CN115360346A - Spheroidal Prussian blue positive electrode material for sodium ion battery and preparation method thereof - Google Patents
Spheroidal Prussian blue positive electrode material for sodium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN115360346A CN115360346A CN202211169321.5A CN202211169321A CN115360346A CN 115360346 A CN115360346 A CN 115360346A CN 202211169321 A CN202211169321 A CN 202211169321A CN 115360346 A CN115360346 A CN 115360346A
- Authority
- CN
- China
- Prior art keywords
- prussian blue
- sodium
- ion battery
- spheroidal
- positive electrode
- 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.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a spheroidal Prussian blue anode material for a sodium ion battery and a preparation method thereof. The chemical general formula of the anode material is Na x Mn y Fe 1‑y [Fe(CN) 6 ] z ·nH 2 O, the preparation method comprises the following steps: dispersing a raw material sodium ferrocyanide in absolute ethyl alcohol to obtain a dispersion liquid, and dissolving a divalent manganese salt and a divalent iron salt in deionized water to obtain a mixed metal salt solution; and slowly adding the mixed metal salt solution into the sodium ferrocyanide dispersion solution for reaction to obtain a blue solid precipitate, and then washing and drying to obtain the cathode material. The positive electrode material has the advantages of large specific capacity, high platform voltage, high coulombic efficiency and the like, and is a stable energy storage sodium ion battery positive electrode material; the positive electrode materialThe preparation method is simple, the cost of the raw materials is low, and the large-scale production capacity is realized.
Description
Technical Field
The invention belongs to the technical field of preparation of a sodium-ion battery positive electrode material, and particularly relates to a spherical Prussian blue positive electrode material for a sodium-ion battery and a preparation method thereof.
Background
With the increasing energy crisis and the problem of carbon emission, large-scale energy storage and utilization of discontinuous clean energy sources such as solar energy, wind energy, geothermal energy and the like are important. Sodium ion batteries are considered to be on a large scale due to the abundance of sodium resources on earthThe energy storage has great potential advantages, so the energy storage device is widely concerned by people. The positive electrode material of the sodium-ion battery is one of the important factors that the performance of the sodium-ion battery is limited. Currently, positive electrode materials of sodium ion batteries are mainly classified into the following three types: transition metal oxides, polyanions and prussian blue and derivatives thereof. The Prussian blue cathode material has an open large frame and tunnel structure, the theoretical capacity is as high as 170mAh/g, the raw material cost is low, the synthesis is simple and environment-friendly, and the Prussian blue cathode material is considered to be one of sodium ion battery cathode materials with great prospects. Iron-based Prussian blue material Na x Fe[Fe(CN) 6 ] y The platform voltage of (3.0V) is low, and the capacity is low, can't satisfy the demand of present large-scale energy storage application. Manganese-based Prussian blue Na as compared with iron-based Prussian blue material x Mn[Fe(CN) 6 ] y The working voltage of the high-voltage capacitor is as high as 3.5V, and the high-voltage capacitor has higher specific capacity and energy density. Tang et al utilize sodium citrate with Mn 2+ Chelation of (2) to reduce Mn 2+ The coprecipitation reaction rate of the solid cubic Na and the ferricyanide ions is improved to obtain uniform and stable solid cubic Na x Mn[Fe(CN) 6 ] y The positive electrode material (Adv Funct Mater 2020, 30 (10), 1908754) has poor permeability of the electrolyte and low rate capability due to an excessively large particle size (about 5 μm). At the same time, na x Mn[Fe(CN) 6 ] y Mn is present during charging and discharging 3+ Ginger-taylor effect, mn 2+ The dissolution and structural phase change of the polymer lead to poor cycle stability.
To solve the above problems of the Prussian blue electrode, na is added x Mn[Fe(CN) 6 ] y The introduction of metal atoms such as Fe, ni and Co into the crystal lattice is considered to be the most effective method. Huang et al for Na x Mn[Fe(CN) 6 ] y The cycle stability of the prussian blue electrode is improved by carrying out inactive Ni doping (Small 2018, 14 (28), 1801246). However, substitution of the active Mn element by doping of the inactive Ni element leads to a decrease in the specific capacity of prussian blue, while substitution of the active Co element causes high production costs. Therefore, the doping of the cheap active Fe element is better than that of Ni and Co elements, and is more suitable for the industryAnd (5) industrial popularization. Gong et al synthesized nano Mn-based Prussian blue (about 50 nm) with different Fe doping amounts by using a dry ball milling solid phase, but the solid phase ball milling method not only has large energy consumption, but also causes severe agglomeration of particles, resulting in very poor battery performance (J Nanopart Res 2019, 21, 274). Therefore, in the prior art, the obtained Fe-doped Mn-based Prussian blue material has the problems of overlarge micron particle size or serious agglomeration of nano particles, so that the rate performance and the cycling stability are poor.
Disclosure of Invention
In view of the above, one of the objectives of the present invention is to provide a spheroidal prussian blue positive electrode material for sodium ion battery, wherein the chemical composition of the positive electrode material is Na x Mn y Fe 1-y [Fe(CN) 6 ] z ·nH 2 O is a Fe-doped Mn-based Prussian blue material, has a stable and highly-dispersed porous hierarchical spheroidal structure, and ensures high rate performance and good cycle stability. The second purpose of the invention is to provide a preparation method of the spherical Prussian blue-like anode material for the sodium-ion battery, which has the advantages of low raw material cost, simple preparation process, easiness in control and low energy consumption and is suitable for industrial popularization.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the preparation method of the spheroidal Prussian blue anode material for the sodium ion battery specifically comprises the following steps:
(1) Dispersing raw material sodium ferrocyanide in absolute ethyl alcohol to obtain milky uniform dispersion liquid, dissolving divalent manganese salt and divalent ferric salt in deionized water, and stirring and dissolving to obtain uniform mixed metal salt solution;
(2) Slowly dripping the mixed metal salt solution in the step (1) into the dispersion liquid, reacting under a certain condition, and then centrifuging or filtering to obtain a blue precipitate;
(3) And (3) washing and drying the blue precipitate in the step (2) to obtain the sphere-like Prussian blue anode material.
Further, the divalent manganese salt comprises MnSO 4 ·H 2 O、Mn(NO 3 ) 2 ·H 2 O or MnCl 2 The ferrous salt comprises FeSO 4 ·7H 2 O、Fe(NO 3 ) 2 Or FeCl 2 ·4H 2 One or more of O.
Furthermore, the ratio of the quantity of the bivalent manganese salt to the bivalent iron salt is 1: 0.01-100, the ratio of the quantity of the sodium ferrocyanide to the quantity of the metal salt (total) is 1: 1-2, the volume ratio of the sodium ferrocyanide dispersion liquid to the mixed metal salt solution is 1: 0.1-1, and the concentration of the sodium ferrocyanide dispersion liquid is 5-50 g/L.
Furthermore, the dropping speed of the mixed metal salt solution is 1-100 mL/min, the reaction temperature is 5-50 ℃, the stirring speed is 100-1500 rpm, and the reaction time is 12-24 h.
Further, the washed solvent comprises deionized water or absolute ethyl alcohol, and the drying condition is that the solvent is dried for more than 2 hours at the temperature of 60-100 ℃.
The chemical composition of the spheroidal Prussian blue anode material for the sodium-ion battery obtained by the invention is Na x Mn y Fe 1-y [Fe(CN) 6 ] z ·nH 2 O, wherein x is 0.01-2, y is 0.01-0.99, z is 0.01-1, n is 0.01-3, and the anode material is in a porous hierarchical spheroidal structure.
The invention also relates to a sodium ion battery with the anode material of the spherical Prussian blue.
According to the technical scheme, compared with the prior art, the spherical Prussian blue anode material for the sodium-ion battery and the preparation method thereof have the following excellent effects:
(1) The invention provides a spherical Prussian blue anode material for a sodium ion battery, which is a Fe-doped Mn-based Prussian blue material with a chemical general formula of Na x Mn y Fe 1-y [Fe(CN) 6 ] z ·nH 2 The doping of O, cheap Fe element not only provides sodium storage active site, but also can relieve Mn 3+ Ginger-taylor effect, mn 2+ Dissolving and coagulatingThe structure phase change ensures the high gram capacity, high rate performance and excellent cycle performance of the Prussian blue anode material;
(2) According to the preparation method of the spheroidal Prussian blue anode material for the sodium ion battery, the characteristic that sodium ferrocyanide is slightly soluble in absolute ethyl alcohol and is soluble in water is utilized, so that the solubility of the sodium ferrocyanide in a mixed solvent with different volume ratios of the absolute ethyl alcohol and the water is different, a reaction system presents solid-liquid two phases, and a new Prussian blue synthesis mechanism is formed. The reaction mechanism of the spheroidic Prussian blue cathode material for the sodium-ion battery is as follows: first, a small amount of solid phase sodium ferrocyanide is partially dissolved in anhydrous ethanol to produce Na + And [ Fe (CN) 6 ] 4- Ions then Na + And [ Fe (CN) 6 ] 4- With water-soluble Mn 2+ And Fe 2+ The coprecipitation reaction in the liquid phase is carried out. The novel synthesis mechanism of the Prussian blue in the two-phase synthesis preparation process is beneficial to reducing the reaction rate and influencing the crystal growth process. The prepared Prussian blue is a stable and high-dispersion porous hierarchical sphere-like micro-nano structure self-assembled by a nano cube, has the characteristics of small crystal grain size, large specific surface area, high sodium ion migration rate and the like, and ensures that high platform voltage, large rate performance and good circulation stability can be obtained;
(3) The invention has the advantages of cheap and easily obtained raw materials, safe and controllable synthesis process, low energy consumption and large-scale production capacity.
Drawings
In order to further explain the technical scheme and the implementation example of the invention, the following will briefly explain the test drawings used in the prior examples or technical process. It is to be noted that the drawings listed below are only some of the embodiments of the present invention, and that other drawings can be obtained by those skilled in the art without inventive effort from the drawings provided.
FIG. 1 is an X-ray diffraction pattern of Prussian blue obtained by the preparation of example 1;
FIG. 2 is a scanning electron micrograph of Prussian blue obtained by the preparation of example 1;
FIG. 3 is an X-ray diffraction pattern of Prussian blue obtained by the preparation of example 2;
FIG. 4 is a scanning electron micrograph of Prussian blue obtained in example 2;
FIG. 5 is an X-ray diffraction pattern of Prussian blue obtained by the preparation of example 3;
FIG. 6 is a scanning electron micrograph of Prussian blue obtained by the preparation of example 3;
FIG. 7 is an X-ray diffraction pattern of Prussian blue obtained by the preparation of comparative example 1;
FIG. 8 is a scanning electron micrograph of Prussian blue prepared in comparative example 1;
FIG. 9 is an X-ray diffraction pattern of Prussian blue obtained by comparative example 2;
FIG. 10 is a scanning electron micrograph of Prussian blue obtained by comparative example 2;
Detailed Description
The processes and techniques of embodiments of the present invention will be described in further detail below with reference to the drawings of the test results of embodiments of the present invention. Furthermore, the embodiments described in this patent are only some examples of the invention and are not intended to be exhaustive or to limit the invention to the precise forms disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a preparation method of a spheroidal Prussian blue anode material for a sodium-ion battery, which comprises the following specific steps:
(1) Mixing the raw material sodium ferrocyanide (Na) 4 Fe(CN) 6 ·10H 2 O) adding the mixture into absolute ethyl alcohol, and stirring for 15 minutes to obtain a milky sodium ferrocyanide dispersion liquid of 5-50 g/L; weighing the divalent manganese salt and the divalent iron salt according to the mass ratio of the divalent manganese salt to the divalent iron salt of 1 to (0.01-100) and the mass ratio of the sodium ferrocyanide to the metal salt (total) of 1 to (1-2), adding the divalent manganese salt and the divalent iron salt into deionized water with a certain volume, ensuring that the volume ratio of the sodium ferrocyanide dispersion liquid to the mixed metal salt solution is 1 to (0.1-1), and stirring and fully dissolving to obtain a transparent mixed metal salt solution;
(2) Slowly dropping the mixed metal salt solution obtained in the step (1) into the sodium ferrocyanide dispersion liquid through a constant-pressure funnel or a peristaltic pump, wherein the dropping speed is 1-100 mL/min, simultaneously reacting for 12-24 h at the reaction temperature of 5-50 ℃ at the stirring speed of 100-1500 rpm, and then filtering or centrifuging to obtain a blue Prussian blue precipitate;
(3) And (3) carrying out suction filtration on the Prussian blue precipitate obtained in the step (2) by using a detergent, and washing the Prussian blue precipitate. And then, drying the anode material in an oven at the temperature of between 60 and 100 ℃ for more than 2 hours to obtain the spheroidal Prussian blue anode material for the sodium ion battery.
Further, the divalent manganese salt in the step (1) includes MnSO 4 ·H 2 O、Mn(NO 3 ) 2 ·H 2 O or MnCl 2 Ferrous salts including FeSO 4 ·7H 2 O、Fe(NO 3 ) 2 Or FeCl 2 ·4H 2 One or more of O.
Further, the detergent in step (3) comprises deionized water or absolute ethyl alcohol.
The technical solution of the present invention will be further described with reference to the following specific embodiments:
example 1
(1) 1.21g of sodium ferrocyanide (Na) was weighed 4 Fe(CN) 6 ·10H 2 O) is added into 50mL of absolute ethyl alcohol, and stirred for 15 minutes to obtain 24g/L of milky white sodium ferrocyanide dispersion liquid; separately, 0.51g of manganese sulfate (MnSO) was weighed 4 ·H 2 O) and 0.56g of ferrous sulfate (FeSO) 4 ·7H 2 O) is dissolved in 50mL deionized water, and is stirred and dissolved to obtain a transparent mixed metal salt solution, wherein the concentration of metal ions (total) is 0.1mol/L;
(2) Slowly dropping the mixed metal salt solution obtained in the step (1) into the sodium ferrocyanide dispersion solution through a constant pressure funnel at a dropping speed of 1mL/min, stirring at 25 ℃ and 1000rpm for 16h, and filtering to obtain a blue Prussian blue precipitate;
(3) And (3) washing the Prussian blue precipitate obtained in the step (2) with water/ethanol alternately, wherein the water is washed twice, and the ethanol is washed once until impurities are removedAnd (5) removing the impurities. Then placing the mixture at 60 ℃ for vacuum drying for 24h to obtain the spheroidal Prussian blue anode material Na for the sodium-ion battery prepared in the invention 0.89 Mn 0.51 Fe 0.49 [Fe(CN) 6 ] 0.60 ·1.48H 2 O。
Example 2
(1) 1.21g of sodium ferrocyanide (Na) was weighed 4 Fe(CN) 6 ·10H 2 O) is added into 80mL of absolute ethyl alcohol, and stirred for 15 minutes to obtain 15g/L of milky white sodium ferrocyanide dispersion liquid; separately, 0.38g of manganese chloride (MnCl) was weighed 2 ) And 0.39g of ferrous chloride (FeCl) 2 ·4H 2 O) is dissolved in 20mL deionized water, and the mixture is stirred and dissolved to obtain a transparent mixed metal salt solution, wherein the concentration of metal ions (total) is 0.25mmol/L;
(2) Slowly dropping the mixed metal salt solution obtained in the step (1) into the sodium ferrocyanide dispersion solution through a constant pressure funnel at a dropping speed of 2mL/min, stirring at 25 ℃ and 500rpm for 20h, and filtering to obtain Prussian blue precipitate;
(3) And (3) washing the Prussian blue precipitate obtained in the step (2) by using water/ethanol alternately, wherein the water is washed twice, and the ethanol is washed once until impurities are removed completely. Then the mixture is placed at 80 ℃ for vacuum drying for 24 hours to obtain the spheroidal Prussian blue anode material Na for the sodium ion battery prepared in the invention 1.25 Mn 0.80 Fe 0.575 [Fe(CN) 6 ]·0.90H 2 O。
Example 3
(1) 1.21g of sodium ferrocyanide (Na) was weighed 4 Fe(CN) 6 ·10H 2 O) is added into 80mL of absolute ethyl alcohol, and stirred for 15 minutes to obtain 15g/L of milky sodium ferrocyanide dispersion liquid; 0.59g of manganese nitrate (Mn (NO) was additionally weighed 3 ) 2 ·H 2 O) and 0.36g ferrous nitrate (Fe (NO) 3 ) 2 ) Dissolving in 20mL of deionized water, stirring and dissolving to obtain a transparent mixed metal salt solution, wherein the (total) concentration of metal ions is 0.25mol/L;
(2) Slowly dropping the mixed metal salt solution obtained in the step (1) into the sodium ferrocyanide dispersion solution through a constant pressure funnel at a dropping speed of 100mL/min, stirring at 800rpm at 50 ℃ for 24h, and centrifuging to obtain a Prussian blue precipitate;
(3) And (3) washing the Prussian blue precipitate obtained in the step (2) by using water/ethanol alternately, wherein the water is washed twice, and the ethanol is washed once until impurities are removed completely. Then placing the mixture at 70 ℃ for vacuum drying for 22h to obtain the spheroidal Prussian blue anode material Na for the sodium ion battery prepared in the invention 1.03 Mn 0.62 Fe 0.38 [Fe(CN) 6 ] 0.64 ·1.75H 2 O。
Comparative example 1
(1) 1.21g of sodium ferrocyanide (Na) was weighed 4 Fe(CN) 6 ·10H 2 O) is added into 80mL of deionized water and stirred uniformly to obtain 15g/L yellow sodium ferrocyanide solution; separately, 0.51g of manganese sulfate (MnSO) was weighed 4 ·H 2 O) and 0.56g of ferrous sulfate (FeSO) 4 ·7H 2 O) is added into 20mL deionized water and stirred to obtain a transparent mixed metal salt solution, wherein the concentration of metal ions (total) is 0.25mol/L;
(2) Dropwise adding the mixed metal salt solution obtained in the step (1) into a sodium ferrocyanide solution at the speed of 1mL/min, stirring at 500rpm for 16h at the temperature of 25 ℃, and then centrifuging to obtain a Prussian blue precipitate;
(3) And (3) washing the Prussian blue precipitate obtained in the step (2) by using water/ethanol alternately, wherein the water is washed twice, and the ethanol is washed once until impurities are removed completely. Then placing the mixture at 60 ℃ for vacuum drying for 24h to finally obtain a cubic Prussian blue positive electrode material Na for the sodium ion battery 1.13 Mn 0.73 Fe 0.42 [Fe(CN) 6 ]·1.24H 2 O。
Comparative example 2
(1) 1.21g of sodium ferrocyanide (Na) was weighed 4 Fe(CN) 6 ·10H 2 O) is added into 100mL of absolute ethyl alcohol and stirred for 15 minutes to obtain 12g/L of milky white sodium ferrocyanide dispersion liquid; separately, 0.51g of manganese sulfate (MnSO) was weighed 4 ·H 2 O) and 0.56g of ferrous sulfate (FeSO) 4 ·7H 2 O) directly adding into the dispersion;
(2) Stirring the mixed solution in the step (1) at 25 ℃ and 500rpm for 16h, and performing suction filtration to obtain a Prussian blue precipitate;
(3) And (3) washing the Prussian blue precipitate in the step (2) with water/ethanol alternately, wherein the water is washed twice, and the ethanol is washed once until impurities are removed completely. Then placing the mixture at 60 ℃ for vacuum drying for 24h to finally obtain the sphere-like Prussian blue anode material Na for the sodium ion battery 0.96 Mn 0.67 Fe 0.33 [Fe(CN)6] 0.74 ·2.08H 2 O。
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The sodium ion batteries prepared in the examples are characterized and tested by using the spheroidal Prussian blue anode material, and the test conditions are as follows:
(1) X-ray diffraction (XRD) testing:
the test was carried out using an X-ray powder diffractometer model Rigaku-D/max-2550p from Hitachi, japan, using Cu-Ka as a radiation source and having a wavelength of 1.5046. Lambda.; a Ni filter plate is adopted, the pipe flow is 40mA, the pipe pressure is 40KV, the scanning range is 10-90 degrees, the scanning speed is 20 degrees/min, and the step length is 0.02 degrees. Placing the material into a glass slide, flattening, and embedding the glass slide into the center of an instrument experiment groove for testing; phase identification and crystal structure information were analyzed by the JADE 6.0 software.
(2) Scanning electron microscopy characterization:
the morphology of the sodium ion battery electrode material prepared in each embodiment was observed by using a scanning electron microscope tester model S-4800 manufactured by HITACHI corporation with an acceleration voltage of 15 KV. The specific test results are as follows:
fig. 1 is an X-ray diffraction pattern of the spheroidal prussian blue cathode material for a sodium ion battery prepared in example 1, wherein the X-axis is the angle 2 θ of X-ray scanning and the ordinate is the intensity of X-rays. As can be seen from fig. 1, the prussian blue cathode material has a characteristic peak on the (200) crystal plane at a scanning angle of 16.92 °, a characteristic peak on the (220) crystal plane at a scanning angle of 24.12 °, a characteristic peak on the (400) crystal plane at a scanning angle of 34.18 °, a characteristic peak on the (420) crystal plane at a scanning angle of 38.56 °, a characteristic peak on the (422) crystal plane at a scanning angle of 42.46 °, a characteristic peak on the (440) crystal plane at a scanning angle of 49.39 °, a characteristic peak on the (600) crystal plane at a scanning angle of 52.78 °, a characteristic peak on the (620) crystal plane at a scanning angle of 55.77 °, belongs to the Fm-3m space group, and has no hetero-peak in the X-ray diffraction pattern, indicating that the cathode material is a pure-phase substance.
Fig. 2 is a scanning electron microscope image of the spherical-like prussian blue cathode material for a sodium ion battery obtained in example 1, and it can be observed that the prussian blue cathode material has a spherical-like structure composed of nano-scale cubic grains, the size of the nano-scale cubic grains is-100 nm, and the size of the spherical-like structure is 3-5 μm.
Fig. 3 is an X-ray diffraction pattern of the spheroidal prussian blue cathode material for a sodium ion battery prepared in example 2, wherein the X-axis is the angle 2 θ of X-ray scanning and the ordinate is the intensity of X-rays. As can be seen from fig. 1, the prussian blue cathode material has a characteristic peak on the (200) crystal plane at a scanning angle of 16.88 °, a characteristic peak on the (220) crystal plane at a scanning angle of 24.06 °, a characteristic peak on the (400) crystal plane at a scanning angle of 34.1 °, a characteristic peak on the (420) crystal plane at a scanning angle of 38.42 °, a characteristic peak on the (422) crystal plane at a scanning angle of 42.38 °, a characteristic peak on the (440) crystal plane at a scanning angle of 49.4 °, a characteristic peak on the (600) crystal plane at a scanning angle of 52.62 °, a characteristic peak on the (620) crystal plane at a scanning angle of 55.67 °, belongs to the Fm-3m space group, and has no hetero-peak in the X-ray diffraction pattern, indicating that the cathode material is a pure-phase substance.
Fig. 4 is a scanning electron microscope image of the spherical-like prussian blue cathode material for a sodium ion battery obtained in example 2, and it can be observed that the prussian blue material has a porous hierarchical spherical-like structure composed of nanocubes, the size of the nanocubes is-100 nm, the size of the hierarchical spherical-like structure is-2 μm, and the dispersibility is good.
Fig. 5 is an X-ray diffraction pattern of the spheroidal prussian blue cathode material for a sodium ion battery prepared in example 3, wherein the X-axis is an angle 2 θ of X-ray scanning and the ordinate is the intensity of X-rays. As can be seen from fig. 1, the prussian blue cathode material has a characteristic peak on the (200) crystal plane at a scanning angle of 17.48 °, a characteristic peak on the (220) crystal plane at a scanning angle of 24.84 °, a characteristic peak on the (400) crystal plane at a scanning angle of 34.44 °, a characteristic peak on the (420) crystal plane at a scanning angle of 38.53 °, a characteristic peak on the (422) crystal plane at a scanning angle of 42.03 °, a characteristic peak on the (440) crystal plane at a scanning angle of 49.61 °, a characteristic peak on the (600) crystal plane at a scanning angle of 50.94 °, a characteristic peak on the (620) crystal plane at a scanning angle of 55.67 °, belongs to the Fm-3m space group, and no impurity peak in the X-ray diffraction pattern, indicating that the cathode material is a pure-phase substance.
Fig. 6 is a scanning electron microscope image of the spherical-like prussian blue cathode material for a sodium ion battery obtained in example 3, and it can be observed that the prussian blue material has a spherical-like structure composed of nano cubic particles, but some of the prussian blue material is broken, the size of the nano cubic particles is 50 to 200nm, and the size of the spherical-like structure is 2 μm.
Fig. 7 is an X-ray diffraction pattern of the cubic prussian blue positive electrode material for a sodium ion battery prepared in comparative example 1, in which the X-axis is the angle 2 θ of X-ray scanning and the ordinate is the intensity of X-rays. As can be seen from fig. 1, the prussian blue cathode material has a characteristic peak on the (200) crystal plane at a scanning angle of 16.94 °, a characteristic peak on the (220) crystal plane at a scanning angle of 24.08 °, a characteristic peak on the (400) crystal plane at a scanning angle of 34.34 °, a characteristic peak on the (420) crystal plane at a scanning angle of 38.56 °, a characteristic peak on the (422) crystal plane at a scanning angle of 42.38 °, a characteristic peak on the (440) crystal plane at a scanning angle of 49.4 °, a characteristic peak on the (600) crystal plane at a scanning angle of 52.36 °, a characteristic peak on the (620) crystal plane at a scanning angle of 55.67 °, belongs to the Fm-3m space group, and no impurity peak in the X-ray diffraction pattern, indicating that the cathode material is a pure-phase substance.
Fig. 8 is a scanning electron microscope image of the cubic prussian blue cathode material for sodium ion batteries obtained in comparative example 1, and it can be observed that the prussian blue material is in a cubic shape formed by agglomeration of nanoparticles, wherein the size of the nanoparticles is 100nm, and the cubic structure is 2 to 8 μm.
Fig. 9 is an X-ray diffraction pattern of the spheroidal prussian blue positive electrode material for a sodium ion battery prepared in comparative example 2, in which the X-axis is an angle 2 θ of X-ray scanning and the ordinate is the intensity of X-rays. As can be seen from fig. 1, the prussian blue cathode material has a characteristic peak on the (200) crystal plane at a scanning angle of 16.82 °, a characteristic peak on the (220) crystal plane at a scanning angle of 23.96 °, a characteristic peak on the (400) crystal plane at a scanning angle of 34.1 °, a characteristic peak on the (420) crystal plane at a scanning angle of 38.35 °, a characteristic peak on the (422) crystal plane at a scanning angle of 42.19 °, a characteristic peak on the (440) crystal plane at a scanning angle of 49.17 °, a characteristic peak on the (600) crystal plane at a scanning angle of 52.26 °, a characteristic peak on the (620) crystal plane at a scanning angle of 55.42 °, belongs to the Fm-3m space group, and has no hetero-peak in the X-ray diffraction pattern, indicating that the cathode material is a pure-phase substance.
Fig. 10 is a scanning electron microscope image of the spherical-like prussian blue cathode material for sodium ion batteries obtained in comparative example 2, and it can be observed that the prussian blue material is a spherical-like structure composed of nano cubic particles, the size of the nano cubic particles is 400-800 nm, and the size of the spherical-like structure is 3-5 μm.
Different sodium ion batteries prepared in the examples use Prussian blue positive electrode materials as positive electrode active materials of the sodium ion batteries, the positive electrode active materials are mixed with a binder (polyvinylidene fluoride PVDF) and a conductive agent (Super P) according to the mass ratio of 8: 1, and dimethyl pyrrolidone (NMP) is added as a solvent to be mixed and stirred into uniform slurry. Uniformly coating the slurry on an aluminum foil, drying, cutting into a sheet as a positive electrode, taking metal sodium as a negative electrode and a glass fiber film as a diaphragm, and adding 1.0mol/L NaClO 4 EC (ethylene carbonate) + PC (polycarbonate) + FEC (fluoroacetate) (EC: PC: FEC = 0.45: 0.05, vol) as an electrolyte, was assembled into CR2032 coin cells in an argon glove box.
The assembled button cell was tested by a Land cell tester manufactured by jinuo electronics ltd, wuhan, under the following test conditions and results:
the button cell is subjected to a constant-current charge-discharge test, the charge-discharge voltage interval is 2-4.2V, in examples 1-3, the Prussian blue electrode in example 2 has the best electrochemical performance, the initial specific capacity of the cell under the current density of 100mA/g is 119mAh/g, the retention rate of the discharge specific capacity after 200 cycles is 86.5%, the capacities after 200 cycles of comparative examples 1 and 2 are only 42% and 30%, in addition, the retention rate of the discharge specific capacity after 500 cycles of the Prussian blue electrode in example 2 is still 68%, and the coulombic efficiency of each cycle is close to 99%; specific data are shown in Table 1
TABLE 1 test results
The inventive content is not limited to the content of the above-mentioned embodiments, wherein combinations of one or several of the embodiments may also achieve the object of the invention.
In the present specification, the embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The method disclosed in the embodiment corresponds to the method disclosed in the embodiment, so that the description is simple, and the relevant points can be referred to the description of the method part.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The spherical Prussian blue anode material for the sodium-ion battery is characterized in that the chemical composition of the anode material is Na x Mn y Fe 1-y [Fe(CN) 6 ] z ·nH 2 O, wherein the value of x is 0.01-2, the value of y is 0.01-0.99, the value of z is 0.01-1, the value of n is 0.01-3, and the anode material is in a porous layer micro-nano spheroidal structure.
2. The preparation method of the spheroidal Prussian blue positive electrode material for the sodium-ion battery, which is characterized by comprising the following steps:
(1) Dispersing raw material sodium ferrocyanide in absolute ethyl alcohol to obtain milky uniform dispersion liquid, dissolving divalent manganese salt and divalent ferric salt in deionized water, and stirring and dissolving to obtain uniform mixed metal salt solution;
(2) Slowly dripping the mixed metal salt solution in the step (1) into the dispersion liquid, reacting under certain conditions, and then centrifuging or filtering to obtain a blue precipitate;
(3) And (3) washing and drying the blue precipitate in the step (2) to obtain the sphere-like Prussian blue cathode material.
3. The method for preparing the spheroidal Prussian blue cathode material for the sodium-ion battery according to claim 2, wherein the divalent manganese salt in the step (1) comprises MnSO 4 ·H 2 O、Mn(NO 3 ) 2 ·H 2 O or MnCl 2 The ferrous salt comprises FeSO 4 ·7H 2 O、Fe(NO 3 ) 2 Or FeCl 2 ·4H 2 One or more of O.
4. The method of claim 2, wherein the ratio of the amounts of the divalent manganese salt and the divalent iron salt in step (1) is 1 to (0.01-100), the ratio of the amounts of the sodium ferrocyanide and the metal salt (total) in step (1) is 1 to (1-2), the volume ratio of the sodium ferrocyanide dispersion to the mixed metal salt solution is 1 to (0.1-1), and the concentration of the sodium ferrocyanide dispersion is 5-50 g/L.
5. The method for preparing the spheroidal Prussian blue cathode material for the sodium-ion battery according to claim 2, wherein the method comprises the following steps: the dropping speed of the mixed metal salt solution in the step (2) is 1-100 mL/min.
6. The method for preparing the spheroidal Prussian blue cathode material for the sodium-ion battery according to claim 2, wherein the method comprises the following steps: in the step (2), the reaction temperature is 5-50 ℃, the stirring speed is 100-1500 rpm, and the reaction lasts 12-24 hours.
7. The method for preparing the spheroidal Prussian blue cathode material for the sodium-ion battery according to claim 2, wherein the method comprises the following steps: the detergent in the step (3) comprises deionized water or absolute ethyl alcohol, the drying temperature is 60-100 ℃, and the drying time is more than 2 hours.
8. A sodium ion battery comprising the spheroidal prussian blue positive electrode material for a sodium ion battery according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211169321.5A CN115360346A (en) | 2022-09-23 | 2022-09-23 | Spheroidal Prussian blue positive electrode material for sodium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211169321.5A CN115360346A (en) | 2022-09-23 | 2022-09-23 | Spheroidal Prussian blue positive electrode material for sodium ion battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115360346A true CN115360346A (en) | 2022-11-18 |
Family
ID=84006694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211169321.5A Pending CN115360346A (en) | 2022-09-23 | 2022-09-23 | Spheroidal Prussian blue positive electrode material for sodium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115360346A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116598484A (en) * | 2023-06-27 | 2023-08-15 | 湖北万润新能源科技股份有限公司 | Prussian blue positive electrode material and preparation method and application thereof |
-
2022
- 2022-09-23 CN CN202211169321.5A patent/CN115360346A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116598484A (en) * | 2023-06-27 | 2023-08-15 | 湖北万润新能源科技股份有限公司 | Prussian blue positive electrode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106564967B (en) | Lithium-rich manganese-based anode material presoma, positive electrode and preparation method thereof | |
| CN111293300B (en) | Zinc-cobalt sulfide/carbon nano anode material and preparation method thereof | |
| WO2020143531A1 (en) | Positive electrode active material and preparation method therefor, sodium ion battery, and device comprising sodium ion battery | |
| WO2022048346A1 (en) | Vanadium pentoxide/rgo-coated lithium nickel cobalt manganese oxide positive electrode material and preparation method therefor | |
| CN111362254A (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| CN113023794B (en) | Cobalt-free high-nickel positive electrode material, preparation method thereof, lithium ion battery positive electrode and lithium ion battery | |
| CN109065847A (en) | A kind of white composite material and preparation method in Prussia and application | |
| CN108493423B (en) | Nano Prussian blue sodium ion battery positive electrode material and preparation method thereof | |
| CN111732112B (en) | Manganese-doped modified zinc ion battery positive electrode active material and preparation method and application thereof | |
| WO2023137859A1 (en) | Sodium ion battery positive electrode active substance, preparation method therefor, and use thereof | |
| CN108807920B (en) | LASO-coated octahedral-structure lithium nickel manganese oxide composite material and preparation method thereof | |
| CN108400296B (en) | Heterogeneous element doped ferroferric oxide/graphene negative electrode material | |
| CN112968173A (en) | Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material | |
| CN110957478B (en) | Titanium yttrium lithium phosphate modified high-nickel cathode composite material and preparation method thereof | |
| CN111342008A (en) | Potassium fluoride doped lithium-rich manganese-based material and preparation method and application thereof | |
| CN115360346A (en) | Spheroidal Prussian blue positive electrode material for sodium ion battery and preparation method thereof | |
| CN113410444A (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN108470892A (en) | A kind of nickelic ternary anode material of lithium battery and preparation method of zinc doping | |
| CN109755486A (en) | The nickle cobalt lithium manganate and preparation method thereof of LiFePO4 cladding | |
| CN112687875A (en) | Preparation method and application of nickel molybdate flexible film composite material | |
| CN109616663B (en) | Nickel-cobalt-aluminum ternary cathode material, preparation method and lithium ion battery | |
| CN103730642A (en) | Negative electrode material of lithium ion battery and preparation method thereof | |
| CN114933292B (en) | Preparation method and application of lithium iron phosphate | |
| WO2018195837A1 (en) | Metal-sulfur battery and preparation method therefor | |
| CN108281632B (en) | Preparation method of vanadium phosphate/carbon as cathode material of hollow spherical lithium ion battery |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230731 Address after: 528000, F1-3, Zhoucun Village Committee, Baini Town, Sanshui District, Foshan City, Guangdong Province, China Applicant after: Guangdong Nayi New Energy Technology Co.,Ltd. Address before: Longpan road Xuanwu District of Nanjing city of Jiangsu Province, No. 159 210037 Applicant before: NANJING FORESTRY University |
|
| TA01 | Transfer of patent application right |