GB2619674A - Deposited sodium iron phosphate positive electrode material, and preparation method therefor and application thereof - Google Patents
Deposited sodium iron phosphate positive electrode material, and preparation method therefor and application thereof Download PDFInfo
- Publication number
- GB2619674A GB2619674A GB2314900.8A GB202314900A GB2619674A GB 2619674 A GB2619674 A GB 2619674A GB 202314900 A GB202314900 A GB 202314900A GB 2619674 A GB2619674 A GB 2619674A
- Authority
- GB
- United Kingdom
- Prior art keywords
- sodium
- positive electrode
- electrode material
- phosphate
- source
- Prior art date
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- Granted
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 19
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 title abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 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
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 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
- 229910052748 manganese 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
- 239000000126 substance Substances 0.000 claims abstract description 4
- 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 57
- 239000011734 sodium Substances 0.000 claims description 57
- 229910052708 sodium Inorganic materials 0.000 claims description 57
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 46
- 239000005955 Ferric phosphate Substances 0.000 claims description 42
- 229940032958 ferric phosphate Drugs 0.000 claims description 42
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 42
- 230000008021 deposition Effects 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 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 9
- 229910000147 aluminium phosphate Inorganic materials 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
- 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
- 238000010438 heat treatment Methods 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 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
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 239000003513 alkali 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
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 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
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- DDSZSJDMRGXEKQ-UHFFFAOYSA-N iron(3+);borate Chemical compound [Fe+3].[O-]B([O-])[O-] DDSZSJDMRGXEKQ-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
- 238000002156 mixing Methods 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
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 17
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 28
- 239000001307 helium Substances 0.000 description 15
- 229910052734 helium Inorganic materials 0.000 description 15
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000015572 biosynthetic process Effects 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
- 239000010949 copper Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 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
- 239000011572 manganese Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910020939 NaC104 Inorganic materials 0.000 description 1
- 229910021312 NaFePO4 Inorganic materials 0.000 description 1
- 229910007541 Zn O Inorganic materials 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
- 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
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 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
- 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Compounds Of Iron (AREA)
Abstract
A deposited sodium iron phosphate positive electrode material, the chemical formula thereof being NaFePO4-xB2O3@A, wherein 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. When a battery prepared from the deposited sodium iron phosphate positive electrode material is charged and discharged, the sodium ion diffusion distance is short, and the transmission rate is high. The deposited sodium iron phosphate positive electrode material comprises boron oxide and a nano oxide; boron oxide can reduce a change degree of the structure in the charging/discharging process of the sodium iron phosphate positive electrode material, the conductivity of the sodium iron phosphate positive electrode material is improved, and the electrochemical performance is improved. The nano oxide can effectively inhibit a shuttle effect existing in the sodium iron phosphate positive electrode material, and the cycle performance of the sodium iron phosphate positive electrode material is improved.
Description
DEPOSITED SODIUM IRON PHOSPHATE POSITIVE ELECTRODE MATERIAL, AND PREPARATION METHOD THEREFOR AND APPLICATION THEREOF
FIELD
[0001] The present disclosure relates to the technical field of sodium ion batteries, and specifically to a deposition type sodium ferric phosphate positive electrode material and a preparation method and application thereof
BACKGROUND
[0002] The materials of sodium-ion batteries and lithium-ion batteries have similar structures.
Compared with lithium-ion batteries, sodium-ion batteries have unique advantages in terms of resources, safety, and cycle life. Therefore, sodium-ion batteries will be a reasonable alternative solution to lithium-ion batteries, especially in the application of non-mobile batteries, such as battery storage power stations, service area charging stations, etc. Currently, it is not a small problem to replace lithium ion with sodium ion batteries.
[0003] In view of the large mass and radius of sodium ion, high standard potential and lower electronegativity, the voltage of sodium ion battery is lower than that of corresponding lithium ion, which makes the quality and energy density of sodium ion battery inferior to that of lithium ion battery, which becomes a main factor of restriction to replace lithium ion battery One of the key parts to improve the performance of sodium ion battery is the positive electrode material, and the positive electrode material is the core element that directly affects the electrochemical performance of sodium ion battery.
[0004] At present, among the researched sodium ion battery electrode materials, the structure of the sodium ferric phosphate positive electrode material is not easy to change. During charge and discharge, the lattice structure restriction, the lattice expansion and collapse have little influence on the sodium ion deintercalation process. Therefore, the battery has higher stability and cycle performance; at the same time, the sodium ferric phosphate positive electrode material has a specific regular spatial shape, so the effect of increasing energy density by depositing oxide is more obvious.
[0005] Therefore, there is urgent need to provide a method for preparing a deposition type
--
sodium ferric phosphate positive electrode material to provide foundation and technical support for the preparation of high-performance sodium-ion batteries and the practical application of sodium-ion batteries.
SUMMARY
[0006] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. For this reason, the present invention proposes a deposition type sodium ferric phosphate positive electrode material and preparation method and application thereof The deposition type sodium ferric phosphate positive electrode material has good recycling performance.
[0007] In order to achieve the above objectives, the present invention adopts the following technical solutions: [0008] A deposition type iron sodium phosphate positive electrode material, having a chemical formula of NaFePO4-xB4O3@ A, x=0.00 I -0.3; the A is at least one of the nano oxides of Zn, Fe, Cu, Ni, Mn, Co, Cr, Ti, Al, Mo, Zr or Ag element.
[0009] A method for preparing a deposition type sodium ferric phosphate positive electrode material, comprising the following steps: MOM (I) mixing sodium source, phosphorus source, ferrous source, boron source, and complexing agent for reaction, adding alkali to adjust pH, performing solid-liquid separation, and concentrating the liquid phase to obtain a gel; [00111 (2) heating and ball milling the gel to obtain sodium ferric phosphate NaFePO4-xB203, x=0.001-0.3; [0012] (3) purging the sodium ferric phosphate NaFePO4-xB4O3 with A in the form of gas to obtain the deposition type sodium ferric phosphate; the A is at least one of nano oxides of Zn, Fe, Cu, Ni, Mn, Co, Cr, Ti, Al, Mo, Zr or Ag element.
[0013] 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.
[0014] Preferably, in step (1), the phosphorus source is at least one of phosphoric acid, sodium phosphate, iron phosphate, ferrous phosphate, ammonium phosphate, ammonium dihydrogen phosphate, iron phosphate, or ammonium hydrogen phosphate.
[0015] Preferably, in step (1), the boron source is at least one of boron oxide, boric acid, sodium borate or iron borate.
[0016] Preferably, in step (1), the ferrous source is at least one of ferrous hydroxide, ferrous phosphate, ferrous oxalate or ferrous acetate.
[0017] Preferably, in step (1), the complex in the complexing agent is at least one of citric acid, oxalic acid or lactic acid.
[0018] Preferably, in step (1), the molar ratio of sodium, phosphate, iron, and boron in the sodium source, phosphorus source, ferrous source, and boron source is (0.01-110): (0.01-120): (0.01 -110): (0.001-30).
[0019] Preferably, in step (1), the mass percentage of the complex in the complexing agent is 0.1-40w%.
[0020] Preferably, in step (2), the alkali is at least one of sodium hydroxide, ferrous hydroxide, and ammonia water.
[0021] Preferably, in step (2), an atmosphere of the ball n011 is an inert atmosphere.
[0022] Further preferably, the inert atmosphere is at least one of argon, helium, neon or xenon. [0023] Preferably, in step (3), the purging airflow is 30-200 ml/min.
[0024] A battery, includes the deposition type iron sodium phosphate positive electrode material.
[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: [0026] 1. The battery prepared by the deposition type sodium ferric phosphate positive electrode material of the present invention has a short sodium ion diffusion distance and a faster transmission rate during charging and discharging. For the boron oxide and nano oxides in the deposition type sodium ferric phosphate positive electrode material, the boron oxide can reduce the degree of structural changes during charging and discharging process, increase the conductivity of sodium ferric phosphate positive electrode materials, and improve -3 -electrochemical performance. The nano oxides can inhibit the shuttle effect in the sodium ferric phosphate positive electrode materials effectively and correspondingly increase the recycling performance of the sodium ferric phosphate positive electrode material.
[0027] 2. When the NaFePO4-x13201 positive electrode material prepared by introducing boron oxide in the preparation method of the present invention is prepared into a sbattery, a short sodium ion diffusion distance and faster transmission rate are obtained during charging and discharging of the battery. In Fig 2, a dense film of about I 5nm is obtained on the surface of the obtained substrate of NaFePO4-3.86B203@ZnO, which improves the coulombic efficiency of the sodium ferric phosphate positive electrode material to be close to 100%.
[0028] 3. The present invention uses nano oxide to deposit sodium ferric phosphate, this is because not only nano oxide has higher conductivity and higher chemical stability, but also some metals (such as Al, Zn, Cu, Fe, Ti, etc.) have more reserves compared with nickel, cobalt, manganese, etc., and the prepared nano oxides are prepared in large quantities and are non-toxic. Therefore, it has a positive role in promoting the improvement of sodium ferric phosphate positive electrode materials, which is beneficial to the commercial application of sodium ferric phosphate positive electrode materials.
BRIEF DESCRIPTION OF DRAWINGS
[0029] Fig. I is a flowchart of Example I of the present invention.
[0030] Fig.2 is a TEM image of ZnO deposition type sodium ferric phosphate prepared in Example I of the present invention.
DETAILED DESCRIPTION
[0031] Hereinafter, the concept of the present invention and the technical effects produced will be described clearly and completely in combination with the embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled -4 -in the art without creative work belong to the scope of protection of the present invention. Example 1 [0032] The formula of the deposition type sodium ferric phosphate positive electrode material in this example is NaFePO4-0.14B203@ZnO.
[0033] The preparation method of the deposition type sodium ferric phosphate positive electrode material of this example comprises the following specific steps: [0034] (1) Gel synthesis: 65g of sodium hydroxide, 173g of ammonium dihydrogen phosphate, and 8.7g of boric acid were dissolved separately, and then mixed together. 215.9g of ferrous oxalate was added so that molar ratio of sodium, phosphoric acid, ferrous and boron was 1.63: 1.5: 1.5: 0.14, and 5.17w% 0.8L citric acid solution was added. The temperature was controlled at about 55°C. Ammonia water was added dropwise and stirred to control the pH at 8.38, and the mixture was mixed and aged for 6114min. The residue was removed, and a gel was obtained.
[0035] (2) Heat treatment: the gel was heated under helium atmosphere and 530°C for 7h4min, and then ball milled with a ball mill for 81126min under helium atmosphere to obtain sodium ferric phosphate NaFePO4-0.14B203.
[0036] (3) ZnO deposition: 80g of NaFePO4-0.14B203 was loaded into the deposition reactor. N, was filled to exhaust. The mixture was heated to 60°C, purged with 1\17-H2 at 60m1/min, and 0.97g of nano-ZnO was loaded through helium. After reacting for 57 minutes, the synthesized ZnO deposited NaFePO4-0.14B203 was washed, and dried at 80°C tbr 2h to obtain ZnO /0 deposited NaFePa4-0. I4B203 CO? Zn O. [0037] Fig. 2 is a TEM image of NaFePO4-0.14B203@ZnO prepared in Example 1 of the present invention.
Example 2
[0038] The formula of the deposition type sodium ferric phosphate positive electrode material 25 in this example is NaFePO4-0.23B203@ZnO.
[0039] The preparation method of the deposition type sodium ferric phosphate positive electrode material of this example comprises the following specific steps: [0049] (I) Gel synthesis: 88g of sodium hydroxide, 242g of ammonium dihydrogen phosphate, -5 -and 12.2g of boric acid were dissolved separately, and then mixed together. 302.2g of ferrous oxalate was added so that molar ratio of sodium, phosphoric acid, ferrous and boron was 2.21: 2.1:2.1:0.23, and 6.20w% IL citric acid solution was added. The temperature was controlled at about 55°C. Ammonia water was added dropwise and stirred to control the pH at 8.37, and the mixture was mixed and aged tbr 6h4min. The residue was removed, and a gel was obtained.
[0041] (2) Heat treatment: the gel was heated under helium atmosphere and 560°C for 6h3Omin, and then ball milled with a ball mill for 8h 19min under helium atmosphere to obtain sodium ferric phosphate NaFePO4-0.23B203.
[0042] (3) ZnO deposition: 80g of NaFePO4-0.23B203 was loaded into the deposition reactor.
N, was filled to exhaust. The mixture was heated to 65°C, purged with N2-1-12 at 75m1/min, and I.22g of nano-ZnO was loaded through helium. After reacting for 62 minutes, the synthesized ZnO deposited NaFePO4-0.23B003 was washed, and dried at 80°C for 2h to obtain ZnO deposited NaFePO4-0.23B203@ZnO.
Example 3
[0043] The formula of the deposition type sodium ferric phosphate positive electrode material in this example is NaFePO4-0.05B203Ce(CuO.
[0044] The preparation method of the deposition type sodium ferric phosphate positive electrode material of this example comprises the following specific steps: [0045] (1) Gel synthesis: 27g of sodium citrate, 34.5g of ammonium clihydrogen phosphate, and 4.9g of boric acid were dissolved separately, and then mixed together. 43.2g of ferrous oxalate was added so that molar ratio of sodium, phosphoric acid, ferrous and boron was 0.315: 0.3: 0.3: 0.05, and 4.03w% IL citric acid solution was added. The temperature was controlled at about 55°C. Ammonia water was added dropwise and stirred to control the pH at 8.72, and the mixture was mixed and aged for 6h4min The residue was removed, and a gel was obtained.
[0046] (2) Heat treatment: the gel was heated under helium atmosphere and 480°C for 8h44min, and then ball milled with a ball mill for 8h34min under helium atmosphere to obtain sodium ferric phosphate NaFePO4-0.05B203.
[0047] (3) CuO deposition: 100g of NaFePO4-0.05B203 was loaded into the deposition reactor. N2 was filled to exhaust. The mixture was heated to 60°C, purged with N2-I12 at 75m1/min, and 0.79g of nano-CuO was loaded through helium. After reacting for 61 minutes, the synthesized CuO deposited NaFePO4-0.05B203 was washed, and dried at 80°C for 2h to obtain CuO deposited NaFePa4-0.05B203C(e CuO.
Example 4
[0048] The formula of the deposition type sodium ferric phosphate positive electrode material in this example is NaFePO4-0.16B203@CuO.
[00491 The preparation method of the deposition type sodium ferric phosphate positive electrode material of this example comprises the following specific steps: [0050] (1) Gel synthesis: 108g of sodium citrate, 138g of ammonium clihydrogen phosphate, and I 5.7g of boric acid were dissolved separately, and then mixed together. I 72g of ferrous oxalate was added so that molar ratio of sodium, phosphoric acid, ferrous and boron was 1.26: 1.2: 1.2: 0.16, and 5.49w% IL oxalic acid solution was added. The temperature was controlled at about 60°C. Ammonia water was added dropwise and stirred to control the pH at 8.57, and the mixture was mixed and aged for 6h4inin The residue was removed, and a gel was obtained.
[00511 (2) Heat treatment: the gel was heated under helium atmosphere and 440°C for I Oh I 2min, and then ball milled with a ball mill for 8h I 7min under helium atmosphere to obtain sodium ferric phosphate NaFePO4-0. I 613203.
[00521 (3) CuO deposition: 100g of NaFePO4-0.16B4O3 was loaded into the deposition reactor. N, was filled to exhaust. The mixture was heated to 65°C, purged with 1\11412 at 80m1/min, and I.27g of nano-CuO was loaded through helium. After reacting for 66 minutes, the synthesized CuO deposited NaFePO4-0. I 613203 was washed, and dried at 80°C for 2h to obtain CuO deposited NaFePa4-0. I 6B203@ CuO.
Comparative example 1 [0053] The preparation method of sodium ferric phosphate positive electrode material of this comparative example comprises the following specific steps: [0054] It is different from Example 1 in that in step (1), 63g of sodium hydroxide and 173g of ammonium dihydrogen phosphate were dissolved separately and then mixed together. 215.9g of ferrous oxalate was added so that the molar ratio of sodium, phosphoric acid, and ferrous was 1.58:1.5: 1.5. and 5.17w% 0.8L citric acid solution was added. The final result was NaFePO4.
Comparative example 2 [00551 The preparation method of sodium ferric phosphate positive electrode material of this comparative example comprises the following specific steps: [00561 (1) Gel synthesis: 65g of sodium hydroxide, 173g of ammonium dihydrogen phosphate, and 8.7g of boric acid were dissolved separately, and then mixed together. 215.9g of ferrous oxalate was added so that molar ratio of sodium, phosphoric acid, ferrous and boron was 1.63: 1.5:1.5:0.14, and 5.17w% 0.8L citric acid solution was added. The temperature was controlled at about 55°C. Ammonia water was added dropwise and stirred to control the pH at 8.38, and the mixture was mixed and aged for 6h4min The residue was removed, and a gel was obtained.
[00571 (2) Heat treatment: the gel was heated under helium atmosphere and 530°C for 7h17min, and then ball milled with a ball mill for 8h under helium atmosphere to obtain sodium ferric phosphate NaFePO4-0.14B203.
Test example:
[00581 The positive electrode material, carbon black conductive agent and polytetrafluoroethylene in Examples 1-4 and Comparative Examples 1-2 were dissolved in deionized water at a mass ratio of 80:15:5 to form a slurry, and then the slurry was coated on a current collector to prepare into a pole piece. The pole piece was dried in a drying oven at 65°C for 8h36min. A sodium sheet was used as the counter electrode, 1.2 mol/L NaC104 was used as the electrolyte, and Celgard 2400 was used as the diaphragm. The battery was assembled in a vacuum glove box under an argon atmosphere. The cycle performance was tested with an electrochemical workstation. The tested current density was 250 mike, the charge-discharge interval was 2.5-3.0V, and the test was performed at a rate of 0.5C.
[00591 Table 1 Data of Examples 1-4 and Comparative Examples 1-2 samples specific discharge capacity coulombic efficiency (%) (mAhig-1) 1st 100th 300th pi 100th 300th Example I 114.5 92.2 77.2 62.4 93.9 99.9 Example 2 118.9 103.8 90.0 63.8 97.1 99.8 Example 3 115.4 95.6 81.2 60.9 91.0 99.9 -8 -Example 4 I I 7.8 106.8 89.9 66.8 97.4 99.8 Comparative 90.6 76.8 65.4 55.9 85.9 99.6
Example 1
Comparative 92.3 76.0 63.3 56.2 86.4 99.7
Example 2
[0060] It can be seen from Table 1 that after 300 cycles, the coulombic efficiency of Example 1 and Example 3 could reach 99.9, and the first specific discharge capacity of Examples 1-4 is as high as 114.5mAhg1, 118.9mAh-g-1, 115.4 mAh-g-1 and 117.8 mAh-g-1, whereas the specific 5 discharge capacities of Comparative Example 1 and Comparative Example 2 are 90.6 mAh-g-1 and 92.3 mAh.g-1, which are much smaller than those of the Examples of the present invention.
[0061] The embodiments of the present invention are described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above-mentioned embodiments. Within the scope of knowledge possessed by those of ordinary skilled in the art, various modifications can be made without departing from the purpose of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can he combined with each other if there is no conflict.
Claims (10)
- CLAIMSI. A deposition type sodium ferric phosphate positive electrode material, wherein the deposition type sodium ferric phosphate positive electrode material has a chemical formula of NaFePO4-x13201@ A, x=0.001 -0.3; the A is at least one of nano oxides of Zn, Fe, Cu, Ni, Mn, Co, Cr, Ti, Al, Mo, Zr or Ag element.
- 2. A method for preparing the deposition type sodium ferric phosphate positive electrode material according to claim I, comprising the following steps: (1) mixing sodium source, phosphorus source, ferrous source, boron source, and complexing agent for reaction, adding alkali to adjust pH, performing solid-liquid separation, and concentrating the liquid phase to obtain a gel; (2) heating and ball milling the gel to obtain sodium ferric phosphate NaFePO4-x13203, x=0.001-0.3; (3) purging the sodium ferric phosphate NaFePO4-xB103 with A in the form of gas to obtain the deposition type sodium ferric phosphate; the A is at least one of nano oxides of Zn, Fe, Cu, Ni, Mn, Co, Cr, Ti, Al, Mo, Zr or Ag element.
- 3. The preparation method according to claim 2, wherein in step (I), 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 preparation method according to claim 2, wherein in step (I), the phosphorus source is at least one of phosphoric acid, sodium phosphate, iron phosphate, ferrous phosphate, ammonium phosphate, ammonium dihydrogen phosphate, iron phosphate or diammonium hydrogen phosphate.
- 5. The preparation method according to claim 2, wherein in step (I), the boron source is at least one of boron oxide, boric acid, sodium borate or iron borate.
- 6. The preparation method according to claim 2, wherein in 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 step (1), a molar ratio of sodium, phosphate, iron, and boron in the sodium source, phosphorus source, ferrous source, and 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 step (1), the complex in the complexing agent is at least one of citric acid, oxalic acid or lactic acid.
- 9. The preparation method according to claim 2, wherein in step (3), the loading amount of A s 0.0001-0.1 of the mass of NaFePO4-x13,03.
- 10. A battery, comprising the deposition type sodium ferric phosphate positive electrode material of claim 1.
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