CN110235292B - Prussian blue cathode material with high sodium content, preparation method and application thereof, and sodium-ion battery - Google Patents

Prussian blue cathode material with high sodium content, preparation method and application thereof, and sodium-ion battery Download PDF

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CN110235292B
CN110235292B CN201880004524.4A CN201880004524A CN110235292B CN 110235292 B CN110235292 B CN 110235292B CN 201880004524 A CN201880004524 A CN 201880004524A CN 110235292 B CN110235292 B CN 110235292B
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sodium
prussian blue
mixed solution
vessel
electrode material
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CN110235292A (en
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王晚林
李用成
李东祥
宫毅涛
李亚书
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Liaoning Xingkong Sodium Battery Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/08—Simple or complex cyanides of metals
    • C01C3/12—Simple or complex iron cyanides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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 belongs to the technical field of new energy storage materials, and relates to a Prussian blue positive electrode material with high sodium content, a preparation method and application thereof, and a sodium-ion battery. The molecular formula of the Prussian blue cathode material with high sodium content is Na x M a N b Fe(CN) 6 Wherein M and N are the same or different transition metals, each independently selected from Fe, Co, Mn, Ni, Cu, Zn, Cr, V, Zr or Ti, 1.8<x<2，0<a<1，0<b<1, a + b is 1. The anode material is in a micron-sized cubic shape, the electrochemical performance is excellent, the preparation method enables the material to be slowly crystallized, the sodium content is high, the method is simple and easy to implement, the production efficiency and the yield are high, the price of the used raw materials is low, and industrial expanded production is easy to realize.

Description

Prussian blue cathode material with high sodium content, preparation method and application thereof, and sodium-ion battery
Technical Field
The invention belongs to the technical field of new energy storage materials, and particularly relates to a Prussian blue positive electrode material with high sodium content, a preparation method and application thereof, and a sodium ion battery.
Background
Due to the fact that greenhouse effect and environmental problems are increased continuously in recent years, development and utilization of clean energy become effective means for improving the environment, and wind energy, solar energy, tidal energy and the like can be stored and utilized through a battery energy storage device. Over the past two decades, lithium ion batteries have occupied a major market. However, the global lithium resource is limited and the price is increasing, and the development and utilization of sodium-ion batteries with abundant resources and low price become the next target and task, and due to the similar chemical properties of sodium and lithium, the sodium-ion batteries are expected to become the most potential battery energy storage devices in the future.
At present, the research on sodium ion battery materials is mainly divided into the research on positive electrodes, negative electrodes and electrolytes. Among them, the negative electrode material having relatively stable performance is mainly made of hard carbon, and has been industrialized by many japan companies. The component types of the sodium ion battery electrolyte are very similar to those of the lithium ion electrolyte, and the sodium ion battery electrolyte is mainly an ester organic electrolyte containing sodium salt. However, the radius of sodium ions is large, and the instability of the anode material in the charging and discharging process becomes a key factor for restricting the development of the sodium ion battery. Among the cathode materials of the sodium ion batteries, compared with other layered oxides, polyanion-type materials and other types of materials, the Prussian blue cathode material has a more stable frame structure, a wider sodium ion deintercalation channel and more stable electrochemical performance, thereby attracting the attention of a large number of researchers.
The Prussian blue type sodium ion battery positive electrode material can be mainly synthesized by a thermal decomposition method, a hydrothermal method and a coprecipitation method. The thermal decomposition method and the hydrothermal method have low production efficiency and yield, and the decomposition of ferrocyanide is easily caused in the synthesis process to generate toxic gas. The coprecipitation method can be regarded as a safe and environment-friendly method capable of preparing such materials on a large scale, and the method for preparing the prussian blue cathode material by the coprecipitation method reported in the current patent literature mainly comprises the following steps: a method for preparing Prussian blue anode material and a sodium ion battery (CN 107364875A), a method for preparing low-defect nano Prussian blue and application thereof (CN 106745068A). The above synthesis method simply mixes the transition metal salt and the sodium ferrocyanide solution, the reaction speed is difficult to control, so that the crystallinity of the material is poor, the sodium content is not high, the solid-liquid separation in the production process is difficult due to the small-particle nano Prussian blue material, the production efficiency is low, and meanwhile, the pole piece coating process is difficult due to the size of the nano particles, thereby affecting the electrochemical performance.
The sodium content in the Prussian blue anode material of the sodium-ion battery plays an important role in the electrochemical performance of the Prussian blue anode material, and the high sodium content can obviously improve the capacity and the structural stability of the Prussian blue anode material. The key of the sodium content in the prussian blue material lies in the concentration of sodium ions in a solution during material synthesis and the reaction speed of transition metal ions and ferrocyanide, and the proper sodium concentration and slow reaction speed become necessary conditions for preparing the prussian blue cathode material with high sodium content. In addition, the micron-sized material can realize fast solid-liquid separation and high production efficiency in the production process. Compared with the nano small particles, the material with the micron-sized size has higher tap density and the battery pole piece is relatively simple to manufacture. Therefore, how to realize large-scale preparation of the prussian blue-based cathode material with high sodium content micron size becomes one direction of future development.
Disclosure of Invention
The invention aims to provide a Prussian blue cathode material with high sodium content and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a high-sodium prussian blue positive electrode material having a molecular formula of Na x M a N b Fe(CN) 6 Wherein M and N are the same or different transition metals, each independently selected from Fe, Co, Mn, Ni, Cu, Zn, Cr, V, Zr or Ti, preferably Fe, Co or Mn, 1.8<x<2，0<a<1，0<b<1，a+b=1。
Further, the Prussian blue positive electrode material with the high sodium content is cubic, and the particle size is 1-30 micrometers. In the present invention, the particle size refers to the size of the diagonal line of the cube of the high-sodium prussian blue positive electrode material.
The second aspect of the invention provides a preparation method of a prussian blue cathode material with high sodium content, which comprises the following steps:
(1) under a protective atmosphere and a certain temperature, dissolving a transition metal salt, an antioxidant, a complexing agent, a pH regulator and a sodium salt in water to obtain a first mixed solution containing the transition metal salt;
(2) dissolving sodium ferrocyanide, an antioxidant, a pH regulator and a sodium salt in water under a protective atmosphere at a certain temperature to obtain a second mixed solution containing sodium ferrocyanide;
(3) and respectively dripping the first mixed solution and the second mixed solution into a container with a protective atmosphere and a certain temperature, stirring, standing, washing, filtering or centrifuging, spraying and vacuum drying to obtain the Prussian blue cathode material with high sodium content.
Further, the pH values of the first mixed solution and the second mixed solution are both 5.5-7.5.
Further, in the step (1), the transition metal salt is selected from at least one of chloride, sulfate, carbonate, nitrate, phosphate, and acetate of a transition metal selected from at least one of Fe, Co, Mn, Ni, Cu, Zn, Cr, V, Zr, and Ti.
Further, the concentration of the transition metal salt in the first mixed solution is 0.01 to 10mol/L, preferably 0.01 to 5mol/L, and more preferably 0.01 to 1 mol/L.
Further, in the step (1), the complexing agent is at least one selected from citric acid, maleic acid, lycic acid, ethylenediaminetetraacetic acid and ammonia water.
Further, the amount of the complexing agent is 1-20 times, preferably 1-5 times, of the molar amount of the transition metal salt in the step (1).
Further, in the step (2), the concentration of the sodium ferrocyanide in the second mixed solution is 0.01 to 10mol/L, preferably 0.01 to 5mol/L, and more preferably 0.01 to 1 mol/L.
Further, in the steps (1) and (2), the antioxidant is selected from at least one of ascorbic acid, isoascorbic acid, hydrazine hydrate, ferrous sulfate, sodium sulfite, and sodium borohydride.
Further, the concentration of the antioxidant in the first mixed solution and the second mixed solution is 0.01-5 mol/L, preferably 0.01-5 mol/L, and more preferably 0.01-1 mol/L.
Further, in the steps (1) and (2), the pH adjusters are each independently selected from at least one of sulfuric acid, hydrochloric acid, nitric acid, citric acid, ascorbic acid, ammonia water, sodium hydroxide, sodium carbonate, and sodium bicarbonate.
Further, in the steps (1) and (2), the sodium salts are each independently selected from at least one of sodium chloride, sodium sulfate, sodium nitrate, sodium acetate, trisodium citrate, disodium ethylenediaminetetraacetate, and tetrasodium ethylenediaminetetraacetate.
Further, the content of sodium salt in the first mixed solution and the second mixed solution is 0.01-10 mol/L, preferably 0.01-5 mol/L, and more preferably 0.01-1.5 mol/L.
According to the present invention, when one substance can serve as a plurality of the above-mentioned functional components at the same time, the amounts of the respective functional components are respectively taken into account.
Further, in the step (3), the dropping speed of the first mixed solution and the dropping speed of the second mixed solution are both 1-500 ml/min, and preferably 1-10 ml/min; the dropwise addition can be achieved by means conventional in the art, for example a peristaltic pump.
Further, in the step (3), the stirring speed is 100-1200 rpm, preferably 800-1200 rpm, and the stirring time is 6-72 hours.
Further, in the step (3), the standing time is 1-48 hours.
Further, in the step (3), the temperature of spraying and vacuum drying is between 60 and 300 ℃.
Further, in all steps, the protective atmosphere is selected from at least one of argon, nitrogen, and hydrogen.
Further, in all the steps, the certain temperature is between 0 and 80 ℃.
The third aspect of the invention provides a prussian blue positive electrode material with high sodium content, which is prepared by the preparation method.
The fourth aspect of the invention provides an application of the prussian blue cathode material with high sodium content.
The fifth aspect of the invention provides a sodium ion battery, which comprises a negative electrode material, a glass fiber diaphragm, an organic electrolyte and a positive electrode material, and is characterized in that the negative electrode material is metal sodium or a hard carbon material, and the positive electrode material is the Prussian blue positive electrode material with high sodium content.
Compared with the Prussian blue sodium ion battery anode material synthesized by the existing reported coprecipitation technology, the Prussian blue sodium ion battery anode material has the following excellent effects:
1. the Prussian blue cathode material has high sodium content, stable material structure and excellent electrochemical performance, and is mainly benefited from controlling the slow crystallization of the material. The addition of the complexing agent enables the transition metal ions to slowly react with ferrocyanide, and in order to avoid the phenomenon that the reaction speed is too high due to the direct mixing of the transition metal salt solution and the sodium ferrocyanide solution, the two solutions are slowly mixed in the third container, so that the reaction concentration can be effectively reduced, and the reaction speed is slowed down. In addition, the pH regulation can increase the complexing ability of the complexing agent and inhibit the hydrolysis effect of the transition metal ions, and the addition of the sodium salt enables the solution to have enough sodium source, so that the sodium content in the Prussian blue material is increased. The purpose of adding the antioxidant and using a protective atmosphere is to keep the transition metal ions in a reduced valence state all the time, thus ensuring a higher sodium content in the final product.
2. The preparation method of the Prussian blue anode material with high sodium content provided by the invention is simple and easy to operate, the material is in a micron-sized cubic shape, and the production efficiency is high. By regulating and controlling the concentration ratio, temperature, pH, rotation speed and other parameters of the reactants, the production yield and yield of the material are high, and industrial scale-up production is easy to realize.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings.
Fig. 1 is an X-ray diffraction pattern of the prussian blue positive electrode material with a high sodium content prepared in example 6 of the present invention.
Fig. 2 is a scanning electron microscope image of the prussian blue cathode material with high sodium content prepared in example 6 of the present invention.
Fig. 3 is a 0.5C first charge-discharge curve diagram of the prussian blue cathode material with high sodium content prepared in example 6 of the present invention.
Fig. 4 is a 0.5C charge-discharge cycle performance diagram of the prussian blue cathode material with high sodium content prepared in example 6 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Example 1
Preparing a Prussian blue positive electrode material:
(1) after introducing nitrogen into the vessel a at 25 ℃ and adding 100ml of deionized water, 0.1g of ascorbic acid, 6mmol of ferrous sulfate heptahydrate, 12mmol of citric acid, and 6mmol of sodium sulfate were dissolved in the vessel a in this order, and the pH =6.5 of the solution in the vessel a was adjusted by adding ammonia. Vessel B was purged with nitrogen at 25 ℃ and 100ml of deionized water was added, followed by dissolving 0.1g of ascorbic acid, 4mmol of sodium ferrocyanide decahydrate, and 6mmol of sodium sulfate in that order in vessel B, the pH of the solution in vessel B = 6.5.
(2) The nitrogen gas was introduced into the vessel C at 25 ℃ and then the solutions in the vessels A and B were simultaneously added dropwise to the vessel C at a rate of 2 ml/min by means of peristaltic pumps, respectively, with stirring at 1000 rpm in the vessel C, and stirring was continued for 12 hours after the solutions in the vessels A and B were all added to the vessel C.
(3) The solution was then allowed to stand for 24 hours, then the solution supernatant was aspirated off, and the remaining slurry was washed 3 times with centrifugal water, then spray dried at 250 ℃ and vacuum dried at 180 ℃ for 12 hours. Obtaining the molecular formula of Na 1.82 FeFe(CN) 6 The obtained Prussian blue anode material is cubic, the particle size is 2.5 microns, and the yield is 90%.
Preparing a sodium ion battery:
and preparing the obtained Prussian blue cathode material into an electrode slice, and assembling the electrode slice with a glass fiber diaphragm, metal sodium and an organic electrolyte to obtain the sodium-ion battery.
Example 2
Preparing a Prussian blue positive electrode material:
(1) after introducing nitrogen into the vessel a at 25 ℃ and adding 100ml of deionized water, 0.1g of ascorbic acid, 6mmol of ferrous sulfate heptahydrate, 12mmol of citric acid, and 8mmol of sodium sulfate were dissolved in the vessel a in this order, and the pH =6.5 of the solution in the vessel a was adjusted by adding ammonia. Vessel B was purged with nitrogen at 25 ℃, 100ml of deionized water was added, and then 0.1g of ascorbic acid, 4mmol of sodium ferrocyanide decahydrate, and 8mmol of sodium sulfate were dissolved in this order in vessel B, and the pH of the solution in vessel B = 6.5.
(2) The nitrogen is introduced into the vessel C at 25 ℃ and the solutions in the vessels A and B are then added simultaneously dropwise to the vessel C by means of peristaltic pumps at a rate of 2 ml/min, respectively, with stirring at 1000 revolutions per hour, and stirring is continued for 12 hours after the solutions in the vessels A and B have been added to the vessel C in their entirety.
(3) The solution was then allowed to stand for 24 hours, then the solution supernatant was aspirated off, and the remaining slurry was washed 3 times with centrifugal water, then spray dried at 250 ℃ and vacuum dried at 180 ℃ for 12 hours. Obtaining the compound with the molecular formula of Na 1.84 FeFe(CN) 6 The obtained Prussian blue anode material is cubic, the particle size is 2 microns, and the yield is 92%.
Preparing a sodium ion battery:
and preparing the obtained Prussian blue cathode material into an electrode slice, and assembling the electrode slice with a glass fiber diaphragm, metal sodium and an organic electrolyte to obtain the sodium-ion battery.
Example 3
Preparing a Prussian blue positive electrode material:
(1) after introducing nitrogen into the container a at 25 ℃, 100ml of deionized water was added, and then 0.1g of ascorbic acid, 4mmol of ferrous sulfate heptahydrate, 2mmol of manganese sulfate monohydrate, 12mmol of citric acid, and 10mmol of sodium sulfate were dissolved in the container a in this order, and the pH =6.5 of the solution in the container a was adjusted by adding ammonia water. Vessel B was purged with nitrogen at 25 ℃, 100ml of deionized water was added, and then 0.1g of ascorbic acid, 4mmol of sodium ferrocyanide decahydrate, and 10mmol of sodium sulfate were dissolved in this order in vessel B, and the pH of the solution in vessel B = 6.5.
(3) The nitrogen gas was introduced into the vessel C at 25 ℃ and then the solutions in the vessels A and B were simultaneously added dropwise to the vessel C at a rate of 2 ml/min by means of peristaltic pumps, respectively, with stirring at 1000 rpm in the vessel C, and stirring was continued for 12 hours after the solutions in the vessels A and B were all added to the vessel C.
(3) The solution was then allowed to stand for 24 hours, then the solution supernatant was aspirated off, and the remaining slurry was washed 3 times with centrifugal water, then spray dried at 250 ℃ and vacuum dried at 180 ℃ for 12 hours. Obtaining the molecular formula of Na 1.86 Fe 0.67 Mn 0.33 Fe(CN) 6 The obtained Prussian blue anode material is cubic, the particle size is 3 micrometers, and the yield is 92%.
Preparing a sodium ion battery:
and manufacturing the obtained Prussian blue positive electrode material into an electrode slice, and assembling the electrode slice with a glass fiber diaphragm, metal sodium and an organic electrolyte to obtain the sodium-ion battery.
Example 4
Preparing a Prussian blue positive electrode material:
(1) after introducing nitrogen into the vessel a at 25 ℃ and adding 100ml of deionized water, 0.1g of ascorbic acid, 4mmol of ferrous sulfate heptahydrate, 2mmol of cobalt sulfate heptahydrate, 12mmol of citric acid, and 12mmol of sodium sulfate were dissolved in the vessel a in this order, and the pH =6.5 of the solution in the vessel a was adjusted by adding ammonia water. Vessel B was purged with nitrogen at 25 ℃ and 100ml of deionized water was added, followed by dissolving 0.1g of ascorbic acid, 4mmol of sodium ferrocyanide decahydrate, and 12mmol of sodium sulfate in that order in vessel B, the pH of the solution in vessel B = 6.5.
(2) The nitrogen gas was introduced into the vessel C at 25 ℃ and then the solutions in the vessels A and B were simultaneously added dropwise to the vessel C at a rate of 2 ml/min by means of peristaltic pumps, respectively, with stirring at 1000 rpm in the vessel C, and stirring was continued for 12 hours after the solutions in the vessels A and B were all added to the vessel C.
(3) The solution was then allowed to stand for 24 hours, then the solution supernatant was aspirated off, and the remaining slurry was washed 3 times with centrifugal water, then spray dried at 250 ℃ and vacuum dried at 180 ℃ for 12 hours. Obtaining the molecular formula of Na 1.89 Fe 0.67 Co 0.33 Fe(CN) 6 The obtained Prussian blue anode material is cubic, the particle size is 3 micrometers, and the yield is 91%.
Preparing a sodium ion battery:
and manufacturing the obtained Prussian blue positive electrode material into an electrode slice, and assembling the electrode slice with a glass fiber diaphragm, metal sodium and an organic electrolyte to obtain the sodium-ion battery.
Example 5
Preparing a Prussian blue positive electrode material:
(1) after introducing nitrogen into the vessel a at 25 ℃ and adding 100ml of deionized water, 0.1g of ascorbic acid, 5mmol of ferrous sulfate heptahydrate, 1mmol of nickel sulfate hexahydrate, 12mmol of citric acid and 14mmol of sodium sulfate were dissolved in the vessel a in this order, and the pH =6.5 of the solution in the vessel a was adjusted by adding ammonia. Vessel B was purged with nitrogen at 25 ℃, 100ml of deionized water was added, and then 0.1g of ascorbic acid, 4mmol of sodium ferrocyanide decahydrate, and 14mmol of sodium sulfate were dissolved in this order in vessel B, and the pH of the solution in vessel B = 6.5.
(2) The nitrogen gas was introduced into the vessel C at 25 ℃ and then the solutions in the vessels A and B were simultaneously added dropwise to the vessel C at a rate of 2 ml/min by means of peristaltic pumps, respectively, with stirring at 1000 rpm in the vessel C, and stirring was continued for 12 hours after the solutions in the vessels A and B were all added to the vessel C.
(3) The solution was then allowed to stand for 24 hours, then the solution supernatant was aspirated off, and the remaining slurry was washed 3 times with centrifugal water, then spray dried at 250 ℃ and vacuum dried at 180 ℃ for 12 hours. Obtaining the molecular formula of Na 1.91 Fe 0.83 Ni 0.17 Fe(CN) 6 The obtained Prussian blue anode material is cubic, the particle size is 3.5 microns, and the yield is 90%.
Preparing a sodium ion battery:
and preparing the obtained Prussian blue cathode material into an electrode slice, and assembling the electrode slice with a glass fiber diaphragm, metal sodium and an organic electrolyte to obtain the sodium-ion battery.
Example 6
Preparing a Prussian blue positive electrode material:
(1) vessel a was purged with nitrogen at 25 ℃ and 100ml of deionized water was added, followed by dissolving 0.1g of ascorbic acid, 6mmol of ferrous sulfate heptahydrate, and 12mmol of trisodium citrate dihydrate in this order in vessel a, the pH of the solution in vessel a = 6.8. Vessel B was purged with nitrogen at 25 ℃ and 100ml of deionized water was added, followed by dissolving 0.1g of ascorbic acid, 4mmol of sodium ferrocyanide decahydrate, and 12mmol of trisodium citrate dihydrate in order in vessel B, the pH of the solution in vessel B = 6.8.
(2) The nitrogen is introduced into the vessel C at 25 ℃ and the solutions in the vessels A and B are then added simultaneously dropwise to the vessel C by means of peristaltic pumps at a rate of 2 ml/min, respectively, with stirring at 1000 revolutions per hour, and stirring is continued for 12 hours after the solutions in the vessels A and B have been added to the vessel C in their entirety.
(3) Then will beThe solution was left to stand for 24 hours, then the supernatant of the solution was extracted, and the remaining slurry was washed with centrifugal water 3 times, followed by spray drying at 250 ℃ and further vacuum drying at 180 ℃ for 12 hours. Obtaining the molecular formula of Na 1.92 FeFe(CN) 6 The obtained Prussian blue anode material is cubic, the particle size is 2 micrometers, and the yield is 90%.
Preparing a sodium ion battery:
and manufacturing the obtained Prussian blue positive electrode material into an electrode slice, and assembling the electrode slice with a glass fiber diaphragm, metal sodium and an organic electrolyte to obtain the sodium-ion battery.
Example 7
Preparing a Prussian blue positive electrode material:
(1) vessel a was purged with nitrogen at 25 ℃, 100ml of deionized water was added, and then 0.2g of ascorbic acid, 6mmol of ferrous sulfate heptahydrate, 6mmol of manganese sulfate monohydrate, and 24mmol of trisodium citrate dihydrate were dissolved in this order in vessel a, and the pH of the solution in vessel a = 6.9. Vessel B was purged with nitrogen at 25 ℃ and 100ml deionized water was added, followed by dissolving 0.2g ascorbic acid, 8mmol sodium ferrocyanide decahydrate, 24mmol trisodium citrate dihydrate in order in vessel B, the pH of the solution in vessel B = 6.9.
(2) The nitrogen is introduced into the vessel C at 25 ℃ and the solutions in the vessels A and B are then added simultaneously dropwise to the vessel C by means of peristaltic pumps at a rate of 2 ml/min, respectively, with stirring at 1000 revolutions per hour, and stirring is continued for 12 hours after the solutions in the vessels A and B have been added to the vessel C in their entirety.
(3) The solution was then allowed to stand for 24 hours, then the solution supernatant was aspirated off, and the remaining slurry was washed 3 times with centrifugal water, then spray dried at 250 ℃ and vacuum dried at 180 ℃ for 12 hours. Obtaining the compound with the molecular formula of Na 1.91 Fe 0.5 Mn 0.5 Fe(CN) 6 The obtained Prussian blue anode material is cubic, the particle size is 3.5 microns, and the yield is 88%.
Preparing a sodium ion battery:
and preparing the obtained Prussian blue cathode material into an electrode slice, and assembling the electrode slice with a glass fiber diaphragm, metal sodium and an organic electrolyte to obtain the sodium-ion battery.
Example 8
Preparing a Prussian blue positive electrode material:
(1) vessel a was purged with nitrogen at 35 ℃ and 100ml of deionized water was added, followed by dissolving 5g of ascorbic acid, 9mmol of ferrous sulfate heptahydrate, 9mmol of cobalt sulfate heptahydrate, and 27mmol of EDTA-4Na in this order in vessel a, the pH of the solution in vessel a = 7. Vessel B was purged with nitrogen at 35 ℃ and 100ml of deionized water was added, followed by dissolving 5g of ascorbic acid, 12mmol of sodium ferrocyanide decahydrate, and 27mmol of EDTA-4Na in this order in vessel B, the pH of the solution in vessel B = 7.
(2) The nitrogen gas was introduced into the vessel C at 35 ℃ and then the solutions in the vessels A and B were simultaneously added dropwise to the vessel C at a rate of 2 ml/min by means of peristaltic pumps, respectively, with stirring at 1000 rpm in the vessel C, and stirring was continued for 12 hours after the solutions in the vessels A and B were all added to the vessel C.
(3) The solution was then allowed to stand for 24 hours, then the solution supernatant was aspirated off, and the remaining slurry was washed 3 times with centrifugal water, then spray dried at 250 ℃ and vacuum dried at 180 ℃ for 12 hours. Obtaining the molecular formula of Na 1.93 Fe 0.5 Co 0.5 Fe(CN) 6 The obtained Prussian blue anode material is cubic, the particle size is 3 micrometers, and the yield is 89%.
Preparing a sodium ion battery:
and preparing the obtained Prussian blue cathode material into an electrode slice, and assembling the electrode slice with a glass fiber diaphragm, metal sodium and an organic electrolyte to obtain the sodium-ion battery.
Example 9
Preparing a Prussian blue positive electrode material:
(1) vessel a was purged with nitrogen at 35 ℃ and 100ml of deionized water was added, followed by dissolving 0.3g of ascorbic acid, 27mmol of cobalt sulfate heptahydrate, 9mmol of nickel sulfate hexahydrate, and 72mmol of trisodium citrate dihydrate in this order in vessel a, the pH of the solution in vessel a = 7. Vessel B was purged with nitrogen at 35 ℃ and 100ml of deionized water was added, followed by dissolving 0.3g of ascorbic acid, 24mmol of sodium ferrocyanide decahydrate, and 72mmol of trisodium citrate dihydrate in order in vessel B, the pH of the solution in vessel B = 7.
(2) The nitrogen gas was introduced into the vessel C at 35 ℃ and then the solutions in the vessels A and B were simultaneously added dropwise to the vessel C at a rate of 2 ml/min by means of peristaltic pumps, respectively, with stirring at 1000 rpm in the vessel C, and stirring was continued for 12 hours after the solutions in the vessels A and B were all added to the vessel C.
(3) The solution was then allowed to stand for 24 hours, then the solution supernatant was aspirated off, and the remaining slurry was washed 3 times with centrifugal water, then spray dried at 250 ℃ and vacuum dried at 180 ℃ for 12 hours. Obtaining the compound with the molecular formula of Na 1.94 Co 0.75 Ni 0.25 Fe(CN) 6 The obtained Prussian blue anode material is cubic, the particle size is 4 micrometers, and the yield is 90%.
Preparing a sodium ion battery:
and manufacturing the obtained Prussian blue positive electrode material into an electrode slice, and assembling the electrode slice with a glass fiber diaphragm, metal sodium and an organic electrolyte to obtain the sodium-ion battery.
Example 10
Preparing a Prussian blue positive electrode material:
(1) vessel a was purged with nitrogen at 60 ℃ and 100ml of deionized water was added, followed by dissolving 0.5g of ascorbic acid, 45mmol of manganese sulfate monohydrate, and 90mmol of trisodium citrate dihydrate in this order in vessel a, the pH of the solution in vessel a = 7. Vessel B was purged with nitrogen at 60 ℃ and 100ml deionized water was added, followed by dissolving 0.5g ascorbic acid, 30mmol sodium ferrocyanide decahydrate, 90mmol trisodium citrate dihydrate in order in vessel B, the pH of the solution in vessel B = 7.
(2) The nitrogen is introduced into the vessel C at 60 ℃ and the solutions in the vessels A and B are then added simultaneously dropwise to the vessel C by means of peristaltic pumps at a rate of 2 ml/min, the stirring rate in the vessel C being 1000 revolutions per hour and stirring being continued for 12 hours after the solutions in the vessels A and B have been added to the vessel C.
(3) The solution was then allowed to stand for 24 hours, then the solution supernatant was aspirated off, and the remaining slurry was washed 3 times with centrifugal water, then spray dried at 250 ℃ and vacuum dried at 180 ℃ for 12 hours. Obtaining the compound with the molecular formula of Na 1.93 MnFe(CN) 6 The obtained Prussian blue anode material is cubic, the particle size is 5 micrometers, and the yield is 89%.
Preparing a sodium ion battery:
and preparing the obtained Prussian blue cathode material into an electrode slice, and assembling the electrode slice with a glass fiber diaphragm, metal sodium and an organic electrolyte to obtain the sodium-ion battery.
Test example
The sodium ion battery prepared in the above example was tested for charge and discharge at a current density of 10mA/g, and the data are shown in table 1:
TABLE 1
Figure DEST_PATH_IMAGE002
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (13)

1. The preparation method of the Prussian blue cathode material with high sodium content is characterized in that the molecular formula of the Prussian blue cathode material with high sodium content is Na x M a N b Fe(CN) 6 Wherein M is Fe, N is selected from Co or Mn, 1.8<x≤1.94，0<a<1，0<b<1，a+b=1；
The Prussian blue positive electrode material with high sodium content is cubic, and the particle size is 1-30 micrometers;
the preparation method comprises the following steps:
(1) under a protective atmosphere and a certain temperature, dissolving a transition metal salt, an antioxidant, a complexing agent, a pH regulator and a sodium salt in water to obtain a first mixed solution containing the transition metal salt;
(2) dissolving sodium ferrocyanide, an antioxidant, a pH regulator and a sodium salt in water under a protective atmosphere at a certain temperature to obtain a second mixed solution containing sodium ferrocyanide;
(3) respectively dripping the first mixed solution and the second mixed solution into a container with a protective atmosphere and a certain temperature, stirring and standing, and then washing, filtering, spraying and vacuum drying to obtain the Prussian blue cathode material with high sodium content; or respectively dripping the first mixed solution and the second mixed solution into a container with a protective atmosphere and a certain temperature, stirring and standing, and then washing, centrifuging, spraying and vacuum drying to obtain the prussian blue positive electrode material with high sodium content.
2. The method according to claim 1, wherein the first mixed solution and the second mixed solution each have a pH of 5.5 to 7.5.
3. The method according to claim 1, wherein in step (1), the transition metal salt is at least one selected from chloride, sulfate, carbonate, nitrate, phosphate and acetate salts of transition metals, wherein M is Fe and N is selected from Co or Mn; the concentration of the transition metal salt in the first mixed solution is 0.01-10 mol/L.
4. The preparation method according to claim 1, wherein in the step (1), the complexing agent is at least one selected from the group consisting of citric acid, maleic acid, lycic acid, ethylenediaminetetraacetic acid, trisodium citrate and aqua ammonia, and the amount of the complexing agent is 1 to 20 times the molar amount of the transition metal salt in the step (1).
5. The method according to claim 1, wherein in the step (2), the concentration of sodium ferrocyanide in the second mixed solution is 0.01-10 mol/L.
6. The preparation method according to claim 1, wherein in steps (1) and (2), the antioxidant is independently selected from at least one of ascorbic acid, isoascorbic acid, hydrazine hydrate, ferrous sulfate, sodium sulfite and sodium borohydride, and the concentration of the antioxidant in the first mixed solution and the second mixed solution is 0.01 to 5 mol/L.
7. The method according to claim 1, wherein in the steps (1) and (2), the pH adjusters are each independently selected from at least one of sulfuric acid, hydrochloric acid, nitric acid, citric acid, ascorbic acid, aqueous ammonia, sodium hydroxide, sodium carbonate, and sodium bicarbonate.
8. The production method according to claim 1, wherein in the steps (1) and (2), the sodium salts are each independently selected from at least one of sodium chloride, sodium sulfate, sodium nitrate, sodium acetate, trisodium citrate, disodium ethylenediaminetetraacetate, and tetrasodium ethylenediaminetetraacetate; and in the first mixed solution and the second mixed solution, the content of sodium salt is 0.01-10 mol/L.
9. The production method according to claim 1, wherein, in the step (3),
the dropping speed of the first mixed solution and the second mixed solution is 1-500 ml/min;
the stirring speed is 100-1200 rpm, and the stirring time is 6-72 hours;
the standing time is 1-48 hours;
the temperature of spraying and vacuum drying is 60-300 ℃.
10. The production method according to claim 1, wherein, in all the steps,
the protective atmosphere is selected from at least one of argon, nitrogen and hydrogen;
the certain temperature is 0-80 ℃.
11. A prussian blue positive electrode material with a high sodium content, which is obtained by the production method according to any one of claims 1 to 10.
12. Use of the high-sodium prussian blue positive electrode material according to claim 11.
13. A sodium ion battery comprising a negative electrode material, a glass fiber separator, an organic electrolyte and a positive electrode material, wherein the negative electrode material is metallic sodium or a hard carbon material, and the positive electrode material is the high-sodium prussian blue positive electrode material according to claim 11.
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