CN111244448B - In-situ carbon-coated high-rate large-size Prussian blue type sodium ion positive electrode material and preparation method thereof - Google Patents

In-situ carbon-coated high-rate large-size Prussian blue type sodium ion positive electrode material and preparation method thereof Download PDF

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CN111244448B
CN111244448B CN202010074561.1A CN202010074561A CN111244448B CN 111244448 B CN111244448 B CN 111244448B CN 202010074561 A CN202010074561 A CN 202010074561A CN 111244448 B CN111244448 B CN 111244448B
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prussian blue
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sodium ion
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positive electrode
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CN111244448A (en
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程博
刘瑞
田光磊
刘相烈
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Ningbo Ronbay Lithium Battery Material Co Ltd
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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
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • 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
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    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0422—Cells or battery with cylindrical casing
    • H01M10/0427—Button cells
    • H—ELECTRICITY
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
    • 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
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Abstract

The invention discloses an in-situ carbon-coated high-magnification large-size Prussian blue sodium ion positive electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Dissolving a soluble transition metal cyano complex and a soluble sodium salt in water to prepare a solution A; placing the solution A in a reaction kettle, and preserving heat; (2) Dissolving soluble transition metal salt in water to prepare solution B, dropwise adding the solution B into the solution A under a stirring state, and preserving heat after dropwise adding to obtain a suspension; (3) Adding the suspension liquid obtained in the step (2) into a high-pressure hydrothermal kettle, adding a carbonizing agent precursor, preserving heat, and stirring to obtain a material; (4) And (4) taking out the material cooled in the step (3), washing and drying to obtain the in-situ carbon-coated high-magnification large-size Prussian blue sodium ion cathode material. The invention promotes the crystal growth of the Prussian blue anode material, and effectively solves the problems of poor conductivity, low rate performance and the like of the Prussian blue anode material.

Description

In-situ carbon-coated high-rate large-size Prussian blue type sodium ion positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of sodium ion positive electrode materials, in particular to an in-situ carbon-coated high-magnification large-size Prussian blue sodium ion positive electrode material and a preparation method thereof.
Background
Prussian blue has a chemical formula of KFe [ Fe (CN) 6 ]Originally a blue dye, compounds having a similar structure have been studied in recent years as positive electrode materials for sodium ion batteries, for example Na 2 Mn[Fe(CN) 6 ]Or Na 2 Fe[Fe(CN) 6 ]And is called Prussian blue type cathode material.
At present, most of sodium ion cathode materials researched mainly comprise three types of cathode materials, namely polyanion compounds, layered oxides and Prussian blue analogues, wherein the Prussian blue cathode material has high theoretical capacity and cycle stability due to the unique three-dimensional MOF structure, and is considered to be a sodium ion battery cathode material with great application potential.
Common cathode materials for sodium ion batteries which can be commercialized in a large scale mainly comprise Prussian blue cathode materials which are usually prepared by a hydrothermal precipitation method, and the prepared Prussian blue cathode materials have the following defects: (1) Transition metal elements in the Prussian blue analogue are easily dissolved in electrolyte in circulation, so that the circulation performance of the Prussian blue analogue is poor; (2) The Prussian blue material has the problem of poor electronic conductivity, so that the rate performance of the Prussian blue material is poor; (3) At present, most prussian blue materials have small particles (< 1 mu m) and are seriously agglomerated in practical application, so that the prussian blue materials are difficult to sieve for use.
For example, chinese patent CN110224130a discloses a conductive polymer-coated prussian blue sodium-ion battery positive electrode material and a preparation method thereof, the method comprises specific steps and an implementation mode, and the main design idea is to prepare a bulk phase material of a prussian blue analog with uniform morphology and excellent electrochemical performance as an inner core, mix the prussian blue analog material with a conductive polymer monomer and an inducer, and obtain the conductive polymer-coated prussian blue sodium-ion battery positive electrode material through in-situ polymerization. The method comprises the following specific steps:
(1) Dissolving soluble transition metal salt and a sustained-release agent in water to prepare a solution A;
(2) Dissolving a soluble transition metal cyano complex and a soluble sodium salt in water to prepare a solution B, placing the solution B in a reaction kettle, introducing protective gas, and keeping a certain temperature;
(3) Under the stirring state, dropwise adding the solution A into the solution B by using a peristaltic pump, and aging after dropwise adding;
(4) Centrifuging, washing and drying the precipitate obtained in the step 3 to obtain a Prussian blue analogue, namely M1HCM2;
(5) Adding a conductive polymer monomer and the M1HCM2 obtained in the step (4) into water, performing ultrasonic dispersion and stirring to obtain a turbid liquid C, and keeping the temperature;
(6) Dissolving an inducer in water to form a solution D;
(7) Adding the solution D into the turbid solution C under the stirring state, and continuing stirring for 6-10 h after the dropwise addition is finished;
(8) And (4) centrifuging, washing and drying the precipitate obtained in the step (7) to obtain the conductive polymer coated Prussian blue type sodium ion battery positive electrode material.
The Prussian blue type positive electrode material is prepared by taking soluble transition metal salt, soluble transition metal cyano complex and soluble sodium salt as raw materials, and then the Prussian blue type material is mixed with conductive high molecular monomer and inducer, so that the capacity is low, the specific capacity of the Prussian blue type sodium ion positive electrode material obtained by the specific examples in the patent is mostly only about 130mAh/g, the cycle performance is poor (about 300 cycles of 1C cycle), the particle size of the obtained positive electrode material is small (generally below 1 mu m), and the small particles have serious agglomeration phenomenon in practical application, so that the positive electrode material is difficult to sieve and use.
Disclosure of Invention
The invention aims to overcome the technical defects of the background technology and provide an in-situ carbon-coated high-magnification large-size Prussian blue sodium ion positive electrode material and a preparation method thereof. According to the invention, the Prussian blue positive electrode material is synthesized through hydrothermal precipitation, and then the carbonization agent precursor is added to generate the nano carbon particles on the surface of the Prussian blue positive electrode material through high-temperature high-pressure hydrothermal method, so that the crystal growth of the Prussian blue positive electrode material is promoted, and the problems of poor conductivity, low rate performance and the like of the Prussian blue positive electrode material are effectively improved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of an in-situ carbon-coated high-magnification large-size Prussian blue type sodium ion positive electrode material comprises the following steps:
(1) Dissolving a soluble transition metal cyano complex and a soluble sodium salt in water to prepare a solution A; placing the solution A in a reaction kettle, and preserving heat;
(2) Dissolving soluble transition metal salt in water to prepare solution B, dropwise adding the solution B into the solution A through a peristaltic pump under a stirring state, and preserving heat after dropwise adding to obtain a suspension;
(3) Adding the suspension obtained in the step (2) into a high-pressure hydrothermal kettle, adding a carbonizing agent precursor, preserving heat, and stirring to obtain a material;
(4) And (4) taking out the material cooled in the step (3), washing and drying to obtain the in-situ carbon-coated high-magnification large-size Prussian blue sodium ion cathode material.
Preferably, in the step (1), the soluble transition metal cyano complex is Na 4 Fe(CN) 6 、Na 4 Co(CN) 6 、Na 4 Cu(CN) 6 、Na 4 Zn(CN) 6 、Na 4 Mn(CN) 6 Any one or more of them.
Preferably, in the step (1), the soluble sodium salt is any one of sodium sulfate, sodium nitrate and sodium chloride.
Preferably, in the step (1), the soluble sodium salt and the soluble transition metal cyano complex are added in a molar ratio of 1: 1 to 10: 1.
More preferably, in the step (1), the soluble sodium salt and the soluble transition metal cyano complex are added in a molar ratio of 1: 1 to 3: 1.
Most preferably, in the step (1), the soluble sodium salt and the soluble transition metal cyano complex are added in a molar ratio of 1: 1 to 2: 1.
Preferably, in the step (1), the concentration of the soluble transition metal cyano complex in the solution a is 0 to 5mol/L.
More preferably, in the step (1), the concentration of the soluble transition metal cyano complex in the solution a is 0 to 3mol/L.
Most preferably, in the step (1), the concentration of the soluble transition metal cyano complex in the solution A is 0.5mol/L.
Preferably, in the step (1), the temperature for heat preservation is 0-100 ℃.
More preferably, in the step (1), the temperature for heat preservation is 60 to 100 ℃.
Preferably, in the step (2), the soluble transition metal salt is any one or more of sulfates, hydrochlorides and nitrates of Mn, fe, co, ni, cu, V and Cr.
Preferably, in the step (2), the concentration of the solution B is 0 to 5mol/L.
More preferably, in the step (2), the concentration of the solution B is 0 to 3mol/L.
Most preferably, in the step (2), the concentration of the solution B is 1.5mol/L.
Preferably, in the step (2), the rate at the time of the dropping is 0 to 500mL/min.
More preferably, in the step (2), the rate at the time of the dropping is 0 to 100mL/min.
More preferably, in the step (2), the rate at the time of the dropping is 10 to 50mL/min.
Preferably, in the step (2), the temperature of the heat preservation is 0-100 ℃.
More preferably, in the step (2), the temperature of the heat preservation is 60 to 100 ℃.
Most preferably, in the step (2), the temperature of the heat preservation is 70 ℃.
Preferably, in the step (2), the heat preservation time is 0-10 h.
More preferably, in the step (2), the time for the heat preservation is 6h.
Preferably, in the step (3), the carbonization agent precursor is any one or more of glucose, fructose, sucrose, maltose, agarose and soluble starch.
Preferably, in the step (3), the adding ratio of the carbonization agent precursor to the suspension is 0 to 1000% by mol ratio.
More preferably, in the step (3), the addition ratio of the carbonization agent precursor to the suspension is 20 to 100% by mol.
Preferably, in the step (3), the temperature for heat preservation is 140-220 ℃.
Preferably, in the step (3), the stirring time is 0 to 40 hours.
More preferably, in the step (3), the stirring time is 20 to 25 hours.
An in-situ carbon-coated high-magnification large-size Prussian blue type sodium ion positive electrode material is prepared by the preparation method.
In the above technical solution, the carbonization agent precursor is a substance that can undergo hydrothermal decomposition under a high-temperature and high-pressure hydrothermal environment to generate nano carbon particles.
In the above technical solution, the endpoint 0 in the value range does not include the value 0.
The basic principle of the invention is as follows:
(1) The Prussian blue type anode material of the sodium ion battery has poor conductivity and rate capability due to the crystal structure of the Prussian blue type anode material, and the conductivity of the Prussian blue type anode material coated by the nano carbon provided by the invention can be improved by effectively coating Prussian blue type anode material particles and the nano carbon, so that the rate capability of the Prussian blue type anode material is improved;
(2) The Prussian blue type anode material of the sodium ion battery is coated with the carbon material on the surface, although the carbon material is reported in other documents/patents, the carbonization agent precursor is subjected to hydrothermal decomposition under high-pressure hydrothermal environment, so that nano carbon particles are generated on the surface of the Prussian blue type anode material, the carbon coating is simultaneously carried out in the crystal optimization process of the Prussian blue type anode material, the Prussian blue type anode material coated with the nano carbon can be obtained, the anode material with large size and excellent crystal structure can be obtained, the nano particles are reduced in the anode material obtained by the method, the nano particles are easier to sieve and use in practical application, and the method is more beneficial to practical application.
Compared with the prior art, the invention has the beneficial effects that:
(1) The Prussian blue type positive electrode material of the conventional sodium ion battery has poor conductivity, and the carbon particles are coated on the surface of the Prussian blue type positive electrode material, so that the conductive transmission between the positive electrode materials is facilitated, the conductive performance of the positive electrode material is improved, and the rate capability of the positive electrode material is improved;
(2) The Prussian blue cathode material prepared by a common hydrothermal precipitation method has small particle size, the common particle size is below 1 mu m, and particles with the size are easy to agglomerate, so that the Prussian blue cathode material is difficult to sieve for use in practical use; the invention is beneficial to the growth of the particle size of the Prussian blue anode material through high-temperature high-pressure hydrothermal treatment; the invention combines the two processes, and in the process of high-temperature high-pressure hydrothermal growth of the particles of the anode material, the nano carbon particles are generated in situ on the surface of the particles of the anode material through the hydrothermal decomposition of the precursor of the carbonizing agent, thereby realizing in-situ coating of the nano carbon particles;
(3) According to the invention, by purposefully controlling the crystal size of the Prussian blue type anode material and adopting a technical means of in-situ coating of the nano carbon particles, the balance among the crystal particle size, the cycle performance and the conductivity is obtained, and the Prussian blue type anode material with good comprehensive performance is finally prepared.
Drawings
Fig. 1 is an SEM image of the prussian blue-based positive electrode material prepared in example 1;
fig. 2 is an XRD pattern of the prussian blue-based positive electrode material prepared in example 1;
fig. 3 shows the constant current charging and discharging test condition of the CR2032 button cell assembled by the prussian blue type positive electrode material prepared in example 1 at a current density of 0.2C;
fig. 4 is an SEM image of the prussian blue-based positive electrode material prepared in comparative example 1.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings. It is to be understood that these examples are for further illustration of the invention and are not intended to limit the scope of the invention. In addition, it should be understood that the invention is not limited to the above-described embodiments, but is capable of various modifications and changes within the scope of the invention.
Example 1
Firstly, 2mol of Na is added into a hydrothermal kettle according to the adding proportion of 1: 1 4 Fe(CN) 6 And 2mol of Na 2 SO 4 And 4L of deionized water is added to prepare Na 4 Fe(CN) 6 The concentration of the solution A is 0.5mol/L, the hydrothermal kettle is heated to 70 ℃ and stirred until the metal cyano-complex and the sodium salt are completely dissolved; taking another 1.5mol of MnSO 4 Dissolving the mixture in deionized water to prepare a solution B with the concentration of 1.5mol/L, after the complex and the sodium salt in the solution A are completely dissolved, dropwise adding the solution into a hydrothermal kettle at the dropwise adding speed of 1Oml/min through a peristaltic pump, and preserving heat and aging at 70 ℃ for 6 hours after the dropwise adding is finished; after the temperature is preserved for Chen Huajie, the mixed liquid is taken out and transferred to a high-pressure hydrothermal kettle, and the ratio of Prussian blue: and C = 100: 20, adding a corresponding amount of glucose, heating the high-pressure hydrothermal kettle to 200 ℃, keeping the temperature for 24h, continuously stirring, cooling to room temperature after the heat preservation is finished, taking out the materials, washing and drying to obtain the C-coated Prussian blue type cathode material.
The scanning electron microscope photo is shown in fig. 1, and the scanning electron microscope can see that the nano carbon particles (less than 1 μm) are scattered on the surface of the prussian blue positive electrode material particles in a platelet shape, wherein the particles of the prussian blue positive electrode material are larger (mostly greater than 2 μm, namely D50 is greater than 2 μm); in addition, as can be seen from the XRD spectrum shown in fig. 2, the obtained nano carbon-coated prussian blue type positive electrode material belongs to the standard prussian blue phase, and the diffraction peak thereof indicates that the crystal structure of the material is well crystallized.
Mixing the prepared nano carbon-coated Prussian blue positive electrode material powder with conductive carbon black and PVDF according to the mass ratio of 86: 7, adding a proper amount of NMP solvent to form slurry, then uniformly coating the slurry on a current collector aluminum foil, drying, and cutting into (8 x 8) mm 2 The pole piece of (2). Drying the pole piece for 10h at 100 ℃ under a vacuum condition, and then transferring the pole piece to a glove box for later use. The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with sodium metal as the counter electrode and 1mol of NaPF 6 Dissolving ethylene carbonate and diethyl carbonate solution with the volume ratio of 1: 1 in 1L to be used as electrolyte to assemble the CR2032 button cell. Using constant current charge-discharge mode, at a current density of 0.2CThen, constant current charge and discharge test is performed. Under the conditions that the charge starting voltage is 2.5V and the discharge cutoff voltage is 4V, the test result is shown in FIG. 3, and as can be seen from FIG. 3, the reversible capacity is 145.4mAh/g, the first-cycle coulombic efficiency is 96.16%, and the high capacity and the high first-cycle coulombic efficiency are realized. The capacity of the capacitor still has 135mAh/g under the current density of 1C, and the capacity of the capacitor still can keep 102mAh/g under the high multiplying power of 10C, so that the capacitor has excellent multiplying power performance. The capacity retention rate of 1000 cycles of the cycle is 82% under 5C multiplying power, and the capacity of 83.5% can be maintained even under 10C multiplying power after 800 cycles of the cycle by performing a cycle charge and discharge test, so that the cycle performance is excellent.
Example 2
Firstly, 2mol of Na is added into a hydrothermal kettle according to the adding proportion of 1: 1 4 Fe(CN) 6 And 2mol of Na 2 SO 4 And 4L of deionized water is added to prepare Na 4 Fe(CN) 6 The concentration of the solution A is 0.5mol/L, the hydrothermal kettle is heated to 70 ℃ and stirred until the metal cyano-complex and the sodium salt are completely dissolved; taking another 1.5mol of MnSO 4 Dissolving the mixture in deionized water to prepare a solution B with the concentration of 1.5mol/L, after the complex and the sodium salt in the solution A are completely dissolved, dropwise adding the solution into a hydrothermal kettle at the dropwise adding speed of 10ml/min through a peristaltic pump, and after dropwise adding is finished, keeping the temperature at 70 ℃ and aging for 6 hours; and after the temperature is preserved for Chen Huajie, taking out the mixed solution and transferring the mixed solution into a high-pressure hydrothermal kettle, adding a corresponding amount of fructose according to the ratio of Prussian blue to C =100 to 20, heating the high-pressure hydrothermal kettle to 200 ℃, preserving the heat for 24 hours and continuously stirring, cooling to room temperature after the heat preservation is finished, taking out the material, washing and drying, and finally obtaining the C-coated Prussian blue positive electrode material.
The prepared nano carbon-coated Prussian blue positive electrode material is used as an active substance of a battery positive electrode material for preparing a sodium ion battery, and an electrochemical charge-discharge test is carried out, wherein the specific preparation process and the test method are the same as those of example 1, the reversible capacity of the obtained material is 142.3mAh/g under the current density of 0.2C, and the first week coulombic efficiency is 96%. Under the current density of 1C, the capacity of the capacitor still has 133.6mAh/g, and under the high multiplying power of 10C, the capacity of the capacitor still can keep 101.5mAh/g, so that the capacitor has excellent multiplying power performance. The capacity retention rate of the battery is 83.2% after 1000 cycles of the cycle under the 5C multiplying factor, and the battery can maintain 84% of capacity even under the 10C multiplying factor after 800 cycles of the cycle and has excellent cycle performance.
Example 3
Firstly, 2mol of Na is added into a hydrothermal kettle according to the adding proportion of 1: 1 4 Fe(CN) 6 And 2mol of Na 2 SO 4 And 4L of deionized water is added to prepare Na 4 Fe(CN) 6 The concentration of the solution A is 0.5mol/L, the hydrothermal kettle is heated to 70 ℃ and stirred until the metal cyano-complex and the sodium salt are completely dissolved; taking another 1.5mol of MnSO 4 Dissolving in deionized water to prepare a 1.5mol/L solution B, after the complex and sodium salt in the solution A are completely dissolved, dropwise adding into a hydrothermal kettle at a dropwise adding rate of 10ml/min by a peristaltic pump, and after dropwise adding, preserving heat at 70 ℃ and aging for 6 hours; and after the temperature is preserved for Chen Huajie, taking out the mixed solution, transferring the mixed solution into a high-pressure hydrothermal kettle, adding a corresponding amount of glucose according to the ratio of Prussian blue to C =100 to 40, heating the high-pressure hydrothermal kettle to 200 ℃, preserving the temperature for 24h, continuously stirring, cooling to room temperature after the temperature preservation is finished, taking out the material, washing and drying, and finally obtaining the C-coated Prussian blue positive electrode material.
The prepared nano carbon-coated Prussian blue positive electrode material is used as an active substance of a battery positive electrode material for preparing a sodium ion battery, and an electrochemical charge-discharge test is carried out, wherein the specific preparation process and the test method are the same as those of example 1, the reversible capacity of the obtained material is 146.2mAh/g under the current density of 0.2C, and the first week coulombic efficiency is 96.3%. Under the current density of 1C, the capacity of the composite material is still 135.7mAh/g, and under the high multiplying power of 10C, the capacity of the composite material can still maintain 104.2mAh/g, so that the composite material has excellent multiplying power performance. The capacity retention rate of the battery is 85.2% at 5C multiplying power after 1000 cycles of cycle, and the capacity of 84.3% can be maintained even at 10C multiplying power after 800 cycles of cycle, so that the battery has excellent cycle performance.
Example 4
Firstly, 2mol of Na is added into a hydrothermal kettle according to the adding proportion of 1: 1 4 Fe(CN) 6 And 2molNa 2 SO 4 And 4L of deionized water is added to prepare Na 4 Fe(CN) 6 Solution A with the concentration of 0.5mol/L, heating a hydrothermal kettle toStirring at 70 ℃ until the metal cyano complex and the sodium salt are completely dissolved; taking another 1.5mol of MnSO 4 Dissolving in deionized water to prepare a 1.5mol/L solution B, after the complex and sodium salt in the solution A are completely dissolved, dropwise adding into a hydrothermal kettle at a dropwise adding rate of 10ml/min by a peristaltic pump, and after dropwise adding, preserving heat at 70 ℃ and aging for 6 hours; and after the temperature is preserved for Chen Huajie, taking out the mixed solution, transferring the mixed solution into a high-pressure hydrothermal kettle, adding a corresponding amount of glucose according to the ratio of Prussian blue to C =100 to 40, heating the high-pressure hydrothermal kettle to 220 ℃, preserving the temperature for 24h, continuously stirring, cooling to room temperature after the temperature preservation is finished, taking out the material, washing and drying, and finally obtaining the C-coated Prussian blue positive electrode material.
The prepared nano carbon-coated Prussian blue positive electrode material is used as an active substance of a battery positive electrode material for preparing a sodium ion battery, and an electrochemical charge-discharge test is carried out, wherein the specific preparation process and the test method are the same as those of example 1, the reversible capacity of the obtained material is 147.2mAh/g under the current density of 0.2C, and the first-week coulombic efficiency is 95.3%. The capacity of the composite material still has 138.7mAh/g under the current density of 1C, and the capacity of the composite material still can keep 106.1mAh/g under the high multiplying power of 10C, so that the composite material has excellent multiplying power performance. The capacity retention rate of 1000 cycles of the cycle is 86.4% under 5C multiplying power, and the capacity of 85% can be maintained even under 10C multiplying power after 800 cycles of the cycle, so that the cycle performance is excellent.
Example 5
Firstly, 2mol of Na is added into a hydrothermal kettle according to the adding proportion of 1: 1 4 Fe(CN) 6 And 2mol of Na 2 SO 4 And 4L of deionized water is added to prepare Na 4 Fe(CN) 6 The concentration of the solution A is 0.5mol/L, the hydrothermal kettle is heated to 70 ℃ and stirred until the metal cyano-complex and the sodium salt are completely dissolved; another 1.5mol of FeSO 4 Dissolving in deionized water to prepare a 1.5mol/L solution B, after the complex and sodium salt in the solution A are completely dissolved, dropwise adding into a hydrothermal kettle at a dropwise adding rate of 10ml/min by a peristaltic pump, and after dropwise adding, preserving heat at 70 ℃ and aging for 6 hours; after the temperature is preserved for Chen Huajie, the mixed solution is taken out and transferred to a high-pressure hydrothermal kettle, glucose with corresponding amount is added according to the ratio of Prussian blue to C =100 to 40, and the high-pressure hydrothermal kettle is heated toKeeping the temperature at 220 ℃ for 24h, stirring continuously, cooling to room temperature after the heat preservation is finished, taking out the materials, washing and drying to obtain the C-coated Prussian blue type cathode material.
The nano carbon-coated Prussian blue positive electrode material obtained by the preparation method is used as an active substance of a battery positive electrode material for preparing a sodium ion battery, and an electrochemical charge-discharge test is carried out, wherein the specific preparation process and the test method are the same as those of example 1, the reversible capacity of the obtained material under the current density of 0.2C is 151.1mAh/g, and the first week coulombic efficiency is 94.8%. Under the current density of 1C, the capacity still has 139.3mAh/g, under the large multiplying power of 10C, the capacity still can keep 112.1mAh/g, and the multiplying power performance is excellent. The capacity retention rate of the battery is 84.1% after 1000 cycles of the battery is cycled under 5C multiplying power, and the capacity of the battery can be maintained at 84.7% even under 10C multiplying power after 800 cycles of the battery is cycled, so that the battery has excellent cycle performance.
Example 6
Firstly, 2mol of Na is added into a hydrothermal kettle according to the adding proportion of 1: 1.5 4 Fe(CN) 6 And 3mol of Na 2 SO 4 And 4L of deionized water is added to prepare Na 4 Fe(CN) 6 The concentration of the solution A is 0.5mol/L, the hydrothermal kettle is heated to 70 ℃ and stirred until the metal cyano-complex and the sodium salt are completely dissolved; taking another 1.5mol of MnSO 4 Dissolving the mixture in deionized water to prepare a solution B with the concentration of 1.5mol/L, after the complex and the sodium salt in the solution A are completely dissolved, dropwise adding the solution into a hydrothermal kettle at the dropwise adding speed of 10ml/min through a peristaltic pump, and after dropwise adding is finished, keeping the temperature at 70 ℃ and aging for 6 hours; and after the temperature is preserved for Chen Huajie, taking out the mixed solution, transferring the mixed solution into a high-pressure hydrothermal kettle, adding a corresponding amount of glucose according to the ratio of Prussian blue to C =100 to 20, heating the high-pressure hydrothermal kettle to 220 ℃, preserving the temperature for 24h, continuously stirring, cooling to room temperature after the temperature preservation is finished, taking out the material, washing and drying, and finally obtaining the C-coated Prussian blue positive electrode material.
The nano carbon-coated Prussian blue cathode material obtained by the preparation method is used as an active substance of a battery cathode material for preparing a sodium-ion battery, and an electrochemical charge and discharge test is carried out, wherein the specific preparation process and the test method are the same as those of example 1, the reversible capacity of the obtained material is 157.2mAh/g under the current density of 0.2C, and the first week coulombic efficiency is 94.3%. Under the current density of 1C, the capacity of the capacitor still has 142.7mAh/g, and under the high multiplying power of 10C, the capacity of the capacitor still can keep 116.1mAh/g, so that the capacitor has excellent multiplying power performance. The capacity retention rate of 1000 cycles of the cycle is 84.7% under 5C multiplying power, and the capacity of 82.3% can be maintained even under 10C multiplying power after 800 cycles of the cycle by performing a cycle charge and discharge test, so that the cycle performance is excellent.
Example 7
Firstly, 2mol of Na is added into a hydrothermal kettle according to the adding proportion of 1: 1 4 Fe(CN) 6 And 2mol of Na 2 SO 4 And 4L of deionized water is added to prepare Na 4 Fe(CN) 6 Heating the hydrothermal kettle to 70 ℃ and stirring until the metal cyano complex and the sodium salt are completely dissolved in the solution A with the concentration of 0.5 mol/L; taking another 1.5mol of MnSO 4 Dissolving in deionized water to prepare a 1.5mol/L solution B, after the complex and sodium salt in the solution A are completely dissolved, dropwise adding into a hydrothermal kettle at a dropwise adding rate of 10ml/min by a peristaltic pump, and after dropwise adding, preserving heat at 70 ℃ and aging for 6 hours; after the temperature is preserved for Chen Huajie, the mixed solution is taken out and transferred to a high-pressure hydrothermal kettle, corresponding amount of glucose and fructose is added according to the ratio of prussian blue to C =100 to 20, wherein the ratio of the glucose to the fructose is 1 to 1, the high-pressure hydrothermal kettle is heated to 220 ℃, the temperature is preserved for 24 hours and is continuously stirred, the mixture is cooled to room temperature after the temperature preservation is finished, the material is taken out, washed and dried, and finally the prussian blue positive electrode material coated with C is obtained.
The prepared nano carbon-coated Prussian blue positive electrode material is used as an active substance of a battery positive electrode material for preparing a sodium ion battery, and an electrochemical charge-discharge test is carried out, wherein the specific preparation process and the test method are the same as those of example 1, the reversible capacity of the obtained material is 146.2mAh/g under the current density of 0.2C, and the first week coulombic efficiency is 94.3%. Under the current density of 1C, the capacity of the capacitor still has 136.7mAh/g, and under the large multiplying power of 10C, the capacity of the capacitor still can keep 104.1mAh/g, and the capacitor has excellent multiplying power performance. When the cyclic charge and discharge test is carried out, the capacity retention rate is 84.4% at 5C multiplying power after 1000 cycles, and the capacity can be maintained at 81.5% even at 10C multiplying power after 800 cycles, so that the cyclic charge and discharge test has excellent cyclic performance.
Example 8
Firstly, 2mol of Na is added into a hydrothermal kettle according to the adding proportion of 1: 1 4 Fe(CN) 6 And 2mol of Na 2 SO 4 And 4L of deionized water is added to prepare Na 4 Fe(CN) 6 Heating the hydrothermal kettle to 70 ℃ and stirring until the metal cyano complex and the sodium salt are completely dissolved in the solution A with the concentration of 0.5 mol/L; taking another 1.5mol of MnSO 4 Dissolving in deionized water to prepare a 1.5mol/L solution B, after the complex and sodium salt in the solution A are completely dissolved, dropwise adding into a hydrothermal kettle at a dropwise adding rate of 10ml/min by a peristaltic pump, and after dropwise adding, preserving heat at 70 ℃ and aging for 6 hours; after the temperature is preserved for Chen Huajie, the mixed liquid is taken out and transferred to a high-pressure hydrothermal kettle, glucose with the corresponding amount is added according to the ratio of prussian blue to C =100 to 800, the high-pressure hydrothermal kettle is heated to 220 ℃, the temperature is preserved, stirring is carried out continuously for 24h, the mixture is cooled to the room temperature after the temperature preservation is finished, the material is taken out, washed and dried, and finally the prussian blue type anode material coated with C is obtained.
The nano carbon-coated Prussian blue positive electrode material obtained by the preparation method is used as an active substance of a battery positive electrode material for preparing a sodium ion battery, and an electrochemical charge-discharge test is carried out, wherein the specific preparation process and the test method are the same as those of example 1, the reversible capacity of the obtained material is 121.3mAh/g under the current density of 0.2C, and the first-week coulombic efficiency is 95.7%. Under the current density of 1C, the capacity of the capacitor still has 101.3mAh/g, under the high multiplying power of 10C, the capacity of the capacitor still can keep 93.4mAh/g, and the multiplying power performance is better; elemental analysis shows that the obtained prussian blue positive electrode material contains more C (more than 50%), and the conductive performance is improved, but the gram capacity is reduced. The capacity retention rate of the battery is 79.3% at 5C multiplying power after 1000 cycles of cycling, and the battery can maintain 80.2% of capacity even at 10C multiplying power after 800 cycles of cycling, and has excellent cycling performance.
Comparative example 1
Firstly, 2mol of Na is added into a hydrothermal kettle according to the adding proportion of 1: 1 4 Fe(CN) 6 And 2mol of Na 2 SO 4 And 4L of deionized water is added to prepare Na 4 Fe(CN) 6 Solution A with the concentration of 0.5mol/L, heating a hydrothermal kettleStirring the mixture at 70 ℃ until the metal cyano complex and the sodium salt are completely dissolved; taking another 1.5mol of MnSO 4 Dissolving in deionized water to prepare a 1.5mol/L solution B, after the complex and sodium salt in the solution A are completely dissolved, dropwise adding into a hydrothermal kettle at a dropwise adding rate of 10ml/min by a peristaltic pump, and after dropwise adding, preserving heat at 70 ℃ and aging for 6 hours; 5363 after Chen Huajie, the obtained suspension was filtered, washed, centrifuged and dried to obtain a prussian blue-based positive electrode material, and its scanning electron micrograph is shown in fig. 4, in which the particles are small (D50 size is 450 nm).
The prussian blue positive electrode material prepared in the above way is used as an active substance of a battery positive electrode material for the preparation of a sodium ion battery, and an electrochemical charge-discharge test is carried out, wherein the specific preparation process and the test method are the same as those of example 1, the reversible capacity of the obtained material under the current density of 0.2C is 137.1mAh/g, and the first week coulombic efficiency is 94.3%. Under the current density of 1C, the capacity of the capacitor still has 107.1mAh/g, under the high multiplying power of 10C, the capacity of the capacitor can only keep 89.1mAh/g, and the multiplying power performance of the capacitor is poor. And (3) performing a cyclic charge and discharge test, wherein the capacity retention rate is 85.4% at 5C multiplying power after 1000 cycles, and the capacity can only be maintained by 80% at 10C multiplying power after 500 cycles, and the cyclic performance is general.
Aiming at the defects of the prior art, the Prussian blue type sodium ion anode material is synthesized by a hydrothermal precipitation method, then the crystal structure of the Prussian blue type anode material is optimized by high-temperature high-pressure hydrothermal method, a carbonizing agent precursor (such as glucose and the like) is added in the high-temperature high-pressure hydrothermal process, and nano carbon particles are generated in situ on the crystal of the Prussian blue type anode material by the high-temperature hydrothermal decomposition of the carbonizing agent precursor, so that the crystal growth of the Prussian blue type anode material is promoted, and the problems of poor conductivity, low rate capability and the like of the Prussian blue type anode material are effectively improved.
The above description is not intended to limit the invention, nor is the invention limited to the examples set forth above. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.

Claims (6)

1. A preparation method of an in-situ carbon-coated high-magnification large-size Prussian blue sodium ion positive electrode material is characterized by comprising the following steps of:
(1) Dissolving a soluble transition metal cyano complex and a soluble sodium salt in water to prepare a solution A; placing the solution A in a reaction kettle, and preserving heat;
(2) Dissolving soluble transition metal salt in water to prepare solution B, dropwise adding the solution B into the solution A through a peristaltic pump under a stirring state, and preserving heat after dropwise adding to obtain a suspension;
(3) Adding the suspension obtained in the step (2) into a high-pressure hydrothermal kettle, adding a carbonizing agent precursor, preserving heat, and stirring to obtain a material;
(4) Taking out the material cooled in the step (3), washing and drying to obtain an in-situ carbon-coated high-magnification large-size Prussian blue type sodium ion positive electrode material;
in the step (1), the adding ratio of the soluble sodium salt to the soluble transition metal cyano complex is 1: 1-10: 1 according to the molar ratio;
in the step (3), the carbonization agent precursor is any one or more of glucose, fructose, sucrose, maltose, agarose and soluble starch;
in the step (3), the adding proportion of the carbonization agent precursor to the suspension is 20-100% according to the molar ratio;
in the step (3), the temperature of the heat preservation is 200-220 ℃;
in the step (3), the stirring time is 20-25 h.
2. The method for preparing an in-situ carbon-coated high-rate large-size prussian blue sodium ion-like cathode material according to claim 1, wherein in the step (1), the soluble transition metal cyano complex is Na 4 Fe(CN) 6 、Na 4 Co(CN) 6 、Na 4 Cu(CN) 6 、Na 4 Zn(CN) 6 、Na 4 Mn(CN) 6 Any one or more of; the soluble sodium salt is sulfuric acidSodium, sodium nitrate, sodium chloride.
3. The method for preparing an in-situ carbon-coated high-magnification large-size prussian blue sodium ion-like cathode material according to claim 1, wherein in the step (1), the concentration of the soluble transition metal cyano complex in the solution a is 0 to 5mol/L.
4. The method for preparing an in-situ carbon-coated high-rate large-size prussian blue sodium ion-like cathode material as claimed in claim 1, wherein in step (2), the soluble transition metal salt is one or more of sulfates, hydrochlorides and nitrates of Mn, fe, co, ni, cu, V and Cr.
5. The method for preparing an in-situ carbon-coated high-rate large-size prussian blue sodium ion-like cathode material according to claim 1, wherein in the step (2), the concentration of the solution B is 0 to 5mol/L.
6. An in-situ carbon-coated high-rate large-size prussian blue sodium ion cathode material, which is characterized by being prepared by the preparation method of the in-situ carbon-coated high-rate large-size prussian blue sodium ion cathode material according to any one of claims 1 to 5.
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