CN116621143A - Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate preparation method and application thereof in sodium ion battery - Google Patents
Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate preparation method and application thereof in sodium ion battery Download PDFInfo
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- 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 60
- 235000019851 ferric sodium diphosphate Nutrition 0.000 title claims abstract description 57
- 239000011645 ferric sodium diphosphate Substances 0.000 title claims abstract description 57
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 41
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 59
- 239000011734 sodium Substances 0.000 claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 46
- 239000007774 positive electrode material Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005054 agglomeration Methods 0.000 claims description 7
- 230000002776 aggregation Effects 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 230000002441 reversible effect Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 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 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 14
- 239000013078 crystal Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- -1 iron ions Chemical class 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000005536 Jahn Teller effect Effects 0.000 abstract description 3
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 239000010405 anode material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 235000014653 Carica parviflora Nutrition 0.000 description 4
- 241000243321 Cnidaria Species 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229960004543 anhydrous citric acid Drugs 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000447 polyanionic polymer Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 229910018651 Mn—Ni Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 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 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/42—Pyrophosphates
-
- 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
- H01M4/58—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
- H01M4/626—Metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate and application thereof in sodium ion batteries. Mn, ni co-doped non-stoichiometric ferric sodium pyrophosphate [ Na ] prepared by the invention 3.12 Fe 2.44‑x Mn x/2 Ni x/2 (P 2 O 7 ) 2 ，X＝0.01‑1]The material has high oxidation-reduction valence and electrochemical activity, and the capacity of Mn ions is improved after the Mn ions partially replace iron ions in the crystal material, while Ni ions can partially replace the iron ions in the crystal material and replace partial manganese ions in the crystal structure to improve the structural stability and ensure that the Mn ionsIn a higher valence state to inhibit the Jahn-Teller effect brought by the catalyst and enhance the cycle life of the catalyst.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage, and particularly relates to a preparation method of Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate and application of the Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate in a sodium ion battery.
Background
In recent years, environmental problems have received widespread attention from countries around the world, and the use of traditional fossil energy causes environmental pollution on the one hand and energy crisis on the other hand due to the non-renewable excessive use thereof. Therefore, development and utilization of new energy become the primary choice of people, however, the generation of new energy is easily restricted by climate and environment, and the new energy produced by the method has the characteristic of instability. The energy storage battery can store clean energy, and then stably output and utilize the clean energy to solve the problem of instability.
Among various energy storage devices, secondary batteries represented by lithium ion batteries have been applied to various portable devices in the vicinity of electric automobiles due to their efficient energy conversion storage devices, portability, environmental friendliness, high energy density and power density. However, due to the wide application of lithium ion batteries, the demand of lithium ore resources is continuously expanding, so that the contradiction between supply and demand of lithium and related lithium salt resources is becoming sharp, and therefore, lithium ion batteries are difficult to be ideal choices of low-cost energy storage technologies. Sodium ion batteries are widely distributed due to the fact that sodium ore resources are rich, meanwhile, due to the fact that physical and chemical properties of sodium and lithium are similar, compounds of the sodium ion batteries have great similarity in research methods and applications, and the sodium ion batteries are considered to be the best choice of large-scale energy storage systems.
As with lithium ion batteries, sodium ion battery cathode materials have been the cathode materials of sodium ion batteries, which have been the difficulties and hot spots in sodium ion research. In the research of the sodium ion battery anode material, people are devoted to searching an anode material with high energy density, good stability and environment-friendly resource saving. Most of polyanion positive electrode materials have an open three-position framework, good multiplying power performance and good cycle performance, but the compounds have lower theoretical capacity and generally poorer conductivity, and in order to improve the conductivity and the capacity of the compounds, means such as doping, carbon coating and the like are often adopted.
Among the sodium ion positive electrode materials, layered transition metal oxides, prussian blue analogues and transition metal polyanions have gained significant attention. Layered metal oxides have been touted for their high redox potential and energy density, however Na + The intercalation/deintercalation of (a) generally results in a very complex multiphase transition, leading to rapid structural degradation of the host material during cycling. In addition, layered metal oxides are very sensitive to atmosphere and water, making application a serious problem. Prussian blue analogues as a metal-organic complex with open framework of cubic structure favoring accommodation of large size Na + Two sodium per structural unit can be extracted reversibly at high rates. However, these conventionally synthesized compounds always contain a large amount of lattice defects and coordinated water, leading to Na + A huge loss of storage active sites. Furthermore, thermally unstable structures also raise concerns about the safety of the applied materials. Polyanionic backbone compounds based on phosphates, fluorophosphates, sulphates and other novel "polyanions" for the development of Na + Provides a great opportunity for new positive electrode systems. Different open frame structures, low energy Na + The presence of migration pathways, the possibility of regulating the operating voltage by changing the local environment, and the advantageous structural energetics of the voltage response provide some important advantages. Furthermore, their strong covalent framework renders them thermally stable and ensures an impressive oxidative stability at high charging voltages, while iron-based pyrophosphates among these materials have attracted increasing attention. Their open framework and convenient ion transport paths make them powerful candidates for energy storage and conversion. Pyrophosphate may be better than phosphate in terms of thermal stability because of oxygen lossCausing condensation of phosphate groups to pyrophosphate groups [ P ] in the range of 500-550 DEG C 2 O 7 Or (PO) 4-x ) 2 ]. Thus, pyrophosphates are considered to be more energy stable than phosphates at higher temperatures. Triclinic Na 2 FeP 2 O 7 As a positive electrode material of the sodium ion battery, na can be extracted + With a capacity of about 90mAhg -1 。Na 2 FeP 2 O 7 Exhibits excellent sodium storage properties, but its low energy density remains critical to its practical use. Thus, compared to stoichiometric phase Na 2 FeP 2 O 7 Na with a series of non-integral stoichiometric ratios with higher theoretical capacity 4-a Fe 2+a/2 (P 2 O 7 ) 2 (a=2/3-7/8) was developed in which Na 3.12 Fe 2.44 (P 2 O 7 ) 2 The theoretical capacity can reach 117.6mAhg -1 Intensive studies have been made. Na (Na) 3.12 Fe 2.44 (P 2 O 7 ) 2 The porous coral structure not only provides a bicontinuous conductive path for rapid electron transport, but the highly porous framework also creates channels for efficient ion transport.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides Mn and Ni co-doped non-stoichiometric sodium ferric pyrophosphate [ Na ] which has low cost, simple preparation process and suitability for quantitative production 3.12 Fe 2.44-x Mn x/2 Ni x/2 (P 2 O 7 ) 2 ，X＝0.01-1]And its application in sodium ion batteries.
The preparation method of Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate comprises the following steps:
step 1: dissolving and stirring
Dissolving metal salt, surfactant and citric acid (the ratio of citric acid to deionized water is 1g:25 ml) in deionized water, stirring for 60-600 minutes at 40-100 ℃, then adding a carbon source, continuously stirring for 60-600 minutes, and then adding sodium phosphate, stirring for 60-600 minutes at 40-100 ℃. The addition of the surfactant promotes dissociation of phosphate to prevent agglomeration and to allow sufficient dissolution of the various metal salts and sodium phosphate salts in the solvent.
Step 2: titration
Adding an anti-polar solvent into the solution obtained in the step 1 for titration (one drop by one drop with deionized water), and stirring until gel is generated after the titration is finished; the reverse polarity solvent is added to replace hydrogen bonds to participate in the reaction between complex molecules in the gel process, so that the gel stability is improved and agglomeration is prevented to a certain extent.
Step 3: drying
And (3) placing the gel generated in the step (2) into a vacuum drying oven for drying (50-140 ℃) to obtain xerogel.
Step 4: presintering
Grinding the xerogel obtained in the step 3, heating to 200-400 ℃ in inert or reducing atmosphere, preserving heat for 60-600 minutes, and presintering, wherein the solid phase reaction is more sufficient after presintering.
Step 5: sintering
Grinding the presintered product, heating to 400-700 ℃ in inert or reducing atmosphere, and preserving heat for 180-840 minutes to obtain Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate.
Preferably, in step 1, the metal salt solution is a mixed solution of iron salt, nickel salt and manganese salt, and the adding proportion is mixed according to the proportion of each metal element in the molecular formula. The mass concentration of the metal salt solution is 0.01-20%.
Preferably, in step 1, the surfactant is one of CTAB, F127, CPC, BAC.
Preferably, in step 1, the molar ratio of iron salt to sodium phosphate salt is (2 to 2.5): 3.12 mixing.
Preferably, in step 1, the sodium phosphate salt includes, but is not limited to, one of sodium dihydrogen phosphate, sodium pyrophosphate.
Preferably, in the step 1, the carbon source is one of glucose, sucrose and asphalt, and is added according to the mass ratio of 5% -20% of the product.
Preferably, in step 2, the anti-polar solvent is one of ethylene glycol and ethanol.
Preferably, in the steps 4 and 5, the inert or reducing atmosphere is one of nitrogen, argon, ammonia and argon-hydrogen mixed gas.
Preferably, in the step 4, the temperature rising rate of the presintered is 2-8 ℃,
preferably, in step 5, the sintering temperature increase rate is 5 to 10 ℃.
The method prepares Mn and Ni co-doped non-stoichiometric sodium ferric pyrophosphate by controlling the generation of gel and then sintering step by step. The diameter of Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate is between 0.01 and 10 mu m.
The Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate prepared by the invention is applied as a positive electrode material of a sodium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, in the sol-gel process, the surfactant is added to promote the dissociation of phosphate radical so as to prevent agglomeration and enable various metal salts and sodium phosphate salt to be fully dissolved in the solvent, and in the gel process, the reverse polarity solvent is added to replace hydrogen bonds to participate in the reaction between complex molecules, so that the gel stability is improved, agglomeration is prevented to a certain extent, and the generation of nano particles is promoted.
The non-stoichiometric ferric sodium pyrophosphate prepared by the invention has a theoretical capacity (117.6 mAhg -1 ) Sodium iron pyrophosphate (97 mAhg) significantly higher than the stoichiometric phase -1 )。
Mn, ni co-doped non-stoichiometric ferric sodium pyrophosphate [ Na ] prepared by the invention 3.12 Fe 2.44-x Mn x/2 Ni x/2 (P 2 O 7 ) 2 ，X＝0.01-1]The material has the advantages that the Mn ions have higher redox valence and electrochemical activity and improve the capacity after partially replacing the Fe ions in the crystal material, while the Ni ions can partially replace the Fe ions in the crystal material and replace the positions of partial Mn ions in the crystal structure to improve the stability of the structure and make the Mn ions in higher valence to inhibit the Jahn-Teller effect brought by the Mn ionsThe cyclic life of the catalyst is prolonged, and a carbon source added in the sol-gel process is uniformly coated on the surface of Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate. By double-doped Na 3.12 Fe 2.44-x Mn x/2 Ni x/2 (P 2 O 7 ) 2 Comparing undoped Na 3.12 Fe 2.44 (P 2 O 7 ) 2 The capacity and the cycle stability of the catalyst are obviously improved. At the same time compared with singly doped Ni ion Na 3.12 Fe 2.44-x Ni x (P 2 O 7 ) 2 (90mAhg -1 ) The double doping capacity is still improved.
The Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate anode material has the advantages of simple preparation process, low raw material price and easy operation, and is suitable for large-scale production. The Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate anode material prepared by the method has the characteristics of high electron conductivity, high reversible discharge capacity, high energy density and the like, and lays a good foundation for further development of sodium ion batteries.
Drawings
FIG. 1 is an X-ray diffraction pattern of Mn, ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in example 1 compared with undoped non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in comparative example.
FIG. 2 is a scanning electron microscope image of the preparation of Mn, ni co-doped non-stoichiometric ferric sodium pyrophosphate cathode material of example 1.
FIG. 3 is a graph showing the cycle performance of Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in example 1 and undoped non-stoichiometric ferric sodium pyrophosphate positive electrode material at a rate of 1A/g.
Fig. 4 is a scanning electron microscope image of a comparative example undoped non-stoichiometric ferric sodium pyrophosphate positive electrode material.
Detailed Description
The invention is further illustrated in the following examples, which are given by way of illustration and are not to be construed as limiting the invention.
Example 1:
the embodiment provides a preparation method of Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material, which comprises the following steps:
1. weigh 4.04g of Fe (NO) 3 ) 3 ·9H 2 O、0.24gMn(NO 3 ) 2 ·4H 2 O、0.36gNi(NO 3 )·6H 2 O, 0.2g CTAD and 4g anhydrous citric acid are dissolved in 100ml water, and stirring is carried out continuously for 8 hours at 50 ℃ to obtain a uniform orange-yellow solution; 2g of glucose is added and stirred for 8 hours; subsequently 4g of NaH are added 2 PO 4 ·2H 2 O is added into the mixed solution, and along with NaH 2 PO 4 ·2H 2 The addition solution of O quickly turned to pale yellow and stirring was continued for 4h. Titrating 40ml of ethylene glycol into the mixed solution, stirring for 8 hours, and then raising the temperature to 100 ℃ to evaporate the solution;
2. drying the gel obtained in the step 1 in a vacuum drying oven at 80 ℃ for 24 hours, grinding the obtained xerogel, heating to 250 ℃ in an inert or reducing atmosphere, preserving heat for 180 minutes to perform presintering, grinding the presintered product in the inert or reducing atmosphere, heating to 500 ℃, and preserving heat for 600 minutes to obtain Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate;
the Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in the embodiment is subjected to X-ray diffraction (XRD) test, and the test result is shown in figure 1.
The Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in the embodiment is subjected to a scanning electron microscope test, and the test result is shown in fig. 2.
The positive electrode material prepared in the embodiment, conductive carbon black and PVDF are mixed and pulped according to the ratio of 7:2:1, and coated on a current collector, and the positive electrode of the sodium ion battery is obtained through solidification. Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material is used as a working electrode, a metal sodium sheet is used as a counter electrode, glass fiber is used as a diaphragm, and 1mol L is used as a diaphragm -1 Sodium perchlorate solution (wherein the solvent adopts a mixture of EC and DEC with volume ratio of 1:1 and added with 5% of FEC) as electrolyte, and the CR2025 button cell is assembled in a glove box filled with argon gasAnd (5) performing electrochemical performance test.
Example 2:
1. weigh 4.04g of Fe (NO) 3 ) 3 ·9H 2 O、0.08gMn(NO 3 ) 2 ·4H 2 O、0.12gNi(NO 3 )·6H 2 O, 0.2g CTAD and 4g anhydrous citric acid are dissolved in 100ml water, and stirring is carried out continuously for 8 hours at 50 ℃ to obtain a uniform orange-yellow solution; 2g of glucose is added and stirred for 8 hours; subsequently 4g of NaH are added 2 PO 4 ·2H 2 O is added into the mixed solution, and along with NaH 2 PO 4 ·2H 2 The addition solution of O quickly turned to pale yellow and stirring was continued for 4h. Titrating 40ml of ethylene glycol into the mixed solution, stirring for 8 hours, and then raising the temperature to 100 ℃ to evaporate the solution;
2. the rest of the steps are the same as those of the first embodiment
The Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in the embodiment still has 85 mAh.g under the 1A/g multiplying power -1
Example 3:
1. weigh 4.04g of Fe (NO) 3 ) 3 ·9H 2 O、0.64gMn(NO 3 ) 2 ·4H 2 O、0.72gNi(NO 3 )·6H 2 O, 0.2g CTAD and 4g anhydrous citric acid are dissolved in 100ml water, and stirring is carried out continuously for 8 hours at 50 ℃ to obtain a uniform orange-yellow solution; 2g of glucose is added and stirred for 8 hours; subsequently 4g of NaH are added 2 PO 4 ·2H 2 O is added into the mixed solution, and along with NaH 2 PO 4 ·2H 2 The addition solution of O quickly turned to pale yellow and stirring was continued for 4h. Titrating 40ml of ethylene glycol into the mixed solution, stirring for 8 hours, and then raising the temperature to 100 ℃ to evaporate the solution;
2. the rest of the steps are the same as those of the first embodiment
The Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in the embodiment still has 90 mAh.g under the 1A/g multiplying power -1
Comparative example:
the comparative example provides a non-stoichiometric ferric sodium pyrophosphate positive electrode material and a preparation method thereof.
1. Weigh 4.04g of Fe (NO) 3 ) 3 ·9H 2 O, 0.2g CTAD and 2.88g anhydrous citric acid were dissolved in 100ml water and stirred for 8 hours at 50℃to give a uniform orange-yellow solution. 2g of glucose was added and stirred for 8h, and 4g of NaH was added 2 PO 4 ·2H 2 O is added into the mixed solution, and along with NaH 2 PO 4 ·2H 2 The addition solution of O quickly turned to pale yellow and stirring was continued for 4h. 50ml of ethylene glycol is titrated into the mixed solution, after stirring for 8 hours, the temperature is increased to 100 ℃ and the solution is evaporated to dryness;
2. drying the gel obtained in the step 1 in a vacuum drying oven at 80 ℃ for 24 hours, grinding the obtained xerogel, heating to 250 ℃ in an inert or reducing atmosphere, preserving heat for 180 minutes to perform presintering, grinding the presintered product in the inert or reducing atmosphere, heating to 500 ℃, and preserving heat for 600 minutes to obtain Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate;
the non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in this example was subjected to an X-ray diffraction (XRD) test, and the test results are shown in fig. 1.
The non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in this example was subjected to scanning electron microscope test, and the test result is shown in fig. 4.
The non-stoichiometric ferric sodium pyrophosphate anode material prepared in the embodiment is mixed with conductive carbon black and PVDF according to the ratio of 7:2:1 for slurrying, and is coated on a current collector for curing to obtain the anode of the sodium ion battery. Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material is used as a working electrode, a metal sodium sheet is used as a counter electrode, glass fiber is used as a diaphragm, and 1mol L is used as a diaphragm -1 The solution of sodium perchlorate (in which the solvent was a mixture of EC and DEC in a volume ratio of 1:1 and 5% fec was added) was used as electrolyte and assembled into CR2025 button cell in a glove box filled with argon for electrochemical performance testing.
Fig. 1 is an X-ray diffraction pattern (XRD pattern) of the Mn, ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in example 1 compared with the undoped non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in comparative example. As shown in fig. 1, the diffraction peak positions of the XRD patterns of the substances before and after doping of Mn and Ni ions did not change significantly, and the intensities of the diffraction peaks became high, indicating that co-doping of Mn and Ni ions caused more thorough crystallization of the substances and higher crystallization degree.
FIG. 2 is a scanning electron microscope image of the preparation of Mn, ni co-doped non-stoichiometric ferric sodium pyrophosphate cathode material of example 1. As shown in FIG. 2, mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate particles have a diameter of about 4.5um, and are spherical, and the spherical surface is porous coral.
FIG. 3 is a graph showing the cycle performance of Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material prepared in example 1 at a rate of 1A/g. As shown in FIG. 3, the discharge capacity of the Mn-Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material at 20 mAh/g is 114 mAh.g -1 117 mAh.g close to theoretical capacity -1 The doping of manganese ions and nickel ions plays a positive role in improving the capacity of the material compared with the undoped non-stoichiometric ferric sodium pyrophosphate positive electrode material in the comparative example, and the cycle chart of the Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material and the undoped non-stoichiometric ferric sodium pyrophosphate positive electrode material under the 1A/g multiplying power can show that 300 circles of capacity of the Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate positive electrode material is not attenuated, the capacity retention rate is 100%, and the capacity retention rate of the undoped non-stoichiometric ferric sodium pyrophosphate positive electrode material after 300 circles is 94%. Meanwhile, the capacity and the cycle stability of the material after co-doping of Mn and Ni are improved.
Fig. 4 is a scanning electron microscope image of a comparative example undoped non-stoichiometric ferric sodium pyrophosphate positive electrode material. As shown in fig. 4, undoped non-stoichiometric ferric sodium pyrophosphate is in a sheet-like coral reef structure instead of a spherical porous coral structure after doping. The effects and effects of the examples:
the sol-gel process according to this example promotes the dissociation of phosphate groups by adding surfactants to prevent agglomeration and to allow various metal salts and sodium phosphate salts to be sufficiently dissolved in the solvent, and adds an anti-polar solvent to replace hydrogen bonds to participate in the reaction between complex molecules during the gel process, thereby improving the gel stability and preventing agglomeration to some extent.
According to the Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate anode material, mn ions have higher valence states and electrochemical activity to partially replace iron ions in a crystal material so as to improve the capacity of the Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate anode material, ni ions can improve the structural stability and partially replace the iron ions in the crystal material and enable the Mn ions to be in higher valence states so as to inhibit Jahn-Teller effect brought by the Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate anode material, the cycle life of the Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate anode material is prolonged, and simultaneously, a carbon source added in the sol-gel process is uniformly coated on the surface of the Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate, so that the conductivity of the material is greatly improved.
The Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate anode material related to the embodiment has the advantages of simple preparation method, rich raw materials and mass production. The Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate anode material prepared by the method has the characteristics of high electronic conductivity, high reversible discharge capacity, good cycle performance and the like, and lays a good foundation for further development of sodium ion batteries.
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (9)
1. The preparation method of Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate is characterized by comprising the following steps of:
step 1: dissolving and stirring
Dissolving metal salt, surfactant and citric acid in deionized water, stirring at 40-100 ℃ for 60-600 minutes, adding a carbon source, continuously stirring for 60-600 minutes, and adding sodium phosphate, stirring at 40-100 ℃ for 60-600 minutes;
step 2: titration
Adding an anti-polar solvent into the solution obtained in the step 1 for titration, and stirring until gel is generated after titration is finished; the reverse polarity solvent is added to replace hydrogen bonds to participate in the reaction between complex molecules in the gel process, so that the gel stability is improved and agglomeration is prevented to a certain extent;
step 3: drying
Putting the gel generated in the step 2 into a vacuum drying oven for drying to obtain xerogel;
step 4: presintering
Grinding the xerogel obtained in the step 3, heating to 200-400 ℃ in inert or reducing atmosphere, preserving heat for 60-600 minutes, and presintering, wherein the presintering and then sintering can enable the solid phase reaction to be more sufficient;
step 5: sintering
Grinding the presintered product, heating to 400-700 ℃ in inert or reducing atmosphere, and preserving heat for 180-840 minutes to obtain Mn, ni co-doped non-stoichiometric sodium ferric pyrophosphate Na 3.12 Fe 2.44-x Mn x/2 Ni x/2 (P 2 O 7 ) 2 ，X＝0.01-1。
2. The method of manufacturing according to claim 1, characterized in that:
in the step 1, the metal salt solution is a mixed solution of ferric salt, nickel salt and manganese salt, and the mass concentration of the metal salt solution is 0.01-20%.
3. The method of manufacturing according to claim 1, characterized in that:
in the step 1, the surfactant is one of CTAB, F127, CPC and BAC.
4. The method of manufacturing according to claim 1, characterized in that:
in the step 1, the mol ratio of iron salt to sodium phosphate is (2-2.5): 3.12 mixing.
5. The method of manufacturing according to claim 4, wherein:
the sodium phosphate salt is selected from one of sodium dihydrogen phosphate, sodium phosphate and sodium pyrophosphate.
6. The method of manufacturing according to claim 1, characterized in that:
in the step 1, the carbon source is one of glucose, sucrose and asphalt.
7. The method of manufacturing according to claim 1, characterized in that:
in the step 2, the reverse polarity solvent is one of glycol and ethanol.
8. The method of manufacturing according to claim 7, wherein:
the volume ratio of the anti-polar solvent in the step 2 to the deionized water in the step 1 is 1:1.
9. The application of Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate prepared by the preparation method according to any one of claims 1 to 8 is characterized in that:
the Mn and Ni co-doped non-stoichiometric ferric sodium pyrophosphate is used as a positive electrode material of a sodium ion battery.
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| CN116911075B (en) * | 2023-09-12 | 2024-01-12 | 天津力神电池股份有限公司 | Method and system for predicting metal ion layered oxide crystal structure evolution |
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