0.01-110): (0.001-30).
Preferably, in the step (1), the mass percentage of the complex in the complexing agent is 0.1-40 w%.
Preferably, in the step (2), the alkali is at least one of sodium hydroxide or ferrous hydroxide and ammonia water.
Preferably, in the step (2), the atmosphere of the ball milling is inert atmosphere.
Further preferably, the inert atmosphere is at least one of argon, helium, neon, or xenon.
Preferably, in the step (3), the flow of the purge gas is 30-200 mL/min.
A battery comprises the deposited sodium iron phosphate cathode material.
Compared with the prior art, the invention has the following beneficial effects:
1. the battery prepared from the deposition type sodium iron phosphate cathode material has short diffusion distance of sodium ions and faster transmission rate during charging and discharging; boron oxide and nano oxide in the deposition type sodium iron phosphate anode material; the boron oxide can reduce the structural change degree in the charge-discharge process, improve the conductivity of the sodium iron phosphate anode material and improve the electrochemical performance; the nanometer oxide can effectively inhibit shuttle effect existing in the sodium iron phosphate anode material, and correspondingly improves the recycling performance of the sodium iron phosphate anode material.
2. NaFePO prepared by introducing boron oxide in the preparation method of the invention4-xB2O3The positive electrode material is prepared into sodium ions during charging and discharging of the batteryThe sub-diffusion distance is short, and the transmission rate is higher; in FIG. 2, NaFePO was obtained4-3.86B2O3The @ ZnO substrate surface obtains a layer of compact film with the thickness of about 15nm, and improves the coulomb efficiency of the ferric sodium phosphate anode material to be higher and close to 100%.
3. The invention uses the nano oxide to deposit the sodium iron phosphate, because the nano oxide not only has higher conductivity and high chemical stability, but also has more reserves of partial metals (such as Al, Zn, Cu, Fe and Ti) compared with nickel, cobalt, manganese and the like, and the prepared nano oxide has large preparation amount and no toxicity, thereby having positive promoting effect on the improvement of the sodium iron phosphate cathode material and being beneficial to the commercial application of the sodium iron phosphate cathode material.
Drawings
FIG. 1 is a flowchart of example 1 of the present invention;
FIG. 2 is a TEM image of ZnO-deposited sodium iron phosphate prepared in example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The chemical formula of the deposition type sodium iron phosphate cathode material of the embodiment is NaFePO4-0.14B2O3@ZnO。
The preparation method of the deposition type sodium iron phosphate cathode material provided by the embodiment comprises the following specific steps:
(1) synthesis of gel: respectively dissolving 65g of sodium hydroxide, 173g of ammonium dihydrogen phosphate and 8.7g of boric acid, mixing, adding 215.9g of ferrous oxalate, wherein the molar ratio of sodium to phosphoric acid to ferrous iron to boron is 1.63: 1.5: 1.5: 0.14, adding 5.17 w% of 0.8L citric acid solution, controlling the temperature at about 55 ℃, dropwise adding ammonia, stirring to control the pH value at 8.38, mixing, aging for 6h and 4min, and removing residues to obtain a gel.
(2) And (3) heat treatment: heating the gel at 530 deg.C for 7h4min under He atmosphere, and ball milling for 8h26min under He atmosphere with ball mill to obtain sodium ferric phosphate NaFePO4-0.14B2O3。
(3) ZnO deposition: mixing 80g NaFePO4-0.14B2O3Charging into a deposition reactor, charging with N2Exhausting, heating to 60 deg.C, and introducing N at 60mL/min2-H2Purging, loading 0.97g of nano ZnO by He, reacting for 57min, and depositing NaFePO on the synthesized ZnO4-0.14B2O3Washing, and drying at 80 deg.C for 2h to obtain ZnO-deposited NaFePO4-0.14B2O3@ZnO。
FIG. 2 shows NaFePO prepared in example 1 of the present invention4-0.14B2O3TEM image of @ ZnO.
Example 2
The chemical formula of the deposition type sodium iron phosphate cathode material of the embodiment is NaFePO4-0.23B2O3@ZnO。
The preparation method of the deposition type sodium iron phosphate cathode material provided by the embodiment comprises the following specific steps:
(1) synthesis of gel: respectively dissolving 88g of sodium hydroxide, 242g of ammonium dihydrogen phosphate and 12.2g of boric acid, mixing, adding 302.2g of ferrous oxalate, wherein the molar ratio of sodium to phosphoric acid to ferrous iron to boron is 2.21: 2.1: 2.1: 0.23, adding 6.20 w% of 1L citric acid solution, controlling the temperature at about 55 ℃, dropwise adding ammonia, stirring to control the pH value at 8.37, mixing, aging for 6h4min, and removing residues to obtain a gel.
(2) And (3) heat treatment: heating the gel at 560 deg.C for 6h30min under He atmosphere, and ball milling for 8h19min under He atmosphere with ball mill to obtain sodium ferric phosphate NaFePO4-0.23B2O3。
(3) ZnO deposition: mixing 80g NaFePO4-0.23B2O3Charging into a deposition reactor, charging with N2Exhausting, heating to 65 deg.C, and introducing N at 75mL/min2-H2Purge, 1.2Loading 2g nano ZnO by He, reacting for 62min, and depositing NaFePO on the synthesized ZnO4-0.23B2O3Washing, and drying at 80 deg.C for 2h to obtain ZnO-deposited NaFePO4-0.23B2O3@ZnO。
Example 3
The chemical formula of the deposition type sodium iron phosphate cathode material of the embodiment is NaFePO4-0.05B2O3@CuO。
The preparation method of the deposition type sodium iron phosphate cathode material provided by the embodiment comprises the following specific steps:
(1) synthesis of gel: respectively dissolving 27g of sodium citrate, 34.5g of ammonium dihydrogen phosphate and 4.9g of boric acid, mixing, adding 43.2g of ferrous oxalate, wherein the molar ratio of sodium to phosphoric acid to ferrous iron to boron is 0.315: 0.3: 0.3: 0.05, adding 1L of oxalic acid solution with the mass fraction of 4.03 w%, controlling the temperature to be about 55 ℃, dropwise adding ammonia, stirring, controlling the pH value to be 8.72, mixing, aging for 6h4min, and removing residues to obtain a gel.
(2) And (3) heat treatment: heating the gel at 480 deg.C for 8.0h44min under He atmosphere, and ball milling for 8h34min under He atmosphere with ball mill to obtain sodium iron phosphate NaFePO4-0.05B2O3。
(3) Deposition of CuO: mixing 100g NaFePO4-0.05B2O3Charging into a deposition reactor, charging with N2Exhausting, heating to 60 deg.C, and introducing N at 75mL/min2-H2Purging, loading 0.79g of nano CuO by He, reacting for 61min, and depositing NaFePO by the synthesized CuO4-0.05B2O3Washing and drying at 80 ℃ for 2h to obtain NaFePO with CuO deposited4-0.05B2O3@CuO。
Example 4
The chemical formula of the deposition type sodium iron phosphate cathode material of the embodiment is NaFePO4-0.16B2O3@CuO。
The preparation method of the deposition type sodium iron phosphate cathode material provided by the embodiment comprises the following specific steps:
(1) synthesis of gel: respectively dissolving 108g of sodium citrate, 138g of ammonium dihydrogen phosphate and 15.7g of boric acid, mixing, adding 172g of ferrous oxalate, wherein the molar ratio of sodium to phosphoric acid to ferrous iron to boron is 1.26: 1.2: 1.2: 0.16, adding 1L oxalic acid solution with the mass fraction of 5.49 w%, controlling the temperature at about 60 ℃, dropwise adding ammonia, stirring, controlling the pH value at 8.57, mixing, aging for 6h4min, and removing residues to obtain a gel.
(2) And (3) heat treatment: heating the gel at 440 deg.C for 10h12min under He atmosphere, and ball milling for 8h17min under He atmosphere to obtain sodium ferric phosphate NaFePO4-0.16B2O3。
(3) Deposition of CuO: mixing 100g NaFePO4-0.16B2O3Charging into a deposition reactor, charging with N2Exhausting, heating to 65 deg.C, and introducing N at 80mL/min2-H2Purging, loading 1.27g of nano CuO by He, reacting for 66min, and depositing NaFePO by the synthesized CuO4-0.16B2O3Washing and drying at 80 ℃ for 2h to obtain NaFePO with CuO deposited4-0.16B2O3@CuO。
Comparative example 1
The preparation method of the sodium iron phosphate cathode material comprises the following specific steps:
the difference from example 1 is that: respectively dissolving 63g of sodium hydroxide and 173g of ammonium dihydrogen phosphate in the step (1), mixing, adding 215.9g of ferrous oxalate, wherein the molar ratio of sodium to phosphoric acid to ferrous is 1.58: 1.5: 1.5, adding 5.17 w% of 0.8L citric acid solution to obtain the final product NaFePO4。
Comparative example 2
The preparation method of the sodium iron phosphate cathode material comprises the following specific steps:
(1) synthesis of gel: respectively dissolving 65g of sodium hydroxide, 173g of ammonium dihydrogen phosphate and 8.7g of boric acid, mixing, adding 215.9g of ferrous oxalate, wherein the molar ratio of sodium to phosphoric acid to ferrous iron to boron is 1.63: 1.5: 1.5: 0.14, adding 5.17 w% of 0.8L citric acid solution, controlling the temperature at about 55 ℃, dropwise adding ammonia, stirring to control the pH value at 8.38, mixing, aging for 6h4min, and removing residues to obtain a gel.
(2) And (3) heat treatment: subjecting the gel to He atmosphere and 530Heating at 7h17min, and ball milling in ball mill under He atmosphere for 8h to obtain sodium iron phosphate NaFePO4-0.14B2O3。
Test example:
dissolving the positive electrode materials, the carbon black conductive agent and the polytetrafluoroethylene in the examples 1-4 and the comparative examples 1-2 in deionized water according to the mass ratio of 80:15:5 to prepare slurry, then coating the slurry on a current collector to prepare a pole piece, and drying the pole piece in a drying oven at 65 ℃ for 8h36 min. Sodium sheet was used as a counter electrode, and the electrolyte was 1.2mol/L NaClO4And Celgard2400 was a separator, and the cell assembly was performed in a vacuum glove box under an argon atmosphere. The cycle performance was tested using an electrochemical workstation at a current density of 250mA g-1The charging and discharging interval is 2.5-3.0V, and the test is carried out under 0.5C multiplying power.
TABLE 1 data for examples 1-4 and comparative examples 1-2
As can be seen from Table 1, after 300 cycles, the coulombic efficiencies of examples 1 and 3 were 99.9, and the first discharge specific capacities of examples 1 to 4 were 114.5mAh · g-1、118.9mAh·g-1、115.4mAh·g-1、117.8mAh·g-1While comparative examples 1 and 2 had specific discharge capacities of 90.6mAh g-1And 92.3mAh · g-1Much smaller than the embodiments of the present invention.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The deposition type sodium iron phosphate cathode material is characterized in that the chemical formula of the deposition type sodium iron phosphate cathode material is NaFePO4-xB2O3@ A, x ═ 0.001-0.3; a is at least one of nano oxides of Zn, Fe, Cu, Ni, Mn, Co, Cr, Ti, Al, Mo, Zr or Ag elements.
2. The preparation method of the deposition type sodium iron phosphate cathode material according to claim 1, characterized by comprising the following steps:
(1) mixing a sodium source, a phosphorus source, a ferrous iron source, a boron source and a complexing agent, reacting, adding alkali to adjust the pH value, carrying out solid-liquid separation, taking a liquid phase, and concentrating to obtain a gel;
(2) carrying out heat treatment and ball milling on the gel to obtain sodium ferric phosphate NaFePO4-xB2O3，x＝0.001-0.3；
(3) Purging A in gas form with the sodium iron phosphate NaFePO4-xB2O3Obtaining deposition type sodium iron phosphate; a is at least one of nano oxides of Zn, Fe, Cu, Ni, Mn, Co, Cr, Ti, Al, Mo, Zr or Ag elements.
3. The method according to claim 2, wherein in the step (1), the sodium source is at least one of sodium hydroxide, sodium formate, sodium acetate, sodium oxalate, sodium phosphate, sodium borate or sodium citrate.
4. The method according to claim 2, wherein in the step (1), the phosphorus source is at least one of phosphoric acid, sodium phosphate, iron phosphate, ferrous phosphate, ammonium dihydrogen phosphate, iron phosphate, or diammonium hydrogen phosphate.
5. The method according to claim 2, wherein in the step (1), the boron source is at least one of boron oxide, boric acid, sodium borate, or iron borate.
6. The method according to claim 2, wherein in the step (1), the ferrous source is at least one of ferrous hydroxide, ferrous phosphate, ferrous oxalate or ferrous acetate.
7. The preparation method according to claim 2, wherein in the step (1), the molar ratio of sodium, phosphate, iron and boron in the sodium source, the phosphorus source, the ferrous source and the boron source is (0.01-110): (0.01-120): (0.01-110): (0.001-30).
8. The preparation method according to claim 2, wherein in the step (1), the complex in the complexing agent is at least one of citric acid, oxalic acid or lactic acid.
9. The method according to claim 2, wherein in the step (3), the loading amount of A is NaFePO4-xB2O30.0001-0.1 mass percent.
10. A battery comprising the deposited sodium iron phosphate positive electrode material of claim 1.
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| GB2314900.8A GB2619674B (en) | 2021-10-15 | 2022-07-28 | Deposited sodium iron phosphate positive electrode material, and preparation method therefor and application thereof |
| DE112022002475.5T DE112022002475T5 (en) | 2021-10-15 | 2022-07-28 | DEPOSITED SODIUM IRON PHOSPHATE MATERIAL FOR POSITIVE ELECTRODE, METHOD FOR PRODUCTION THEREOF AND ITS USE |
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| WO2023060989A1 (en) * | 2021-10-15 | 2023-04-20 | 广东邦普循环科技有限公司 | Deposited sodium iron phosphate positive electrode material, and preparation method therefor and application thereof |
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