CN115504487B - Preparation method of positive electrode material, positive electrode material and sodium ion battery - Google Patents
Preparation method of positive electrode material, positive electrode material and sodium ion battery Download PDFInfo
- Publication number
- CN115504487B CN115504487B CN202211249401.1A CN202211249401A CN115504487B CN 115504487 B CN115504487 B CN 115504487B CN 202211249401 A CN202211249401 A CN 202211249401A CN 115504487 B CN115504487 B CN 115504487B
- Authority
- CN
- China
- Prior art keywords
- solution
- preparation
- protective agent
- prussian
- hydrochloric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 239000007774 positive electrode material Substances 0.000 title claims description 24
- 229910001415 sodium ion Inorganic materials 0.000 title abstract description 22
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000003223 protective agent Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000011734 sodium Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 44
- 235000010323 ascorbic acid Nutrition 0.000 claims description 22
- 229960005070 ascorbic acid Drugs 0.000 claims description 22
- 239000011668 ascorbic acid Substances 0.000 claims description 22
- 239000011241 protective layer Substances 0.000 claims description 21
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 15
- 229940094933 n-dodecane Drugs 0.000 claims description 15
- 235000006708 antioxidants Nutrition 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 229940057995 liquid paraffin Drugs 0.000 claims description 7
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 125000005456 glyceride group Chemical group 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 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 12
- 229910052708 sodium Inorganic materials 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 108
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 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 15
- 239000013225 prussian blue Substances 0.000 description 15
- 229960003351 prussian blue Drugs 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000002441 reversible effect Effects 0.000 description 11
- 229910002547 FeII Inorganic materials 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 9
- 229910001448 ferrous ion Inorganic materials 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 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 description 4
- 239000000264 sodium ferrocyanide Substances 0.000 description 4
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021260 NaFe Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910002553 FeIII Inorganic materials 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
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002699 waste material Substances 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses Prussian white, a preparation method thereof and a sodium ion battery. The method comprises the following steps: mixing ferrous inorganic salt, an antioxidant, hydrochloric acid, a protective agent and water to obtain a solution A; mixing alkali metal ferrocyanide, an antioxidant, hydrochloric acid, a protective agent and water to obtain a solution B; under the condition of not stirring, adding the solution B into the solution A, and standing to obtain the Prussian Bai Zheng pole material; wherein the protective agent is liquid under the preparation condition, insoluble in water and less than water in density. The method has simple and convenient operation and obvious effect, can obtain the Prussian Bai Zheng pole material with higher theoretical capacity of sodium storage, has cheap and easily obtained raw materials, is environment-friendly in the synthesis process, and is suitable for wide application.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method of a positive electrode material, the positive electrode material and a sodium ion battery.
Background
In recent years, with the widespread use of lithium ion batteries in power automobiles and portable communication devices, the price of lithium ion batteries is rapidly rising. In order to cope with the rapid rise of lithium prices, many research and development enterprises and scientific research institutions focus on sodium ion batteries with rich raw materials and low price.
The energy storage mechanism of the sodium ion battery is similar to that of a lithium ion battery, sodium ions migrate back and forth between the anode and the cathode and are embedded into/separated from an electrode material in the charging and discharging process, and meanwhile electrons flow through an external circuit, so that energy storage is realized. Among the sodium ion battery cathode materials, prussian blue type cathode materials exhibit excellent sodium storage performance due to higher theoretical capacity and an open lattice structure. Especially, the Prussian Bai Zheng pole material-Na 2FeⅡFeⅡ(CN)6 can realize two-step sodium storage reaction from Na 2FeIIFeII(CN)6 to NaFe IIIFeII(CN)6 to Fe IIIFeIII(CN)6, so that the Prussian Bai Zheng pole material has high theoretical capacity of 170mAh g -1, and has excellent application prospect (Nat. Commun.,2020,11,980).
Disclosure of Invention
The invention aims to provide a preparation method of a positive electrode material, the positive electrode material and a sodium ion battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a method for preparing a positive electrode material, the method comprising the steps of:
mixing ferrous inorganic salt, an antioxidant, hydrochloric acid, a protective agent and water to obtain a solution A;
Mixing alkali metal ferrocyanide, an antioxidant, hydrochloric acid, a protective agent and water to obtain a solution B;
under the condition of not stirring, adding the solution B into the solution A, and standing to obtain the Prussian Bai Zheng pole material;
Wherein the protective agent is liquid under the preparation condition, insoluble in water and less in density than water.
In the method of the present invention, the preparation conditions refer to the preparation conditions of the above-mentioned Prussian white preparation method, and may be, for example, normal temperature and normal pressure. Generally, normal temperature means 25 ℃.
In the method, the preparation of the solution A and the solution B is not sequential, the solution A can be prepared first and then the solution B can be prepared, the solution B can be prepared first and then the solution A can be prepared, and the solution A and the solution B can be prepared simultaneously and respectively.
Prussian blue type cathode materials are generally synthesized by a coprecipitation method or a hydrothermal method. The coprecipitation method is to mix an iron source solution and a sodium ferrocyanide solution to perform precipitation reaction, and then remove supernatant by centrifugation, so that the Prussian blue type anode material can be obtained. The coprecipitation method has simple and easy synthesis process, and is suitable for large-scale popularization and application. In addition, prussian blue positive electrode materials can be synthesized by a hydrothermal method. The hydrothermal method generally uses a single iron source (sodium ferrocyanide), and partial iron ions are separated out through heating and pressurizing, so that the Prussian blue type positive electrode material is generated through reaction. The Prussian blue positive electrode material obtained by the hydrothermal method has the advantages of less defects of general lattice structures and good sodium storage performance, but has more severe synthesis conditions and lower yield, and is not beneficial to large-scale production and application.
The iron ions and sodium ferrocyanide are used for coprecipitation reaction, so that Prussian white with high capacity can be obtained. However, during the synthesis process, one iron ion of Prussian white-Na 2FeⅡFeⅡ(CN)6 is very easily oxidized to a ferric ion, thereby obtaining Prussian blue-NaFe ⅢFeⅡ(CN)6. Prussian blue generally can only realize one-step sodium storage reaction, namely one sodium ion is embedded/extracted, so that the sodium storage capacity of the Prussian blue is far lower than that of Prussian white, and the energy density and the power density of a full battery of the Prussian blue are seriously reduced (adv. Funct. Mater.2020, 2006970).
In the preparation method of the Prussian Bai Zheng pole material, the solution A and the solution B are creatively prepared by adopting the protective agent, so that a liquid protective layer can be formed, and the reaction liquid is isolated from air, thereby reducing the oxidation of oxygen to Prussian white; an antioxidant (e.g., ascorbic acid) is added to both solution a and solution B prior to the reaction to consume oxygen contained in the solution and maintain protection against ferrous ions from oxidation.
The present invention particularly points out that solution B was added to solution a without stirring, left to stand, and subjected to a coprecipitation reaction by slow diffusion of the solution to obtain prussian white. If stirring is carried out, a large amount of oxygen enters the solution, and the generation of Prussian white is seriously affected.
The preparation method is simple and convenient to operate, has obvious effect, can obtain the Prussian Bai Zheng pole material with higher theoretical capacity of sodium storage, has low-cost and easily-obtained raw materials, is environment-friendly in the synthesis process, and is suitable for wide application.
The following preferred technical solutions are used as the present invention, but not as limitations on the technical solutions provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solutions.
Preferably, in the preparation process of the solution A, after mixing, the solution A is slowly stirred and kept stand, and the slow stirring speed is 60-200 r/min, such as 60r/min、70r/min、80r/min、90r/min、100r/min、110r/min、120r/min、130r/min、140r/min、150r/min、160r/min、170r/min、180r/min or 200 r/min; the time of slow stirring is 5-15 min, such as 5min, 8min, 10min, 12min or 15 min; the standing time is 2 to 12 hours, for example, 2 hours, 4 hours, 5 hours, 6 hours, 8 hours, 10 hours, 11 hours or 12 hours, etc.
Preferably, during the preparation of the solution a, the ferrous inorganic salt is selected from FeSO 4·7H2 O.
Preferably, in the preparation of the solution a, the antioxidant includes at least one of ascorbic acid, sodium borohydride, sodium sulfite, and hypophosphorous acid.
Preferably, the concentration of the hydrochloric acid in the preparation of the solution a is 0.25 to 1M, for example 0.25M, 0.3M, 0.35M, 0.4M, 0.45M, 0.5M, 0.55M, 0.6M, 0.65M, 0.7M, 0.8M, 0.9M or 1M, etc.
In the invention, hydrochloric acid can prevent ferrous ion from hydrolyzing.
Preferably, during the preparation of the solution a, the protective agent comprises at least one of a liquid hydrocarbon, a liquid halogenated hydrocarbon and a liquid higher fatty glyceride, and the liquid hydrocarbon preferably comprises a hydrocarbon compound of C5 to C16 (e.g., C5, C6, C7, C8, C9, C10, C12, C14, C16, etc.).
Preferably, during the preparation of the solution a, the protecting agent is selected from n-dodecane or liquid paraffin.
In one embodiment, the protective agent has low oxygen solubility, thereby better isolating oxygen and avoiding oxidation of Prussian white.
Preferably, in the preparation of the solution A, the antioxidant is added in an amount of 0.05 to 0.5g (e.g., 0.05g, 0.06g, 0.07g, 0.08g, 0.09g, 0.1g, 0.15g, 0.2g, 0.3g, 0.4g, and 0.5g, etc.) per 0.01mol of the ferrous ion, the hydrochloric acid is added in an amount of 0.05 to 0.5mL (e.g., 0.05mL, 0.06mL, 0.07mL, 0.08mL, 0.09mL, 0.1mL, 0.15mL, 0.2mL, 0.3mL, 0.4mL, 0.5mL, etc.), and the protective agent is added to form a protective layer having a height of 3 to 10mm (e.g., the protective layer height of 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, etc.).
In the invention, if the content of the protective agent is too small, the solution can be directly contacted with air, so that ferrous ions are rapidly oxidized; if the content of the protective agent is too much, the further improvement effect on the performance of the prepared product is not obvious, the waste of the protective agent is caused, and the material synthesis cost is increased.
Preferably, in the preparation process of the solution B, the solution B is slowly stirred and kept stand after being mixed, and the slow stirring speed is 60-200 r/min, such as 60r/min、70r/min、80r/min、90r/min、100r/min、110r/min、120r/min、130r/min、140r/min、150r/min、160r/min、170r/min、180r/min or 200 r/min; the time of slow stirring is 5-15 min, such as 5min, 8min, 10min, 12min or 15 min; the standing time is 2 to 12 hours, for example, 2 hours, 4 hours, 5 hours, 6 hours, 8 hours, 10 hours, 11 hours or 12 hours, etc.
As a preferred embodiment of the process according to the invention, the alkali metal ferrocyanide salt is Na 4Fe(CN)6 during the preparation of the solution B.
Preferably, in the preparation of the solution B, the antioxidant includes at least one of ascorbic acid, sodium borohydride, sodium sulfite, and hypophosphorous acid.
Preferably, the concentration of the hydrochloric acid in the preparation of the solution B is 0.25 to 1M, for example 0.25M, 0.3M, 0.35M, 0.4M, 0.45M, 0.5M, 0.55M, 0.6M, 0.65M, 0.7M, 0.8M, 0.9M or 1M, etc.
Preferably, during the preparation of the solution B, the protective agent comprises at least one of a liquid hydrocarbon, a liquid halogenated hydrocarbon and a liquid higher fatty glyceride, and the liquid hydrocarbon preferably comprises a hydrocarbon compound of C5 to C16 (e.g., C5, C6, C7, C8, C9, C10, C12, C14, C16, etc.).
Preferably, in the preparation process of the solution B, the protective agent is selected from n-dodecane or liquid paraffin.
In the preferred embodiment of the invention, the oxygen solubility of the protective agent is low, so that oxygen can be better isolated, and oxidation of Prussian white can be avoided.
Preferably, in the preparation of the solution B, the antioxidant is added in an amount of 0.05 to 0.5g (for example, 0.05g, 0.06g, 0.07g, 0.08g, 0.09g, 0.1g, 0.15g, 0.2g, 0.3g, 0.4g, 0.5g, etc.), the hydrochloric acid is added in an amount of 0.05 to 0.5mL (for example, 0.05mL, 0.06mL, 0.07mL, 0.08mL, 0.09mL, 0.1mL, 0.15mL, 0.2mL, 0.3mL, 0.4mL, 0.5mL, etc.), and the protective agent is added to form a protective layer having a height of 3 to 10mm (for example, the protective layer having a height of 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, etc.).
As a further preferred embodiment of the method according to the present invention, the step of adding the solution B to the solution a is performed in a rapid and smooth manner, wherein air mixing is minimized, and the rapid rate is as follows: the addition rate is 5 to 10mL/s, for example, 5mL/s, 6mL/s, 7mL/s, 8mL/s, 9mL/s, 10mL/s, or the like.
Preferably, the step of adding the solution B to the solution A followed by standing is performed for a period of preferably 2 to 12 hours, for example, 2 hours, 4 hours, 5 hours, 6 hours, 8 hours, 10 hours, 11 hours, 12 hours, or the like. By standing, the reactants can be freely diffused to react, stirring is avoided, and air mixing is reduced.
Preferably, after the reaction is allowed to stand, the excess solution is filtered off and dried.
Preferably, the drying is freeze-drying. The drying time is not particularly limited, and may be, for example, 8 to 12 hours, for example, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, or the like.
As a further preferred embodiment of the method according to the invention, the method comprises the following steps:
S1: adding ferrous sulfate, ascorbic acid, hydrochloric acid and a protective agent into water, slowly stirring, and standing to obtain a solution A;
Adding sodium ferrocyanide, ascorbic acid, hydrochloric acid and a protective agent into water, slowly stirring, and standing to obtain a solution B;
S2: adding the solution B into the solution A without stirring, standing, filtering to remove redundant solution, and freeze-drying to obtain Prussian white;
Wherein the protective agent used for preparing the solution A and the solution B is independently selected from n-dodecane or liquid paraffin.
In a second aspect, the present invention provides a positive electrode material prepared by using the method of the first aspect, where the positive electrode material has a chemical formula of Na 2FeⅡFeⅡ(CN)6 and is white powder.
In a third aspect, the present invention provides a sodium ion battery, wherein the positive electrode of the sodium ion battery comprises the positive electrode material of the second aspect.
The negative electrode of the sodium ion battery is not particularly limited by the present invention, such as, but not limited to, hard carbon, amorphous carbon. The preparation methods of the positive plate and the negative plate can be used for preparing the positive plate and the negative plate of the sodium ion battery, which are known in the art. In some embodiments of the present invention, the negative electrode active material in the negative electrode sheet may use hard carbon. The electrolyte of the sodium ion battery may be a sodium salt electrolyte suitable for use in sodium ion batteries in the art.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts the specific protective agent to prepare the solution A and the solution B, and can form a liquid protective layer to isolate the reaction liquid from air, thereby reducing the oxidation of the Prussian white by oxygen. Simultaneously, ascorbic acid is added into A, B solutions before the reaction, so as to consume oxygen contained in the solutions and keep the ferrous ions from being oxidized.
(2) The preparation method is simple and convenient to operate, has obvious effect, can obtain the Prussian Bai Zheng pole material with higher theoretical capacity of sodium storage, has low-cost and easily-obtained raw materials, is environment-friendly in the synthesis process, and is suitable for wide application.
Drawings
Fig. 1 is a photograph of prussian white prepared in example 1.
Fig. 2 is a third round of charge-discharge curves of prussian white prepared in example 1.
Fig. 3 is a photograph of Prussian white prepared in example 2.
Fig. 4 is a third round of charge-discharge curve of prussian white prepared in example 2.
Fig. 5 is a third round of charge-discharge curves of prussian white prepared in example 3.
Fig. 6 is a third round of charge-discharge curve of prussian white prepared in example 4.
Fig. 7 is a third round of charge-discharge curve of prussian white prepared in example 5.
Fig. 8 is a third round of charge-discharge curve of prussian white prepared in example 6.
Fig. 9 is a photograph of prussian blue prepared in comparative example 1.
Fig. 10 is a third-round charge-discharge curve of prussian blue prepared in example 1.
Fig. 11 is a comparative preparation flow chart of example 1 and comparative example 1, the upper portion corresponds to example 1, and the lower portion corresponds to example 1.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
Example 1
The embodiment provides a preparation method of a positive electrode material, which comprises the following steps:
Step 1), adding 1.39g of FeSO 4·7H2 O, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) into 50mL of water, adding n-dodecane until a protective layer with the height of 5mm is formed, slowly stirring for 10min at 120r/min, and standing for 4h to obtain a solution A;
1.52g of Na 4Fe(CN)6, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) are added into 20mL of water, n-dodecane is added until a protective layer with the height of 5mm is formed, and the mixture is slowly stirred at 120r/min and is kept stand for 4 hours to obtain a solution B;
And 2) rapidly and stably adding the solution B into the solution A at the speed of 10mL/s, reducing air mixing as much as possible, standing for 12h, preparing a Prussian white photo, referring to FIG. 1, filtering to remove redundant solution, and freeze-drying for 12h to obtain the Prussian Bai Zheng pole material.
Step 3), preparing a working electrode by using Prussian Bai Zheng electrode materials: prussian Bai Zheng electrode material, PVDF and KS-6 according to the mass ratio of 94:4:2 grinding and mixing for 30min, adding deionized water with the mass being 1 time, stirring for 2h, uniformly stirring, coating on an aluminum foil, and drying at 140 ℃ to obtain the working electrode.
Using metal sodium as a counter electrode, and assembling a 2032 type button cell; the electrolyte solute is NaClO 4, the electrolyte solvent is a mixed solution of PC, EC, DEC, the volume ratio of PC, EC, DEC is 1:1:1, and the electrolyte additive is 1.5vol% VC, 1.5vol% FEC and 1.5vol% PS; the diaphragm is made of glass fiber; the battery should be left to stand for 24 hours after assembly, after which its reversible capacity is tested.
Reversible capacity test: discharging the test battery to 2.0V at 100mA/g at room temperature (25 ℃), standing for 1min, charging to 4.2V at 100mA/g, standing for 1min, and cycling for 3 times; and obtaining the reversible capacity of the test battery according to the third discharge capacity.
FIG. 2 is a third charge-discharge curve of Prussian white prepared in example 1, showing that the reversible capacity is 122.0mAh/g.
The remaining examples and comparative examples test batteries were prepared in the same manner as in example 1, and were subjected to reversible capacity testing.
Example 2
The embodiment provides a preparation method of a positive electrode material, which comprises the following steps:
step 1), adding 1.39g of FeSO 4·7H2 O, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) into 50mL of water, adding liquid paraffin until a protective layer with the height of 5mm is formed, slowly stirring for 10min at 150r/min, and standing for 3h to obtain a solution A;
1.52g of Na 4Fe(CN)6, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) are added into 20mL of water, liquid paraffin is added until a protective layer with the height of 5mm is formed, 150r/min is slowly stirred for 10min, and the mixture is left stand for 3h to obtain a solution B;
And 2) rapidly and stably adding the solution B into the solution A at the speed of 8mL/s, reducing air mixing as much as possible, standing for 12h, preparing a Prussian white photo, referring to FIG. 3, filtering to remove redundant solution, and freeze-drying for 12h to obtain the Prussian Bai Zheng pole material.
FIG. 4 is a third charge-discharge curve of Prussian white prepared in example 2, showing that the reversible capacity is 121.3mAh/g.
Example 3
The embodiment provides a preparation method of a positive electrode material, which comprises the following steps:
step 1), adding 1.39g of FeSO 4·7H2 O, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) into 50mL of water, adding n-dodecane until a protective layer with the height of 2mm is formed, slowly stirring for 10min at 120r/min, and standing for 4h to obtain a solution A;
1.52g of Na 4Fe(CN)6, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) are added into 20mL of water, n-dodecane is added until a protective layer with the height of 2mm is formed, and the mixture is slowly stirred at 120r/min and is kept stand for 4 hours to obtain a solution B;
And 2) rapidly and stably adding the solution B into the solution A at the speed of 10mL/s, reducing air mixing as much as possible, standing for 12h, filtering to remove redundant solution, and freeze-drying for 12h to obtain the Prussian Bai Zheng pole material.
In this embodiment, since the thickness of the protective layer is relatively low, a part of oxygen may be mixed into the solution A, B, so that ferrous ions are oxidized, and the quality of the produced Prussian Bai Zheng electrode material is relatively reduced. FIG. 5 shows the third charge-discharge curve of Prussian white prepared in example 3, showing that the reversible capacity is 99.0mAh/g.
Example 4
The embodiment provides a preparation method of a positive electrode material, which comprises the following steps:
Step 1), adding 1.39g of FeSO 4·7H2 O, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) into 50mL of water, adding n-dodecane until a protective layer with the height of 5mm is formed, slowly stirring for 10min at 500r/min, and standing for 4h to obtain a solution A;
1.52g of Na 4Fe(CN)6, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) are added into 20mL of water, n-dodecane is added until a protective layer with the height of 5mm is formed, and the mixture is slowly stirred at 500r/min and is kept stand for 4 hours to obtain a solution B;
And 2) rapidly and stably adding the solution B into the solution A at the speed of 10mL/s, reducing air mixing as much as possible, standing for 12h, filtering to remove redundant solution, and freeze-drying for 12h to obtain the Prussian Bai Zheng pole material.
In this embodiment, since the stirring speed is relatively high when the A, B solution is disposed, a part of oxygen may be mixed into the solution A, B, so that the ferrous ions are oxidized, and the quality of the resulting Prussian Bai Zheng electrode material is relatively reduced. FIG. 6 is a third charge-discharge curve of Prussian white prepared in example 4, showing a reversible capacity of 96.3mAh/g.
Example 5
The embodiment provides a preparation method of a positive electrode material of a sodium ion battery, which comprises the following steps:
Step 1), adding 1.39g of FeSO 4·7H2 O, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) into 50mL of water, adding n-dodecane until a protective layer with the height of 5mm is formed, slowly stirring for 10min at 120r/min, and standing for 4h to obtain a solution A;
1.52g of Na 4Fe(CN)6, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) are added into 20mL of water, n-dodecane is added until a protective layer with the height of 5mm is formed, and the mixture is slowly stirred at 120r/min and is kept stand for 4 hours to obtain a solution B;
And 2) stably adding the solution B into the solution A at the speed of 100mL/min, standing for 12h, filtering to remove redundant solution, and freeze-drying for 12h to obtain the Prussian Bai Zheng pole material.
In this embodiment, since the solution B is added to the solution a at a relatively low speed, a part of oxygen may be mixed into the mixed solution, so that the ferrous ions are oxidized, and the quality of the resulting prussian Bai Zheng electrode material is relatively slightly reduced. FIG. 7 is a third charge-discharge curve of Prussian white prepared in example 5, showing a reversible capacity of 117.5mAh/g.
Example 6
The embodiment provides a preparation method of a positive electrode material, which comprises the following steps:
Step 1), adding 1.39g of FeSO 4·7H2 O, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) into 50mL of water, adding n-dodecane until a protective layer with the height of 5mm is formed, slowly stirring for 10min at 120r/min, and standing for 4h to obtain a solution A;
1.52g of Na 4Fe(CN)6, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) are added into 20mL of water, n-dodecane is added until a protective layer with the height of 5mm is formed, and the mixture is slowly stirred at 120r/min and is kept stand for 4 hours to obtain a solution B;
And 2) rapidly and stably adding the solution B into the solution A at the speed of 10mL/s, reducing air mixing as much as possible, standing for 30min, filtering to remove redundant solution, and freeze-drying for 12h to obtain the Prussian Bai Zheng pole material.
In this embodiment, the solution B and the solution a are mixed and then allowed to stand for a relatively short period of time, so that the Prussian white reaction is insufficient, and the crystal defects are relatively many, resulting in a relatively reduced sodium storage capacity. FIG. 8 is a third charge-discharge curve of Prussian white prepared in example 6, showing that the reversible capacity is 98.6mAh/g.
Comparative example 1
The embodiment provides a preparation method of a positive electrode material, which comprises the following steps:
Step 1), adding 1.39g of FeSO 4·7H2 O, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) into 50mL of water, slowly stirring for 10min at 120r/min, and standing for 4h to obtain a solution A;
1.52g of Na 4Fe(CN)6, 0.1g of ascorbic acid and 0.1mL of hydrochloric acid (0.5M) are added into 20mL of water, slowly stirred at 120r/min and left stand for 4h to obtain a solution B;
And 2) rapidly and stably adding the solution B into the solution A at the speed of 10mL/s, stirring for 1h, standing for 12h, preparing a Prussian blue photo, referring to FIG. 9, filtering to remove the redundant solution, and freeze-drying for 12h to obtain the Prussian blue anode material.
FIG. 10 is a third charge-discharge curve of Prussian blue prepared in comparative example 1, showing that its reversible capacity is 89.7mAh/g.
Fig. 11 is a comparative preparation flow chart of example 1 and comparative example 1, the upper portion corresponds to example 1, and the lower portion corresponds to example 1.
Comparative example 1 compared with example 1, the solution obtained by mixing the solution a and the solution B without adding the protective agent, resulted in oxidation of ferrous ions by oxygen, and finally Prussian blue was obtained, reducing the sodium storage capacity of the obtained positive electrode material.
As is apparent from the above examples and comparative examples, according to the present invention, the Prussian white having a high sodium storage capacity is prepared by optimizing the synthesis conditions of Prussian white, using a simple treatment, effectively isolating the reaction solution from air using a protecting agent, reducing oxidation of divalent iron ions, and standing the reaction solution after obtaining a mixed solution of solution a and solution B, thereby preventing re-mixing of oxygen.
The embodiment of the invention also provides a sodium ion battery, which uses the Prussian Bai Zheng electrode material prepared in the embodiments 1-6. The preparation method of the sodium ion battery comprises the following steps:
Preparing a positive plate: prussian Bai Zheng electrode materials prepared in examples 1-6 were used as active materials with CMC, SBR, conductive carbon black according to 92:2:2:4, fully mixing the materials in a proper amount of deionized water to obtain positive electrode slurry, coating the positive electrode slurry on the surface of an aluminum foil, and drying, cold pressing and cutting the aluminum foil to obtain the positive electrode plate.
Preparing a negative plate: hard carbon, CMC, SBR, KS-6 was mixed at 94:2:2: and 2, fully mixing the materials in a proper amount of deionized water to obtain negative electrode slurry, coating the negative electrode slurry on the surface of the copper foil, and drying, cold pressing and cutting the copper foil to obtain the negative electrode plate.
The sodium ion battery is assembled by the negative plate and the positive plate, the solute of the electrolyte is NaClO 4, the solvent of the electrolyte is a mixed solution of PC, EC, DEC, the volume ratio of PC, EC, DEC is 1:1:1, and the additive of the electrolyte is 1.5vol% VC, 1.5vol% FEC and 1.5vol% PS; and the diaphragm is a glass fiber diaphragm, and after the assembly is completed in a glove box, the diaphragm is subjected to standing formation to obtain a sodium ion battery product. The sodium ion battery has higher battery capacity. Taking Prussian Bai Zheng pole material prepared in example 1 as an example, performing full cell test, wherein the full cell energy density is 107Wh/kg; the full cell test was performed using the Prussian Bai Zheng electrode material prepared in comparative example 1 as an example, and the full cell energy density was only 82Wh/kg.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (15)
1. A method for preparing a positive electrode material, comprising the steps of:
mixing ferrous inorganic salt, an antioxidant, hydrochloric acid, a protective agent and water to obtain a solution A;
Mixing alkali metal ferrocyanide, an antioxidant, hydrochloric acid, a protective agent and water to obtain a solution B;
under the condition of no stirring, adding the solution B into the solution A in a rapid and stable manner, standing for 2-12 h, filtering to remove redundant solution after standing, and freeze-drying to obtain the Prussian Bai Zheng pole material;
Wherein the protective agent is liquid under the preparation condition, insoluble in water and less than water in density;
In the preparation process of the solution A, the addition amount of the antioxidant is 0.05-0.5 g, the addition amount of the hydrochloric acid is 0.05-0.5 mL, the protective agent is added to form a protective layer with the height of 3-10 mm, and after mixing, the solution A is slowly stirred and kept stand, wherein the slow stirring speed is 60-200 r/min;
in the preparation process of the solution B, the addition amount of the antioxidant is 0.05-0.5 g, the addition amount of the hydrochloric acid is 0.05-0.5 mL, the protective agent is added to form a protective layer with the height of 3-10 mm, and after mixing, the solution B is slowly stirred, wherein the slow stirring speed is 60-200 r/min;
The quick speed is as follows: the adding speed is 5-10 mL/s.
2. The method according to claim 1, wherein in the preparation process of the solution a, the slow stirring time is 5-15 min, and the standing time is 2-12 h.
3. The method of claim 1, wherein the ferrous inorganic salt is FeSO 4·7H2 O during the preparation of the solution a.
4. The method of claim 1, wherein the antioxidant comprises at least one of ascorbic acid, sodium borohydride, sodium sulfite, and hypophosphorous acid during the preparation of the solution a.
5. The method according to claim 1, wherein the concentration of the hydrochloric acid in the preparation process of the solution A is 0.25-1 mol/L.
6. The method according to claim 1, wherein the protective agent is selected from one or more of liquid hydrocarbon, liquid halogenated hydrocarbon and liquid higher fatty glyceride during the preparation of the solution a.
7. The method according to claim 1, wherein in the preparation of the solution a, the liquid hydrocarbon is a C5 to C16 hydrocarbon compound.
8. The method according to claim 1, wherein the protective agent is selected from n-dodecane or liquid paraffin during the preparation of the solution a.
9. The method according to claim 1, wherein the slow stirring time is 5-15 min and the standing time is 2-12 h during the preparation of the solution B.
10. The method of claim 1, wherein the alkali metal ferrocyanide salt is Na 4Fe(CN)6 during the preparation of solution B.
11. The method of claim 1, wherein the antioxidant comprises at least one of ascorbic acid, sodium borohydride, sodium sulfite, and hypophosphorous acid during the preparation of the solution B.
12. The method according to claim 1, wherein the concentration of the hydrochloric acid in the preparation process of the solution B is 0.25-1 mol/L.
13. The method of claim 1, wherein the protective agent comprises at least one of a liquid hydrocarbon, a liquid halogenated hydrocarbon, and a liquid higher fatty acid glyceride during the preparation of the solution B.
14. The method according to claim 1, wherein in the preparation of the solution B, the liquid hydrocarbon is a C5 to C16 hydrocarbon compound.
15. The method according to claim 1, wherein the protective agent is selected from n-dodecane or liquid paraffin during the preparation of the solution B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211249401.1A CN115504487B (en) | 2022-10-12 | 2022-10-12 | Preparation method of positive electrode material, positive electrode material and sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211249401.1A CN115504487B (en) | 2022-10-12 | 2022-10-12 | Preparation method of positive electrode material, positive electrode material and sodium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115504487A CN115504487A (en) | 2022-12-23 |
| CN115504487B true CN115504487B (en) | 2024-07-09 |
Family
ID=84510979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211249401.1A Active CN115504487B (en) | 2022-10-12 | 2022-10-12 | Preparation method of positive electrode material, positive electrode material and sodium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115504487B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397234A (en) * | 2016-09-05 | 2017-02-15 | 河北东华冀衡化工有限公司 | Preparation method of interfering ion-free ferrous glycinate |
| CN110235292A (en) * | 2018-09-04 | 2019-09-13 | 辽宁星空钠电电池有限公司 | A kind of Prussian blue positive electrode of high sodium content and its preparation method and application and sodium-ion battery |
| CN114388757A (en) * | 2021-12-28 | 2022-04-22 | 大连中比动力电池有限公司 | Prussian white material for positive electrode of sodium-ion battery and preparation method thereof |
| CN114853033A (en) * | 2022-06-06 | 2022-08-05 | 华中科技大学 | Prussian white synthesis process and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110451525B (en) * | 2019-08-07 | 2021-05-11 | 清华大学 | Method for rapidly preparing Prussian blue analogue with monoclinic crystal structure |
| CN112209409B (en) * | 2020-09-28 | 2022-07-01 | 宇恒电池股份有限公司 | Method for rapidly preparing Prussian white serving as positive electrode material of sodium-ion battery |
| CN113839032A (en) * | 2021-09-15 | 2021-12-24 | 杭州思拓瑞吉科技有限公司 | Low-cost Prussian white material, and preparation method and application thereof |
-
2022
- 2022-10-12 CN CN202211249401.1A patent/CN115504487B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397234A (en) * | 2016-09-05 | 2017-02-15 | 河北东华冀衡化工有限公司 | Preparation method of interfering ion-free ferrous glycinate |
| CN110235292A (en) * | 2018-09-04 | 2019-09-13 | 辽宁星空钠电电池有限公司 | A kind of Prussian blue positive electrode of high sodium content and its preparation method and application and sodium-ion battery |
| CN114388757A (en) * | 2021-12-28 | 2022-04-22 | 大连中比动力电池有限公司 | Prussian white material for positive electrode of sodium-ion battery and preparation method thereof |
| CN114853033A (en) * | 2022-06-06 | 2022-08-05 | 华中科技大学 | Prussian white synthesis process and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115504487A (en) | 2022-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104009235B (en) | A kind of preparation method of porous silicon/graphene composite material | |
| CN114944478B (en) | Sodium ion battery positive electrode material, and preparation method and application thereof | |
| CN105006561B (en) | A kind of barium oxide ultrathin nanometer band of ion insertion and its preparation method and application | |
| CN107910539A (en) | A kind of nickel cobalt lithium aluminate cathode material of lithium metasilicate cladding and preparation method thereof | |
| CN109473657A (en) | A kind of nickel cobalt aluminium manganese quaternary lithium-ion battery positive electrode material being mixed with, Preparation method and use | |
| CN113659141B (en) | SiO@Mg/C composite material and preparation method and application thereof | |
| CN112447962A (en) | Precursor for doped lithium ion battery, positive electrode material and preparation methods of precursor and positive electrode material | |
| CN111916701B (en) | Coated positive electrode material and preparation method and application thereof | |
| CN113104863A (en) | Inert transition metal element doped iron-based Prussian blue sodium ion battery positive electrode material | |
| CN109037602A (en) | A kind of double oxide cladding tertiary cathode material and preparation method thereof | |
| CN114229870A (en) | In-situ carbon-coated Prussian blue positive electrode material and preparation method and application thereof | |
| CN109037649A (en) | It is a kind of to be mixed with modified nickel cobalt lithium aluminate cathode material and preparation method thereof | |
| CN115092902B (en) | Method for preparing lithium iron manganese phosphate positive electrode material by using iron-manganese-rich slag | |
| WO2024055521A1 (en) | Preparation method and use of bismuth-based cathode material | |
| CN104810513B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| CN114920267A (en) | Production method and application of hybrid Prussian blue | |
| CN104292100A (en) | Preparation method of calcium terephthalate, and application of calcium terephthalate in lithium ion battery | |
| CN108767214A (en) | A kind of preparation method of alumina-graphite alkene composite lithium ion battery cathode material | |
| CN108390050B (en) | Coating method of spinel type lithium manganate positive electrode material for lithium battery | |
| CN115504487B (en) | Preparation method of positive electrode material, positive electrode material and sodium ion battery | |
| CN107317019B (en) | Ferrous carbonate/graphene composite material for sodium ion battery cathode and preparation method and application thereof | |
| CN116364898B (en) | Sodium ion positive electrode material, preparation method thereof and sodium ion battery | |
| CN110474051B (en) | Application of common dye rhodamine B as organic anode material of lithium ion battery | |
| CN107195884A (en) | A kind of lithium metasilicate doped graphene lithium ion battery negative material and preparation method thereof | |
| CN105845927A (en) | Preparation method of lithium ion battery cathode material lithium cobalt oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |