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CN118405679A - Method for synthesizing carbon-coated ferric sodium pyrophosphate based on microwave method - Google Patents

Method for synthesizing carbon-coated ferric sodium pyrophosphate based on microwave method Download PDF

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Publication number
CN118405679A
CN118405679A CN202410467286.8A CN202410467286A CN118405679A CN 118405679 A CN118405679 A CN 118405679A CN 202410467286 A CN202410467286 A CN 202410467286A CN 118405679 A CN118405679 A CN 118405679A
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sodium
source
ferric
microwave treatment
microwave
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CN202410467286.8A
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Inventor
涂全
胡培
黄强
史德友
陈鹏
万奎
廖华明
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Huanggang Qina New Energy Technology Co ltd
Wuhan Qina New Energy Technology Co ltd
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Huanggang Qina New Energy Technology Co ltd
Wuhan Qina New Energy Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/38—Condensed phosphates
    • C01B25/42—Pyrophosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a method for synthesizing carbon-coated ferric sodium pyrophosphate based on a microwave method, and belongs to the technical field of sodium ion battery anode materials. The method comprises the following steps: 1) Dissolving an iron source, a phosphorus source, a sodium source and a complexing agent in water, and preparing to obtain a mixed aqueous solution; 2) Carrying out microwave treatment on the prepared mixed aqueous solution obtained in the step 1) under the protection of inert atmosphere, wherein the heating rate of the microwave treatment is 100-300 ℃/min, and the time of the microwave treatment is 1-6min; 3) And after the reaction is finished, carrying out post-treatment to obtain the carbon-coated ferric sodium pyrophosphate. The method has the advantages of simple process, few steps, extremely short synthesis time, high efficiency, no need of high-temperature calcination and low energy consumption, and the obtained carbon-coated ferric sodium pyrophosphate is used as a positive electrode material of a sodium ion battery, and has higher energy density and good cycle stability.

Description

Method for synthesizing carbon-coated ferric sodium pyrophosphate based on microwave method
Technical Field
The invention belongs to the technical field of sodium ion anode materials, and particularly relates to a method for synthesizing carbon-coated sodium ferric pyrophosphate based on a microwave method.
Background
As the use of lithium ion batteries has been drastically increased, lithium resources have been scarce, and in contrast, sodium has been widely stored and widely distributed, and has low cost, and thus, sodium ion batteries have been widely paid attention to use as alternatives to lithium ion batteries.
In sodium ion battery systems, the positive electrode material is the most critical factor affecting the battery energy density. Among them, sodium iron pyrophosphate Na 4Fe3(PO4)2P2O7 is one of the most promising commercial sodium ion battery positive electrode materials because of its strong structural stability, excellent rate capability and cycle performance.
The synthesis of the ferric sodium phosphate cathode material is a complex material system, and is a solid phase synthesis method or a sol-gel synthesis method, wherein: the solid phase synthesis method is to prepare the positive electrode material of the sodium ion battery at high temperature through solid phase reaction. The appropriate proportions of the raw materials are typically solid phase mixed together and then calcined at elevated temperatures to ultimately form the desired positive electrode material. The device has the advantages of mature equipment and high productivity; the disadvantage is that the prepared material has general performance and poor consistency. Sol-gel synthesis is commonly used to prepare positive electrode materials with high specific surface area and good electrochemical properties. The sol-gel process is to prepare sol from metal organic or inorganic compound through solution, dewater the sol under certain condition, to become soft solid gel with slight elasticity, and to dry and bake the gel to obtain nanometer level product. Although the anode material obtained by the sol-gel process has better performance, the reaction speed is slower, generally longer time is needed, and meanwhile, high-temperature roasting is needed, so that the energy consumption is high, the efficiency is low, and the industrial application is not facilitated.
Disclosure of Invention
The invention aims to provide a method for synthesizing carbon-coated sodium ferric pyrophosphate based on a microwave method, which has the advantages of simple process, few steps, extremely short synthesis time, high efficiency, no need of high-temperature calcination and low energy consumption, and the obtained carbon-coated sodium ferric pyrophosphate is used as a positive electrode material of a sodium ion battery, and has higher energy density and good cycle stability.
In order to solve the technical problems, the invention adopts the following technical scheme:
the method for synthesizing the carbon-coated ferric sodium pyrophosphate based on the microwave method comprises the following steps:
1) Dissolving an iron source, a phosphorus source, a sodium source and a complexing agent in water, and preparing to obtain a mixed aqueous solution;
2) Carrying out microwave treatment on the prepared mixed aqueous solution obtained in the step 1) under the protection of inert atmosphere, wherein the heating rate of the microwave treatment is 100-300 ℃/min, and the time of the microwave treatment is 1-6min;
3) And after the reaction is finished, carrying out post-treatment to obtain the carbon-coated ferric sodium pyrophosphate.
According to the above scheme, in the step 1), the ferric salt, the phosphorus source, the sodium source and the complexing agent are all water-soluble.
According to the scheme, in the step 1), the molar ratio of Fe element to complexing agent in the iron source is 1:1-2.
According to the scheme, in the step 1), the iron element in the iron source, the phosphorus element in the phosphorus source and the sodium element in the sodium source are fed according to the stoichiometric ratio of Na 4Fe3(PO4)2P2O7.
According to the scheme, in the step 1), the concentration of Fe element in the mixed aqueous solution is 0.8-1.2mol/L.
According to the scheme, in the step 1), the iron source is selected from ferrous sulfate, ferric chloride, ferrous acetate, ferric nitrate, ferric bromide, ferric iodide and ferric fluoride; the phosphorus source is selected from phosphoric acid; the sodium source is selected from sodium carbonate, sodium dihydrogen phosphate and sodium oxalate; the complexing agent is selected from sodium Nitrilotriacetate (NTA), ethylenediamine tetraacetic acid, diethylenetriamine pentacarboxylic acid, glucose, sucrose, oxalic acid, citric acid, and tartaric acid.
According to the scheme, in the step 2), the power of the microwave treatment is 600-800W.
According to the scheme, in the step 2), the microwave treatment time is 3-5min.
According to the scheme, in the step 2), the inert atmosphere protection is nitrogen protection.
According to the above scheme, in the step 3), the post-treatment is as follows: after the reaction is finished, cooling, then carrying out solid-liquid separation, and washing and drying the separated solid product.
The beneficial effects of the invention are as follows:
The invention discloses a method for synthesizing carbon-coated ferric sodium pyrophosphate based on a microwave method, which comprises the steps of dissolving soluble ferric salt, a phosphorus source, a sodium source and a complexing agent in water, mixing, and carrying out microwave treatment reaction to obtain the carbon-coated ferric sodium pyrophosphate by one-step synthesis within 6 min; the method has the advantages of low raw material cost, simple process, few steps, extremely short synthesis time, high efficiency, no need of high-temperature calcination, low energy consumption, environmental friendliness, safety and no toxicity, and is suitable for large-scale production and amplification; the obtained carbon-coated ferric sodium pyrophosphate is used as a positive electrode material of a sodium ion battery, has higher energy density and good cycle stability, and has wide application prospect.
Drawings
FIG. 1 is an SEM image of the composite sodium iron phosphate prepared in example 1.
Fig. 2 is an XRD pattern of the composite sodium iron phosphate prepared in example 1.
FIG. 3 is an electrical property graph of the composite sodium iron phosphate prepared in example 1.
Fig. 4 is an SEM image of the composite sodium iron phosphate prepared in example 2.
Fig. 5 is an XRD pattern of the composite sodium iron phosphate prepared in example 2.
FIG. 6 is an electrical property graph of the composite sodium iron phosphate prepared in example 2.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a method for synthesizing carbon-coated ferric sodium pyrophosphate based on a microwave method, which comprises the following steps:
according to the element mole ratio of Fe: na: p: complexing agent = 3:4:4:3, mixing an iron source, a phosphorus source, a sodium source, a complexing agent and water to prepare a mixed water solution, wherein the Fe source is ferrous acetate, the Na source is sodium acetate, the P source is phosphoric acid, the complexing agent is citric acid, and the molar concentration of Fe in the mixed water solution is 1mol/L. Placing the mixture into a microwave oven in nitrogen atmosphere, carrying out microwave treatment for 5min at the power of 700W and the heating rate of 170 ℃/min, cooling the mixture with the oven to room temperature, carrying out solid-liquid separation, washing the separated solid product with hot water for 3 times, and carrying out suction filtration and drying to obtain the carbon-coated ferric sodium pyrophosphate.
The obtained positive electrode material is subjected to a half-cell charge and discharge test, and the method comprises the following steps: CR2032 button cell was assembled in an argon-filled glove box with sodium metal sheet as the negative electrode, glass fiber membrane (GF/AWhat-man) as the separator, and NP-009 (1M NaPF 6 in (PC) with 5% (FEC)) mixed slurry ratio NFPP was used as the electrolyte: SP: pvdf=8: 1:1, coated on carbon-coated aluminum foil, dried at 60 ℃ for ten hours, with a loading of active substance of about 3.52mg cm -2, tested: and the mixture is placed for 4 hours, and the multiplying power (0.1C) voltage range is 2.0V-4.6V.
FIGS. 1-3 are SEM and XRD patterns and electrical properties of the composite material obtained in example 1.
The figure shows: the primary particles of the material synthesized by the microwave method are uniform and smaller in the range of 50-100nm, and the dispersibility is good, so that the performance of the material is favorably exerted. XRD showed characteristic peaks meeting the standard card of sodium ferric pyrophosphate. The charge capacity was 111mAh/g and the discharge capacity was 99mAh/g under the test of 0.1C (1C=129 mAh).
Example 2
The embodiment provides a method for synthesizing carbon-coated ferric sodium pyrophosphate based on a microwave method, which comprises the following steps:
According to the element mole ratio of Fe: na: p: complexing agent = 3:4:4:4.5, mixing an iron source, a phosphorus source, a sodium source, a complexing agent and water to prepare a mixed water solution, wherein the Fe source is ferrous sulfate, the Na source is sodium oxalate, the P source is phosphoric acid, the complexing agent is tartaric acid, and the molar concentration of Fe in the mixed water solution is 1 mol/L. Placing the mixture into a microwave oven in nitrogen atmosphere, carrying out microwave treatment for 5min at the power of 700W and the heating rate of 170 ℃/min, cooling the mixture with the oven to room temperature, carrying out solid-liquid separation, washing the separated solid product with hot water for 3 times, and carrying out suction filtration and drying to obtain the carbon-coated ferric sodium pyrophosphate.
The obtained positive electrode material is subjected to a half-cell charge and discharge test, and the method comprises the following steps: CR2032 button cell was assembled in an argon-filled glove box with sodium metal sheet as the negative electrode, glass fiber membrane (GF/AWhat-man) as the separator, and NP-009 (1M NaPF 6 in (PC) with 5% (FEC)) mixed slurry ratio NFPP was used as the electrolyte: SP: pvdf=8: 1:1, coated on carbon-coated aluminum foil, dried at 60 ℃ for ten hours, with a loading of active substance of about 3.52mg cm -2, tested: and the mixture is placed for 4 hours, and the multiplying power (0.1C) voltage range is 2.0V-4.0V.
Fig. 4-6 are SEM images and XRD images and electrical properties of the composite material prepared in example 2.
The figure shows that the primary particles of the material synthesized by the microwave method are uniform and smaller within the range of 50-100nm, and the dispersibility is better, thereby being beneficial to the performance of the material. XRD showed characteristic peaks meeting the standard card of sodium ferric pyrophosphate. The charge capacity was 112mAh/g and the discharge capacity was 103mAh/g under the test of 0.1C (1C=129 mAh).
It will be understood that modifications and variations will be apparent to those skilled in the art from the foregoing description, and it is intended that all such modifications and variations be included within the scope of the following claims.

Claims (9)

1. The method for synthesizing the carbon-coated ferric sodium pyrophosphate based on the microwave method is characterized by comprising the following steps of:
1) Dissolving an iron source, a phosphorus source, a sodium source and a complexing agent in water, and preparing to obtain a mixed aqueous solution;
2) Carrying out microwave treatment on the prepared mixed aqueous solution obtained in the step 1) under the protection of inert atmosphere, wherein the heating rate of the microwave treatment is 100-300 ℃/min, and the time of the microwave treatment is 1-6min;
3) And after the reaction is finished, carrying out post-treatment to obtain the carbon-coated ferric sodium pyrophosphate.
2. The method according to claim 1, wherein in the step 1), the molar ratio of the Fe element and the complexing agent in the iron source is 1:1-2.
3. The method according to claim 1, wherein in step 1), the iron element in the iron source, the phosphorus element in the phosphorus source and the sodium element in the sodium source are fed in a stoichiometric ratio in Na 4Fe3(PO4)2P2O7.
4. The method according to claim 1, wherein in the step 1), the concentration of the Fe element in the iron source in the mixed aqueous solution is 0.8 to 1.2mol/L.
5. The method according to claim 1, wherein in step 1), the iron source is selected from the group consisting of ferrous sulfate, ferric chloride, ferrous acetate, ferric nitrate, ferric bromide, ferric iodide, ferric fluoride; the phosphorus source is selected from phosphoric acid; the sodium source is selected from sodium carbonate, sodium dihydrogen phosphate and sodium oxalate; the complexing agent is selected from sodium nitrilotriacetic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentacarboxylic acid, glucose, sucrose, oxalic acid, citric acid and tartaric acid.
6. The method according to claim 1, wherein in the step 2), the power of the microwave treatment is 600-800W.
7. The method according to claim 1, wherein in the step 2), the microwave treatment is performed for 3 to 5 minutes.
8. The method according to claim 1, wherein in the step 2), the inert atmosphere is nitrogen.
9. The method according to claim 1, wherein in the step 3), the post-processing is: after the reaction is finished, cooling, then carrying out solid-liquid separation, and washing and drying the separated solid product.
CN202410467286.8A 2024-04-18 2024-04-18 Method for synthesizing carbon-coated ferric sodium pyrophosphate based on microwave method Pending CN118405679A (en)

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