CN117125740A - Sodium ferrous sulfate positive electrode material, preparation method and application thereof - Google Patents
Sodium ferrous sulfate positive electrode material, preparation method and application thereof Download PDFInfo
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- CN117125740A CN117125740A CN202311092252.7A CN202311092252A CN117125740A CN 117125740 A CN117125740 A CN 117125740A CN 202311092252 A CN202311092252 A CN 202311092252A CN 117125740 A CN117125740 A CN 117125740A
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- ferrous
- sodium
- positive electrode
- electrode material
- solution
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- 239000011734 sodium Substances 0.000 title claims abstract description 74
- 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 title claims abstract description 72
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 72
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims abstract description 66
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 62
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 62
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 62
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229940062993 ferrous oxalate Drugs 0.000 claims abstract description 52
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 238000001694 spray drying Methods 0.000 claims abstract description 30
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims abstract description 29
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 28
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 28
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 37
- 235000006408 oxalic acid Nutrition 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011247 coating layer Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229960002089 ferrous chloride Drugs 0.000 claims description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004108 freeze drying Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 229920005552 sodium lignosulfonate Polymers 0.000 abstract 2
- 239000010406 cathode material Substances 0.000 description 12
- 238000011056 performance test Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000005056 compaction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [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 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
- C01P2006/11—Powder tap density
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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
- C01P2006/12—Surface area
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- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
- C01P2006/90—Other properties not specified above
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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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- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ferrous sulfate positive electrode material, a preparation method and application thereof. The preparation method of the ferrous sodium sulfate positive electrode material comprises the following steps: a) Mixing sodium lignin sulfonate, ferrous oxalate and water to obtain a mixed solution; b) Spray drying the mixed solution to obtain a spray-dried material; c) Calcining the spray-dried material to obtain the ferrous sodium sulfate anode material. According to the invention, sodium lignosulfonate is utilized to provide sodium, sulfate radical and a carbon source, and an iron source adopts ferrous oxalate and a spray drying mode, so that the structure that sodium lignosulfonate coats ferrous oxalate is realized, and more uniform mixing is realized. In the preparation method, liquid nitrogen and freeze drying are not needed to be adopted for realizing drying, the oxidation of ferrous iron is prevented, and the cost is low. Meanwhile, the raw material is carbonized and decomposed to form a carbon layer, the electronic conductivity of the product is better, and the soft-package battery prepared from the finally obtained sodium ferrous sulfate positive electrode material has better electrochemical performance.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ferrous sulfate positive electrode material, a preparation method and application thereof.
Background
Research and development of new energy and renewable energy, and the search for advanced methods for improving energy utilization rate have become a global common concern.
Compared with other modes of energy storage, the electrochemical energy storage has high efficiency, low input cost, flexibility and variability, and can realize miniaturization and dispersion. The large-scale application of lithium batteries enables the lithium batteries to be developed vigorously, and up to the present, the scale of nearly hundred GWH is reached. However, with the development of power batteries and new energy automobiles, various resources are gradually increased, so that the price of each raw material of the lithium battery is increased, including lithium resources, nickel resources, cobalt resources and the like, and the development and popularization of large-scale energy storage are hindered.
Sodium batteries occur earlier than lithium batteries, but industrialization has been lagging behind, and as lithium batteries are increasingly priced, sodium batteries are increasingly industrialized. Searching for inexpensive sodium battery materials to further reduce the cost of sodium batteries has become a key to sodium battery industrialization, however, sodium batteries suffer from low energy density.
At present, a sodium battery cathode generally adopts hard carbon, the types of cathode materials are more, the cathode materials comprise polyanion, layered oxide and Prussian blue structural materials, the material with the best circulation performance, the lowest price and moderate energy density at present is ferrous sodium sulfate, the voltage platform is 3.8V, the capacity can reach more than 80mAh/g, the cost of the ferrous sodium sulfate can be controlled within 2 ten thousand/ton, and compared with other sodium battery materials, the sodium battery cathode has obvious advantages.
A method for preparing sodium ferrous sulfate is proposed in the patent of application No. 202210238876.4, wherein ferrous sulfate and sodium sulfate are mixed and sanded under the protection of inert gas to prepare a precursor of a positive electrode material; sintering a precursor of the anode material at 300-500 ℃ under the protection of inert gas to obtain sodium ferrous sulfate; mixing sodium ferrous sulfate with sodium bicarbonate material under inert gas protection atmosphere, and sintering at 50-270 ℃ to obtain sodium ferrous sulfate coated with sodium carbonate. The preparation method is beneficial to controlling the particle size and morphology of the material to improve the performance of the positive electrode material, but the process has the problems that the continuous production is difficult to realize by sanding under the protection of inert atmosphere, and the material is not coated with carbon, so that the electronic conductivity of the material is lower, and the cycle performance and capacity of the material are lower.
The structure and preparation method of sodium ferrous sulfate proposed by the patent with application number 201710091514.6 are as follows, and Na for sodium ion battery 2 Fe 2 (SO 4 ) 3 The graphene composite positive electrode material comprises graphene with a three-dimensional structure, wherein Na is in situ compounded on the surface of the graphene 2 Fe 2 (SO 4 ) 3 . In addition, it also discloses a preparation method of the composite positive electrode material, which comprises the step of oxidizingDispersing graphene, a sodium source, a sulfur source and ferrous salt in water to obtain a suspension, carrying out hydrothermal reaction at 90-140 ℃, and carrying out solid-liquid separation, liquid nitrogen quenching and drying on a product of the hydrothermal reaction to obtain a precursor; and roasting the precursor to obtain the composite anode material. In the prepared composite anode material, the active substance is tightly combined with the carbon substrate, and the composite anode material has good coating and good physical and chemical properties. The synthesis method is simple, the condition is mild, the yield is high, and the active substances in the prepared composite material are uniformly dispersed, so that the composite material has high specific capacity, high working voltage, good cycle stability and excellent rate capability when being used as a sodium ion positive electrode material. However, this technical scheme has following defect, and at first the graphite alkene price is more expensive, and graphite alkene itself is inorganic carbon material, and the homogeneity degree of its cladding is poor than normal position carbon cladding, and in order to prevent ferrous oxidation, it adopts freeze drying's mode to realize drying, adopts liquid nitrogen simultaneously, and its cost improves greatly.
How to prepare sodium ferrous sulfate by adopting a low-cost process, how to avoid the introduction of ferric iron in the preparation process and how to uniformly coat carbon become the key of industrialization of sodium ferrous sulfate materials.
Disclosure of Invention
In view of the above, the invention aims to provide a sodium ferrous sulfate positive electrode material, a preparation method and application thereof, and aims to solve the problems of high cost and poor carbon coating effect of the existing preparation method of sodium ferrous sulfate.
The invention provides a preparation method of a sodium ferrous sulfate positive electrode material, which comprises the following steps:
a) Mixing sodium lignin sulfonate, ferrous oxalate and water to obtain a mixed solution;
b) Spray drying the mixed solution to obtain a spray-dried material;
c) And calcining the spray drying material to obtain the sodium ferrous sulfate anode material.
Preferably, in the step a), the molar ratio of sodium lignin sulfonate to ferrous oxalate is 1:0.95 to 0.98.
Preferably, in the step a), the preparation method of the ferrous oxalate comprises the following steps:
and (3) regulating the pH value of the ferrous solution to 8-10, mixing with the oxalic acid solution, and carrying out precipitation reaction to obtain ferrous oxalate.
Preferably, the concentration of the ammonia water is 8-10 mol/L;
or/and the combination of the two,
when the pH value of the ferrous solution is regulated, the temperature of the ferrous solution is 20-35 ℃;
the concentration of the ferrous solution is 2-3 mol/L;
or/and the combination of the two,
the ferrous salt in the ferrous solution comprises at least one of ferrous sulfate, ferrous chloride and ferrous acetate; the concentration of the oxalic acid solution is 1.5-2.5 mol/L;
or/and the combination of the two,
the temperature of the mixture with the oxalic acid solution is 40-60 ℃;
the molar ratio of oxalic acid contained in the oxalic acid solution to ferrous ions in the ferrous solution is 1:0.95 to 0.98;
or/and the combination of the two,
the temperature of the precipitation reaction is 40-60 ℃ and the time is 15-30 min.
Preferably, after the precipitation reaction, the method further comprises: and filtering, washing and drying the reacted slurry.
Preferably, in the step B), the spray drying process controls the discharge particle size to be 3-6 mu m, and D100 is less than or equal to 35 mu m.
Preferably, in step C), calcining the spray-dried material comprises:
heating the spray drying material to 400-450 ℃, and preserving heat for 10-18 h;
or/and the combination of the two,
the heating speed is 2-3 ℃/h;
or/and the combination of the two,
after the heat preservation, still include: cooling to the temperature of the material of less than or equal to 80 ℃;
or/and the combination of the two,
the calcination is carried out at an oxygen content of less than 1ppm.
The invention also provides the sodium ferrous sulfate anode material prepared by the preparation method.
Preferably, the ferrous sodium sulfate positive electrode material includes:
a kernel; the inner core is made of sodium lignin sulfonate;
a carbon coating layer coated on the inner core;
the thickness of the carbon coating layer is 2-10 nm.
The invention also provides a sodium ion battery, which is characterized in that the positive electrode of the sodium ion battery comprises the ferrous sodium sulfate positive electrode material.
The invention provides a preparation method of a sodium ferrous sulfate positive electrode material, which comprises the following steps: a) Mixing sodium lignin sulfonate, ferrous oxalate and water to obtain a mixed solution; b) Spray drying the mixed solution to obtain a spray-dried material; c) And calcining the spray drying material to obtain the sodium ferrous sulfate anode material. The invention skillfully utilizes a raw material which is low in price and contains carbon chains, sulfur and sodium, namely sodium lignin sulfonate to provide sodium, sulfate radical and a carbon source, and the iron source adopts ferrous oxalate, so that the soft-package battery prepared by the finally obtained ferrous sodium sulfate anode material has better electrochemical performance. Meanwhile, the invention realizes the structure that sodium lignin sulfonate coats ferrous oxalate in a spray drying mode, realizes uniform mixing, and has higher mixing uniformity compared with solid phase mixing. Meanwhile, the invention does not need to additionally add a carbon source, but the raw material is carbonized and decomposed to form a carbon layer, so that the electronic conductivity of the product is better, the internal resistance of the powder is lower, and the capacity and the low-temperature performance are better. According to the preparation method provided by the invention, drying is realized without adopting liquid nitrogen and freeze drying modes, the oxidation of ferrous is prevented, and the cost is low. The soft-package battery prepared from the finally obtained ferrous sodium sulfate positive electrode material has excellent electrochemical performance.
Drawings
FIG. 1 is an SEM image of the iron oxalate prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a sodium ferrous sulfate positive electrode material prepared in example 1 of the present invention;
FIG. 3 is a TEM image of the sodium ferrous sulfate positive electrode material prepared in example 1 of the present invention;
fig. 4 is a graph showing the first charge and discharge of the soft pack battery prepared in example 1 of the present invention;
fig. 5 is a graph showing the cycle performance of the soft pack battery prepared in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a sodium ferrous sulfate positive electrode material, which comprises the following steps:
a) Mixing sodium lignin sulfonate, ferrous oxalate and water to obtain a mixed solution;
b) Spray drying the mixed solution to obtain a spray-dried material;
c) And calcining the spray drying material to obtain the sodium ferrous sulfate anode material.
In step A):
mixing sodium lignin sulfonate, ferrous oxalate and water to obtain a mixed solution.
In certain embodiments of the invention, the molar ratio of sodium lignin sulfonate to ferrous oxalate is 1:0.95 to 0.98; the method specifically comprises the following steps of 1:0.965, 1:0.95 or 1:0.98.
the solid content of the mixed liquid is 30% -40%, such as 35%.
In certain embodiments of the invention, the ferrous oxalate comprises 99.0% -99.8% by mass of ferrous oxalate dihydrate, such as 99.26%, 99.31%, 99.16%; the BET of the ferrous oxalate is10～16m 2 /g, e.g. 12.5m 2 /g、15.1m 2 /g、10.2m 2 /g。
In certain embodiments of the present invention, the method for preparing ferrous oxalate comprises the steps of:
and (3) regulating the pH value of the ferrous solution to 8-10, mixing with the oxalic acid solution, and carrying out precipitation reaction to obtain ferrous oxalate.
Specifically, the method comprises the following steps:
adding a pH value regulator into the stirred ferrous solution until the pH value is 8-10, continuously stirring for 30-60 min, adding oxalic acid solution, and performing precipitation reaction to obtain ferrous oxalate.
The pH regulator comprises ammonia water, sodium hydroxide or potassium hydroxide.
In certain embodiments of the invention, a pH adjustor is added to the stirred ferrous solution to a pH of 9, 8, or 10 and stirring is continued for 40 minutes, 30 minutes, or 60 minutes.
The concentration of the ammonia water is 8-10 mol/L; specifically 9mol/L, 8mol/L or 10mol/L.
The stirring speed is 200-400 r/min; specifically 300r/min, 200r/min or 400r/min.
The concentration of the ferrous solution is 2-3 mol/L; specifically, the concentration is 2.5mol/L, 2mol/L or 3mol/L.
The temperature of the ferrous solution is 20-35 ℃; specifically 30 ℃, 20 ℃ or 35 ℃.
The ferrous salt in the ferrous solution comprises at least one of ferrous sulfate, ferrous chloride and ferrous acetate. The solvent in the ferrous solution is water.
In the invention, stirring is continued for 30-60 min, so that the reaction is more sufficient, namely the formation effect.
The concentration of the oxalic acid solution is 1.5-2.5 mol/L; specifically, it is 2mol/L, 1.5mol/L or 2.5mol/L. The solvent in the oxalic acid solution is water.
The temperature of the mixture with oxalic acid solution is 40-60 ℃. Specifically, before adding oxalic acid solution, still include: heating to 40-60 ℃; specifically 50 ℃, 40 ℃ or 60 ℃.
The molar ratio of the oxalic acid to ferrous ions in the ferrous solution is 1:0.95 to 0.98; the method specifically comprises the following steps of 1:0.97, 1:0.95 or 1:0.98.
the reaction temperature is 40-60 ℃, specifically 50 ℃, 40 ℃ or 60 ℃; the time is 15-30 min, specifically 20min, 15min or 30min.
After the precipitation reaction, the method further comprises the following steps: and filtering, washing and drying the slurry after the precipitation reaction.
In certain embodiments of the invention, the preparation of the ferrous oxalate is performed in a closed container, and in particular, may be performed in a closed reaction kettle.
In some embodiments of the invention, the ferrous oxalate is in a granular morphology with a primary particle size of 30-300 nm.
In step B):
and (3) carrying out spray drying on the mixed solution to obtain a spray drying material.
In certain embodiments of the invention, the spray drying process is controlled to have a discharge particle size of 3 to 6 μm and a d100.ltoreq.35 μm. Specifically, the discharge particle diameter was controlled to be 5.2 μm, 3 μm or 6 μm, and D100 was controlled to be 31.6 μm, 19.6 μm or 35 μm.
The resulting spray-dried material included:
a kernel; the material of the inner core is ferrous oxalate;
and a sodium lignin sulfonate layer coated on the inner core.
In step C):
and calcining the spray drying material to obtain the sodium ferrous sulfate anode material.
In certain embodiments of the invention, calcining the spray-dried material comprises:
heating the spray drying material to 400-450 ℃, and preserving heat for 10-18 h.
Specifically, the spray-dried material is heated to 420 ℃, 400 ℃ or 450 ℃, and is kept for 15 hours, 10 hours or 18 hours.
The heating speed is 2-3 ℃/h; specifically, 2.5 ℃/h, 2 ℃/h or 3 ℃/h.
After the heat preservation, still include: cooling to the temperature of less than or equal to 80 ℃.
After cooling to the material temperature of less than or equal to 80 ℃, the method further comprises the following steps: and (5) screening and removing iron to obtain sodium ferrous sulfate. In certain embodiments, the method further comprises, prior to screening: and (5) discharging. The iron is removed to remove magnetic impurities.
The calcination is performed under the condition that the oxygen content is lower than 1ppm (or under the condition of no oxygen); in particular, the oxygen content in the tube furnace can be maintained below 1ppm by introducing nitrogen.
The calcination is carried out in a tube furnace.
And calcining to carbonize lignin sulfonate in the sodium lignin sulfonate at high temperature to obtain a carbon layer, and synthesizing sodium to obtain sodium ferrous sulfate.
The invention also provides the sodium ferrous sulfate anode material prepared by the preparation method.
The ferrous sodium sulfate positive electrode material comprises:
a kernel; the inner core is made of sodium lignin sulfonate;
and a carbon coating layer coated on the inner core.
The carbon coating layer is uniformly coated.
In certain embodiments of the invention, the carbon coating layer has a thickness of 2 to 10nm; such as 3 to 4nm, 5 to 7nm or 2 to 3nm.
The invention also provides a sodium ion battery, and the positive electrode of the sodium ion battery comprises the ferrous sodium sulfate positive electrode material.
Specifically, the preparation method of the positive electrode of the sodium ion battery comprises the following steps:
uniformly mixing the sodium ferrous sulfate positive electrode material, conductive carbon black (SP) and PVDF, coating (the thickness of coating is 50-100 mu m, such as 30 mu m) on aluminum foil, and drying to obtain a positive electrode plate of the sodium ion battery; the mass ratio of the ferrous sodium sulfate positive electrode material to the conductive carbon black to the PVDF is 90:5:5.
in certain embodiments of the present invention, the positive electrode sheet of the sodium ion battery described above is used as the positive electrode, the negative electrode is hard carbon, and 1mol/L NaPF is used 6 Solutions (solvents include DMC, EC and E)MC, volume ratio 1:1: 1) As an electrolyte, a flexible battery was assembled.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
The invention skillfully utilizes a raw material which is low in price and contains carbon chains, sulfur and sodium, namely sodium lignin sulfonate to provide sodium, sulfate radical and a carbon source, and the iron source adopts ferrous oxalate, so that the soft-package battery prepared by the finally obtained ferrous sodium sulfate anode material has better electrochemical performance.
The invention further prepares ferrous oxalate through precipitation conversion, namely, firstly prepares colloid of ferrous hydroxide, adds oxalic acid to realize precipitation conversion, and obtains ferrous oxalate, and finally, the purity of the obtained ferrous oxalate is higher.
According to the invention, a structure that sodium lignin sulfonate is coated with ferrous oxalate is realized by a spray drying mode, uniform mixing is realized, and compared with solid-phase mixing, the mixing uniformity is higher.
Sodium lignin sulfonate (C) of the present invention 20 H 24 Na2O 10 S2) long alkyl is contained, and high-temperature carbonization and decomposition can be carried out under the anaerobic condition, so that the invention can realize carbon coating, and the carbon coating is more uniform, and meanwhile, the invention does not need to additionally add a carbon source, but a carbon layer formed by carbonizing and decomposing the raw material, so that the electronic conductivity of the product is better, the internal resistance of the powder is lower, and the capacity and the low-temperature performance are better.
According to the preparation method provided by the invention, drying is realized without adopting liquid nitrogen and freeze drying modes, the oxidation of ferrous is prevented, and the cost is low.
In order to further illustrate the present invention, the following examples are provided to describe in detail a sodium ferrous sulfate positive electrode material, a preparation method and an application thereof, but the present invention is not to be construed as limiting the scope of protection.
Example 1
Preparing a ferrous sodium sulfate positive electrode material:
1) And (3) preparation of ferrous oxalate:
adding 2.5mol/L ferrous sulfate solution into a closed reaction kettle, adding 9mol/L ammonia water to adjust the pH value to 9 in the stirred ferrous sulfate solution (30 ℃) at the stirring speed of 300r/min, continuously stirring for 40min to obtain colloid precipitate, heating to 50 ℃, adding 2mol/L oxalic acid solution (the molar ratio of oxalic acid to ferrous ions in the ferrous sulfate solution is 1:0.97), reacting for 20min at 50 ℃, filtering, washing and drying the reacted slurry to obtain ferrous oxalate;
the detection data of the ferrous oxalate are shown in table 1.
TABLE 1 detection data for ferrous oxalate
Fig. 1 is an SEM image of ferrous oxalate prepared in example 1 of the present invention. As can be seen from FIG. 1, the ferrous oxalate has a granular morphology, and the primary particle size is 30-300 nm.
2) Mixing sodium lignin sulfonate, ferrous oxalate and water to obtain a mixed solution; the molar ratio of the sodium lignin sulfonate to the ferrous oxalate is 1:0.965;
3) Spray drying the mixed solution to obtain a spray-dried material; the spray drying process is characterized in that the particle size of discharged material is controlled to be 5.2 mu m, and D100 is controlled to be 31.6 mu m;
4) Calcining: heating the spray drying material to 420 ℃, keeping the temperature at the heating rate of 2.5 ℃/h, keeping the temperature at 420 ℃ for 15h, cooling to the material temperature of less than or equal to 80 ℃, discharging, screening, and removing iron to obtain a ferrous sodium sulfate anode material;
the calcination is carried out in a tube furnace, and nitrogen is introduced in the calcination process to maintain the oxygen content in the tube furnace to be lower than 1ppm.
The performance test data of the sodium ferrous sulfate positive electrode material are shown in table 2.
Table 2 performance test data for sodium ferrous sulfate cathode material of example 1
| Index (I) | Na | Fe | S | C |
| Data | 15.24％ | 18.01％ | 21.01％ | 5.3％ |
| Bulk density of the product | Tap density | Density of compaction | Fe 3+ | BET |
| 0.5g/mL | 1.0g/mL | 1.43g/mL | 23.6ppm | 23.1m 2 /g |
| Internal resistance of powder | Iron dissolution | Ca | Mg | Zn |
| 24.6Ω.cm | 35.8mg/L | 489ppm | 423ppm | 26.9ppm |
| Cu | Magnetic substance | D10 | D50 | D90 |
| 0.6ppm | 0.3ppm | 2.7μm | 5.4μm | 34.7μm |
As can be seen from Table 2, the ferric iron content of the sodium ferrous sulfate positive electrode material prepared by the invention is very low.
The ferrous sodium sulfate positive electrode material comprises:
a kernel; the inner core is made of sodium lignin sulfonate;
and a carbon coating layer coated on the inner core.
The carbon coating layer is uniformly coated;
the thickness of the carbon coating layer is 3-4 nm.
Fig. 2 is an SEM image of the sodium ferrous sulfate positive electrode material prepared in example 1 of the present invention. As can be seen from fig. 2, the positive electrode material of sodium ferrous sulfate is spherical particles, the surface is smooth, the morphology can effectively improve the solid content in the final homogenization process, particle agglomeration and dispersion in the homogenization process are avoided, meanwhile, the spherical particles can improve the pole piece compaction of the product, and the cycle performance of the product is improved.
Fig. 3 is a TEM image of the sodium ferrous sulfate positive electrode material prepared in example 1 of the present invention, and it is known from TEM that the surface of the material is obviously coated with a layer of carbon, and the thickness is between 3 and 4nm.
Uniformly mixing the sodium ferrous sulfate positive electrode material, conductive carbon black (SP) and PVDF, coating (the coating thickness is 30 mu m) on an aluminum foil, and drying to obtain a positive electrode plate of the sodium ion battery; the mass ratio of the ferrous sodium sulfate positive electrode material to the conductive carbon black to the PVDF is 90:5:5.
the positive plate of the sodium ion battery is used as the positive electrode, the negative electrode is hard carbon, and 1mol/L NaPF is used 6 The solution (solvent comprises DMC, EC and EMC, the volume ratio is 1:1:1) is taken as electrolyte, and the soft package battery is assembled.
And (3) performing electrochemical performance test on the obtained soft-package battery, wherein the test temperature is 25 ℃, and the charge-discharge voltage is 2-4.5V.
Fig. 4 is a graph showing the first charge and discharge of the soft pack battery prepared in example 1 of the present invention. As can be seen from fig. 4, the soft-pack battery prepared by the invention has an obvious discharge platform, has smaller polarization and higher electrical property, and has a first charge capacity of 108.3mAh/g, a first discharge capacity of 102.1mAh/g and a first discharge efficiency of 94.3% at a multiplying power of 0.1C.
Fig. 5 is a graph showing the cycle performance of the soft pack battery prepared in example 1 of the present invention. As can be seen from fig. 5, at a multiplying power of 0.5C, the soft pack battery was relatively fast in capacity retention rate decrease in the first 80 weeks, relatively stable in capacity retention rate in the latter, and very excellent in cycle performance in a nearly straight line. After 500 weeks of circulation, the capacity retention was 92.3%.
Experimental results show that the soft-packaged battery prepared by the method is excellent in circularity, higher in capacity, and higher in median voltage which is 3.4V and is similar to that of lithium iron phosphate, and compared with a common polyanion sodium battery material.
Example 2
Preparing a ferrous sodium sulfate positive electrode material:
1) And (3) preparation of ferrous oxalate:
adding 2mol/L of ferrous acetate solution into a closed reaction kettle, adding 8mol/L ammonia water to adjust the pH value to 10 in the stirred ferrous acetate solution (20 ℃) at the stirring speed of 200r/min, continuously stirring for 30min, heating to 40 ℃, adding 1.5mol/L oxalic acid solution (the molar ratio of oxalic acid to ferrous ions in the ferrous acetate solution is 1:0.95), reacting for 15min at 40 ℃, and filtering, washing and drying the reacted slurry to obtain ferrous oxalate;
the detection data of the ferrous oxalate are shown in table 3.
TABLE 3 detection data for ferrous oxalate
2) Mixing sodium lignin sulfonate, ferrous oxalate and water to obtain a mixed solution; the molar ratio of the sodium lignin sulfonate to the ferrous oxalate is 1:0.95;
3) Spray drying the mixed solution to obtain a spray-dried material; the spray drying process is characterized in that the particle size of discharged material is controlled to be 3 mu m, and D100 is controlled to be 19.6 mu m;
4) Calcining: heating the spray drying material to 400 ℃, keeping the temperature at the heating rate of 2 ℃/h and at the temperature of 400 ℃ for 10h, cooling to the temperature of less than or equal to 80 ℃, discharging, screening and removing iron to obtain a ferrous sodium sulfate anode material;
the calcination is carried out in a tube furnace, and nitrogen is introduced in the calcination process to maintain the oxygen content in the tube furnace to be lower than 1ppm.
The ferrous sodium sulfate positive electrode material comprises:
a kernel; the inner core is made of sodium lignin sulfonate;
and a carbon coating layer coated on the inner core.
The carbon coating layer is uniformly coated;
the thickness of the carbon coating layer is 5-7 nm.
The performance test data of the sodium ferrous sulfate positive electrode material are shown in table 4.
Table 4 performance test data for sodium ferrous sulfate cathode material of example 2
The sodium ferrous sulfate positive electrode material was prepared into a soft-pack battery according to the method of example 1, and the electrochemical performance of the obtained soft-pack battery was tested according to the method of example 1. The test data are shown in table 5.
TABLE 5 Performance test data for sodium ferrous sulfate cathode materials of example 2
Example 3
Preparing a ferrous sodium sulfate positive electrode material:
1) And (3) preparation of ferrous oxalate:
adding 3mol/L of ferrous chloride solution into a closed reaction kettle, adding 10mol/L ammonia water to adjust the pH value to 8 in the stirred (stirring speed is 400 r/min) ferrous chloride solution (35 ℃), continuously stirring for 60min, heating to 60 ℃, adding 2.5mol/L oxalic acid solution (the molar ratio of oxalic acid to ferrous ions in the ferrous chloride solution is 1:0.98), reacting for 30min at 60 ℃, and filtering, washing and drying the reacted slurry to obtain ferrous oxalate;
the detection data of the ferrous oxalate are shown in table 6.
TABLE 6 detection data for ferrous oxalate
2) Mixing sodium lignin sulfonate, ferrous oxalate and water to obtain a mixed solution; the molar ratio of the sodium lignin sulfonate to the ferrous oxalate is 1:0.98;
3) Spray drying the mixed solution to obtain a spray-dried material; the spray drying process is characterized in that the particle size of discharged material is controlled to be 6 mu m, and D100 is controlled to be 35 mu m;
4) Calcining: heating the spray drying material to 450 ℃, keeping the temperature at the heating rate of 3 ℃/h and the temperature of 450 ℃ for 18h, cooling to the material temperature of less than or equal to 80 ℃, discharging, screening and removing iron to obtain a ferrous sodium sulfate anode material;
the calcination is carried out in a tube furnace, and nitrogen is introduced during the calcination to maintain the oxygen content in the tube furnace below 1ppm.
The ferrous sodium sulfate positive electrode material comprises:
a kernel; the inner core is made of sodium lignin sulfonate;
and a carbon coating layer coated on the inner core.
The carbon coating layer is uniformly coated;
the thickness of the carbon coating layer is 2-3 nm.
The performance test data of the sodium ferrous sulfate cathode material are shown in table 7.
TABLE 7 Performance test data for sodium ferrous sulfate cathode materials of example 3
The sodium ferrous sulfate positive electrode material was prepared into a soft-pack battery according to the method of example 1, and the electrochemical performance of the obtained soft-pack battery was tested according to the method of example 1. The test data are shown in table 8.
Table 8 data for performance testing of sodium ferrous sulfate cathode material of example 3
Comparative example 1
The properties of the sodium ferrous sulfate positive electrode material obtained by the test with the sodium ligninsulfonate of example 1 replaced with an equimolar amount of sodium thiosulfate, the others being unchanged, are shown in table 9.
Table 9 data of performance test of sodium ferrous sulfate cathode material of comparative example 1
| Index (I) | Na | Fe | S | C |
| Data | 15.15％ | 18.21％ | 21.11％ | 3.6％ |
| Bulk density of the product | Tap density | Density of compaction | Fe 3+ | BET |
| 0.6g/mL | 1.1g/mL | 1.48g/mL | 75.9ppm | 17.5m 2 /g |
| Internal resistance of powder | Iron dissolution | Ca | Mg | Zn |
| 66.9Ω.cm | 50.5mg/L | 410ppm | 411ppm | 20.4ppm |
| Cu | Magnetic substance | D10 | D50 | D90 |
| 0.9ppm | 0.3ppm | 2.5m | 5.7μm | 34.1μm |
The sodium ferrous sulfate positive electrode material was prepared into a soft-pack battery according to the method of example 1, and the electrochemical performance of the obtained soft-pack battery was tested according to the method of example 1. The test data are shown in table 10.
Table 10 data of performance test of sodium ferrous sulfate cathode material of comparative example 1
Comparative example 2
The performance of the sodium ferrous sulfate positive electrode material obtained by testing the ferrous oxalate of step 2) of example 1 was replaced with an equimolar amount of ferrous acetate, the others being unchanged, as shown in table 11.
Table 11 data of performance test of sodium ferrous sulfate cathode material of comparative example 2
| Index (I) | Na | Fe | S | C |
| Data | 14.25％ | 18.45％ | 20.11％ | 5.3％ |
| Bulk density of the product | Tap density | Density of compaction | Fe 3+ | BET |
| 0.4g/mL | 1.1g/mL | 1.43g/mL | 19.4ppm | 28.7m 2 /g |
| Internal resistance of powder | Iron dissolution | Ca | Mg | Zn |
| 20.1Ω.cm | 43.2mg/L | 309ppm | 527ppm | 20.1ppm |
| Cu | Magnetic substance | D10 | D50 | D90 |
| 0.2ppm | 0.3ppm | 2.7μm | 5.3μm | 37.9μm |
The sodium ferrous sulfate positive electrode material was prepared into a soft-pack battery according to the method of example 1, and the electrochemical performance of the obtained soft-pack battery was tested according to the method of example 1. The test data are shown in table 12.
Table 12 data of performance test of sodium ferrous sulfate cathode material of comparative example 2
Experimental results show that the sodium ferrous sulfate positive electrode material prepared by the method can realize more uniform carbon coating, liquid nitrogen and freeze drying are not needed to be adopted in the preparation method for realizing drying, so that ferrous oxidation is prevented, and the cost is low. The soft-package battery prepared from the sodium ferrous sulfate positive electrode material has a first charge capacity higher than 105mAh/g and a first discharge capacity higher than 99mAh/g and a first discharge efficiency higher than 93% at a multiplying power of 0.1C; after 500 weeks of cycling, the capacity retention was higher than 91%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the ferrous sodium sulfate positive electrode material comprises the following steps:
a) Mixing sodium lignin sulfonate, ferrous oxalate and water to obtain a mixed solution;
b) Spray drying the mixed solution to obtain a spray-dried material;
c) And calcining the spray drying material to obtain the sodium ferrous sulfate anode material.
2. The method according to claim 1, wherein in step a), the molar ratio of sodium lignin sulfonate to ferrous oxalate is 1:0.95 to 0.98.
3. The method according to claim 1, wherein in step a), the method for producing ferrous oxalate comprises the steps of:
and (3) regulating the pH value of the ferrous solution to 8-10, mixing with the oxalic acid solution, and carrying out precipitation reaction to obtain ferrous oxalate.
4. The method according to claim 3, wherein the concentration of the aqueous ammonia is 8 to 10mol/L;
or/and the combination of the two,
when the pH value of the ferrous solution is regulated, the temperature of the ferrous solution is 20-35 ℃;
the concentration of the ferrous solution is 2-3 mol/L;
or/and the combination of the two,
the ferrous salt in the ferrous solution comprises at least one of ferrous sulfate, ferrous chloride and ferrous acetate; the concentration of the oxalic acid solution is 1.5-2.5 mol/L;
or/and the combination of the two,
the temperature of the mixture with the oxalic acid solution is 40-60 ℃;
the molar ratio of oxalic acid contained in the oxalic acid solution to ferrous ions in the ferrous solution is 1:0.95 to 0.98;
or/and the combination of the two,
the temperature of the precipitation reaction is 40-60 ℃ and the time is 15-30 min.
5. The method according to claim 3, wherein after the precipitation reaction, further comprising: and filtering, washing and drying the reacted slurry.
6. The method according to claim 1, wherein in the step B), the spray-drying process is controlled to have a discharge particle diameter of 3 to 6 μm and a d100.ltoreq.35. Mu.m.
7. The method of claim 1, wherein in step C), calcining the spray-dried material comprises:
heating the spray drying material to 400-450 ℃, and preserving heat for 10-18 h;
or/and the combination of the two,
the heating speed is 2-3 ℃/h;
or/and the combination of the two,
after the heat preservation, still include: cooling to the temperature of the material of less than or equal to 80 ℃;
or/and the combination of the two,
the calcination is carried out at an oxygen content of less than 1ppm.
8. The ferrous sodium sulfate positive electrode material produced by the production method according to any one of claims 1 to 7.
9. The ferrous sodium sulfate positive electrode material of claim 8, wherein the ferrous sodium sulfate positive electrode material comprises:
a kernel; the inner core is made of sodium lignin sulfonate;
a carbon coating layer coated on the inner core;
the thickness of the carbon coating layer is 2-10 nm.
10. A sodium ion battery, wherein the positive electrode of the sodium ion battery comprises the ferrous sodium sulfate positive electrode material of any one of claims 8-9.
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| US20210323825A1 (en) * | 2018-11-19 | 2021-10-21 | South China University Of Technology | Lignin Porous Carbon Nanosheet, Preparation Method Therefor, and Application Thereof in Supercapacitor Electrode Materials |
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