CN107017395B - Carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with sandwich structure and preparation method and application thereof - Google Patents

Carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with sandwich structure and preparation method and application thereof Download PDF

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CN107017395B
CN107017395B CN201710365046.7A CN201710365046A CN107017395B CN 107017395 B CN107017395 B CN 107017395B CN 201710365046 A CN201710365046 A CN 201710365046A CN 107017395 B CN107017395 B CN 107017395B
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sodium
manganese
graphene oxide
carbon
pyrophosphate
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CN107017395A (en
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张治安
赖延清
李煌旭
尚国志
陈晓彬
肖志伟
张凯
李劼
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Hunan Nabang New Energy Co ltd
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a carbon-coated sodium manganese pyrophosphate @ graphene oxide composite material with a sandwich structure, and a preparation method and application thereof. Adding graphene oxide into an aqueous solution in which a phosphorus source, a sodium source, a manganese source and a complexing agent are dissolved, and then sequentially carrying out ultrasonic treatment, liquid nitrogen freezing and freeze drying to obtain a precursor; the precursor is placed in a protective atmosphere and subjected to heat treatment to obtain the carbon-coated sodium manganese pyrophosphate @ graphene oxide composite material with a sandwich structure, the carbon-coated sodium manganese pyrophosphate @ graphene oxide composite material has excellent electrochemical performance as a sodium ion battery positive electrode material, the Na-Mn-P-O system is rich in resources and low in cost, and the preparation method is simple to operate and has a wide commercial application prospect.

Description

Carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with sandwich structure and preparation method and application thereof
Technical Field
The invention relates to a positive electrode material of a sodium-ion battery, in particular to a composite positive electrode material of carbon-coated sodium manganese pyrophosphate and graphene oxide with a sandwich structure, a preparation method thereof and application of the composite material as a sodium-ion battery, belonging to the field of sodium-ion batteries.
Background
Lithium ion batteries have rapidly occupied the market for portable electronic products (notebook computers, smart mobile devices, tablet computers, etc.) due to their advantages of high energy density, high stability, long life, etc., and have continuously permeated the field of electric vehicles. However, the reserve of lithium resources in the earth crust is low, and the regional distribution is uneven, so that the lithium price of the lithium ion battery is continuously increased in the process of large-scale popularization and application, and the price of the lithium ion battery is high. Therefore, the application of lithium ion batteries to the field of large-scale power storage is limited. Sodium ion batteries are considered to be an ideal large-scale electricity storage application technology due to abundant sodium resource and environmental friendliness, and therefore have attracted much attention in the world.
During the past decades, researchers have conducted extensive research into positive electrode materials for sodium ion batteries. Among the existing positive electrode material systems, the polyanion-type compound system is considered to be the most commercially promising sodium-electric positive electrode material system. Among polyanionic compound systems, pyrophosphate system materials have been receiving attention from researchers because of their advantages such as open three-dimensional channels and high structural stability and thermal stability. At present, more sodium ferric pyrophosphate is reported to have excellent electrochemical performance, and the reversible specific capacity is close to the theoretical specific capacity of 95mAh/g under the multiplying power of 0.1C. But Fe2+/Fe3+The redox potential of (a) is low, so that the sodium iron pyrophosphate discharge plateau is low, and therefore the energy density is not high. Sodium manganese pyrophosphate has a theoretical specific capacity of 97.5mAh/g, and 3.7V (vs Na/Na)+) The high voltage has better sodium storage performance and low cost. However, the sodium manganese pyrophosphate material has poor conductivity, so that the rate capability and the cycle performance of the material as an electrode material are poor. In addition, most of the existing methods for synthesizing the sodium manganese pyrophosphate material are traditional solid-phase sintering methods, and the obtained product has large particle size and poor material dynamic performance, so that the method is not beneficial to the exertion of material capacity. Therefore, how to improve the rate capability and the cycle performance of the sodium manganese pyrophosphate and improve the specific capacity of the material becomes the research on the sodium manganese pyrophosphate as the positive electrode material of the sodium ion batteryThe key problem is solved.
Disclosure of Invention
Aiming at the defects of the sodium ion anode material of the existing pyrophosphate system, the invention aims to provide the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material which has good stability, good dispersibility of active substances, uniform appearance and a special sandwich structure.
The invention also aims to provide the method for preparing the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material, which has the advantages of good repeatability, simplicity in operation, environmental friendliness and low cost and has an industrial application prospect.
The third purpose of the invention is to provide an application of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material as a sodium ion battery positive electrode material, and the prepared sodium ion battery has high charge-discharge specific capacity, good rate capability and cycling stability.
In order to achieve the technical purpose, the invention provides a carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material with a sandwich structure, which is formed by stacking reduced graphene oxide sheets with carbon-coated manganese sodium pyrophosphate particles uniformly distributed on the surface.
According to the technical scheme, the manganese sodium pyrophosphate particles are uniformly coated by the carbon layer, so that the conductivity of the manganese sodium pyrophosphate particles is improved, higher capacity exertion and rate capability can be obtained, and the thermal stability and chemical stability of the manganese sodium pyrophosphate are improved by the carbon layer coating, and the cycle performance of the manganese sodium pyrophosphate is favorably improved. Meanwhile, the carbon-coated sodium manganese pyrophosphate particles are uniformly loaded on the surface of the reduced graphene oxide sheet, so that the uniform dispersion of the carbon-coated sodium manganese pyrophosphate particles is improved, a higher specific surface is obtained, the electrochemical activity is improved, and the reduced graphene oxide sheet form a sandwich structure in a stacking form, so that the stability of the composite material is further improved.
According to the preferable scheme, the specific surface area of the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with the sandwich structure is 60-120 m2g-1(ii) a Carbon bagThe particle size of the sodium manganese pyrophosphate-coated particles is 300-1000 nm; preferably 300-700 nm; more preferably 300 to 500 nm.
In a more preferable scheme, the mass of the manganese sodium pyrophosphate is 85-99% of that of the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material with a sandwich structure; more preferably 94% to 97%; most preferably 95% to 96%.
The invention also provides a preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure, which comprises the steps of adding graphene oxide into an aqueous solution in which a phosphorus source, a sodium source, a manganese source and a complexing agent are dissolved, and then sequentially carrying out ultrasonic treatment, liquid nitrogen freezing and freeze drying to obtain a precursor; and (3) placing the precursor in a protective atmosphere, and carrying out heat treatment at 500-800 ℃ to obtain the catalyst.
According to the technical scheme, the complexing agent is adopted, on one hand, the complexing agent can coordinate and complex metal ions, not only can promote the generation and uniform dispersion of the sodium manganese pyrophosphate crystals and be beneficial to the generation of uniform-appearance sodium manganese pyrophosphate particles, but also can be used as a carbon source, the complexing agent is adsorbed on the surfaces of the sodium manganese pyrophosphate particles and is converted into the conductive carbon coating layer through high-temperature carbonization, the conductivity of the sodium manganese pyrophosphate material can be effectively improved, and the stability of the sodium manganese pyrophosphate material is improved. According to the technical scheme, the graphene oxide is introduced and used as a dispersing carrier, so that the carbon-coated sodium manganese pyrophosphate particles are uniformly dispersed and form a sandwich structure, the specific surface area and the stability of the composite material are improved, and the graphene oxide provides a good conductive substrate for the composite material and effectively improves the conductivity of the sodium manganese pyrophosphate. The technical scheme of the invention also adopts the processes of liquid nitrogen freezing and freeze drying, can effectively maintain the morphology of the composite material, and avoids electrochemical performance reduction caused by serious agglomeration.
In the preferred scheme, the ratio of the phosphorus source, the sodium source and the manganese source is measured by the molar ratio of P to Na to Mn being 1.8-2.2: 0.8-1.2; the most preferred ratio is measured as a molar ratio of P to Na to Mn of 2:2: 1.
In a preferable scheme, the molar ratio of the complexing agent to manganese in the manganese source is 2-5: 1. More preferably 3 to 4: 1, most preferably 3: 1.
in a more preferred embodiment, the phosphorus source comprises at least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and phosphoric acid.
In a more preferred embodiment, the sodium source includes at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, and sodium citrate. The sodium source is preferably anhydrous sodium carbonate and/or sodium bicarbonate, most preferably anhydrous sodium carbonate.
More preferably, the manganese source is a water-soluble inorganic manganese compound known to those skilled in the art. Preferred manganese sources include at least one of manganese acetate, manganese nitrate, manganese oxalate. The most preferred manganese source is manganese acetate.
Mn in the aqueous solution in the technical scheme of the invention2+The concentration is 0.05-0.3 mol/L. Mn2+The concentration is preferably 0.1 to 0.2 mol/L.
In a more preferred embodiment, the complexing agent is at least one of citric acid, oxalic acid, ascorbic acid, sucrose and glucose. The complexing agent is more preferably citric acid and/or sucrose.
In a more preferable scheme, the heat treatment temperature is 600-700 ℃, and most preferably 600 ℃.
In a more preferable scheme, the heat treatment time is 6-12 h.
The protective gas in the solution according to the invention is preferably an inert gas, such as argon.
In the technical scheme of the invention, the mass of the added graphene oxide sheet is 1-10% of that of the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with a sandwich structure.
The invention also provides an application of the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material with a sandwich structure, and the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material is applied as a positive electrode material of a sodium ion battery.
The preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure comprises the following steps of:
step (1): push buttonWeighing manganese acetate tetrahydrate, ammonium dihydrogen phosphate and anhydrous sodium carbonate according to a stoichiometric ratio, and mixing the manganese acetate, the ammonium dihydrogen phosphate and the anhydrous sodium carbonate with the complexing agent and Mn2+The molar ratio of (A) to (B) is 2-5: 1, weighing anhydrous citric acid, dissolving the anhydrous citric acid in deionized water, and fully stirring to obtain a mixed solution; mn of the mixed solution2+The concentration is 0.05-0.3 mol/L;
step (2): adding graphene oxide accounting for 3% -6% of the mass of a theoretical product into the solution, carrying out ultrasonic treatment for 30min, carrying out water bath at 80 ℃ for 6h, freezing by using liquid nitrogen, placing the obtained precursor into a freeze dryer, carrying out freeze drying, sintering the obtained precursor in a tube furnace at 600-700 ℃ for 8-10 h under an inert atmosphere, and finally obtaining the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with a sandwich structure.
The invention also discloses a method for preparing the positive electrode of the sodium ion battery by using the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite positive electrode material with the sandwich structure, and testing the electrochemical performance of the positive electrode.
For example, the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material is mixed with a conductive agent and a binder, and then coated on an aluminum foil to prepare the positive electrode of the sodium-ion battery. The conductive agent and the binder used may be those known to those skilled in the art. The method for assembling and preparing the positive electrode material of the sodium-ion battery can also refer to the existing method.
For example, the conductive carbon black of the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with the sandwich structure prepared by the invention and the PVDF binder are ground according to the mass ratio of 8:1:1, NMP is added after the materials are fully mixed to form uniform slurry, the slurry is coated on an aluminum foil to be used as a test electrode, metal sodium is used as a counter electrode, and the electrolyte is 1M NaClO 4100% PC, preparing a sodium half cell and testing the electrochemical performance of the sodium half cell.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material has a special sandwich structure, reduced graphene oxide sheets are stacked, and carbon-coated manganese sodium pyrophosphate particles are uniformly dispersed and loaded on the surfaces of the reduced graphene oxide sheets and between two adjacent reduced graphene oxide sheets. The graphene can improve the dispersibility of the carbon-coated manganese sodium pyrophosphate particle active substance, improve the specific surface area of the carbon-coated manganese sodium pyrophosphate particle active substance, increase active sites and improve the electrochemical activity; the reduced graphene oxide sheets and the carbon-coated sodium manganese pyrophosphate particles form a sandwich structure, so that the physical and chemical stability of the composite material is improved; and the reduced graphene oxide is used as a good conductive matrix of the carbon-coated sodium manganese pyrophosphate particles, so that the conductivity of the reduced graphene oxide is improved, and the capacity exertion and rate capability of the composite anode material are greatly improved. The manganese sodium pyrophosphate particles are uniformly coated by the carbon layer, so that the conductivity of the manganese sodium pyrophosphate particles is improved, higher capacity exertion and rate performance can be obtained, and the thermal stability and chemical stability of the manganese sodium pyrophosphate are improved by the carbon layer coating, thereby being beneficial to improving the cycle performance of the manganese sodium pyrophosphate particles.
The carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material is synthesized by combining a solution method with high-temperature heat treatment. The precursor material is synthesized by a solution method, a complexing agent is adopted in the solution method, the complexing agent not only plays a complexing role, but also serves as a carbon source, on one hand, the generation and uniform dispersibility of the sodium manganese pyrophosphate crystal can be promoted, and in addition, the sodium manganese pyrophosphate crystal is converted into conductive carbon at high temperature, so that the conductivity of the sodium manganese pyrophosphate material can be effectively improved. Meanwhile, graphene oxide is used as a carrier material, reduced graphene oxide can promote dispersion of the sodium manganese pyrophosphate crystals by using polar groups contained on the surface of the reduced graphene oxide, the sodium manganese pyrophosphate crystals with uniform particle size and good appearance are easy to obtain, the reduced graphene oxide provides a good conductive substrate for the composite material, and the conductivity of the sodium manganese pyrophosphate is effectively improved. The precursor is frozen by liquid nitrogen and freeze-dried to effectively maintain the morphology of the material, and avoid the reduction of electrochemical performance caused by serious agglomeration. The high-temperature heat treatment process realizes the generation of the carbon coating and the synchronous realization of the in-situ coating of the sodium manganese pyrophosphate particles, and greatly simplifies the process steps.
The carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material with the sandwich structure has high electrochemical activity, high physicochemical stability and high safety, and shows excellent electrochemical performance when being used as a sodium ion positive electrode material for a sodium ion battery, the discharge specific capacity of 50 cycles of the sodium ion battery can reach 70mAh/g under the multiplying power of 0.2C, and the capacity retention rate can reach more than 90%.
The method for preparing the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure is simple and reliable, environment-friendly, rich in 'Na-Mn-P-O' system resource, low in cost and wide in industrial application prospect.
Drawings
Fig. 1 is an X-ray diffraction pattern (XRD) of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite positive electrode material with a sandwich structure prepared in example 1;
fig. 2 is a Scanning Electron Microscope (SEM) image of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite positive electrode material with the sandwich structure prepared in example 1;
fig. 3 is a charge-discharge curve of the sodium ion battery assembled by the sandwich-structured carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite positive electrode material prepared in example 1 at a magnification of 0.1C;
fig. 4 is a CV curve of the sodium ion battery assembled by the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite cathode material with the sandwich structure prepared in example 1 at a sweep rate of 0.1 mV/s.
Detailed Description
The following examples are intended to illustrate the invention in further detail; and the scope of the claims of the present invention is not limited by the examples.
Example 1
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 50mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, and after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6 h. The solution was frozen with liquid nitrogen and then lyophilized in a lyophilizer. Placing the precursor into an inert atmosphere tube furnace, sintering for 9h at 600 ℃ to obtain a solid productThe carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite cathode material has a sandwich structure. The X-ray diffraction pattern (XRD) of the prepared carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite cathode material with the sandwich structure is shown in figure 1. The Scanning Electron Microscope (SEM) of the prepared carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite cathode material with the sandwich structure is shown in figure 2, and as can be seen from figure 2, the material is prepared by uniformly compounding sodium manganese pyrophosphate and graphene, wherein the particle size of sodium manganese pyrophosphate particles is 300-500 nm, and the specific surface area is 110m2g-1。
The button cell is assembled by adopting the sodium ion battery composite positive electrode material prepared by the embodiment and a sodium sheet, and as can be seen from a 0.2C multiplying power cycle diagram, the discharge specific capacity of 50 cycles of the cycle reaches 73mAh/g, and the capacity retention rate reaches over 90 percent.
Example 2
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 3.84g (molar ratio of the anhydrous sodium carbonate to the manganese is 4: 1) of anhydrous citric acid are dissolved in 50mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, then liquid nitrogen freezing is carried out, and then the solution is freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 9h at 600 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure. The particle size of the sodium manganese pyrophosphate particles is 300-500 nm, and the specific surface area is 110m2g-1。
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 65mAh/g after 50 cycles under the multiplying power of 0.2C. The excessive organic carbon with poor conductivity has no obvious effect on improving the material performance.
Example 3
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 50mL of deionized water and fully stirred to obtain a clear solution. Then 0.134g (8% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 9h at 600 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The button cell assembled by the sodium-ion battery composite positive electrode material prepared by the embodiment and the sodium sheet has a specific capacity of 70mAh/g after circulating for 50 circles under a multiplying power of 0.2C. The excessive graphene does not have obvious improvement effect on the material performance.
Example 4
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 40mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 9h at 600 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure. The particle size of the sodium manganese pyrophosphate particles is 500-800 nm, and the specific surface area is 80m2g-1。
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 62mAh/g after 50 cycles under the multiplying power of 0.2C. Illustrating that solution solubility affects the particle size of the material.
Example 5
Firstly, 0.005mol of manganese acetate tetrahydrate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.64g (molar ratio to manganese is 3: 1) of ascorbic acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering at 600 ℃ for 12h to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 62mAh/g after 50 cycles under the multiplying power of 0.2C. The electrochemical performance of the material sintered for 12 hours is obviously reduced.
Example 6
Firstly, 0.005mol of manganese acetate tetrahydrate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.64g (molar ratio to manganese is 3: 1) of ascorbic acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 6h at 600 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 59mAh/g after circulation for 50 circles under the multiplying power of 0.2C. The electrochemical performance of the material sintered for 6h is obviously reduced.
Example 7
Firstly, 0.005mol of manganese acetate tetrahydrate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.64g (molar ratio to manganese is 3: 1) of ascorbic acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 8h at 600 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 67mAh/g after 50 cycles under the multiplying power of 0.2C. The electrochemical performance of the sintered material for 8 hours is better.
Example 8
Firstly, 0.005mol of manganese acetate tetrahydrate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.64g (molar ratio to manganese is 3: 1) of ascorbic acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 10h at 600 ℃ to obtain a solid product, namely the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 67mAh/g after 50 cycles under the multiplying power of 0.2C. The electrochemical performance of the material sintered for 10 hours is better.
Example 9
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering for 9h at 500 ℃ to obtain a solid product, namely the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite anode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 56mAh/g after 50 cycles under the multiplying power of 0.2C. The material sintered at 500 ℃ has obviously poor performance.
Example 10
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the precursor into an inert atmosphere tube furnace, and sintering at 700 ℃ for 9h to obtain a solid product, namely the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite cathode material with a sandwich structure. The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 61mAh/g after circulation for 50 circles under the multiplying power of 0.2C.
Example 11
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.412g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, and sintering at 800 ℃ for 9h to obtain a solid product, namely the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite cathode material with a sandwich structure.
The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 52mAh/g after circulation for 50 circles under the multiplying power of 0.2C.
Comparative example 1
Firstly, 0.005mol of manganese acetate tetrahydrate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 0g of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5%) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, liquid nitrogen freezing is carried out, and then the solution is freeze-dried in a freeze dryer. And putting the obtained precursor into an inert atmosphere tube furnace, sintering for 9 hours at 600 ℃, and collecting a product. XRD did not detect a phase of sodium manganese pyrophosphate.
Comparative example 2
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. And (3) performing water bath at 80 ℃ for 6h, performing liquid nitrogen freezing, and then freeze-drying in a freeze dryer. And putting the obtained precursor into an inert atmosphere tube furnace, sintering for 9 hours at 600 ℃, and collecting a product. XRD showed a phase of sodium manganese pyrophosphate. The button cell assembled by the sodium-ion battery composite positive electrode material prepared by the embodiment and the sodium sheet has obviously reduced electrochemical performance. The method shows that the graphene is important for improving the performance of the material.
Comparative example 3
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 1.92g (molar ratio of the anhydrous sodium carbonate to the manganese is 1: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And putting the obtained precursor into an inert atmosphere tube furnace, sintering for 9 hours at 600 ℃, and collecting a product. XRD showed no phase with sodium manganese pyrophosphate,
comparative example 4
Firstly, 0.03mol of tetrahydrate manganese acetate, 0.06mol of ammonium dihydrogen phosphate, 0.03mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And putting the obtained precursor into an inert atmosphere tube furnace, sintering for 9h at 400 ℃, and collecting a product. XRD did not detect a phase of sodium manganese pyrophosphate.
Comparative example 5
Firstly, 0.005mol of tetrahydrate manganese acetate, 0.01mol of ammonium dihydrogen phosphate, 0.005mol of anhydrous sodium carbonate and 2.88g (molar ratio to manganese is 3: 1) of anhydrous citric acid are dissolved in 60mL of deionized water and fully stirred to obtain a clear solution. Then 0.067g (5% of the mass of the sodium manganese pyrophosphate) of graphene oxide is added into the solution, after 30min of ultrasonic treatment, the solution is subjected to water bath at 80 ℃ for 6h, frozen by liquid nitrogen and then freeze-dried in a freeze dryer. And placing the obtained precursor into an inert atmosphere tube furnace, sintering for 9h at 900 ℃, and collecting a product. XRD did not detect a phase of sodium manganese pyrophosphate.

Claims (6)

1. A preparation method of a carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with a sandwich structure is characterized by comprising the following steps of: adding graphene oxide into an aqueous solution in which a phosphorus source, a sodium source, a manganese source and a complexing agent are dissolved, and then sequentially carrying out ultrasonic treatment, liquid nitrogen freezing and freeze drying to obtain a precursor; placing the precursor in a protective atmosphere, and carrying out heat treatment at 500-800 ℃ to obtain a carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with a sandwich structure, wherein the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material is formed by stacking reduced graphene oxide sheets with carbon-coated manganese pyrophosphate sodium particles uniformly distributed on the surfaces of the reduced graphene oxide sheets; the carbon-coated manganese pyrophosphate sodium @ reduced graphene oxide composite material with the sandwich structure has a specific surface area of 60-120 m2g-1(ii) a The particle size of the carbon-coated sodium manganese pyrophosphate particles is 300-1000 nm;
the molar ratio of the complexing agent to manganese in the manganese source is 2-5: 1;
the complexing agent is at least one of citric acid and ascorbic acid;
the phosphorus source comprises at least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid;
the sodium source comprises at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate and sodium citrate;
the manganese source comprises at least one of manganese acetate, manganese nitrate and manganese oxalate.
2. The preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure according to claim 1 is characterized in that: the mass of the manganese sodium pyrophosphate is 85-99% of that of the carbon-coated manganese sodium pyrophosphate @ reduced graphene oxide composite material with the sandwich structure.
3. The preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure according to claim 1 is characterized in that:
the ratio of the phosphorus source, the sodium source and the manganese source is measured by the molar ratio of P to Na to Mn being 1.8-2.2: 0.8-1.2.
4. The preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure according to any one of claims 1 to 3, which is characterized in that: the heat treatment temperature is 600-700 ℃.
5. The preparation method of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure according to claim 4 is characterized in that: the heat treatment time is 6-12 h.
6. The application of the carbon-coated sodium manganese pyrophosphate @ reduced graphene oxide composite material with the sandwich structure prepared by the preparation method of any one of claims 1 to 5 is characterized in that: the lithium ion battery cathode material is applied as a cathode material of a sodium ion battery.
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