CN117566764A - Prussian blue sodium ion battery positive electrode material and preparation method and application thereof - Google Patents
Prussian blue sodium ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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- CN117566764A CN117566764A CN202311520113.XA CN202311520113A CN117566764A CN 117566764 A CN117566764 A CN 117566764A CN 202311520113 A CN202311520113 A CN 202311520113A CN 117566764 A CN117566764 A CN 117566764A
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- prussian blue
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- 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 title claims abstract description 55
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 50
- 239000013225 prussian blue Substances 0.000 title claims abstract description 50
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 46
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 51
- 239000008139 complexing agent Substances 0.000 claims abstract description 45
- XYKQMCAWQYSNKA-UHFFFAOYSA-N 3-(carboxymethyl)pentanedioic acid Chemical compound OC(=O)CC(CC(O)=O)CC(O)=O XYKQMCAWQYSNKA-UHFFFAOYSA-N 0.000 claims abstract description 15
- MNZHBXZOPHQGMD-UHFFFAOYSA-N acetic acid;azane Chemical compound N.CC(O)=O.CC(O)=O.CC(O)=O MNZHBXZOPHQGMD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 104
- 239000007788 liquid Substances 0.000 claims description 79
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 30
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 29
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 18
- 230000002572 peristaltic effect Effects 0.000 claims description 18
- 159000000000 sodium salts Chemical class 0.000 claims description 18
- 239000010405 anode material Substances 0.000 claims description 17
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 17
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 17
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000011790 ferrous sulphate Substances 0.000 claims description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 11
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 36
- 239000011734 sodium Substances 0.000 abstract description 17
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 abstract description 14
- 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 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 9
- 239000001509 sodium citrate Substances 0.000 abstract description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 abstract description 9
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000010828 elution Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000006911 nucleation Effects 0.000 abstract description 2
- 238000010899 nucleation Methods 0.000 abstract description 2
- 238000010951 particle size reduction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a Prussian blue sodium ion battery positive electrode material, a preparation method and application thereof. In the preparation method, when the Prussian blue sodium ion battery positive electrode material is prepared, a specific complexing agent (trimellitic acid, methane triacetic acid or ammonia triacetic acid) is selected, and a nonionic surfactant is added, so that the growth of the Prussian blue material can be guided, and the problems of particle size reduction, uneven distribution and the like caused by overhigh concentration when the conventional complexing agent such as sodium citrate is used are solved. The preparation method not only can improve the sodium content of the Prussian blue material, and further improve the specific capacity of the material, but also can control the nucleation and growth speed of the Prussian blue material, so as to form large-size single crystals, and the low defect structure of the single crystals is beneficial to extremely low metal ion elution,Excellent specific capacity and excellent Na + Diffusion kinetics, the rate and capacity decay caused by the long sodium ion diffusion path of the polycrystalline structure are relieved.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a Prussian blue sodium ion battery positive electrode material, a preparation method and application thereof.
Background
With the rapid development of industries such as electric automobiles, large-scale energy storage power stations, smart grids and the like, the demand for energy storage devices in the industry is increasing. Lithium ion batteries are the most commonly used energy storage devices, and various processes are mature and have excellent energy storage performance, but further development of the lithium ion batteries is limited by the problem of lithium resource shortage, so that development of a new electrochemical energy storage system is particularly important. Among them, the sodium ion battery is promising because of similar performance and the same operating principle as the lithium ion battery.
The development of sodium ion batteries is limited by the cathode material. The positive electrode material that can be used for sodium ion batteries mainly includes layered transition metal oxides, polyanion compounds, prussian blue analogues, and the like. Wherein, prussian blue analogues are free of oxygen lattice with Na due to the three-dimensional open frame structure built by cyanide + Weak interaction, thus being capable of realizing Na + Is quickly and reversibly detached. When the Prussian blue analogues are used as the positive electrode material of the sodium ion battery, the theoretical mass specific capacity of the Prussian blue analogues is up to 170mAh/g, the sodium storage potential is higher, the cycling stability is better, and the Prussian blue analogues are considered as one of the most promising positive electrode materials of the sodium ion battery.
Prussian blue type materials have a polycrystalline structure and a single crystal structure. In general, there are a large number of surfaces and interiors of polycrystalline structure materialsWhen the crystal boundary is used as an electrode material, a channel is provided for the permeation of electrolyte, so that more serious side reaction occurs between the electrode and the organic electrolyte, which not only can lead to slow ion diffusion dynamics in the electrode, but also can lead to pulverization of the active material of the electrode to lose electrical contact. For Prussian blue-based materials, the polycrystalline structure also means that the structure of the material is generally rich in defects and water, which can lead to Na + Migration can be enhanced to affect the relevant electrochemical performance. Meanwhile, the nano particles of the polycrystalline structure material are seriously agglomerated, so that the volume of clusters is overlarge, and the tap density of the nano polycrystalline material is often not suitable for commercial application. In contrast, single crystal structure materials can attenuate the effects of the above aspects, exhibiting superior performance in terms of ion diffusion kinetics and cycling stability. In addition, the positive electrode material of single crystal structure shows more reliable safety and competitiveness than the polycrystalline positive electrode material in practical application due to higher thermal stability, tap density and volumetric energy density.
Prussian blue materials are generally synthesized by adopting a solvent coprecipitation method, raw materials such as transition metal salt, sodium ferrocyanide and the like are reacted in an aqueous solution and are kept stand for a period of time, and then the prepared Prussian blue materials are separated from the aqueous solution. In the related art, in order to increase the sodium content of the Prussian blue material, a conventional complexing agent such as sodium citrate is generally added to a high concentration in the preparation process of the Prussian blue material so as to manufacture a sodium-rich environment, thereby increasing the specific capacity of the battery.
However, in the process of implementing the present invention, the inventor found that the Prussian blue material prepared in the related art still has a series of problems of excessively low specific capacity (caused by excessively low sodium content and excessively high water content), poor dynamic performance, low yield, etc., so that the obtained material formula does not have the requirement of an amplification test.
Disclosure of Invention
The inventor researches find that a series of problems such as low specific capacity (caused by low sodium content and high water content), poor dynamic performance, low yield and the like of the Prussian blue material prepared in the related technology are caused by the fact that the particle size of the Prussian blue material generated by reaction is reduced and uneven distribution is caused when the concentration of a complexing agent such as sodium citrate which is conventionally used is too high, and finally the prepared Prussian blue material is of a polycrystalline structure.
In view of the above, the invention provides a Prussian blue sodium ion battery positive electrode material, and a preparation method and application thereof, so as to solve the problems of low specific capacity, poor dynamic performance, low yield and the like of Prussian blue materials prepared in the related technology.
In a first aspect, the invention provides a preparation method of a Prussian blue sodium ion battery positive electrode material, which comprises the following steps:
dissolving sodium ferrocyanide, a complexing agent and a nonionic surfactant in deionized water to obtain a first precursor liquid; wherein the complexing agent comprises at least one of trimesic acid, methane triacetic acid and ammonia triacetic acid;
dissolving ferrous salt, complexing agent and nonionic surfactant in deionized water to obtain a second precursor solution;
dissolving sodium salt and nonionic surfactant in deionized water to obtain a third precursor solution;
dripping the first precursor liquid and the second precursor liquid into the third precursor liquid under the action of a peristaltic pump, performing coprecipitation reaction, and aging to obtain a reaction product;
and (3) carrying out solid-liquid separation on the reaction product, and taking the solid for washing and drying.
In the preparation method, when the Prussian blue sodium ion battery positive electrode material is prepared, a specific complexing agent (trimellitic acid, methane triacetic acid or ammonia triacetic acid) is selected, and a nonionic surfactant is added, so that the growth of the Prussian blue material can be guided, and the problems of particle size reduction, uneven distribution and the like caused by over-high concentration when the conventional complexing agent such as sodium citrate is used are solved. The introduction of the nonionic surfactant can further improve the concentration of the specific complexing agents to a near-saturation state, so that on one hand, a limited sodium-rich environment can be provided, on the other hand, the complexing capacity of the complexing agents can be obviously improved, and Fe is greatly inhibited 2+ Is more advantageous in that the reaction kinetics are further reducedSynthesizing a product with large particle size and high crystallinity; meanwhile, the saturation of the complexing agent in the precursor liquid is improved, so that the molar ratio of water molecules in the precursor liquid is reduced, and the activity of water molecules is further reduced, and Na in the synthesis process can be reduced + Can compete for more binding sites. Therefore, the preparation method not only can improve the sodium content of the Prussian blue material, and further improve the specific capacity of the material, but also can control the nucleation and growth speed of the Prussian blue material, and form large-size single crystals, and the low-defect structure of the single crystals is beneficial to extremely low metal ion elution, excellent specific capacity and excellent Na + Diffusion kinetics, the rate and capacity decay caused by the long sodium ion diffusion path of the polycrystalline structure are relieved. Meanwhile, compared with a polycrystalline structure, the thermal stability and the tap density of the monocrystalline material are also obviously improved.
Wherein, the chemical structural formulas of the trimesic acid, the methane triacetic acid and the glycine are shown as follows:
in an alternative embodiment, in the first precursor solution, the concentration of the sodium ferrocyanide is 20-60 mmol/L, the concentration of the complexing agent is 200-300 mmol/L, and the concentration of the nonionic surfactant is 5-20 g/L.
In an alternative embodiment, in the second precursor solution, the concentration of the ferrous salt is 40-80 mmol/L, the concentration of the complexing agent is 200-300 mmol/L, and the concentration of the nonionic surfactant is 5-20 g/L.
In an alternative embodiment, in the third precursor solution, the concentration of the sodium salt is 20 to 100mmol/L, and the concentration of the nonionic surfactant is 5 to 20g/L.
In an alternative embodiment, the nonionic surfactant comprises polyvinyl alcohol and/or polyvinylpyrrolidone;
and/or the ferrous salt comprises ferrous sulfate and/or ferrous chloride;
and/or the sodium salt comprises at least one of sodium chloride, sodium sulfate and sodium pyrophosphate.
In an alternative embodiment, the peristaltic pump has a peristaltic rate of 60-140 mL/min when the first precursor liquid and the second precursor liquid are dripped into the third precursor liquid;
and/or the coprecipitation reaction is carried out under stirring condition, the reaction temperature is 80-100 ℃, the stirring speed is 50-200 rpm, and the stirring time is 6-10 h;
and/or the aging time is 10-60 hours;
and/or, the drying conditions include: the drying temperature is 100-140 ℃, and the drying time is 12-96 h.
In an alternative embodiment, the preparation process is carried out in an atmosphere of a shielding gas selected from nitrogen and/or argon.
In a second aspect, the invention provides a Prussian blue sodium ion battery anode material, which is prepared by adopting the preparation method.
In a third aspect, the invention provides an application of the Prussian blue sodium ion battery anode material in preparing a sodium ion battery.
In a fourth aspect, the invention provides a sodium ion battery, which comprises the Prussian blue sodium ion battery positive electrode material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing XRD test results of the positive electrode materials prepared in examples 1 to 3;
FIG. 2 is a graph showing SEM test results of the positive electrode material prepared in example 1;
FIG. 3 is a graph showing SEM test results of the positive electrode material prepared in comparative example 1;
FIG. 4 is a graph showing SEM test results of the positive electrode material prepared in comparative example 2;
fig. 5 is a graph showing SEM test results of the positive electrode material prepared in comparative example 3.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The invention is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the invention as claimed.
Example 1
The Prussian blue sodium ion battery anode material is prepared according to the following method:
(1) Under the protection of nitrogen, sodium ferrocyanide, complexing agent (trimesic acid) and nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water, and stirred to form a first precursor liquid;
wherein, in the obtained first precursor solution, the concentration of sodium ferrocyanide is 40mmol/L, the concentration of complexing agent (trimesic acid) is 250mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(2) Under the protection of nitrogen, ferrous salt (ferrous sulfate), complexing agent (trimesic acid) and nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water to form a second precursor liquid;
wherein, in the second precursor solution, the concentration of ferrous salt (ferrous sulfate) is 60mmol/L, the concentration of complexing agent (trimellitic acid) is 250mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(3) Under the protection of nitrogen, sodium salt (sodium chloride) and nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water in a reaction kettle to form a third precursor liquid;
wherein, in the obtained third precursor solution, the concentration of sodium salt (sodium chloride) is 40mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(4) Under the protection of nitrogen, the first precursor liquid and the second precursor liquid are dripped into the third precursor liquid of the reaction kettle at a constant speed under the action of a peristaltic pump (the peristaltic speed is 100 mL/min) to carry out coprecipitation reaction, and after the dripping of the first precursor liquid and the second precursor liquid is finished, the first precursor liquid and the second precursor liquid are kept at a constant temperature of 90 ℃ and stirred for 8 hours at a stirring speed of 100 rpm;
(5) After the reaction is finished, standing and ageing the obtained material for 12 hours at room temperature to obtain a reaction product;
(6) And (3) centrifuging the reaction product obtained in the step (5), washing the obtained solid by using deionized water and absolute ethyl alcohol, and then drying the solid in a vacuum oven at 120 ℃ for 96 hours to obtain the Prussian blue sodium ion battery anode material.
Example 2
The Prussian blue sodium ion battery anode material is prepared according to the following method:
(1) Under the protection of nitrogen, sodium ferrocyanide, a complexing agent (methane triacetic acid) and a nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water, and the mixture is stirred to form a first precursor liquid;
wherein, in the obtained first precursor solution, the concentration of sodium ferrocyanide is 40mmol/L, the concentration of complexing agent (methane triacetic acid) is 250mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(2) Under the protection of nitrogen, ferrous salt (ferrous chloride), complexing agent (methane triacetic acid) and nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water to form a second precursor liquid;
wherein, in the obtained second precursor solution, the concentration of ferrous salt (ferrous chloride) is 60mmol/L, the concentration of complexing agent (methane triacetic acid) is 250mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(3) Under the protection of nitrogen, sodium salt (sodium sulfate) and nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water in a reaction kettle to form a third precursor liquid;
wherein, in the obtained third precursor solution, the concentration of sodium salt (sodium sulfate) is 40mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(4) Under the protection of nitrogen, the first precursor liquid and the second precursor liquid are dripped into the third precursor liquid of the reaction kettle at a constant speed under the action of a peristaltic pump (the peristaltic speed is 100 mL/min) to carry out coprecipitation reaction, and after the dripping of the first precursor liquid and the second precursor liquid is finished, the first precursor liquid and the second precursor liquid are kept at a constant temperature of 90 ℃ and stirred for 8 hours at a stirring speed of 100 rpm;
(5) After the reaction is finished, standing and ageing the obtained material for 12 hours at room temperature to obtain a reaction product;
(6) And (3) centrifuging the reaction product obtained in the step (5), washing the obtained solid by using deionized water and absolute ethyl alcohol, and then drying the solid in a vacuum oven at 120 ℃ for 96 hours to obtain the Prussian blue sodium ion battery anode material.
Example 3
The Prussian blue sodium ion battery anode material is prepared according to the following method:
(1) Under the protection of nitrogen, sodium ferrocyanide, complexing agent (nitrilotriacetic acid) and nonionic surfactant (polyvinylpyrrolidone) are dissolved in deionized water, and stirred to form a first precursor liquid;
wherein, in the obtained first precursor solution, the concentration of sodium ferrocyanide is 40mmol/L, the concentration of complexing agent (nitrilotriacetic acid) is 250mmol/L, and the concentration of nonionic surfactant (polyvinylpyrrolidone) is 10g/L;
(2) Under the protection of nitrogen, ferrous salt (ferrous sulfate), complexing agent (nitrilotriacetic acid) and nonionic surfactant (polyvinylpyrrolidone) are dissolved in deionized water to form a second precursor liquid;
wherein, in the obtained second precursor solution, the concentration of ferrous salt (ferrous sulfate) is 60mmol/L, the concentration of complexing agent (nitrilotriacetic acid) is 250mmol/L, and the concentration of nonionic surfactant (polyvinylpyrrolidone) is 10g/L;
(3) Under the protection of nitrogen, sodium salt (sodium pyrophosphate) and nonionic surfactant (polyvinylpyrrolidone) are dissolved in deionized water in a reaction kettle to form a third precursor liquid;
wherein, in the obtained third precursor solution, the concentration of sodium salt (sodium pyrophosphate) is 40mmol/L, and the concentration of nonionic surfactant (polyvinylpyrrolidone) is 10g/L;
(4) Under the protection of nitrogen, the first precursor liquid and the second precursor liquid are dripped into the third precursor liquid of the reaction kettle at a constant speed under the action of a peristaltic pump (the peristaltic speed is 100 mL/min) to carry out coprecipitation reaction, and after the dripping of the first precursor liquid and the second precursor liquid is finished, the first precursor liquid and the second precursor liquid are kept at a constant temperature of 90 ℃ and stirred for 8 hours at a stirring speed of 100 rpm;
(5) After the reaction is finished, standing and ageing the obtained material for 12 hours at room temperature to obtain a reaction product;
(6) And (3) centrifuging the reaction product obtained in the step (5), washing the obtained solid by using deionized water and absolute ethyl alcohol, and then drying the solid in a vacuum oven at 120 ℃ for 96 hours to obtain the Prussian blue sodium ion battery anode material.
Comparative example 1
The Prussian blue sodium ion battery anode material is prepared according to the following method:
(1) Under the protection of nitrogen, sodium ferrocyanide, a complexing agent (sodium citrate) and a nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water, and are stirred to form a first precursor liquid;
wherein, in the obtained first precursor solution, the concentration of sodium ferrocyanide is 40mmol/L, the concentration of complexing agent (sodium citrate) is 250mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(2) Under the protection of nitrogen, ferrous salt (ferrous sulfate), complexing agent (sodium citrate) and nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water to form a second precursor liquid;
wherein, in the second precursor solution, the concentration of ferrous salt (ferrous sulfate) is 60mmol/L, the concentration of complexing agent (sodium citrate) is 250mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(3) Under the protection of nitrogen, sodium salt (sodium chloride) and nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water in a reaction kettle to form a third precursor liquid;
wherein, in the obtained third precursor solution, the concentration of sodium salt (sodium chloride) is 40mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(4) Under the protection of nitrogen, the first precursor liquid and the second precursor liquid are dripped into the third precursor liquid of the reaction kettle at a constant speed under the action of a peristaltic pump (the peristaltic speed is 100 mL/min) to carry out coprecipitation reaction, and after the dripping of the first precursor liquid and the second precursor liquid is finished, the first precursor liquid and the second precursor liquid are kept at a constant temperature of 90 ℃ and stirred for 8 hours at a stirring speed of 100 rpm;
(5) After the reaction is finished, standing and ageing the obtained material for 12 hours at room temperature to obtain a reaction product;
(6) And (3) centrifuging the reaction product obtained in the step (5), washing the obtained solid by using deionized water and absolute ethyl alcohol, and then drying the solid in a vacuum oven at 120 ℃ for 96 hours to obtain the Prussian blue sodium ion battery anode material.
Comparative example 2
The Prussian blue sodium ion battery anode material is prepared according to the following method:
(1) Under the protection of nitrogen, sodium ferrocyanide and complexing agent (trimesic acid) are dissolved in deionized water, and are stirred to form a first precursor liquid;
wherein, in the obtained first precursor solution, the concentration of sodium ferrocyanide is 40mmol/L, and the concentration of complexing agent (trimesic acid) is 150mmol/L;
(2) Under the protection of nitrogen, ferrous salt (ferrous sulfate) and complexing agent (trimesic acid) are dissolved in deionized water to form a second precursor liquid;
wherein, in the second precursor solution, the concentration of ferrous salt (ferrous sulfate) is 60mmol/L, and the concentration of complexing agent (trimellitic acid) is 150mmol/L;
(3) Under the protection of nitrogen, sodium salt (sodium chloride) is dissolved in deionized water in a reaction kettle to form a third precursor liquid;
wherein, in the obtained third precursor solution, the concentration of sodium salt (sodium chloride) is 40mmol/L;
(4) Under the protection of nitrogen, the first precursor liquid and the second precursor liquid are dripped into the third precursor liquid of the reaction kettle at a constant speed under the action of a peristaltic pump (the peristaltic speed is 100 mL/min) to carry out coprecipitation reaction, and after the dripping of the first precursor liquid and the second precursor liquid is finished, the first precursor liquid and the second precursor liquid are kept at a constant temperature of 90 ℃ and stirred for 8 hours at a stirring speed of 100 rpm;
(5) After the reaction is finished, standing and ageing the obtained material for 12 hours at room temperature to obtain a reaction product;
(6) And (3) centrifuging the reaction product obtained in the step (5), washing the obtained solid by using deionized water and absolute ethyl alcohol, and then drying the solid in a vacuum oven at 120 ℃ for 96 hours to obtain the Prussian blue sodium ion battery anode material.
Comparative example 3
The Prussian blue sodium ion battery anode material is prepared according to the following method:
(1) Under the protection of nitrogen, sodium ferrocyanide and a nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water, and a first precursor liquid is formed by stirring;
wherein, in the obtained first precursor solution, the concentration of sodium ferrocyanide is 40mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(2) Under the protection of nitrogen, ferrous salt (ferrous sulfate) and nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water to form a second precursor liquid;
wherein, in the second precursor solution, the concentration of ferrous salt (ferrous sulfate) is 60mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(3) Under the protection of nitrogen, sodium salt (sodium chloride) and nonionic surfactant (polyvinyl alcohol) are dissolved in deionized water in a reaction kettle to form a third precursor liquid;
wherein, in the obtained third precursor solution, the concentration of sodium salt (sodium chloride) is 40mmol/L, and the concentration of nonionic surfactant (polyvinyl alcohol) is 10g/L;
(4) Under the protection of nitrogen, the first precursor liquid and the second precursor liquid are dripped into the third precursor liquid of the reaction kettle at a constant speed under the action of a peristaltic pump (the peristaltic speed is 100 mL/min) to carry out coprecipitation reaction, and after the dripping of the first precursor liquid and the second precursor liquid is finished, the first precursor liquid and the second precursor liquid are kept at a constant temperature of 90 ℃ and stirred for 8 hours at a stirring speed of 100 rpm;
(5) After the reaction is finished, standing and ageing the obtained material for 12 hours at room temperature to obtain a reaction product;
(6) And (3) centrifuging the reaction product obtained in the step (5), washing the obtained solid by using deionized water and absolute ethyl alcohol, and then drying the solid in a vacuum oven at 120 ℃ for 96 hours to obtain the Prussian blue sodium ion battery anode material.
Experimental example 1
XRD tests were performed on the positive electrode materials prepared in examples 1 to 3, respectively, and the test results are shown in FIG. 1. SEM tests were performed on the positive electrode materials prepared in example 1 and comparative examples 1 to 3, respectively, and the test results are shown in fig. 2 to 5. Fig. 1 is an XRD test result chart of the positive electrode material prepared in examples 1 to 3, fig. 2 is an SEM test result chart of the positive electrode material prepared in example 1, fig. 3 is an SEM test result chart of the positive electrode material prepared in comparative example 1, fig. 4 is an SEM test result chart of the positive electrode material prepared in comparative example 2, and fig. 5 is an SEM test result chart of the positive electrode material prepared in comparative example 3.
As can be seen from fig. 1, the XRD patterns of the positive electrode materials prepared in examples 1 to 3 show that as the complexing agent is changed from nitrilotriacetic acid (example 3) to methane triacetic acid (example 2) and then to trimellitic acid (example 1), the product is changed from cubic phase to monoclinic phase, and the color of the product is changed from dark blue to white. In particular, the XRD pattern of example 1 shows cleavage of peaks around 27 °, indicating that the material is distorted in lattice due to an increase in sodium content, thereby exhibiting a monoclinic phase structure. According to the report of the literature, the phenomenon indicates that the sodium content in the product is improved, namely, the change of the complexing agent contributes to the improvement of the initial sodium content of the product.
As can be seen from fig. 2, the prussian blue material prepared in example 1 using trimellitic acid as a complexing agent and polyvinyl alcohol as a nonionic surfactant shows a more regular appearance, shows a single crystal morphology, and has no adhesion of fine grains on the surface; as can be seen from fig. 3, the surface of the Prussian blue material particle prepared in comparative example 1 using sodium citrate as the complexing agent and polyvinyl alcohol as the nonionic surfactant forms a multi-layer stacked step morphology, and the particle size is about 1 μm and the size is uneven; as can be seen from fig. 4, the surface of the prussian blue material prepared in comparative example 2, which uses trimellitic acid as a complexing agent and does not use a nonionic surfactant, forms a multi-layered stacked step morphology, and the particle size is about 3 μm and is not uniform in size; as can be seen from fig. 5, the prussian blue material prepared in comparative example 3 using polyvinyl alcohol as a nonionic surfactant without using a complexing agent has fine grains and serious agglomeration, because the reaction kinetics of the prussian blue preparation process is faster, and nano-scale grains are generally generated.
Experimental example 2
The positive electrode materials prepared in examples 1 to 3 and comparative examples 1 to 3 were taken, respectively, and sodium-ion half batteries were prepared as follows:
the sodium ion half cell is a CR2025 button cell. The positive electrode active material was dried in a vacuum atmosphere (10-5 pa) at 120℃for 10 hours before the experiment. The positive electrode slurry consists of active matter, conductive agent (KB) and binder (PVDF) according to the weight ratio of 7:2:1, and after adding a proper amount of NMP, the mixture is stirred by a high-speed vibration refiner, and then coated on 15 mu m carbon-coated aluminum foil. And (5) placing the obtained slurry-coated pole piece in a vacuum oven at 120 ℃ for drying for 24 hours, and cutting into a wafer for standby after drying. When the battery is assembled, the battery is operated in a glove box protected by Ar atmosphere according to the positive electrode shell, the positive electrode plate, the glass fiber diaphragm, the negative electrode plate, the sodium metal plate, the current collector, the spring piece and the negative electrode shell, and a proper amount of electrolyte is dripped. And carrying out electrochemical test after the obtained electricity is buckled and is placed for 24 hours.
The prepared sodium ion batteries were tested for the specific capacity for initial discharge and the capacity retention after 25, 50, 100 and 200 cycles, respectively, under the following test conditions: the constant-current charge and discharge test is carried out by adopting a battery test system, the prepared button battery is clamped on a test channel after being placed for 24 hours, and the process steps of constant-current charge and discharge are set by software, wherein the process steps of constant-current charge and discharge are placing, constant-current charge (100 mA/g, 4V), placing, constant-current discharge (100 mA/g, 2V), circulation and ending, the placing time is input in the placing, the cut-off voltage and current density are input in the constant-current charge and the constant-current discharge, and the process steps and the circulation times are input in the circulation.
The test results are shown in Table 1.
Table 1 results of testing the capacity and cycle performance of each sodium ion battery
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The preparation method of the Prussian blue sodium ion battery anode material is characterized by comprising the following steps of:
dissolving sodium ferrocyanide, a complexing agent and a nonionic surfactant in deionized water to obtain a first precursor liquid; wherein the complexing agent comprises at least one of trimesic acid, methane triacetic acid and ammonia triacetic acid;
dissolving ferrous salt, complexing agent and nonionic surfactant in deionized water to obtain a second precursor solution;
dissolving sodium salt and nonionic surfactant in deionized water to obtain a third precursor solution;
dripping the first precursor liquid and the second precursor liquid into the third precursor liquid under the action of a peristaltic pump, performing coprecipitation reaction, and aging to obtain a reaction product;
and (3) carrying out solid-liquid separation on the reaction product, and taking the solid for washing and drying.
2. The method according to claim 1, wherein the concentration of the sodium ferrocyanide in the first precursor solution is 20 to 60mmol/L, the concentration of the complexing agent is 200 to 300mmol/L, and the concentration of the nonionic surfactant is 5 to 20g/L.
3. The method according to claim 1 or 2, wherein in the second precursor solution, the concentration of the ferrous salt is 40 to 80mmol/L, the concentration of the complexing agent is 200 to 300mmol/L, and the concentration of the nonionic surfactant is 5 to 20g/L.
4. A production method according to any one of claims 1 to 3, wherein in the third precursor liquid, the concentration of the sodium salt is 20 to 100mmol/L, and the concentration of the nonionic surfactant is 5 to 20g/L.
5. The method according to any one of claims 1 to 4, wherein the nonionic surfactant comprises polyvinyl alcohol and/or polyvinylpyrrolidone;
and/or the ferrous salt comprises ferrous sulfate and/or ferrous chloride;
and/or the sodium salt comprises at least one of sodium chloride, sodium sulfate and sodium pyrophosphate.
6. The production method according to any one of claims 1 to 5, wherein a peristaltic rate of the peristaltic pump is 60 to 140mL/min when the first precursor liquid and the second precursor liquid are dropped into the third precursor liquid;
and/or the coprecipitation reaction is carried out under stirring condition, the reaction temperature is 80-100 ℃, the stirring speed is 50-200 rpm, and the stirring time is 6-10 h;
and/or the aging time is 10-60 hours;
and/or, the drying conditions include: the drying temperature is 100-140 ℃, and the drying time is 12-96 h.
7. The preparation method according to any one of claims 1 to 6, wherein the preparation method is carried out in a protective gas atmosphere, the protective gas being selected from nitrogen and/or argon.
8. The Prussian blue sodium ion battery anode material is characterized in that the Prussian blue sodium ion battery anode material is prepared by adopting the preparation method of any one of claims 1 to 7.
9. The use of the positive electrode material of Prussian blue sodium ion battery as defined in claim 8 in preparing sodium ion battery.
10. A sodium ion battery, characterized in that the sodium ion battery comprises the prussian blue sodium ion battery cathode material of claim 8.
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