CN116534830A - Sodium ion battery positive electrode material and preparation method and application thereof - Google Patents
Sodium ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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- CN116534830A CN116534830A CN202310619400.XA CN202310619400A CN116534830A CN 116534830 A CN116534830 A CN 116534830A CN 202310619400 A CN202310619400 A CN 202310619400A CN 116534830 A CN116534830 A CN 116534830A
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- Prior art keywords
- ion battery
- positive electrode
- electrode material
- sodium ion
- sodium
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 46
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000011734 sodium Substances 0.000 claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 238000001694 spray drying Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 17
- 239000004576 sand Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 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 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 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 9
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000005955 Ferric phosphate Substances 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229940032958 ferric phosphate Drugs 0.000 claims description 8
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 claims description 2
- 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 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 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
- 238000007599 discharging Methods 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011640 ferrous citrate Substances 0.000 claims description 2
- 235000019850 ferrous citrate Nutrition 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 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
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 229940001516 sodium nitrate Drugs 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
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 239000007787 solid 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
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 14
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 28
- 239000000203 mixture Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000010406 cathode material Substances 0.000 description 10
- 235000015424 sodium Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 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
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- -1 sodium iron pyrophosphate phosphate Chemical compound 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/42—Pyrophosphates
-
- 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
- C01B25/425—Pyrophosphates of alkali metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- Composite Materials (AREA)
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- Crystallography & Structural Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a positive electrode material of a sodium ion battery, and a preparation method and application thereof, and belongs to the technical field of sodium ion batteries. The invention synthesizes Na by using a composite iron source 4 [Fe x Fe 3‑x ](PO4) 2 (P 2 O 7 ) Positive electrode material of@C sodium ion battery, and enhanced crystallinity of the materialThe conductivity of the electrode material is improved, thereby improving the discharge specific capacity and the cycling stability of the material.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery positive electrode material, a preparation method and application thereof.
Background
In recent years, global problems such as shortage of fossil fuel, environmental pollution and the like are increasingly serious, and clean energy sources such as solar energy, wind energy, water energy and the like are urgently developed. However, these clean energy sources have the disadvantages of large volatility, poor stability, intermittent supply, etc., and can be reasonably utilized only after the integration and conversion of the large-scale energy storage device. Among the existing energy storage technologies, secondary batteries are considered as one of ideal choices of large-scale energy storage technologies due to their high flexibility and high energy conversion efficiency. Although lithium ion batteries have achieved great success in the field of portable electronic devices and electric automobiles due to their high energy density and good cycling stability, they cannot meet the low-cost requirements for large-scale energy storage due to the lack and uneven distribution of lithium resources. However, sodium ion batteries have a similar working principle as lithium ion batteries, and are more abundant in reserves and more widely distributed. Considering the important characteristics of large-scale energy storage devices that cost more than energy density, sodium ion batteries are considered one of the potential candidates for large-scale energy storage systems.
A large number of sodium ion battery cathode materials have been reported to exhibit good electrochemical properties, such as vanadium-based phosphates, iron-based phosphates, and prussian blue analogues, in only a few of the materials. Moreover, during commercialization of laboratory results, these materials also face serious problems such as high toxicity and high cost of vanadium-based materials, and structural instability of Prussian blue analogues. In the iron-based phosphate, sodium iron pyrophosphate phosphate (Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 ) Integrates the advantages of all iron-based phosphates: low cost, environment-friendly, high theoretical capacity (129 mAh g) -1 ) High and flatAverage operating voltage (3.1 VS. Na + Na) and low volume expansion (4% less), and iron-based mixed phosphate cathode materials are a class of sodium ion battery cathode materials with great commercial application potential from the standpoint of raw material acquisition and structural stability. Is considered as the most potential positive electrode material of sodium ion batteries. However, the specific capacity of the iron-based mixed phosphate cathode material synthesized by the solid phase method is low. In addition, the PO is large in size 4 3- The inherent isolation characteristic of the groups causes lower electronic conductivity and slow ion diffusion, and limits the specific capacity of the groups, so that the problem of low specific capacity of the iron-based mixed phosphate positive electrode material is particularly important to be solved.
For example, patent application publication No. CN112768673A discloses a Na 4 Fe 3-x (PO 4 ) 2 P 2 O 7 Positive electrode material of sodium ion battery, preparation method and application thereof; the sodium ion battery anode material is structurally introduced with iron defects, can be simply prepared by reducing the content of iron sources in raw materials, does not need new raw materials and additional synthesis processes, has little influence on the existing manufacturing process, is easy to control, and is prepared into Na 4 Fe 3-x (PO 4 ) 2 P 2 O 7 The purity of the/C is high, the crystallinity is good, the conductivity of ions and electrons is high, the specific capacity and the multiplying power performance of the anode material are greatly improved, and the anode material is suitable for mass production and application.
Disclosure of Invention
In view of this, the present invention provides a Na 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) Positive electrode material of@C sodium ion battery, preparation method and application thereof, wherein the positive electrode material comprises Na 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) And a composite amorphous carbon layer supported on the surface of the compound. The method is characterized by uniformly mixing a raw material sodium source, a composite iron source, a phosphorus source and a carbon source and calcining. The synthesis process of the positive electrode material only uses a composite iron source on the selection of the iron source, does not need new raw materials and additional synthesis process, and shadows the existing manufacturing processThe cathode material synthesized by the composite iron source has the characteristics of high crystallinity, high capacity, good cycle stability, excellent low-temperature performance and the like.
The specific technical scheme of the invention is as follows:
a positive electrode material of a sodium ion battery, which has a general formula of Na 4 [Fe x Fe 3-x ](PO4) 2 (P 2 O 7 ) @C, wherein the positive electrode material of the sodium ion battery is Na 4 [Fe x Fe 3-x ](PO4) 2 (P 2 O 7 ) And a complex of C, and a compound of C,
wherein x is more than or equal to 0.9 and less than 2.1, fe x The iron source is a first iron source, fe 3-x The iron source is a second iron source, and the first iron source and the second iron source are any two of ferric phosphate, ferric oxide, ferrous citrate, ferrous oxalate, ferrous acetylacetonate, ferric nitrate, ferric chloride and ferrous sulfate;
the preparation method comprises the following steps:
(1) Adding a sodium source, a phosphorus source and a carbon source into water, uniformly mixing to form a solution, adding a first iron source and a second iron source, uniformly mixing to form slurry, and drying to obtain precursor powder;
(2) Calcining the precursor powder obtained in the step (1) in an inert atmosphere to obtain the sodium ion battery anode material.
According to the scheme, na 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) And the mass ratio of C is 98:2-97:3.
According to the scheme, x is more than or equal to 0.9 and less than or equal to 1.5.
Specifically, in the step (1),
the sodium source is at least one of sodium carbonate, sodium chloride, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium nitrate, sodium oxalate, sodium pyrophosphate, tripolyphosphate and sodium ethoxide;
the carbon source is at least one of sucrose, glucose, citric acid, polyethylene glycol, oxalic acid, sodium carbonate and ascorbic acid.
Specifically, in the step (1), grinding is performed by using a sand mill before drying;
the rotating speed of the sand mill is 2000r/min, the flow is 200L/h, and the grinding time is 40-100min;
the solid content of the ground slurry is 45-50%, and the sand grain diameter is 300-350nm.
In the step (1), the drying method is spray drying, forced air drying or vacuum drying;
when the drying method is spray drying, the feeding rate of spray drying is 60-90mL/min, the frequency of the atomizing disk is 450Hz, the feeding temperature is 220 ℃, and the discharging temperature is 90-100 ℃.
The wet homogeneous sand grinding and spray drying combined method is an effective method for realizing batch preparation of spherical powder with uniform particle size, and can realize uniform dispersion of precursor salt on nanometer scale and improve the purity and electrical property of the powder.
Preferably, in step (2), the calcining conditions are: calcining at 500-550 deg.C for 10-13 hr.
The formation of the final material is more facilitated under the condition of the calcination parameters, if the calcination temperature is too high, the material is over-calcined and has impurity phases, and if the calcination temperature is too low, the sintering is insufficient, and the crystallinity of the material is low. Due to the high-temperature decomposition of sucrose in inert atmosphere, part of carbon is coated on the surface of the main material, and the carbon coating is beneficial to increasing the conductivity of the material.
The invention also provides the sodium ion battery anode material prepared by the preparation method.
The invention also provides application of the positive electrode material of the sodium ion battery in preparation of the sodium ion battery.
The invention also provides a sodium ion battery, which comprises the sodium ion battery anode material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention synthesizes Na by using a composite iron source 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) Positive electrode material of@C sodium ion batteryThe crystallinity of the material is improved, and the conductivity of the electrode material is enhanced, so that the discharge specific capacity and the cycling stability of the material are improved. Na is mixed with 4 [Fe x Fe 3-x ](PO4) 2 (P 2 O 7 ) The @ C material is assembled into a battery, and the charge-discharge gram capacity can reach 107 mAh.g under the 0.1C multiplying power within the voltage range of 1.7-4.0V -1 The method comprises the steps of carrying out a first treatment on the surface of the In the charge and discharge process, the battery has better cycle performance due to a stable structure, and the capacity is hardly attenuated after the battery is cycled for 500 times at 10C. Composite iron source for synthesizing Na 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) The @ C cathode material exhibits excellent electrochemical properties.
(2) Synthesis of Na by Complex iron Source 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) The @ C sodium ion battery anode material has no difference in process synthesis except that two different iron sources are used in the raw material input stage, and is suitable for industrial mass production.
Drawings
Fig. 1 is an XRD curve of the composite cathode material prepared in example 2.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the composite cathode material prepared in example 2.
Fig. 3 is an XRD curve of the composite positive electrode material prepared in comparative example 1.
Fig. 4 is a Scanning Electron Microscope (SEM) image of the composite cathode material prepared in comparative example 1.
Fig. 5 is a Scanning Electron Microscope (SEM) image of the composite cathode material prepared in comparative example 2.
Detailed Description
Example 1
Sodium ion secondary battery positive electrode material Na 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) A process for the preparation of @ C, wherein x = 0.9, comprising the steps of:
(1) According to the stoichiometric ratio, 847.9g of sodium carbonate, 1438.8g of ammonium dihydrogen phosphate and a composite carbon source consisting of 130g of sucrose and 180g of polyethylene glycol are weighed and added into deionized water, and the mixture is stirred uniformly to form a solution; adding 543.0g of ferric phosphate and 670.7g of ferric oxide, and uniformly stirring to form slurry; pouring the slurry into a storage tank, grinding for 100min in a sand mill at a rotating speed of 2000r/min and a flow rate of 200L/h, and controlling the grain diameter after sand grinding to be between 200 and 300 nm; the mole ratio of the sodium element, the iron element and the phosphorus element in the mixture is 4:3:4;
(2) Spray drying the slurry obtained in the step (1) at an inlet temperature of 220 ℃ and an outlet temperature of 95 ℃ to obtain precursor powder;
(3) Heating precursor powder obtained by spray drying to 300 ℃ at a heating rate of 2 ℃/min under inert gas of nitrogen, preserving heat for 5h, heating to 500 ℃ at a heating rate of 2 ℃/min, calcining, and preserving heat for 10h; to obtain Na 4 [Fe 0.9 Fe 2.1 ](PO 4 ) 2 (P 2 O 7 ) And @ C composite positive electrode material.
Example 2
Sodium ion secondary battery positive electrode material Na 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) A process for the preparation of @ C, wherein x = 1.2, comprising the steps of:
(1) According to the stoichiometric ratio, 847.9g of sodium carbonate, 1438.8g of ammonium dihydrogen phosphate and a composite carbon source consisting of 130g of sucrose and 180g of polyethylene glycol are weighed and added into deionized water, and the mixture is stirred uniformly to form a solution; adding 723.9g of ferric phosphate and 574.9g of ferric oxide, and uniformly stirring to form slurry; pouring the slurry into a storage tank, grinding for 120min in a sand mill at a rotating speed of 2000r/min and a flow rate of 200L/h, and controlling the grain diameter after grinding to be between 200 and 300 nm; the mole ratio of the sodium element, the iron element and the phosphorus element in the mixture is 4:3:4;
(2) Spray drying the slurry obtained in the step (1) at an inlet temperature of 220 ℃ and an outlet temperature of 95 ℃ to obtain precursor powder;
(3) Heating precursor powder obtained by spray drying to 300 ℃ at a heating rate of 2 ℃/min under inert gas of nitrogen, preserving heat for 5h, heating to 500 ℃ at a heating rate of 2 ℃/min, calcining, and preserving heat for 10h; to be used forObtain Na 4 [Fe 1.2 Fe 1.8 ](PO 4 ) 2 (P 2 O 7 ) And @ C composite positive electrode material.
Example 3
Sodium ion secondary battery positive electrode material Na 4 [Fe x Fe 3-x ](PO4) 2 (P 2 O 7 ) A process for the preparation of @ C, wherein x = 1.5, comprising the steps of:
(1) According to the stoichiometric ratio, 847.9g of sodium carbonate, 1438.8g of ammonium dihydrogen phosphate and a composite carbon source consisting of 130g of sucrose and 180g of polyethylene glycol are weighed and added into deionized water, and the mixture is stirred uniformly to form a solution; then 904.9g of ferric phosphate and 479.1g of ferric oxide are added, and the mixture is stirred uniformly to form slurry; pouring the slurry into a storage tank, grinding for 120min in a sand mill at a rotating speed of 2000r/min and a flow rate of 200L/h, and controlling the grain diameter after grinding to be between 200 and 300 nm; the mole ratio of the sodium element, the iron element and the phosphorus element in the mixture is 4:3:4;
(2) Spray drying the slurry obtained in the step (1) at an inlet temperature of 220 ℃ and an outlet temperature of 95 ℃ to obtain precursor powder;
(3) Heating precursor powder obtained by spray drying to 300 ℃ at a heating rate of 2 ℃/min under inert gas of nitrogen, preserving heat for 5h, heating to 500 ℃ at a heating rate of 2 ℃/min, calcining, and preserving heat for 10h; to obtain Na 4 [Fe 1.5 Fe 1.5 ](PO 4 ) 2 (P 2 O 7 ) And @ C composite positive electrode material.
Example 4
Sodium ion secondary battery positive electrode material Na 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) A process for the preparation of @ C, wherein x = 1.8, comprising the steps of:
(1) According to the stoichiometric ratio, 847.9g of sodium carbonate, 1438.8g of ammonium dihydrogen phosphate and a composite carbon source consisting of 130g of sucrose and 180g of polyethylene glycol are weighed and added into deionized water, and the mixture is stirred uniformly to form a solution; adding 1053.3g of ferric phosphate and 383.3g of ferric oxide, and uniformly stirring to form slurry; pouring the slurry into a storage tank, grinding for 100min in a sand mill at a rotating speed of 2000r/min and a flow rate of 200L/h, and controlling the grain diameter after sand grinding to be between 200 and 300 nm; the mole ratio of the sodium element, the iron element and the phosphorus element in the mixture is 4:3:4;
(2) Spray drying the slurry obtained in the step (1) at an inlet temperature of 220 ℃ and an outlet temperature of 95 ℃ to obtain precursor powder;
(3) Heating precursor powder obtained by spray drying to 300 ℃ at a heating rate of 2 ℃/min under inert gas of nitrogen, preserving heat for 5h, heating to 500 ℃ at a heating rate of 2 ℃/min, calcining, and preserving heat for 10h; to obtain Na 4 [Fe 1.8 Fe 1.2 ](PO 4 ) 2 (P 2 O 7 ) And @ C composite positive electrode material.
Example 5
Sodium ion secondary battery positive electrode material Na 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) A process for the preparation of @ C, wherein x = 2.1, comprising the steps of:
(1) According to the stoichiometric ratio, 847.9g of sodium carbonate, 1438.8g of ammonium dihydrogen phosphate and a composite carbon source consisting of 130g of sucrose and 180g of polyethylene glycol are weighed and added into deionized water, and the mixture is stirred uniformly to form a solution; then adding 1228.8g of ferric phosphate and 287.4g of ferric oxide, and uniformly stirring to form slurry; pouring the slurry into a storage tank, grinding for 120min in a sand mill at a rotating speed of 2000r/min and a flow rate of 200L/h, and controlling the grain diameter after grinding to be between 200 and 300 nm; the mole ratio of the sodium element, the iron element and the phosphorus element in the mixture is 4:3:4;
(2) Spray drying the slurry obtained in the step (1) at an inlet temperature of 220 ℃ and an outlet temperature of 95 ℃ to obtain precursor powder;
(3) Heating precursor powder obtained by spray drying to 300 ℃ at a heating rate of 2 ℃/min under inert gas of nitrogen, preserving heat for 5h, heating to 500 ℃ at a heating rate of 2 ℃/min, calcining, and preserving heat for 10h; to obtain Na 4 [Fe 2.1 Fe 0.9 ](PO 4 ) 2 (P 2 O 7 ) Composite positive electrode @ CA material.
Comparative example 1
Sodium ion secondary battery positive electrode material Na 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) A process for the preparation of @ C, wherein x = 3, comprising the steps of:
(1) According to the stoichiometric ratio, 847.9g of sodium carbonate, 1438.8g of ammonium dihydrogen phosphate and a composite carbon source consisting of 130g of sucrose and 180g of polyethylene glycol are weighed and added into deionized water, and the mixture is stirred uniformly to form a solution; adding 1809.8g of ferric phosphate, and uniformly stirring to form slurry; pouring the slurry into a storage tank, grinding for 100min in a sand mill at a rotating speed of 2000r/min and a flow rate of 200L/h, and controlling the grain diameter after sand grinding to be between 200 and 300 nm; the mole ratio of the sodium element, the iron element and the phosphorus element in the mixture is 4:3:4;
(2) Spray drying the slurry obtained in the step (1) at an inlet temperature of 220 ℃ and an outlet temperature of 95 ℃ to obtain precursor powder;
(3) Heating precursor powder obtained by spray drying to 300 ℃ at a heating rate of 2 ℃/min under inert gas of nitrogen, preserving heat for 5h, heating to 500 ℃ at a heating rate of 2 ℃/min, calcining, and preserving heat for 10h; to obtain Na 4 [Fe 3 Fe 0 ](PO 4 ) 2 (P 2 O 7 ) And @ C composite positive electrode material.
Comparative example 2
Sodium ion secondary battery positive electrode material Na 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) A process for the preparation of @ C, wherein x = 0, comprising the steps of:
(1) According to the stoichiometric ratio, 847.9g of sodium carbonate, 1438.8g of ammonium dihydrogen phosphate and a composite carbon source consisting of 130g of sucrose and 180g of polyethylene glycol are weighed and added into deionized water, and the mixture is stirred uniformly to form a solution; adding 958.1g of ferric oxide, and uniformly stirring to form slurry; pouring the slurry into a storage tank, grinding for 120min in a sand mill at a rotating speed of 2000r/min and a flow rate of 200L/h, and controlling the grain diameter after grinding to be between 200 and 300 nm; the mole ratio of the sodium element, the iron element and the phosphorus element in the mixture is 4:3:4;
(2) Spray drying the slurry obtained in the step (1) at an inlet temperature of 220 ℃ and an outlet temperature of 95 ℃ to obtain precursor powder;
(3) Heating precursor powder obtained by spray drying to 300 ℃ at a heating rate of 2 ℃/min under inert gas of nitrogen, preserving heat for 5h, heating to 500 ℃ at a heating rate of 2 ℃/min, calcining, and preserving heat for 10h; to obtain Na 4 [Fe 0 Fe 3 ](PO 4 ) 2 (P 2 O 7 ) And @ C composite positive electrode material.
Test example 1
The samples prepared in examples 1-5 and comparative examples 1-2 were subjected to button cell test, and the results are shown in Table 1 below.
The testing method of the button cell comprises the following steps: the active material: super p: PVDF slurry in a mass ratio of 8:1:1 was assembled into a button cell and tested at a cut-off voltage of 2.0 to 4.0 gV.
TABLE 1 results of testing materials of examples 1-5 and comparative examples 1-2
It is shown by examples 1-5 and comparative examples 1-2 that the discharge capacity of the mixed iron source at 0.1C is superior to the electrochemical performance of the single iron source sample. The electrochemical performance obtained is optimal when the ratio of iron phosphate to iron oxide is 4:6. Below this ratio, the optimal electrochemical performance is not fully demonstrated; above this ratio, the electrochemical performance gradually decreases.
Claims (10)
1. A preparation method of a sodium ion battery positive electrode material is characterized in that the general formula of the sodium ion battery positive electrode material is Na 4 [Fe x Fe 3-x ](PO4) 2 (P 2 O 7 ) @C, wherein the positive electrode material of the sodium ion battery is Na 4 [Fe x Fe 3-x ](PO4) 2 (P 2 O 7 ) And CThe object of the present invention is to provide a method for manufacturing a semiconductor device,
wherein x is 0.9.ltoreq.x<2.1，Fe x The iron source is a first iron source, fe 3-x The iron source is a second iron source, and the first iron source and the second iron source are any two of ferric phosphate, ferric oxide, ferrous citrate, ferrous oxalate, ferrous acetylacetonate, ferric nitrate, ferric chloride and ferrous sulfate;
the preparation method comprises the following steps:
(1) Adding a sodium source, a phosphorus source and a carbon source into water, uniformly mixing to form a solution, adding a first iron source and a second iron source, uniformly mixing to form slurry, and drying to obtain precursor powder;
(2) Calcining the precursor powder obtained in the step (1) in an inert atmosphere to obtain the sodium ion battery anode material.
2. The method for preparing a positive electrode material of a sodium ion battery according to claim 1, wherein Na 4 [Fe x Fe 3-x ](PO 4 ) 2 (P 2 O 7 ) And the mass ratio of C is 98:2-97:3.
3. The method for preparing a positive electrode material of a sodium ion battery according to claim 1, wherein x is more than or equal to 0.9 and less than or equal to 1.5.
4. The method for preparing a positive electrode material for sodium ion battery according to claim 1, wherein in the step (1),
the sodium source is at least one of sodium carbonate, sodium chloride, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium nitrate, sodium oxalate, sodium pyrophosphate, tripolyphosphate and sodium ethoxide;
the carbon source is at least one of sucrose, glucose, citric acid, polyethylene glycol, oxalic acid, sodium carbonate and ascorbic acid.
5. The method for producing a positive electrode material for sodium ion battery according to claim 1, wherein in the step (1), grinding is performed by using a sand mill before drying;
the rotating speed of the sand mill is 2000r/min, the flow is 200L/h, and the grinding time is 40-100min;
the solid content of the ground slurry is 45-50%, and the sand grain diameter is 300-350nm.
6. The method for preparing a positive electrode material of a sodium ion battery according to claim 1, wherein in the step (1), the drying method is spray drying, air drying or vacuum drying;
when the drying method is spray drying, the feeding rate of spray drying is 60-90mL/min, the frequency of the atomizing disk is 450Hz, the feeding temperature is 220 ℃, and the discharging temperature is 90-100 ℃.
7. The method for preparing a positive electrode material for sodium ion battery according to claim 1, wherein in the step (2), the condition of calcination is: calcining at 500-550 deg.C for 10-13 hr.
8. A sodium ion battery positive electrode material prepared by the preparation method of any one of claims 1 to 7.
9. The use of the positive electrode material of sodium ion battery of claim 8 in the preparation of sodium ion battery.
10. A sodium ion battery comprising the sodium ion battery positive electrode material of claim 8.
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| CN113060713A (en) * | 2021-02-25 | 2021-07-02 | 湖北万润新能源科技股份有限公司 | Preparation of Na by homogeneous phase method4Fe3(PO4)2(P2O7) Method and application of |
| CN115986080A (en) * | 2022-12-30 | 2023-04-18 | 蜂巢能源科技股份有限公司 | Sodium ion battery positive electrode material and preparation method thereof |
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| CN113060713A (en) * | 2021-02-25 | 2021-07-02 | 湖北万润新能源科技股份有限公司 | Preparation of Na by homogeneous phase method4Fe3(PO4)2(P2O7) Method and application of |
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