CN115207316A - Preparation method and application of Prussian blue analogue cathode material - Google Patents

Preparation method and application of Prussian blue analogue cathode material Download PDF

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CN115207316A
CN115207316A CN202210927720.7A CN202210927720A CN115207316A CN 115207316 A CN115207316 A CN 115207316A CN 202210927720 A CN202210927720 A CN 202210927720A CN 115207316 A CN115207316 A CN 115207316A
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prussian blue
sodium
blue analogue
solution
ion battery
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王�华
王莹毓
朱乔楠
郭林
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Beihang University
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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
    • 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
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 provides a preparation method and application of a Prussian blue analogue positive electrode material. The invention takes hydroxyl ethylidene diphosphonate with high complexation constant as a chelating agent for the first time and transition metal ions Mn 2+ 、Fe 2+ Form stable complex, and can slowly release transition metal ion Mn after mixing with sodium ferrocyanide aqueous solution 2+ 、Fe 2+ And further controlling the growth speed of the crystal so as to improve the crystallinity of the material and finally obtain the Prussian blue analogue with low crystal water and low defect. The Prussian blue analogue-based sodium ion battery positive electrode material and the corresponding sodium ion battery prepared by the method have excellent charge-discharge specific capacity, rate capability and cycling stability. The preparation process has low cost, simple operation and short preparation period, and is suitable for large scale productionLarge-scale industrial production.

Description

Preparation method and application of Prussian blue analogue positive electrode material
Technical Field
The invention relates to the technical field of new energy, in particular to a preparation method and application of a Prussian blue analogue cathode material.
Background
With the rapid development of social economy, traditional fossil energy such as coal, petroleum, natural gas and the like is continuously consumed, and the accompanying environmental problems are increasingly remarkable, so that the research of sustainable energy capable of being vigorously developed is one of urgent tasks at the present stage. However, clean energy sources such as wind energy and solar energy have intermittency and instability, and an energy storage device is urgently needed to store the energy sources. Lithium ion batteries are gradually developing from portable electronic devices to electric vehicles, large-scale energy storage power grids, and the like as one of emerging electrochemical energy storage modes. However, due to the shortage of lithium resources, the short supply of lithium material causes a sharp rise in the production cost of the battery in a short period of time, and has a significant cost advantage with sodium of the lithium congener group. On one hand, sodium resources are abundant in crusta and low in price; on the other hand, since aluminum does not react with sodium, the aluminum current collector can be applied to the positive electrode and the negative electrode of a sodium battery, thereby further reducing the cost of the battery. Therefore, the sodium ion battery has wider application prospect in the directions of electric vehicles, large-scale energy storage and the like.
As an effective supplement to lithium ion batteries, sodium ion batteries are similar in composition to lithium ion batteries and mainly consist of an anode, an electrolyte and a cathode. At present, the negative electrode material and the electrolyte of the sodium ion battery have made a breakthrough progress, wherein the negative electrode material is mainly hard carbon, the electrolyte is mainly sodium salt, ester or ether solvent, and the selection of the positive electrode material is a bottleneck for hindering the further development of the sodium ion battery.
The positive electrode materials of the sodium ion battery can be divided into three main categories: the composite material comprises a transition metal layered oxide, a polyanion compound and a Prussian blue compound, wherein the transition metal layered oxide has higher specific capacity but poor air stability, and the high-temperature sintering is mostly needed in the synthesis process, so that the production cost of the material is increased; polyanion compounds represented by sodium vanadium phosphate have high stability and cycle performance, but are limited by inherent properties of materials, and have low energy density and poor conductivity. The Prussian blue analogue has the advantages of high theoretical specific capacity, low cost and the like, and the framework structure of the Prussian blue analogue can enable sodium ions to be rapidly removed/inserted, so that excellent structural stability and rate capability are shown, but the problems of crystallization water, defects and the like are generated in the synthesis process, the electrochemical stability of the material is directly influenced, the Prussian blue analogue faces the problem of serious capacity attenuation and the like, and although the circulation stability of the battery can be improved by using complexing agents such as sodium citrate and the like, the material still contains a large amount of crystallization water and defects.
Therefore, the method which is more efficient, convenient and low in cost is adopted to reduce the content of crystal water and defects in the Prussian blue analogue material, so that the Prussian blue analogue has important significance in realizing the cycle stability of the Prussian blue analogue in the sodium-ion battery.
Disclosure of Invention
In view of this, the invention provides a method for mixing a complexing agent with a high complexing stability constant with a transition metal salt solution, which is used for preparing a prussian blue analogue cathode material with low crystal water and low defect by controlling the crystallization speed in the reaction process; the material synthesis method is simple, has low cost and is suitable for large-scale production; the anode material of the sodium-ion battery prepared from the synthetic material has high capacity and stable cycle electrochemical performance, and is beneficial to further industrial development of the sodium-ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a Prussian blue analogue cathode material comprises the following preparation steps:
(1) Dissolving divalent metal salt and complexing agent in deionized water according to different molar ratios, wherein the concentration is 0.05 mol/L-1 mol/L, then adding acetic acid-sodium acetate buffer solution to adjust the pH value in the solution to 3-7 to obtain solution A,
wherein the metal salt comprises a divalent manganese salt or a divalent iron salt;
(2) Dissolving sodium ferrocyanide or a hydrate thereof in deionized water to prepare a sodium ferrocyanide solution with the concentration of 0.05 mol/L-1 mol/L to obtain a solution B;
(3) And adding the solution B into the solution A, stirring, standing, filtering, washing and drying the solution to obtain the Prussian blue analogue cathode material.
Preferably, in the step (1), the divalent manganese salt comprises one or more of manganese acetate, manganese sulfate, manganese chloride, manganese nitrate or hydrates of the divalent manganese salts;
the ferrous salt comprises one or more of ferrous acetate, ferrous sulfate, ferrous chloride, ferrous nitrate or hydrate of the ferrous salt;
the complexing agent comprises one or more of hydroxyethylidene diphosphonic acid, disodium hydroxyethylidene diphosphonic acid, tetrasodium hydroxyethylidene diphosphonic acid or hydrate of the hydroxyethylidene diphosphonic acid salt.
Preferably, in the step (1), the molar ratio of the divalent manganese salt or the divalent iron salt to the complexing agent is 1: x is more than or equal to 1 and less than or equal to 2.
Preferably, in the step (3), the process is carried out at room temperature, and the stirring time is less than or equal to 2 hours; the standing is to stand for 2 to 60 hours at the temperature of between 20 and 60 ℃; the drying is carried out in vacuum at high temperature, wherein the temperature is 60-150 ℃, and the drying time is 12-24h.
The invention also aims to provide application of the Prussian blue analogue positive electrode material prepared by the preparation method of the Prussian blue analogue positive electrode material in a sodium-ion battery.
Preferably, the sodium ion battery comprises a positive electrode, a negative electrode and an electrolyte;
wherein, the positive electrode comprises the Prussian blue analogue positive electrode material;
the electrolyte includes a sodium salt, an organic solvent, and an additive.
Preferably, the positive electrode is prepared by the following method:
1) Weighing Prussian blue analogue positive electrode material, conductive agent and binder, fully grinding and uniformly mixing according to different mass ratios to obtain a mixture;
2) Adding N-methyl-2-pyrrolidone or deionized water as a solvent into the mixture, and fully stirring to obtain mixed slurry;
3) And coating the mixed slurry on an aluminum foil, and performing vacuum drying to obtain the positive electrode of the sodium-ion battery.
Preferably, the conductive agent in the step 1) comprises one or more of SuperP, acetylene black, ketjen black, conductive graphite, carbon nanotubes, graphene and carbon fibers;
the binder comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid and carboxymethyl cellulose/sodium carboxymethyl cellulose;
preferably, the mass ratio of the prussian blue analogue positive electrode material, the conductive agent and the binder in the step 1) is as follows: (6-9.8): (0.1-2): (0.1-2).
Preferably, the sodium salt is selected from NaTFSI, naFSI, naCF 3 SO 3 、NaPF 6 、NaClO 4 、NaNO 3 And NaBF 4 At least one of;
the organic solvent is at least one selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, 1,3 dioxolane, dioxane, tetrahydrofuran, 2-methyl tetrahydrofuran, fluoroethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate and vinylene carbonate;
the additive is at least one of fluoroethylene carbonate with the volume content of 0.01-10% and vinylene carbonate with the volume content of 0.01-10%.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1) The preparation process is simple, the price of the used material is low, the material can be prepared by a simple coprecipitation method, the generation cost is reduced, the preparation period of the material is short, and the large-scale production is easy to realize.
2) Adding chelating agent into the solution A to enable transition metal ions Mn 2+ Or Fe 2+ The transition metal ions in the solution A can be slowly released when the solution A and the solution B are mixed, so that the reaction speed is greatly reduced, and the crystallinity of the product is improved. By controlling the reaction of transition metal ions with the solutionAnd B, obtaining the Prussian blue analogue with low crystal water, low defect and stable structure.
3) The prepared Prussian blue analogue is assembled into a sodium-ion battery, and the high discharge specific capacity of 130mAh/g can be obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is an X-ray diffraction pattern of a prussian blue analog positive electrode material 1 according to the present invention;
fig. 2 is a scanning electron microscope image of the prussian blue analog positive electrode material 1 of the present invention;
fig. 3 is an infrared spectrum of the prussian blue analog positive electrode material 1 of the present invention;
FIG. 4 is a charge-discharge curve diagram of 25mA/g of Prussian blue analogue cathode material 1 serving as a sodium-ion battery cathode;
FIG. 5 is a rate performance graph of the Prussian blue analogue positive electrode material 1 as a sodium ion battery positive electrode;
FIG. 6 is a charge-discharge curve diagram of the Prussian blue analogue cathode material 2 of the present invention as a sodium ion battery cathode at 25mA/g.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Example 1
The method comprises the following steps: preparation of solution A
Weighing 0.1471g of MnAc 2 ·4H 2 O, dissolving in 10mL hydroxyl ethylidene diphosphonic acid solution with the concentration of 0.075mol/L, adding acetic acid-sodium acetate buffer solution to adjust the pH value of the solution to 3.5, and stirring to obtain solution A.
Step two: preparation of solution B
0.2904g Na was weighed 4 Fe(CN) 6 ·10H 2 O, dissolved in 15mL of deionized water and stirred to obtain a solution B.
Step three: and adding the solution B into the solution A, continuously stirring, standing the solution at normal temperature for 60 hours, filtering the obtained precipitate, washing the precipitate by using ethanol and deionized water, and drying the precipitate at 100 ℃ for 12 hours to obtain the Prussian blue analogue cathode material 1.
Example 2
The method comprises the following steps: preparation of solution A
0.1471g of MnAc was weighed out 2 ·4H 2 Dissolving O in 10mL of 0.075mol/L hydroxyethylidene diphosphonic acid solution, adding acetic acid-sodium acetate buffer solution to adjust the pH value of the solution to 6.0, and stirring to obtain a solution A.
Step two: preparation of solution B
0.2904g Na was weighed 4 Fe(CN) 6 ·10H 2 O, dissolved in 15mL of deionized water and stirred to obtain a solution B.
Step three: and adding the solution B into the solution A, continuously stirring, standing the solution at normal temperature for 60 hours, filtering the obtained precipitate, washing the precipitate by using ethanol and deionized water, and drying the precipitate at 100 ℃ for 12 hours to obtain the Prussian blue analogue cathode material 2.
Example 3
The method comprises the following steps: preparation of solution A
0.1668g of FeSO is weighed 4 ·7H 2 Dissolving O in 10mL of 0.075mol/L hydroxyethylidene diphosphonic acid solution, adding acetic acid-sodium acetate buffer solution to adjust the pH value of the solution to 3.5, and stirring to obtain a solution A.
Step two: preparation of solution B
0.2904g Na was weighed 4 Fe(CN) 6 ·10H 2 O, dissolved in 15mL of deionized water and stirred to obtain solution B.
Step three: and adding the solution B into the solution A, continuously stirring, standing the solution at normal temperature for 60 hours, filtering the obtained precipitate, washing the precipitate by using ethanol and deionized water, and drying the precipitate at 100 ℃ for 12 hours to obtain the Prussian blue analogue cathode material 3.
Example 4
The method comprises the following steps: preparation of solution A
0.1668g of FeSO was weighed 4 ·7H 2 Dissolving the O in 10mL of 0.075mol/L hydroxyethylidene diphosphonate disodium solution, adding acetic acid-sodium acetate buffer solution to adjust the pH value of the solution to 6.0, and stirring to obtain a solution A.
Step two: preparation of solution B
0.2904g Na was weighed 4 Fe(CN) 6 ·10H 2 O, dissolved in 15mL of deionized water and stirred to obtain a solution B.
Step three: and adding the solution B into the solution A, continuously stirring, standing the solution at normal temperature for 60 hours, filtering the obtained precipitate, washing the precipitate by using ethanol and deionized water, and drying the precipitate at 100 ℃ for 12 hours to obtain the Prussian blue analogue cathode material 4.
Example 5
Structural characterization of prussian blue analogs
The prussian blue analogue 1 was structurally characterized by an X-ray diffractometer, and an X-ray diffraction pattern of the prussian blue analogue of the present invention was obtained (fig. 1). As can be seen from the figure, the XRD pattern is in combination with Na x Mn[Fe(CN) 6 ] y Has the same XRD and no obvious impurity peak, and indicates that the prepared material is Na x Mn[Fe(CN) 6 ] y 。
Example 6
Morphological characterization of Prussian blue analogs
The prussian blue analogue 1 was subjected to microscopic morphology characterization by a scanning electron microscope to obtain a scanning electron micrograph (fig. 2) of the prussian blue analogue of the present invention. As can be seen from the figure, the Prussian blue analogue has a grain size of about 500nm, indicating thatDuring the reaction, mn passes through 2+ Is slowly released and complexed with [ Fe (CN) through the complexation of the chelating agent 6 ] 4- And reacting to form a cubic structure with uniform size.
Example 7
Infrared spectroscopic characterization of Prussian blue analogs
By performing infrared spectrum test on the prussian blue analogue 1, an infrared spectrogram of the prussian blue analogue of the invention is obtained (figure 3). As can be seen, at 1620 and 3534cm -1 The absorption peak at (A) is weaker and corresponds to the O-H stretching and H-O-H bonding of water, and 3604cm -1 The peak at the position where the water is adsorbed on the free surface is also weak, which shows that the addition of the chelating agent can promote the generation of the low crystal water Prussian blue analogue.
Example 8
A preparation method of a Prussian blue analogue sodium-ion battery positive electrode comprises the following steps:
the method comprises the following steps: weighing 70mg of Prussian blue analogue 1, 20mg of Ketjen black and 10mg of polyvinylidene fluoride, and grinding in a mortar until the powder is uniformly distributed;
step two: adding a proper amount of N-methyl-2-pyrrolidone serving as a solvent into the mixture obtained in the step one, and fully stirring until no granular sensation exists to obtain mixed slurry;
step three: coating the mixed slurry obtained in the step two on an aluminum foil, and performing vacuum drying at 100 ℃ for 12 hours to obtain a sodium ion battery anode 1;
example 9
A preparation method of a Prussian blue analogue sodium-ion battery positive electrode comprises the following steps:
the method comprises the following steps: weighing 80mg of Prussian blue analogue 2, 10mg of SuperP and 10mg of polyvinylidene fluoride, and grinding in a mortar until the powder is uniformly distributed;
step two: adding a proper amount of N-methyl-2-pyrrolidone serving as a solvent into the mixture obtained in the step one, and fully stirring until no granular sensation exists to obtain mixed slurry;
step three: and (4) coating the mixed slurry obtained in the step two on an aluminum foil, and performing vacuum drying at 100 ℃ for 12 hours to obtain the sodium-ion battery anode 2.
Example 10
Filling a sodium ion battery anode 1 and a sodium sheet with a diaphragm and electrolyte to form a battery, wherein the diaphragm is a glass fiber diaphragm of a lithium ion battery; 1.0M NaClO is selected as electrolyte 4 Dissolved in ethylene carbonate/propylene carbonate (volume ratio 1), and fluoroethylene carbonate was added as an additive in an amount of 5% by volume.
The battery was subjected to a constant current charge and discharge test at a current density of 25mA/g to obtain a charge and discharge curve (FIG. 4). As can be seen from the figure, the positive electrode material has the capacity of about 92mAh/g, and after three-turn discharge, the capacity can be maintained at 99 percent, and the higher capacity is shown. Then, constant current charge and discharge tests were performed at different current densities to obtain a rate performance graph (fig. 5). As can be seen from the figure, the capacities of the positive electrode material were 90.2mAh/g,84.4mAh/g,70mAh/g and 54mAh/g at current densities of 100mA/g, 200mA/g, 500mA/g and 1000mA/g, respectively. When the current is increased back to 100mA/g, the capacity of the material can be stabilized at about 82mAh/g, and excellent rate performance is shown.
Example 11
Filling a sodium ion battery anode 2 and a sodium sheet with a diaphragm and electrolyte to form a battery, wherein the diaphragm is a glass fiber diaphragm of a lithium ion battery; 1.0M NaClO is selected as electrolyte 4 Dissolved in ethylene carbonate/propylene carbonate (volume ratio 1), and fluoroethylene carbonate was added as an additive in an amount of 5% by volume.
And (3) carrying out constant-current charge and discharge tests on the battery, wherein the current density is 25mA/g. A charge-discharge curve was obtained (fig. 6). As can be seen from the figure, the first-turn discharge capacity of the cathode material is about 120mAh/g, and the capacity in the subsequent circulation can reach 130mAh/g. The pH value of the solution is increased so as to increase the chelating agent and Mn 2+ The anode material with higher capacity is finally obtained.
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 device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
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 (10)

1. The preparation method of the Prussian blue analogue cathode material is characterized by comprising the following preparation steps of:
(1) Dissolving divalent metal salt and a complexing agent in deionized water according to different molar ratios, wherein the concentration is 0.05 mol/L-1 mol/L, then adding acetic acid-sodium acetate buffer solution to adjust the pH value in the solution to 3-7 to obtain a solution A,
wherein the metal salt comprises a divalent manganese salt or a divalent iron salt;
(2) Dissolving sodium ferrocyanide or a hydrate thereof in deionized water to prepare a sodium ferrocyanide solution with the concentration of 0.05 mol/L-1 mol/L to obtain a solution B;
(3) And adding the solution B into the solution A, stirring, standing, filtering, washing and drying the solution to obtain the Prussian blue analogue cathode material.
2. The method for preparing the Prussian blue analogue cathode material according to claim 1,
in the step (1), the divalent manganese salt comprises one or more of manganese acetate, manganese sulfate, manganese chloride, manganese nitrate or hydrates of the divalent manganese salts;
the ferrous salt comprises one or more of ferrous acetate, ferrous sulfate, ferrous chloride, ferrous nitrate or hydrate of the ferrous salt;
the complexing agent comprises one or more of hydroxyethylidene diphosphonic acid, disodium hydroxyethylidene diphosphonate, tetrasodium hydroxyethylidene diphosphonate or hydrates of the hydroxyethylidene diphosphonates.
3. The method for preparing the Prussian blue analogue cathode material according to claim 1,
in the step (1), the molar ratio of the divalent manganese salt or the divalent iron salt to the complexing agent is 1: x is more than or equal to 1 and less than or equal to 2.
4. The method for preparing the Prussian blue analogue cathode material according to claim 1,
in the step (3), the process is carried out at room temperature, and the stirring time is less than or equal to 2h; the standing is to stand for 2 to 60 hours at the temperature of between 20 and 60 ℃; the drying is carried out in vacuum at high temperature, wherein the temperature is 60-150 ℃, and the drying time is 12-24h.
5. The use of the Prussian blue analogue positive electrode material prepared by the preparation method of the Prussian blue analogue positive electrode material as claimed in any one of claims 1 to 4 in a sodium-ion battery.
6. The application of the Prussian blue analogue cathode material in the sodium-ion battery according to claim 5, wherein the sodium-ion battery comprises a cathode, an anode and an electrolyte;
wherein the positive electrode comprises the Prussian blue analogue positive electrode material as recited in claim 5;
the electrolyte comprises a sodium salt, an organic solvent and an additive.
7. The application of the Prussian blue analogue cathode material in the sodium-ion battery, which is characterized in that the cathode is prepared by the following method:
1) Weighing Prussian blue analogue positive electrode material, conductive agent and binder, fully grinding and uniformly mixing according to different mass ratios to obtain a mixture;
2) Adding N-methyl-2-pyrrolidone or deionized water as a solvent into the mixture, and fully stirring to obtain mixed slurry;
3) And coating the mixed slurry on an aluminum foil, and performing vacuum drying to obtain the positive electrode of the sodium-ion battery.
8. The application of the Prussian blue analogue cathode material in the sodium-ion battery according to claim 7,
the conductive agent in the step 1) comprises one or more of SuperP, acetylene black, ketjen black, conductive graphite, carbon nano tube, graphene and carbon fiber;
the binder comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid and carboxymethyl cellulose/sodium carboxymethyl cellulose.
9. The application of the Prussian blue analogue cathode material in the sodium-ion battery as claimed in claim 7, wherein the mass ratio of the Prussian blue analogue cathode material, the conductive agent and the binder in step 1) is as follows: (6-9.8): (0.1-2): (0.1-2).
10. The application of the Prussian blue analogue cathode material in the sodium-ion battery according to claim 6,
the sodium salt is selected from NaTFSI, naFSI, naCF3SO 3 、NaPF 6 、NaClO 4 、NaNO 3 And NaBF 4 At least one of;
the organic solvent is at least one selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, 1,3 dioxolane, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, fluoroethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate and vinylene carbonate;
the additive is at least one of fluoroethylene carbonate with the volume content of 0.01-10% and vinylene carbonate with the volume content of 0.01-10%.
CN202210927720.7A 2022-08-03 2022-08-03 Preparation method and application of Prussian blue analogue cathode material Pending CN115207316A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115676852A (en) * 2022-11-14 2023-02-03 中国地质大学（武汉） Manganese-iron-based Prussian blue potassium ion battery positive electrode material and preparation method and application thereof
KR102532065B1 (en) * 2022-11-14 2023-05-11 경북대학교 산학협력단 CoHCF POSITIVE ELECTRODE ACTIVE MATERIAL, METHOD FOR PREPARATION THE SAME
CN116393096A (en) * 2023-06-06 2023-07-07 中国农业科学院农业环境与可持续发展研究所 Composite material, method for synchronously producing methane and removing ammonia nitrogen and application

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115676852A (en) * 2022-11-14 2023-02-03 中国地质大学（武汉） Manganese-iron-based Prussian blue potassium ion battery positive electrode material and preparation method and application thereof
KR102532065B1 (en) * 2022-11-14 2023-05-11 경북대학교 산학협력단 CoHCF POSITIVE ELECTRODE ACTIVE MATERIAL, METHOD FOR PREPARATION THE SAME
CN116393096A (en) * 2023-06-06 2023-07-07 中国农业科学院农业环境与可持续发展研究所 Composite material, method for synchronously producing methane and removing ammonia nitrogen and application
CN116393096B (en) * 2023-06-06 2023-09-19 中国农业科学院农业环境与可持续发展研究所 Composite material, method for synchronously producing methane and removing ammonia nitrogen and application

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