CN118016822A - Preparation method of potassium-rich manganese-based Prussian blue sodium ion battery anode material - Google Patents
Preparation method of potassium-rich manganese-based Prussian blue sodium ion battery anode material Download PDFInfo
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 50
- 239000011591 potassium Substances 0.000 title claims abstract description 50
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 41
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011572 manganese Substances 0.000 title claims abstract description 26
- 239000010405 anode material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 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 12
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 12
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 12
- 239000013225 prussian blue Substances 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 12
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims 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 claims abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 239000001509 sodium citrate Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 6
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims abstract description 3
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 75
- 239000007774 positive electrode material Substances 0.000 claims description 45
- 239000011734 sodium Substances 0.000 claims description 26
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 19
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000006230 acetylene black Substances 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000004080 punching Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 4
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims 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 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- -1 drying Substances 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 229940091252 sodium supplement Drugs 0.000 claims 2
- 239000012535 impurity Substances 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 230000002572 peristaltic effect Effects 0.000 abstract description 4
- JFSUDVTVQZUDOP-UHFFFAOYSA-N tetrasodium;iron(2+);hexacyanide;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] JFSUDVTVQZUDOP-UHFFFAOYSA-N 0.000 abstract description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 19
- 230000001351 cycling effect Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001414 potassium ion Inorganic materials 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910021135 KPF6 Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention relates to a potassium-rich manganese-based Prussian blue (Mn-PB) sodium ion battery anode material and a preparation method thereof. Manganese acetate tetrahydrate and sodium citrate are dissolved in deionized water to form a solution A, sodium ferrocyanide decahydrate and ascorbic acid are dissolved in deionized water to form a solution B, and polyvinylpyrrolidone and sodium chloride are dissolved in deionized water to form a solution C. Under the conditions of N 2 atmosphere and heating and stirring, simultaneously adding the solution A and the solution B into the solution C through a peristaltic pump, and changing the solution into white suspension after the dripping is finished; and (3) aging at room temperature after heating and stirring, sequentially centrifugally washing with water and absolute ethyl alcohol for several times, and then drying in vacuum to obtain the Mn-PB material. And after preparing the Mn-PB material into an electrode plate, dropwise adding a mixed sodium perchlorate and potassium hexafluorophosphate electrolyte on the electrode plate, assembling a battery, and carrying out potassium doping on the material by an electrochemical process of constant-current charge and discharge to obtain the potassium-rich Mn-PB sodium ion battery anode material.
Description
Technical Field
The invention relates to a potassium-rich manganese-based Prussian blue sodium ion battery anode material and a preparation method thereof, and belongs to the technical field of sodium ion batteries.
Background
With the continuous development of clean energy sources worldwide, energy storage technologies are receiving more and more attention. The lithium ion battery has the advantages of high energy density, long cycle life, high charging efficiency and the like, is widely applied to the fields of energy storage power stations, new energy automobiles and the like, and can form dendrites due to the fact that lithium resources which are deficient are frosted due to excessive use, so that the diaphragm is pierced to cause short circuits, and personal safety and equipment safety are endangered. Compared with lithium, sodium has high crust abundance, uniform distribution and low cost, and sodium and lithium have similar physicochemical properties, so that sodium ion batteries are widely paid attention to domestic and foreign academia and industry. Compared with a lithium ion battery, the sodium ion battery has relatively low energy density, and is not suitable for being applied to the fields of portable electronic equipment and electric automobiles with high requirements on energy density. Because of the good high-low temperature performance and low cost, the method is very suitable for being applied to the fields of power grid energy storage (particularly excellent performance in cold areas of the highland), low-speed electric vehicles and the like.
Sodium ion batteries are similar to lithium ion batteries in working principle and structure, but the radius of sodium ions is large, and the deintercalation of sodium ions is relatively difficult in the process of oxidation-reduction reaction, so that the search of suitable sodium ion electrode materials becomes a key for developing sodium ion batteries and realizing industrialization. Compared with the cathode material, the cathode material is more critical to select, and needs to meet electrochemical performances such as high capacity, high voltage, high multiplying power, long cycle and the like, and also needs to consider various conditions such as resources, cost, manufacturing and the like. Among various sodium ion battery anode materials studied at present, manganese-based Prussian blue (molecular formula is Na 2Mn[Fe(CN)6, abbreviated as Mn-PB) anode materials are receiving attention because of the advantages of an open frame structure favorable for sodium ion deintercalation, environmental protection, low toxicity and the like. Among the Prussian blue materials, mn-PB has a higher theoretical capacity, but its cycling stability is poor. According to the invention, an electrode plate is prepared from an Mn-PB material synthesized by a sodium citrate-assisted coprecipitation method, sodium perchlorate and potassium hexafluorophosphate electrolyte mixed according to a certain proportion are dripped on the electrode plate, a battery is assembled, and the material is doped with potassium through a constant current charge-discharge process, so that a potassium-rich Mn-PB material is prepared. On one hand, as the radius of potassium ions is larger, the potassium ions occupy part of the position of crystal water, so that the content of the crystal water in the material is reduced; on the other hand, because potassium ions with larger radius can play a structural supporting role in the material, mn-PB can keep stable structure even in the rapid deintercalation process of sodium ions. In addition, the diffusion migration energy barrier of sodium ions can be reduced after potassium doping, more sodium ion storage sites and larger sodium ion intercalation channels are provided, and therefore Mn-PB electrochemical performance after potassium doping is obviously improved.
Disclosure of Invention
The invention aims to provide a method for preparing a potassium-rich manganese-based Prussian blue (Mn-PB) sodium ion battery anode material by using a simple electrochemical method. The related synthetic raw materials of the positive electrode material of the potassium-rich Mn-PB sodium ion battery comprise: the manganese-containing salt is manganese acetate tetrahydrate Mn (CH 3COO)2·4H2 O (or manganese sulfate MnSO 4, manganese chloride Mn (Cl) 2), trisodium citrate dihydrate C 6H5Na3O7•2H2 O, sodium ferrocyanide decahydrate Na 4Fe(CN)6·10H2 O, ascorbic acid C 6H8O6, polyvinylpyrrolidone PVP and sodium chloride NaCl (or sodium carbonate Na 2CO3, sodium acetate CH 3 COONa), deionized water (or distilled water, purified water, tap water).
The preparation method comprises the following steps:
one of the technical schemes of the invention provides a positive electrode material of a potassium-rich Mn-PB sodium ion battery and a preparation method thereof, and the positive electrode material comprises the following steps:
(1) Dissolving manganese-containing salt and chelating agent sodium citrate in deionized water to prepare solution A; dissolving proper amount of sodium ferrocyanide and antioxidant ascorbic acid in proper amount of deionized water to prepare solution B, and dissolving dispersing agent polyvinylpyrrolidone and proper amount of sodium supplementing agent in proper amount of deionized water to obtain solution C;
(2) Under the conditions of N 2 atmosphere and heating and stirring, simultaneously adding the solution A and the solution B into the solution C through a peristaltic pump, and changing the solution into white suspension after the dripping is finished; and (5) continuing heating and stirring for 10-12 h, and finally aging for 20-30 h at room temperature. Pouring out the supernatant, sequentially centrifugally washing the lower white precipitate with deionized water and absolute ethyl alcohol for several times, and vacuum drying at 100-120 ℃ for 12h to obtain the Mn-PB material;
(3) Stirring Mn-PB material, acetylene black and polyvinylidene fluoride into slurry, coating the slurry on aluminum foil, drying, film punching and film pressing to prepare a positive electrode material pole piece, dripping electrolyte on the pole piece, assembling a battery, and carrying out electrochemical potassium doping on the material through constant-current charge and discharge to obtain the positive electrode material of the potassium-rich Mn-PB sodium ion battery.
In the step (1), the manganese salt is one of Mn (CH 3COO)2·4H2 O, manganese sulfate MnSO 4, or manganese chloride Mn (Cl) 2), the molar ratio of the manganese-containing salt to sodium citrate is 1:1-5, and more preferably the molar ratio of the manganese-containing salt to sodium citrate is 1:1.
The molar ratio of sodium ferrocyanide Na 4Fe(CN)6·10H2 O, transition metal salt and ascorbic acid in the step (1) is 1:0.5-1.5:3-10.
The sodium supplementing agent in the step (1) is at least one of sodium chloride NaCl, sodium carbonate Na 2CO3, sodium acetate CH 3 COONa.
The mass ratio of the polyvinylpyrrolidone to the sodium supplementing agent is 1-1.5:5.5-7.
The dropping speed of the solution A and the solution B is controlled to be 10 ml/h, the stirring speed is 400-600 rpm under the atmosphere of N 2, and the reaction temperature is 40-50 ℃.
In the step (2), the aged white precipitate is sequentially centrifugally washed for three times with deionized water and absolute ethyl alcohol at a centrifugal speed of ∈ 8000 rpm/min, so as to obtain a clean precipitate.
The drying mode is vacuum drying, the temperature is 100-120 o ℃ and the time is 25-30 h.
In the step (3), the mass ratio of the Mn-PB material to the acetylene black to the polyvinylidene fluoride is 7:2:1.
The electrolyte in the step (3) is sodium perchlorate solution or a mixed solution formed by sodium perchlorate solution and potassium hexafluorophosphate solution; when the electrolyte is a mixed solution formed by a sodium perchlorate solution and a potassium hexafluorophosphate solution, the ratio of NaClO 4 to KPF 6 electrolyte is 1-10:1-7; preferably 3-10:3-7; further preferably any of 3:7 or 1:1 or 7:3.
In some embodiments, the sodium perchlorate solution is a solution formed by dissolving sodium perchlorate in ethylene carbonate EC, dimethyl carbonate DMC and ethyl methyl carbonate EMC, and the volume ratio of the ethylene carbonate EC, the dimethyl carbonate DMC and the ethyl methyl carbonate EMC is relatively fixed, so that the dissolution of sodium perchlorate is realized, and the dissolution of sodium perchlorate can be realized in other proportion ranges.
In some embodiments, the potassium hexafluorophosphate solution is a solution formed by dissolving potassium hexafluorophosphate in ethylene carbonate EC, dimethyl carbonate DMC and ethyl methyl carbonate EMC, wherein the ethylene carbonate EC, the dimethyl carbonate DMC and the ethyl methyl carbonate EMC are relatively fixed, the volume ratio is 4:3:2, the purpose of dissolving potassium hexafluorophosphate is realized, and the solution of potassium hexafluorophosphate can be realized in other proportion ranges.
The constant-current charge and discharge technology in the step (3) carries out potassium doping on the material, and the current density of constant-current discharge is 50-100 mA g -1; preferably 50 mA g-1、60 mA g-1、70 mA g-1、80 mA g-1、90 mA g-1、100 mA g-1.
And carrying out electrochemical potassium doping on the material by constant-current charging and discharging, wherein the current density of the constant-current discharging is 50-100 mA g -1.
The above-mentioned drugs are all analytically pure.
The positive electrode material of the potassium-rich Mn-PB sodium ion battery is prepared by adopting the method, the molecular formula of the Prussian blue material is Na 2-xKxMn[Fe(CN)6, wherein x is more than 0 and less than or equal to 2; preferably 0.25 < x.ltoreq.0.35, preferably 0.25 < x.ltoreq.0.65, preferably 0.25 < x.ltoreq.1, or preferably 0 < x.ltoreq.2.
Compared with the prior art, the positive electrode material of the potassium-enriched Mn-PB sodium ion battery and the preparation method thereof have the following characteristics:
(1) The invention discloses an Mn-PB material synthesized by a slow coprecipitation method, and potassium doping is carried out by an electrochemical process, so that on one hand, the content of crystal water in the material is reduced because potassium ions with larger ionic radius are introduced to occupy the position of partial crystal water; the potassium ions with larger ionic radius can play a structural supporting role in the material, so that Mn-PB can keep stable structure even in the rapid deintercalation process of sodium ions. In addition, the diffusion migration energy barrier of sodium ions can be reduced after potassium doping, more sodium ion storage sites and larger sodium ion intercalation channels are provided, and therefore the Mn-PB material after potassium doping has excellent electrochemical performance.
(2) The synthesis process is simple and easy to control, does not need high-temperature calcination, simplifies the production flow, reduces the production cost, and is suitable for commercial mass production.
Drawings
FIG. 1 is a charge-discharge curve of the sample prepared in comparative example 1 at circles 1, 2 and 3 at a current density of 100 mA g -1.
FIG. 2 shows CV curves of the samples prepared in comparative example 1 at circles 1,2 and 3 at 0.1 mV s -1.
FIG. 3 is a graph showing the cycle performance of the sample prepared in comparative example 1 at a current density of 100 mA g -1.
FIG. 4 is the CV curves for the samples prepared in example 1 at circles 1,2 and 3 at 0.1 mV s -1.
Fig. 5 is a charge-discharge curve of the samples prepared in example 1 at circles 1, 2 and 3 at a current density of 100 mA g -1.
FIG. 6 is a charge-discharge curve of the sample prepared in example 2 at circles 1, 2 and 3 at a current density of 100 mA g -1.
FIG. 7 is a charge-discharge curve of the sample prepared in example 3 at circles 1, 2 and 3 at a current density of 100 mA g -1.
Fig. 8 is a graph comparing XRD before and after sample cycling prepared in examples 1, 4 with standard cards.
FIG. 9 is the CV curves for the samples prepared in example 4 at circles 1,2 and 3 at 0.1 mV s -1.
Fig. 10 is a charge-discharge curve of the samples prepared in example 4 at circles 1,2 and 3 at a current density of 100 mA g -1.
FIG. 11 is a graph comparing cycle performance of samples prepared in examples 1, 2,3, and 4 at a current density of 100 mA g -1.
Detailed Description
The essential features and advantages of the invention are further illustrated by the following description of examples and comparison with comparative examples.
Comparative example 1
6 Mmol Mn (CH 3COO)2·4H2 O and 6 mmol Na 3C6H5O7·2H2 O dissolved in 50 ml deionized water to form solution A,2.7 mmol Na4Fe(CN)6·10H2O, 0.3 mmol K4Fe(CN)6·3H2O, and 0.6 g C 6H8O6 dissolved in 50 ml deionized water to form solution B;1g polyvinylpyrrolidone PVP and 3 g NaCl were dissolved in deionized water to form solution C; under the conditions of N 2 atmosphere and heating and stirring, simultaneously adding the solution A and the solution B into the solution C through a peristaltic pump, and changing the solution into white suspension after the dripping is finished; continuing heating and stirring 12 to h, finally aging 24 to h at room temperature, pouring supernatant, sequentially centrifuging and washing the lower white precipitate with deionized water and absolute ethyl alcohol for several times, and then vacuum drying 12 to h at 120 ℃ to obtain a Mn-PB positive electrode material doped with potassium in the material synthesis process, wherein the chemical formula of the material is Na 2-xKxMn[Fe(CN)6, x is more than 0.15 and less than or equal to 0.25, stirring the obtained positive electrode material with acetylene black and polyvinylidene fluoride (PVDF) to form a slurry, coating the slurry on an aluminum foil, drying, punching and pressing to prepare a positive electrode material pole piece, taking metal sodium as a counter electrode, grade GF/D as a diaphragm, taking a solution containing 2 to wt% FEC 1/(EC+DMC+EMC) (EC: DMC) (. 1:1:1 vol.) (EC) as electrolyte), and performing constant current charge and discharge test on the material, wherein the voltage range is between 2.0 and 4.2V, FIG. 1 is a first charge and discharge capacity of the material of the positive electrode material of the first 1st circle, 2nd circle and 3rd circle of current density of 100 to be equal to 3 nd circle (4.2V), and a first circle of positive electrode material of the second circle to be equal to 3.3, a graph of the positive electrode material of the positive electrode material of the positive electrode positive electrode positive, indicating that its reversibility is poor. As can be seen from the cycle performance chart of the material at 100 mA g -1 current density (fig. 3), the capacity of the material after 150 cycles is only 54.7 mAh g -1, and the capacity retention is only 46.0%. It can be seen that when potassium doping is performed by replacing Na 4Fe(CN)6·10H2 O with a part of K 4Fe(CN)6·3H2 O during the synthesis of Mn-PB, the cycling stability of Mn-PB is poor.
Example 1
6 Mmol Mn (CH 3COO)2·4H2 O and 6 mmol Na 3C6H5O7·2H2 O dissolved in 50 ml deionized water to form solution a,3 mmol Na 4Fe(CN)6·10H2 O and 0.6 g C 6H8O6 dissolved in 50 ml deionized water to form solution B;1g polyvinylpyrrolidone PVP and 3g NaCl are dissolved in deionized water to form a solution C; adding solution A and solution B into solution C under N 2 atmosphere and heating and stirring condition, adding the solution A and solution B into solution C by peristaltic pump, dropping, heating and stirring for 12 h, aging at room temperature for 24 h, pouring out supernatant, centrifuging and washing the lower white precipitate with deionized water and absolute ethyl alcohol for several times, vacuum drying at 120deg.C for 12 h to obtain Mn-PB positive electrode material, marking as Mn-PB., stirring the obtained Mn-PB positive electrode material with acetylene black and polyvinylidene fluoride (PVDF) to obtain slurry, coating on aluminum foil, drying, punching and pressing to obtain positive electrode sheet, using metallic sodium as counter electrode, using Grade GF/D as diaphragm, using DMC solution containing 2M NaClO 4/(EC+DMC+EMC) (EC: DMC: EMC=1:1:1:1) vol%) solution as electrolyte, assembling to obtain battery PB positive electrode material, comparing PB diffraction peak with standard PB (JPcPdS, no. 35 is a standard PB diffraction peak and Mn-37 is a standard PB, and a standard PB is obtained, a standard PB is obtained by measuring the positive electrode sheet, a standard charge and discharge of Mn-37 is more than shown in 35, a standard test is carried out, the positive electrode sheet is obtained by using Mn-37 is more than has more than 37, and a standard test is shown in a standard test table is shown, the voltage range is 2.0-4.2V. Fig. 4 is a CV curve of the cathode material when NaClO 4 was added dropwise as an electrolyte only (i.e., naClO 4:KPF6 =10:0 (vol.%)), and the 3-turn curve overlap was smaller before the material was added with KPF 6 electrolyte, indicating that the reversibility was poor. Fig. 5 is a charge-discharge curve for the material at circles 1, 2 and 3 at a current density of 100 mAg -1. Obviously, the first discharge capacity of the positive electrode material is only 106.4 mAh g -1, but the capacities of the 2 nd turn and the 3 rd turn are obviously increased, and 110.8 mAh g -1 and 110 mAh g -1 are respectively reached. As can be seen from the comparison of the cycle performance of 100 mA g -1 of fig. 11, the capacity of the positive electrode material after 300 cycles was only 33.7. 33.7 mAh g -1 and the capacity retention rate was only 48.5% when NaClO 4 was merely added dropwise as an electrolyte. It can be seen that the cycling stability of Mn-PB is poor when the electrolyte contains only NaClO 4.
Example 2
The preparation steps are the same as in example 1, the obtained Mn-PB material, acetylene black and polyvinylidene fluoride (PVDF) are stirred into slurry, the slurry is coated on aluminum foil, and the anode material pole piece is prepared through drying, film punching and film pressing. The battery was assembled using sodium metal as the counter electrode, grade GF/D as the separator, and a mixture of 1M NaClO 4/(ec+dmc+emc) (EC: DMC: emc=1:1:1 vol.%, containing 2wt.% FEC) solution and 1M KPF 6/(ec+dmc+emc) (EC: DMC: emc=4:3:2 vol.%, containing 5wt.% FEC) solution as the electrolyte (the volume ratio of NaClO 4 solution to KPF 6 solution was 7:3). And carrying out electrochemical doping on the initial Mn-PB by constant current charge and discharge, wherein the voltage range is 2.0-4.2V. After electrochemical doping of potassium, the chemical formula of the material is Na 2-xKxMn[Fe(CN)6, wherein x is more than 0.25 and less than or equal to 0.35. Fig. 6 is charge-discharge curves of the positive electrode material obtained by electrochemical doping of potassium at a current density of 100 mA g -1 at 1 st, 2 nd and 3 rd turns when the volume ratio of NaClO 4 solution to KPF 6 solution in the electrolyte is 7:3. The first discharge capacity of the positive electrode material is only 102.4 mAh g -1, and the capacities of 2 circles and 3 circles of circulation are 102.8 mAh g -1 and 100.4 mAh g -1 respectively. Fig. 11 shows the cycle performance of the positive electrode material at a current density of 100 mA g -1, the capacity retention rate was 65.2% after 300 cycles, and the cycle stability of Mn-PB was improved with the addition of KPF 6 electrolyte.
Example 3
The preparation steps are the same as in example 1, the obtained Mn-PB anode material, acetylene black and polyvinylidene fluoride (PVDF) are stirred into slurry, the slurry is coated on aluminum foil, and the anode material pole piece is prepared through drying, film punching and film pressing. The battery was assembled using sodium metal as the counter electrode, grade GF/D as the separator, and a mixture of 1M NaClO 4/(ec+dmc+emc) (EC: DMC: emc=1:1:1 vol.%, containing 2wt.% FEC) solution and 1M KPF 6/(ec+dmc+emc) (EC: DMC: emc=4:3:2 vol.%, containing 5wt.% FEC) solution as the electrolyte (the volume ratio of NaClO 4 solution to KPF 6 solution was 5:5). And carrying out electrochemical doping on the Mn-PB material by constant current charge and discharge, wherein the voltage range is 2.0-4.2V. After electrochemical doping of potassium, the chemical formula of the material is Na 2- xKxMn[Fe(CN)6, wherein x is more than 0.55 and less than or equal to 0.65. Fig. 7 is charge-discharge curves of the positive electrode material obtained by electrochemical doping of potassium at a current density of 100 mA g -1 at1 st, 2 nd and 3 rd turns when the volume ratio of NaClO 4 solution to KPF 6 solution in the electrolyte is 5:5. The first discharge capacity of the material is up to 116.8 mAh g -1, and the capacities of 2 circles and 3 circles of circulation are 113.8 mAh g -1 and 110.5 mAh g -1 respectively. Fig. 11 is a graph showing the cycle performance of the positive electrode material at a current density of 100 mA g -1, and the capacity retention rate reached 82.7% after 300 cycles. Compared with a positive electrode material obtained by electrochemical doping of potassium when the volume ratio of NaClO 4 solution to KPF 6 solution in the electrolyte is 7:3, the introduction of K + further improves the poor cycling stability of Mn-PB.
Example 4
The preparation steps are the same as in example 1, the obtained Mn-PB anode material, acetylene black and polyvinylidene fluoride (PVDF) are stirred into slurry, the slurry is coated on aluminum foil, and the anode material pole piece is prepared through drying, film punching and film pressing. The battery was assembled using sodium metal as the counter electrode, grade GF/D as the separator, and a mixture of 1M NaClO 4/(ec+dmc+emc) (EC: DMC: emc=1:1:1 vol.%, containing 2wt.% FEC) solution and 1M KPF 6/(ec+dmc+emc) (EC: DMC: emc=4:3:2 vol.%, containing 5wt.% FEC) solution as the electrolyte (the volume ratio of NaClO 4 solution to KPF 6 solution was 3:7). And carrying out electrochemical doping on the initial Mn-PB by constant current charge and discharge, wherein the voltage range is 2.0-4.2V. Fig. 8 is a graph comparing XRD of positive electrode material obtained by electrochemical doping of potassium with standard card at a volume ratio of NaClO 4 solution to KPF 6 solution in electrolyte of 3:7. Obviously, the positive electrode material after electrochemical potassium doping shows good crystallinity, the diffraction peak of the positive electrode material is basically matched with that of a standard card (JCPLDS, no. 089-8979), the potassium content in a sample is increased, the electrochemical potassium doping is successful, no peak separation occurs before and after circulation, and the material is in a cubic phase. The chemical formula of the electrochemical potassium doped material obtained through ICP calculation is Na 0.07K0.94Mn[Fe(CN)6]0.86, and it can be seen that after circulation, K + in the KPF 6 electrolyte successfully enters the Prussian blue, and the electrochemical potassium doped material has lower [ Fe (CN) 6 ] defect compared with a material only added with NaClO 4 electrolyte. FIG. 9 is a CV curve of the positive electrode material at 0.1 mV s -1, from which it can be seen that the potassium-doped material has a large peak area, which corresponds to its high initial capacity; and the overlap ratio of the curves is higher, which indicates that the electrolyte has better reversibility, and fig. 10 is the charge-discharge curves of the 1 st circle, the 2 nd circle and the 3 rd circle of the positive electrode material obtained by electrochemical doping of potassium under the current density of 100 mA g -1 when the volume ratio of NaClO 4 solution to KPF 6 solution in the electrolyte is 3:7. The first discharge capacity of the positive electrode material is 129.6 mAh g -1, the capacities of 2 circles and 3 circles of cycles are 127.3 mAh g -1 and 124.6 mAh g -1 respectively, and the capacity attenuation rate of the first 3 circles is lower. Fig. 11 is a graph of the cycling performance of the positive electrode material at a current density of 100 mA g -1, with a capacity retention of up to 85.6% after 300 cycles. When more KPF 6 electrolyte is added, the electrochemical performance of Mn-PB can be improved well. In all samples, when the volume ratio of NaClO 4 solution to KPF 6 solution in the electrolyte is 3:7, the positive electrode material obtained by electrochemical doping of potassium has the highest initial capacity, meanwhile, the problem of poor Mn-PB stability is remarkably improved, and the high capacity retention rate is still achieved after long circulation.
Claims (10)
1. The preparation method of the potassium-rich manganese-based Prussian blue Mn-PB sodium ion battery anode material is characterized by comprising the following steps of:
(1) Dissolving manganese salt and sodium citrate in water to obtain solution A; dissolving sodium ferrocyanide and ascorbic acid in water to obtain a solution B, and dissolving polyvinylpyrrolidone serving as a dispersing agent and a sodium supplementing agent in water to obtain a solution C;
(2) Pumping the solution A and the solution B into the solution C under the conditions of N 2 atmosphere and heating and stirring to obtain white suspension; continuously heating and stirring for 10-12h, and finally aging for 20-30 h at room temperature; washing the obtained white precipitate with water and absolute ethyl alcohol, and drying to obtain Mn-PB material;
(3) Stirring Mn-PB material, acetylene black and polyvinylidene fluoride into slurry, coating the slurry on aluminum foil, drying, film punching and film pressing to prepare a positive electrode material pole piece, dripping electrolyte on the pole piece, assembling a battery, and carrying out electrochemical potassium doping on the material through constant-current charge and discharge to obtain the positive electrode material of the potassium-rich manganese-based Prussian blue Mn-PB sodium ion battery.
2. The method for preparing a positive electrode material of a potassium-rich Mn-PB sodium ion battery of claim 1 wherein in step (1), the Mn salt is any one of manganese acetate tetrahydrate and manganese sulfate; the molar ratio of the manganese salt to the sodium citrate is 1:1-5, and preferably the molar ratio of the manganese salt to the sodium citrate is 1:1;
The molar ratio of the sodium ferrocyanide to the manganese salt to the ascorbic acid is 1:0.5-1.5:3-10.
3. The preparation method of the positive electrode material of the potassium-rich Mn-PB sodium ion battery, according to claim 1, is characterized in that the sodium supplement in the step (1) is at least one of sodium chloride NaCl, sodium carbonate Na 2CO3 and sodium acetate CH 3 COONa, and the mass ratio of polyvinylpyrrolidone to the sodium supplement is 1-1.5:5.5-7.
4. The method for preparing the positive electrode material of the potassium-rich Mn-PB sodium ion battery according to claim 1, wherein in the step (2), the dropping speed of the solution A and the solution B is controlled to be 8-10 ml/h, the stirring speed is 400-600 rpm under the atmosphere of N 2, and the reaction temperature is 45-55 ℃.
5. The method for preparing the positive electrode material of the potassium-enriched Mn-PB sodium ion battery according to claim 1, wherein in the step (3), the aged white precipitate is sequentially centrifugally washed three times with deionized water and absolute ethyl alcohol at a centrifugal speed of not less than 8000 rpm/min to obtain the precipitate with the impurities removed.
6. The method for preparing the positive electrode material of the potassium-enriched Mn-PB sodium ion battery according to claim 1, wherein the drying mode in the step (2) is vacuum drying, the temperature is 100-140 ℃, and the time is 20-30h.
7. The preparation method of the positive electrode material of the potassium-rich Mn-PB sodium ion battery, according to claim 1, wherein the mass ratio of the positive electrode material of the Mn-PB sodium ion battery to acetylene black and polyvinylidene fluoride in the step (3) is 7:2:1.
8. The method for preparing the positive electrode material of the potassium-rich Mn-PB sodium ion battery according to claim 1, wherein the electrolyte in the step (3) is a sodium perchlorate solution or a mixed solution formed by a sodium perchlorate solution and a potassium hexafluorophosphate solution; when the electrolyte is a mixed solution formed by a sodium perchlorate solution and a potassium hexafluorophosphate solution, the ratio of NaClO 4 to KPF 6 electrolyte is 1-10:1-7; preferably 3-10:3-7; further preferably any of 3:7 or 1:1 or 7:3.
9. The preparation method of the positive electrode material of the potassium-rich Mn-PB sodium ion battery, which is characterized in that the constant current charge and discharge process in the step (3) is used for carrying out potassium doping on the material, and the current density of constant current discharge is 50-100 mA g -1; preferably 50 mA g-1、60 mA g-1、70 mA g-1、80 mA g-1、90 mA g-1、100 mA g-1.
10. The positive electrode material of the potassium-rich Mn-PB sodium ion battery prepared by adopting the method of any one of claims 1-9, which is characterized in that the molecular formula of the Prussian blue material is Na 2-xKxMn[Fe(CN)6, wherein x is more than 0 and less than or equal to 2.
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