CN115172741A - Preparation method and application of ternary metal Prussian blue positive electrode material - Google Patents

Preparation method and application of ternary metal Prussian blue positive electrode material Download PDF

Info

Publication number
CN115172741A
CN115172741A CN202210896986.XA CN202210896986A CN115172741A CN 115172741 A CN115172741 A CN 115172741A CN 202210896986 A CN202210896986 A CN 202210896986A CN 115172741 A CN115172741 A CN 115172741A
Authority
CN
China
Prior art keywords
prussian blue
preparation
application
metal
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
Application number
CN202210896986.XA
Other languages
Chinese (zh)
Inventor
雷振东
李丽
侴树春
高云
侴术雷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute Of Carbon Neutralization Technology Innovation Wenzhou University
Original Assignee
Institute Of Carbon Neutralization Technology Innovation Wenzhou University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Institute Of Carbon Neutralization Technology Innovation Wenzhou University filed Critical Institute Of Carbon Neutralization Technology Innovation Wenzhou University
Priority to CN202210896986.XA priority Critical patent/CN115172741A/en
Publication of CN115172741A publication Critical patent/CN115172741A/en
Pending legal-status Critical Current

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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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 relates to the field of sodium ion battery energy storage, and provides a low-cost Prussian blue positive electrode material obtained by a simple preparation method. The material is synthesized by adopting a transition metal source with cheap raw materials and a chelating agent-assisted coprecipitation method, so that the difficulty that the traditional self-sacrifice method cannot realize mass production is overcome, and the method has the advantages of low raw material price and suitability for large-scale production. The obtained Prussian blue analogue has better electrochemical energy storage performance in a sodium ion energy storage system and has good production benefit.

Description

Preparation method and application of ternary metal Prussian blue positive electrode material
Technical Field
The invention relates to the field of sodium ion battery materials, in particular to preparation and application of a low-cost and easily-synthesized Na2Cu0.5Mn0.5Fe (CN) 6 positive electrode material.
Background
In the last decade, the field of energy storage has gradually entered the late lithium battery age, marked by the revival of sodium ion batteries. As early as around 2010, when lithium ion batteries are changing social life deeply, the scientific research community has noticed the problems of shortage of lithium resources and serious global uneven distribution. Therefore, the technology of sodium ion batteries gradually returns to the field of scientific research, and is rapidly developed by virtue of the experience accumulated in the research of the technology of lithium ion batteries. Only five years later, 2015, the first generation of sodium-ion batteries has been advancing into commercialization. Due to the large difference in radius between sodium and transition metal ions, there are many functional structures that can achieve reversible deintercalation of sodium ions. The main positive electrode materials include: layered transition metal oxides, polyanionic compounds, prussian Blue Analogues (PBA), conversion reaction-based materials, and organic materials.
Among the above material types, prussian blue analogues (PBA, na2M [ Fe (CN) 6], where M = Fe, co, mn, ni, cu, etc.) have an open framework structure and strong structural stability, have a large number of redox sites within the framework, are highly tunable in properties and strong in adaptability, and can be synthesized at a lower temperature. Very high energy densities (approximately 500-600Wh kg-1) are currently achievable with such materials. Among them, fe-, mn-, cu-PBA is regarded as a sodium ion battery anode material with great prospect because the metal source is wide and easy to obtain and the price is low. Because of these unique advantages and limitations, prussian blue is primarily used for fixed, grid-scale energy storage, and these systems have relaxed energy density requirements but high requirements for cost, cycle life, and rate capability. Cu-PBA is low in cost and has good cycling stability, but shows lower specific capacity due to the single metal active center. For Mn-PBA with double active centers, in the process of sodium ion extraction, stable Mn2+ (3 d 4) is converted into unstable Mn3+ (3 d 5) to generate Jahn-Teller distortion, thereby causing severe distortion and irreversible phase change of Mn-N6 octahedron. Due to the continued occurrence of the Jahn-Teller effect, mn-PBA suffers from severe structural destruction and gradual dissolution of transition metals in the framework into the electrolyte, resulting in a drastic decline in capacity. In addition, the high vacancy fraction and interstitial water concentration in the backbone lead to fewer sodium storage sites, which in turn leads to poor coulombic efficiency and short cycle life of Mn-PBA-based organic sodium-ion batteries.
The method has the advantages of improving the crystallinity of the prussian blue material, reducing the defects of the prussian blue material, improving the cycling stability and the dynamic performance of the material and minimizing the capacity loss, and becomes the research focus of the prussian blue anode material. In order to solve the above problems, the prussian blue material needs to be precisely designed in structure and regulated in performance. In recent years, researchers at home and abroad have made a great deal of work, such as hydrothermal recrystallization to improve the crystallinity of the prussian blue, in-situ composite conductive material to improve the dynamic performance of the prussian blue, nickel doping to improve the cycle performance of the prussian blue, and acid and alkali etching regulation and control structures to obtain prussian blue analogues with core-shell structures. Although the methods have certain effect, the methods also have some problems, the hydrothermal reaction needs an additional heat source to maintain the reaction temperature, the energy consumption is increased, the cost is increased, and the methods are not suitable for large-scale production; the in-situ composite conductive material is difficult to ensure the uniformity of the composite, and although the nickel doping has good effect, the nickel resource is short and the price is high, thereby undoubtedly increasing the cost; although prussian blue analogue with good electrochemical performance is obtained by acid-base etching, the introduction of strong acid and strong base can cause environmental pollution, and is not suitable for industrial production.
The invention aims to overcome the defects of the prior art and provide a Prussian blue cathode material which is low in cost, high in energy density and capable of being produced in a large scale and a preparation method thereof.
Disclosure of Invention
The invention provides a sodium ion battery anode material with stable circulation and low cost and a preparation method thereof. The method has the advantages of simple flow, simple equipment, wide and easily-obtained raw materials, low cost of the used metal and good industrial prospect. The prepared material is used for the anode of the sodium-ion battery, has the high capacity of the manganese-based Prussian blue material and the excellent characteristics of the copper-based Prussian blue material of stable circulation, and shows better electrochemical behavior.
The invention adopts the following technical scheme:
the invention provides a Prussian blue type sodium ion battery anode material, and the synthesis process is simple and efficient. The Prussian blue material is prepared by substituting Mn ions in Mn-N octahedrons in Mn-based Prussian blue lattices with inert metal M, wherein the inert transition metal is any one of Cu and Zn, prussian blue materials with different substitution degrees are obtained by reasonably regulating and controlling the proportion of the inert metal M, and the molecular formula of the materials is NaxMyMn1-y [ Fe (CN) 6]z, wherein M = Cu, any one of Zn, x is more than or equal to 0.3 and less than or equal to 2,0 and less than or equal to 1, and z is less than or equal to 0 & lt 1.
The invention also provides a preparation method of the Prussian blue type sodium ion battery anode material, which comprises the following steps:
(1) A certain amount of manganese source, inert metal source M and chelating agent are dissolved in 100mL of deionized water and stirred for 3 hours, and the solution A is marked.
(2) A quantity of sodium ferrocyanide was dissolved in 100mL of deionized water and stirred for 3 hours, and recorded as solution B.
(3) And slowly dripping the solution A into the solution B at a certain dripping speed, stirring for 3 hours, and aging for a period of time to obtain a suspension C.
(4) And then washing the lower-layer precipitate with water and ethanol, putting the lower-layer precipitate in a vacuum drying box at the temperature of 120 ℃ for vacuum drying for 12 hours, and collecting the Prussian blue analogue.
(5) In the whole reaction process, protective gas does not need to be introduced into the reactor, and heating is not needed.
(6) The preparation method of the positive electrode material of the sodium-ion battery comprises the following steps: mixing the Prussian blue analogue active positive electrode material, the conductive agent and the binder according to a certain proportion, fully grinding and uniformly mixing the obtained mixture by using a mortar, transferring the mixture into a 2mL oscillation tube, adding a plurality of zirconium dioxide beads with the diameter of 3mm, fully oscillating to obtain uniform slurry, coating the uniform slurry on a carbon-coated aluminum foil, placing the carbon-coated aluminum foil in a vacuum drying oven at 100 ℃ for vacuum drying for 12 hours to completely evaporate the solvent, and tabletting to obtain the positive electrode plate.
Preferably, the chelating agent is one of sodium citrate and sodium pyrophosphate, more preferably, the manganese salt is manganese sulfate, the inert metal source is copper sulfate, and the chelating agent is sodium citrate.
Preferably, the concentration of the Mn source is 0 to 0.1mol/L, the concentration of the inert metal is 0 to 0.1mol/L, and the concentration of the chelating agent is 0 to 0.3mol/L, more preferably, the concentration of the Mn source is 0.05mol/L, the concentration of the inert metal is 0.05mol/L, and the concentration of the chelating agent is 0.2mol/L.
Preferably, the Mn source: the molar ratio of the metal M source is 0:1 to 1:0, more preferably, mn source: the molar ratio of the metal M source is 1:1, mn Source + Metal M Source: the molar ratio of the chelating agent is 1:2.
preferably, the concentration of sodium ferrocyanide is 0.1-0.3mol/L, the Mn source + the metal M source: the molar ratio of the chelating agent is 1:0 to 1:3, more preferably, the concentration of sodium ferrocyanide is 0.2mol/L, the source of Mn + the source of metal M: the molar ratio of the chelating agent is 1:2.
preferably, the dropping speed in the step (3) is 10mL/h-50mL/h, and the aging time is 1-36 hours; more preferably, the dropping speed in the step (3) is 10mL/h and the aging time is 24 hours.
The invention provides a sodium-ion battery cathode material, which is prepared from the Prussian blue analogue material.
Preferably, the conductive agent is any one of Super P, carbon nano tube, acetylene black and Ketjen Black (KB), and the binder is one of polyvinylidene fluoride (PVDF), sodium Alginate (SA) and sodium carboxymethylcellulose (CMC); more preferably, the conductive agent is ketjen black, binder sodium carboxymethyl cellulose (CMC).
Preferably, the mass percentage of the prussian blue analogue is 60-80%, the mass percentage of the conductive agent is 10-30%, and the mass percentage of the binder is 10-20%, more preferably, the mass percentage of the prussian blue analogue is 70%, the mass percentage of the conductive agent is 20%, and the mass percentage of the binder is 10%.
The invention can prepare the non-ionic liquid by controlling the content of the substitution element Cu in the mixed solutionPrussian blue analogue positive electrode materials (marked as CuHCF-1, cuHCF-2 and CuHCF-3) with the same substitution degree realize the regulation and control of the capacity and stability of the materials. Mn, which benefits from the stabilization of the structure and the activity of the inert Cu, provides a redox couple when the Cu source: the molar ratio of the Mn source is 1:1, a prussian blue analogue with minimized capacity sacrifice and high structural stability, namely CuHCF-2 (chemical formula Na) 2 Cu 0.5 Mn 0.5 Fe(CN) 6 ). The compound CuHCF-2 has the advantages of high capacity of manganese-based Prussian blue materials and stable circulation of copper-based Prussian blue materials, and the electrochemical performance of the compound is compared with that of a single-metal copper Prussian blue material CuHCF-1 (Na) under the same condition 2 CuFe(CN) 6 ) The specific capacity is greatly improved, and compared with a manganese Prussian blue material CuHCF-3 (Na) of single metal 2 MnFe(CN) 6 ) The cycling stability is obviously improved, and the better comprehensive electrochemical performance is shown. The preparation process disclosed by the invention does not need procedures such as atmosphere protection and heating, is simple to operate, does not relate to expensive Ni and Co elements, is low in cost, is high in industrial popularization and has a good application prospect.
The invention has the beneficial effects that:
(1) The preparation method adopts a coprecipitation method to prepare the Prussian blue analogue material, has easily obtained raw materials, low price of contained metal, simple process and low production cost, and has the potential of large-scale production.
(2) The preparation process does not need atmosphere protection and additional heating operation, and reduces the production cost.
(3) The prepared Prussian blue analogue material has an open-frame structure, a larger ion tunnel structure, abundant sodium storage sites, good crystallinity and stable structure.
(4) The sodium ion battery prepared by adopting the material as the anode has excellent rate performance, high reversible specific capacity and good capacity retention rate after multiple charge-discharge cycles.
Drawings
FIG. 1 is a scanning electron micrograph of CuHCF-1, cuHCF-2, and CuHCF-3, three products of examples 1-3.
FIG. 2 is a comparative XRD plot of CuHCF-1, cuHCF-2, and CuHCF-3, three products from examples 1-3.
FIG. 3 is a comparative plot of constant current charge and discharge at a current density of 10mA g-1 for the three products CuHCF-1, cuHCF-2, and CuHCF-3 of examples 1-3.
FIG. 4 is a graph comparing the cycling performance of three products of examples 1-3, cuHCF-1, cuHCF-2, and CuHCF-3 at a current density of 100mA g-1.
FIG. 5 is a graph of the rate capability of three products, cuHCF-1, cuHCF-2, and CuHCF-3, of examples 1-3 at different current densities.
Detailed Description
The invention is further illustrated but is not in any way limited by the following specific examples. Any simple modification, equivalent change and modification made to the following examples according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
(1) Weighing manganese sulfate (5 mmol), sodium citrate (20 mmol) and copper sulfate (5 mmol) to dissolve in 100mL of deionized water, stirring for 3 hours, and recording as solution A, wherein the concentration of Mn in the obtained solution is 0.05mol/L, the concentration of Cu is 0.05mol/L, and the concentration of chelating agent sodium citrate is 0.2mol/L, wherein the Mn source: the molar ratio of the inert metal Cu source is 1:1.
(2) Sodium ferrocyanide (20 mmol) was dissolved in 100ml deionized water and stirred for 3 hours, denoted as solution B, and the concentration of sodium ferrocyanide in the resulting solution was 0.2mol/L.
(3) Dripping the solution A into the solution B at a dripping speed of 10mL/h, stirring for 3 hours, and aging for 24 hours to obtain a suspension C;
(4) Then washing the lower layer precipitate with water and ethanol, vacuum drying in a vacuum drying oven at 120 deg.C for 12 hr, and collecting to obtain CuHCF-2 (chemical formula Na) 2 Cu 0.5 Mn 0.5 Fe(CN) 6 ) And (3) obtaining the product.
(5) Preparing an electrode: mixing the CuHCF-2 material, the conductive agent and the binder in the step (4) according to a certain mass ratio, transferring the obtained mixture into a vibrating tube, adding 6 zirconium dioxide beads with the diameter of 3mm, fully vibrating to obtain uniform slurry, uniformly coating the uniform slurry on a carbon-coated aluminum foil through a coating machine (MSK-AFA-I), placing the carbon-coated aluminum foil on a vacuum drying oven with the temperature of 100 ℃ for vacuum drying for 12 hours, cutting the carbon-coated aluminum foil into a circular pole piece with the diameter of 10mm by using a cutting machine (MSK-T10) after the solvent is completely evaporated, weighing, and calculating the mass of the active substance to be 1mg. Wherein the conductive agent is Ketjen black, the binder is sodium carboxymethylcellulose, the mass percentage of the Prussian blue analogue is 70%, the mass percentage of the conductive agent is 20%, and the mass percentage of the binder is 10%.
(6) And (3) electrochemical performance testing: all the batteries are assembled in a glove box (O wt% is less than or equal to 0.01 2 O wt% is less than or equal to 0.01), constant current charge and discharge test and long cycle test of the R2032 button cell are realized by Neware CT4000, the test voltage window is 2-4.2V, and the current density is 100mAg -1 。
For comparison, cuHCF-1 (Na) was prepared under the same conditions, respectively 2 CuFe(CN) 6 ) And CuHCF-3 (Na) 2 MnFe(CN) 6 )。
Example 2
(1) Weighing sodium citrate (20 mmol) and copper sulfate (10 mmol) to dissolve in 100mL of deionized water, stirring for 3 hours to obtain a solution A with the Cu concentration of 0.1mol/L and the chelating agent sodium citrate concentration of 0.2mol/L, wherein the Mn source: the molar ratio of the inert metal Cu source is 0:1.
(2) Sodium ferrocyanide (20 mmol) is dissolved in 100ml deionized water and stirred for 3 hours, denoted as solution B, and the concentration of sodium ferrocyanide in the obtained solution is 0.2mol/L.
(3) Dropwise adding the solution A into the solution B at a dropping speed of 10mL/h, stirring for 3 hours, and aging for 24 hours to obtain a suspension C;
(4) Then washing the lower layer precipitate with water and ethanol, vacuum drying in a vacuum drying oven at 120 deg.C for 12 hr, and collecting to obtain CuHCF-1 (chemical formula Na) 2 CuFe(CN) 6 ) And (3) obtaining the product.
(5) Preparing an electrode: mixing the CuHCF-1 material, the conductive agent and the binder in the step (4) according to a certain mass ratio, transferring the obtained mixture into a vibrating tube, adding 6 zirconium dioxide beads with the diameter of 3mm, fully vibrating to obtain uniform slurry, uniformly coating the uniform slurry on a carbon-coated aluminum foil through a coating machine (MSK-AFA-I), placing the carbon-coated aluminum foil in a vacuum drying oven with the temperature of 100 ℃ for vacuum drying for 12 hours, cutting the carbon-coated aluminum foil into a circular pole piece with the diameter of 10mm by using a cutting machine (MSK-T10) after the solvent is completely evaporated, weighing, and calculating the mass of the active substance to be 1mg. The conductive agent is Keqin black, the binder is sodium carboxymethylcellulose, the mass percentage of the Prussian blue analogue is 70%, the mass percentage of the conductive agent is 20%, and the mass percentage of the binder is 10%.
(6) And (3) electrochemical performance testing: all the batteries are assembled in a glove box (O wt% is less than or equal to 0.01 2 O wt% is less than or equal to 0.01), constant current charge and discharge test and long cycle test of the R2032 button cell are realized by Neware CT4000, the test voltage window is 2-4.2V, and the current density is 100mAg -1 。
Example 3
(1) Weighing manganese sulfate (10 mmol) and sodium citrate (20 mmol) and dissolving in 100mL deionized water, stirring for 3 hours, and recording as solution A, wherein the concentration of Mn in the obtained solution is 0.1mol/L, the concentration of a chelating agent sodium citrate is 0.2mol/L, and the Mn source: the molar ratio of the inert metal Cu source is 1:0.
(2) Sodium ferrocyanide (20 mmol) was dissolved in 100ml deionized water and stirred for 3 hours, denoted as solution B, and the concentration of sodium ferrocyanide in the resulting solution was 0.2mol/L.
(3) Dripping the solution A into the solution B at a dripping speed of 10mL/h, stirring for 3 hours, and aging for 24 hours to obtain a suspension C;
(4) Then washing the lower layer precipitate with water and ethanol, vacuum drying in a vacuum drying oven at 120 deg.C for 12 hr, and collecting to obtain CuHCF-2 (chemical formula Na) 2 MnFe(CN) 6 ) And (3) obtaining the product.
(5) Preparing an electrode: mixing the CuHCF-3 material, the conductive agent and the binder in the step (4) according to a certain mass ratio, transferring the obtained mixture into a vibrating tube, adding 6 zirconium dioxide beads with the diameter of 3mm, fully vibrating to obtain uniform slurry, uniformly coating the uniform slurry on a carbon-coated aluminum foil through a coating machine (MSK-AFA-I), placing the carbon-coated aluminum foil on a vacuum drying oven with the temperature of 100 ℃ for vacuum drying for 12 hours, cutting the carbon-coated aluminum foil into a circular pole piece with the diameter of 10mm by using a cutting machine (MSK-T10) after the solvent is completely evaporated, weighing, and calculating the mass of the active substance to be 1mg. The conductive agent is Keqin black, the binder is sodium carboxymethylcellulose, the mass percentage of the Prussian blue analogue is 70%, the mass percentage of the conductive agent is 20%, and the mass percentage of the binder is 10%.
(6) And (3) electrochemical performance testing: all the batteries are assembled in a glove box (O wt% is less than or equal to 0.01 2 O wt% is less than or equal to 0.01), constant current charge and discharge test and long cycle test of the R2032 button cell are realized by Neware CT4000, the test voltage window is 2-4.2V, and the current density is 100mAg -1 。
FIG. 1 is a scanning electron micrograph of the three products of examples 1-3, and it can be seen that both CuHCF-1, cuHCF-2 and CuHCF-3 exhibit large platelets.
FIG. 2 is a comparative XRD pattern of the three products of examples 1-3, demonstrating that CuHCF-1, cuHCF-2 and CuHCF-3 are monoclinic phases.
FIG. 3 shows the results of examples 1-2 at 10mA g of three products -1 Comparison of constant current charge and discharge at current density shows that the CuHCF-2 and CuHCF-3 materials with two-electron reactivity have high specific capacities, while the product of example 1 exhibits lower specific capacities due to the presence of more electrochemically inert metallic copper.
FIG. 4 shows the results of examples 1-3 at 100mA g of three products -1 According to a comparison graph of the cycle performance under the current density, the CuHCF-2 material has very good cycle stability, has the highest reversible specific capacity after multi-cycle, and shows the excellent characteristics of the material.
FIG. 5 is a graph of the rate capability of the three products of examples 1-3, and it can be seen that the product of example 1 has excellent rate capability, even at 1000mA g -1 The reversible specific capacity is higher.

Claims (10)

1. A preparation method and application of a ternary metal Prussian blue anode material are disclosed, firstly, an active transition metal Mn source, an inert transition metal M source and a chelating agent are respectively weighed according to a metering ratio, stirred and dissolved in water to form a mixed solution; and slowly dripping a sodium ferrocyanide solution with a certain concentration into the mixed solution, uniformly mixing, and aging for a certain time. Taking the lower layer precipitate, repeatedly washing and drying for many times to obtain the prussian blue product.
2. The preparation method and the application of the ternary metal Prussian blue positive electrode material as claimed in claim 1, wherein an electrochemically inert element is used to replace an active metal center. The Mn source is one of manganese sulfate, manganese chloride, manganese carbonate and manganese nitrate, the inert metal element is at least one of Cu and Zn, and the chelating agent is one of sodium citrate and sodium pyrophosphate.
3. The preparation method and the application of the ternary metal Prussian blue positive electrode material as claimed in claim 1, wherein the concentration of the Mn source is 0-0.1mol/L, the concentration of the inert metal is 0-0.1mol/L, and the concentration of the chelating agent is 0-0.3mol/L.
4. The preparation method and the application of the ternary metal Prussian blue positive electrode material as claimed in claim 1, wherein the proportion of the electrochemical inert elements in the total transition metal elements is 0-100%.
5. The preparation method and the application of the ternary metal Prussian blue cathode material as claimed in claim 1, wherein the stirring speed of the mixed solution is 300-500rmp, and the stirring time is 1-12h.
6. The preparation method and the application of the ternary metal Prussian blue positive electrode material as claimed in claim 1, wherein the concentration of the sodium ferrocyanide is 0.1-0.3mol/L, the stirring speed is 300-500rmp, the stirring time is 1-12h, the Mn source + the metal M source: the molar ratio of the chelating agent is 1:0 to 1:3.
7. the preparation method and the application of the ternary metal Prussian blue positive electrode material as claimed in claim 1, wherein the dropping speed is 10ml/h-50ml/h, and the aging time is 1-48 hours.
8. The preparation method and the application of the ternary metal Prussian blue positive electrode material as claimed in claim 1, wherein the washing mode is suction filtration or centrifugal washing.
9. The preparation method and the application of the ternary metal Prussian blue cathode material as claimed in claim 1, wherein the washing and drying process comprises the following steps: washing with deionized water for several times, washing with ethanol for several times, and drying at 80-120 deg.C under vacuum for 6-24 hr.
10. The preparation method and the application of the ternary metal Prussian blue positive electrode material as claimed in claim 1, wherein the active material as claimed in claim 1 is used for a positive electrode of a sodium-ion battery.
CN202210896986.XA 2022-07-28 2022-07-28 Preparation method and application of ternary metal Prussian blue positive electrode material Pending CN115172741A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210896986.XA CN115172741A (en) 2022-07-28 2022-07-28 Preparation method and application of ternary metal Prussian blue positive electrode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210896986.XA CN115172741A (en) 2022-07-28 2022-07-28 Preparation method and application of ternary metal Prussian blue positive electrode material

Publications (1)

Publication Number Publication Date
CN115172741A true CN115172741A (en) 2022-10-11

Family

ID=83476622

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210896986.XA Pending CN115172741A (en) 2022-07-28 2022-07-28 Preparation method and application of ternary metal Prussian blue positive electrode material

Country Status (1)

Country Link
CN (1) CN115172741A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115784260A (en) * 2022-12-28 2023-03-14 中国科学技术大学 Preparation method of sodium-ion battery cathode material manganese-based Prussian white and sodium-ion battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115784260A (en) * 2022-12-28 2023-03-14 中国科学技术大学 Preparation method of sodium-ion battery cathode material manganese-based Prussian white and sodium-ion battery

Similar Documents

Publication Publication Date Title
CN106920964B (en) Prussian blue type sodium ion battery positive electrode material and preparation method thereof
CN110002465B (en) Prussian white analogue positive electrode material, and preparation method and application thereof
CN102214819B (en) Method for manufacturing cobalt nickel lithium manganate oxide as gradient anode active material of lithium ion battery
CN109244390B (en) Phosphorus-doped lithium-rich manganese-based positive electrode material for lithium ion battery and preparation method thereof
CN109755540B (en) Lithium-sulfur battery positive electrode material and preparation method thereof
CN108963228A (en) A kind of method preparing ternary cathode material of lithium ion battery on metal-organic framework materials ZIF-8 and product
CN106935828A (en) A kind of modified height ratio capacity positive electrode and preparation method thereof
CN112599765A (en) Sodium/potassium-doped high-performance lithium-manganese-nickel-based positive electrode material and preparation method thereof
CN108963267A (en) The preparation method of three-dimensional porous carbon coating zinc oxide collector for lithium an- ode
CN107946564B (en) Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof
CN109950523A (en) Lithium ion battery negative material transition metal oxide/carbon preparation method
CN114530590A (en) High-entropy oxide negative electrode energy storage material containing bismuth, tin and antimony and preparation method and application thereof
CN110931755B (en) High-specific-capacity lithium ion battery material, preparation method and lithium ion battery
CN114590838B (en) Amorphous metal sulfide coated modified binary manganese-based sodium electro-precursor and preparation method thereof
CN110790248B (en) Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof
CN106374102B (en) A kind of preparation method of pyrophosphoric acid cobalt sodium and its application in sodium-ion battery
CN111717934A (en) Metal iron ion doped MoS2Preparation method of sodium ion battery negative electrode material
CN111592045A (en) Potassium manganate potassium ion battery anode material
CN108110250A (en) Zinc manganate/lithium iron oxide ion battery cathode material and preparation method thereof
CN114671468A (en) Preparation method and application of polyanion and Prussian blue composite positive electrode material
CN108511750B (en) Multi-metal sulfide catalyst for lithium air battery and preparation method thereof
CN108598463B (en) Preparation method of nano flaky lithium-rich manganese-based positive electrode material
CN115172741A (en) Preparation method and application of ternary metal Prussian blue positive electrode material
CN106129400A (en) A kind of lanthanum part replaces spherical lithium-rich manganese-based anode material of manganese and preparation method thereof
CN110197902B (en) Porous structure open walnut shell-shaped sodium ion battery positive electrode material and preparation method thereof

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