CN115448327B - Preparation method and application of low-defect Prussian blue positive electrode material - Google Patents
Preparation method and application of low-defect Prussian blue positive electrode material Download PDFInfo
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- CN115448327B CN115448327B CN202211200183.2A CN202211200183A CN115448327B CN 115448327 B CN115448327 B CN 115448327B CN 202211200183 A CN202211200183 A CN 202211200183A CN 115448327 B CN115448327 B CN 115448327B
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 35
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 35
- 239000013225 prussian blue Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011259 mixed solution Substances 0.000 claims abstract description 37
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- 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 abstract description 12
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims abstract description 12
- 239000000264 sodium ferrocyanide Substances 0.000 claims abstract description 12
- -1 transition metal salt Chemical class 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 9
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 description 22
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 229910052748 manganese Inorganic materials 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 235000002639 sodium chloride Nutrition 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 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 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method and application of a low-defect Prussian blue positive electrode material, wherein sodium ferrocyanide and inorganic sodium salt are dissolved in water to prepare a mixed solution A, a transition metal salt and a ligand are dissolved in water to prepare a mixed solution B, the mixed solution B is dropwise added into the mixed solution A for reaction, aging is carried out after the reaction is finished, solid-liquid separation is carried out, and obtained precipitate is washed and dried in vacuum to obtain the low-defect Prussian blue positive electrode material. The invention is realized by introducing a small radius of [ Fe (CN) 6 ] 4‑ And a ligand capable of forming a coordinate bond with the transition metal, on the one hand, the ligand can complex with the transition metal to retard the transition metal and [ Fe (CN) 6 ] 4‑ On the other hand, the ligand can be precipitated together to occupy [ Fe (CN) with the coordinated water 6 ] 4‑ Vacancy is avoided from the source, and the transition metal and coordination water are combined, so that the Prussian blue positive electrode material prepared by the method has fewer coordination water and crystallization water, and has better gram capacity and cycle stability.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a preparation method and application of a low-defect Prussian blue positive electrode material.
Background
With the development of the economic society, various energy storage devices, such as lithium ion batteries, are developed as energy storage devices with mature technology, and are widely applied to the fields of consumer electronics, electric automobiles and the like, however, because the reserves of lithium resources are scarce and concentrated in the america area, the requirements of the rapidly developed lithium ion batteries are difficult to meet, and thus other novel energy storage systems are necessary to develop, wherein the sodium ion batteries are considered as one of several directions of the optimal prospects. The sodium ion battery comprises a transition metal oxide system, a Prussian system, a polyanion system and the like, wherein the Prussian system has obvious economic and safety advantages and has great application value, but a few technical problems to be solved still exist.
The preparation method of the Prussian sodium ion battery mainly comprises the following steps: coprecipitation, hydrothermal and mechanical mixing methods, among which, because of Na 2 M1[M2(CN) 6 ]Is small, precipitates rapidly, and easily causes a large amount of [ M2 (CN) to be generated in the crystal structure of the cathode material 6 ]The empty coordination point of the transition metal exposed at the empty position is easy to be further combined with water in the reaction system to form coordination water, the coordination water can be further combined with crystal water in a crystal structure through hydrogen bonds to occupy a storage site of sodium ions, and the specific capacity is reduced. Meanwhile, in the battery cycle process, the crystallized water can be separated from the positive electrode material to further react with the electrolyte, so that the cycle performance of the battery is reduced. Thus, how to reduce [ M (CN) 6 ]Vacancy is an important problem faced by Prussian sodium ion batteries.
The prior art generally improves the crystallinity of Prussian blue positive electrode materials by reducing the reaction rate, thereby reducing [ M (CN) 6 ]And (5) a vacancy. For example, sodium citrateAs complexing agent and transition metal Mn 2+ Complexing to regulate and control [ Fe (CN) 6 ] 4- The nucleation reaction speed, however, cannot inhibit the combination of the vacancy defects which are generated in the precipitation and the coordinated water, so that the Prussian blue positive electrode material prepared by the method still has higher water content and defects.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the preparation method and the application of the low-defect Prussian blue positive electrode material provided by the invention not only can slow down the reaction rate, but also can avoid the combination of coordinated water and transition metal, and greatly reduce the water content and defects of the Prussian blue positive electrode material.
According to one aspect of the invention, a preparation method of a low-defect Prussian blue positive electrode material is provided, which comprises the following steps:
s1: dissolving sodium ferrocyanide and inorganic sodium salt in water to prepare a mixed solution A, and dissolving transition metal salt and a ligand in water to prepare a mixed solution B; the coordination compound is at least one of sodium fluoborate, soluble fluoro-organic matters, acetonitrile, ammonia water or pyridine;
s2: under the heating condition, dropwise adding the mixed solution B into the mixed solution A for reaction, aging after the reaction is finished, and carrying out solid-liquid separation to obtain a precipitate;
s3: and washing and vacuum drying the precipitate to obtain the low-defect Prussian blue positive electrode material.
In some embodiments of the present invention, the low-defect Prussian blue-based positive electrode material has a chemical formula of Na x M1 y [Fe(CN) 6 ] 1-z □ z D a ·(6z-a)H 2 O, wherein M1 is a transition metal, +.sup.representing a vacancy, D is the ligand, H 2 O represents the coordinated water content, x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 1, a is more than 0.05 and less than or equal to 6z, and z is more than 0.01 and less than or equal to 0.2.
In some embodiments of the present invention, in step S1, the concentration of sodium ferrocyanide in the mixed solution a is 0.01-1mol/L, and the concentration of sodium ions in the mixed solution a is 0.01-10mol/L.
In some embodiments of the invention, in step S1, the molar ratio of sodium ferrocyanide to transition metal salt is 1: (0.2-2).
In some embodiments of the present invention, in step S1, the concentration of the transition metal salt in the mixed solution B is 0.1 to 2.5mol/L, and the molar ratio of the ligand to the transition metal salt is (2.0 to 2.2): 1.
in some embodiments of the present invention, in step S1, the fluorinated organic compound is at least one of fluoroacetic acid or fluoroethanol.
In some embodiments of the invention, in step S1, the inorganic sodium salt is at least one of sodium chloride, sodium sulfate, or sodium nitrate.
In some embodiments of the invention, in step S1, the transition metal salt is a sulfate, nitrate or chloride of nickel, cobalt, manganese or iron.
In some embodiments of the invention, in step S2, the temperature of the reaction is 60-90 ℃.
In some embodiments of the invention, in step S2, the aging time is 4-8 hours.
In some embodiments of the present invention, in step S2, the mixed solution B is dropped into the mixed solution a at a rate of 0.1 to 3ml/min.
In some embodiments of the invention, in step S3, the washing process is: washing with water and then with an organic solvent. Further, the organic solvent is acetonitrile.
In some embodiments of the present invention, in step S3, the temperature of the vacuum drying is 100 to 160 ℃ and the time of the vacuum drying is 10 to 15 hours.
The invention also provides application of the preparation method in preparing sodium ion batteries.
According to a preferred embodiment of the invention, there is at least the following advantageous effect:
the invention is realized by introducing a small radius of [ Fe (CN) 6 ] 4- And forming coordination bonds with transition metalsAnd the complex is a boron/fluorine/nitrogen compound capable of forming a stronger coordination bond with the transition metal to prevent coordination water from reacting with [ Fe (CN) 6 ] 4- The transition metal exposed at the vacancies binds; the above-mentioned ligands can, on the one hand, complex with the transition metal during the coprecipitation process to delay the transition metal and [ Fe (CN) ] 6 ] 4- On the other hand, the ligand can be precipitated together to occupy [ Fe (CN) with the coordinated water 6 ] 4- Vacancy, avoid transition metal and coordination water to combine from the source, the reduction of coordination water can further reduce crystallization water simultaneously. The Prussian blue positive electrode material prepared by the method has less coordination water and crystallization water, greatly reduces the water content and defects of the material, and has better gram capacity and cycle stability.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
fig. 1 is an SEM image of a prussian blue type positive electrode material prepared in example 1 of the present invention;
fig. 2 is a charge-discharge graph at 0.1C using the positive electrode material prepared in example 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The manganese-based Prussian blue positive electrode material is prepared by the method, and the specific process is as follows:
adding 1L of deionized water into a reactor, adding 1mol of sodium ferrocyanide and 1mol of sodium chloride, heating to 60 ℃ for stirring and dissolving to obtain a mixed solution A, dissolving 0.6mol of manganese sulfate and 1.2mol of sodium fluoroborate into 250mL of 60 ℃ deionized water to obtain a mixed solution B, dropwise adding the mixed solution B into the reactor at 1mL/min through a peristaltic pump, continuously stirring, keeping the pH in the reactor at 6.5, keeping the reaction temperature at 70 ℃, aging for 6h after the precipitation is finished, filtering to obtain a precipitate, washing twice with deionized water, washing twice with acetonitrile, transferring to a vacuum drying oven at 150 ℃ for drying for 12h, and obtaining the manganese-based Prussian blue cathode material. SEM images are shown in fig. 1, which are stacked nanocube morphologies.
ICP and TG test results show that the molecular formula of the manganese-based Prussian blue positive electrode material is Na 1.69 Mn[Fe(CN) 6 ] 0.92 □ 0.08 (BF 4 ) 0.31 ·0.17H 2 O。
Example 2
The manganese-based Prussian blue positive electrode material is prepared by the method, and the specific process is as follows:
adding 1L of deionized water into a reactor, adding 1mol of sodium ferrocyanide and 1mol of sodium chloride, heating to 60 ℃ for stirring and dissolving to obtain a mixed solution A, dissolving 0.6mol of manganese sulfate and 1.2mol of fluoroacetic acid into 250mL of 60 ℃ deionized water to obtain a mixed solution B, dropwise adding the mixed solution B into the reactor at a speed of 1mL/min through a peristaltic pump, continuously stirring, keeping the pH in the reactor at 6.5, keeping the reaction temperature at 70 ℃, aging for 6h after the precipitation is finished, filtering to obtain a precipitate, washing twice with deionized water, washing twice with acetonitrile, transferring to a vacuum drying oven at 150 ℃, and drying for 12h to obtain the manganese-based Prussian blue cathode material.
ICP and TG test results show that the molecular formula of the manganese-based Prussian blue positive electrode material is Na 1.72 Mn[Fe(CN) 6 ] 0.92 □ 0.08 (C 2 H 3 FO 2 ) 0.37 ·0.11H 2 O。
Example 3
The manganese-based Prussian blue positive electrode material is prepared by the method, and the specific process is as follows:
adding 1L of deionized water into a reactor, adding 1mol of sodium ferrocyanide and 1mol of sodium chloride, heating to 60 ℃ for stirring and dissolving to obtain a mixed solution A, dissolving 0.6mol of manganese sulfate and 1.2mol of acetonitrile into 250mL of 60 ℃ of deionized water to obtain a mixed solution B, dropwise adding the mixed solution B into the reactor at the speed of 1mL/min through a peristaltic pump, continuously stirring, keeping the pH in the reactor at 6.5, keeping the reaction temperature at 70 ℃, aging for 6h after the completion of precipitation, filtering to obtain a precipitate, washing twice with deionized water, washing twice with acetonitrile, and transferring to a vacuum drying oven at 150 ℃ for drying for 12h to obtain the manganese-based Prussian blue positive electrode material.
ICP and TG test results show that the molecular formula of the manganese-based Prussian blue positive electrode material is Na 1.65 Mn[Fe(CN) 6 ] 0.92 □ 0.08 (CH 3 CN) 0.28 ·0.20H 2 O。
Comparative example 1
The comparative example prepares a manganese-based Prussian blue positive electrode material, which is different from example 1 in that the ligand is sodium citrate, and the specific process is as follows:
adding 1L of deionized water into a reactor, adding 1mol of sodium ferrocyanide and 1mol of sodium chloride, heating to 60 ℃ for stirring and dissolving to obtain a mixed solution A, dissolving 0.6mol of manganese sulfate and 1.2mol of sodium citrate into 250mL of 60 ℃ deionized water to obtain a mixed solution B, dropwise adding the mixed solution B into the reactor at the speed of 1mL/min through a peristaltic pump, continuously stirring, keeping the pH in the reactor at 6.5, keeping the reaction temperature at 70 ℃, aging for 6h after the completion of precipitation, filtering to obtain a precipitate, washing twice with deionized water, washing twice with acetonitrile, and transferring to a vacuum drying oven at 150 ℃ for drying for 12h to obtain the manganese-based Prussian blue positive electrode material.
The ICP and TG test results show that the molecular formula of the sample is Na 1.60 Mn[Fe(CN) 6 ] 0.91 □ 0.09 ·0.54H 2 O。
Comparative example 2
The comparative example prepared a manganese-based Prussian blue type positive electrode material, which was different from example 1 in that no ligand was added, and the specific procedure was as follows:
adding 1L of deionized water into a reactor, adding 1mol of sodium ferrocyanide and 1mol of sodium chloride, heating to 60 ℃ for stirring and dissolving to obtain a mixed solution A, dissolving 0.6mol of manganese sulfate into 250mL of 60 ℃ deionized water to obtain a mixed solution B, dropwise adding the mixed solution B into the reactor at a speed of 1mL/min through a peristaltic pump, continuously stirring, keeping the pH value in the reactor at 6.5, reacting at 70 ℃, aging for 6h after finishing precipitation, filtering to obtain a precipitate, washing twice with deionized water, washing twice with acetonitrile, and transferring into a vacuum drying oven at 150 ℃ for drying for 12h to obtain the manganese-based Prussian blue positive electrode material.
The ICP and TG test results show that the molecular formula of the sample is Na 1.50 Mn[Fe(CN) 6 ] 0.86 □ 0.14 ·0.84H 2 O。
Test examples
In order to verify the performance of the manganese-based Prussian blue positive electrode material prepared by the method, the product prepared by each example is taken as a positive electrode, sodium metal is taken as a negative electrode, glass fiber is taken as a diaphragm, EC/DEC solution of sodium hexafluorophosphate is taken as electrolyte, a sodium ion half cell is assembled in a glove box, charge and discharge tests are carried out under the working voltage of 2-4V and different current densities, meanwhile, the product of comparative example 1-2 is taken as a control sample and the same test is carried out, and the result is shown in a table 1, wherein the charge and discharge curve of the product obtained by example 1 when the battery is assembled is shown in a graph of FIG. 2.
TABLE 1
As can be seen from Table 1, the first charge-discharge specific capacity of the Prussian blue positive electrode material prepared by the method is obviously improved compared with that of comparative examples 1 and 2, wherein the performance of comparative example 1 is still inferior to that of example 1 although the complex is added, because the molecular size of sodium citrate is too large to be retained in the crystal structure of the product, and a part of coordinated water still exists in the material, thereby affecting the specific capacity and the cycle performance. Table 1 shows that the Prussian blue positive electrode material has higher specific capacity, better rate capability and cycle performance. The lower water content of example 2 is because F of fluoroacetic acid can form stronger coordination bonds with Mn and is not easily replaced by coordinated water.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (6)
1. The preparation method of the low-defect Prussian blue positive electrode material is characterized by comprising the following steps of:
s1: dissolving sodium ferrocyanide and inorganic sodium salt in water to prepare a mixed solution A, and dissolving transition metal salt and a ligand in water to prepare a mixed solution B; the coordination compound is at least one of sodium fluoborate, acetonitrile, ammonia water or pyridine;
s2: under the heating condition, dropwise adding the mixed solution B into the mixed solution A for reaction, aging after the reaction is finished, and carrying out solid-liquid separation to obtain a precipitate;
s3: washing and vacuum drying the precipitate to obtain the low-defect Prussian blue positive electrode material;
in the step S1, the concentration of sodium ferrocyanide in the mixed solution A is 0.01-1mol/L, and the concentration of sodium ions in the mixed solution A is 0.01-10 mol/L;
in the step S1, the molar ratio of the sodium ferrocyanide to the transition metal salt is 1: (0.2-2);
in the step S1, the concentration of the transition metal salt in the mixed solution B is 0.1-2.5mol/L, and the mol ratio of the ligand to the transition metal salt is (2.0-2.2): 1, a step of;
in the step S2, the speed of dripping the mixed solution B into the mixed solution A is 0.1-3ml/min;
the radius of the ligand is smaller than [ Fe (CN) 6 ] 4- 。
2. The preparation method according to claim 1, wherein the low-defect Prussian blue positive electrode material has a chemical formula of Na x M1 y [Fe(CN) 6 ] 1-z □ z Da·（6z-a）H 2 O, wherein M1 is a transition metal, +.sup.representing a vacancy, D is the ligand, H 2 O represents the coordinated water content, x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 1, a is more than 0.05 and less than or equal to 6z, and z is more than 0.01 and less than or equal to 0.2.
3. The method according to claim 1, wherein the temperature of the reaction in step S2 is 60 to 90 ℃.
4. The method according to claim 1, wherein in step S3, the washing is performed by: washing with water and then with an organic solvent.
5. The method according to claim 1, wherein in step S3, the vacuum drying is performed at a temperature of 100 to 160 ℃ for a time of 10 to 15 hours.
6. The use of the low-defect Prussian blue type positive electrode material prepared by the preparation method according to any one of claims 1 to 5 in the preparation of sodium ion batteries.
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