CN110589792A - Preparation method of anode material ferric pyrophosphate - Google Patents
Preparation method of anode material ferric pyrophosphate Download PDFInfo
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- CN110589792A CN110589792A CN201910833420.0A CN201910833420A CN110589792A CN 110589792 A CN110589792 A CN 110589792A CN 201910833420 A CN201910833420 A CN 201910833420A CN 110589792 A CN110589792 A CN 110589792A
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- ferric pyrophosphate
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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
- C01B25/38—Condensed phosphates
- C01B25/42—Pyrophosphates
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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
- H01M4/58—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
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- 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
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- 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
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- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
A method for preparing ferric pyrophosphate serving as a negative electrode material. Firstly, using alcohol as a solvent, and using soluble ferric salt and pyrophosphoric acid as raw materials to react to prepare an iron pyrophosphate compound; and then sintering the ferric pyrophosphate compound in an inert gas atmosphere to obtain the ferric pyrophosphate serving as the anode material. The preparation method creatively synthesizes the ferric pyrophosphate material, directly adopts the less-than-selected pyrophosphoric acid as the raw material, is simple and convenient, has easily obtained raw materials, is economical and practical, and is suitable for large-scale production; the ferric pyrophosphate serving as the negative material has excellent electrochemical performance, and develops a good prospect for the field of new energy storage materials.
Description
Technical Field
The invention relates to the field of battery negative electrode materials, in particular to a preparation method of a negative electrode material ferric pyrophosphate.
Background
In the world, with the increasing environmental pollution and global warming caused by the burning of fossil fuels, countries are changing the economic model based on fossil fuels to the economic model based on new energy, and the development of renewable energy and clean energy is a major strategic task for the economic and social development of China. The high-speed development of the society demands high-safety and low-cost energy storage technology urgently. Lithium ion batteries are considered one of the most promising energy storage technologies to meet these demands, and have been successfully used in portable electronic devices, plug-in hybrid vehicles, and pure electric vehicles, effectively reducing the amount of carbon dioxide emissions generated during urban transportation.
The lithium ion battery is a device for converting chemical energy into electric energy through chemical reaction, is one of important ways for storing and converting energy, is widely applied in almost all fields, and is an important product for relieving the current energy crisis and reducing environmental pollution. Among secondary batteries, lithium ion batteries are rapidly becoming the first choice for rechargeable power sources of portable electronic products today due to their advantages of high operating voltage, long cycle life, large capacity, small volume, small self-discharge, no memory effect, little environmental pollution, etc. For lithium ion batteries, the negative electrode material has a decisive role in the capacity of the battery and is closely related to the cost and the safety performance of the battery, and the negative electrode material becomes a key factor for restricting the further improvement of the overall performance of the lithium ion battery. Therefore, the development of a novel lithium ion battery cathode material is very important.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and provide a preparation method of a novel anode material ferric pyrophosphate.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of ferric pyrophosphate serving as a negative electrode material comprises the following steps of firstly, reacting by taking alcohol as a solvent and soluble ferric salt and pyrophosphoric acid as raw materials to prepare a ferric pyrophosphate compound; and then sintering the ferric pyrophosphate compound in an inert gas atmosphere to obtain the ferric pyrophosphate serving as the anode material.
Preferably, the alcohol is selected from one or more of methanol, ethanol, ethylene glycol and isopropanol, and the water content in the alcohol is not more than 1%. The pyrophosphoric acid is hydrolyzed to phosphoric acid by contacting with water, resulting in the formation of iron phosphate, resulting in impure phases.
Preferably, the amount ratio of the iron element in the soluble iron salt to the pyrophosphoric acid is 1:0.5 ~ 3, preferably 1:0.8 ~ 1.5.5
Preferably, the soluble iron salt is selected from one or more of ferrous chloride, ferrous sulfate, ferrous acetate and ferrous nitrate and their hydrates; preferably ferrous sulfate
Preferably, the temperature of the reaction is 0 ~ 80 deg.C, preferably 25 ~ 50 deg.C.
Preferably, the reaction time is 0.1 ~ 12h, preferably 0.5 ~ 4 h.
Preferably, the sintering temperature is 400 ~ 600 ℃, preferably 500 ~ 550 DEG C
Preferably, the sintering time is 2 ~ 10h, preferably 5 ~ 8 h.
Preferably, the temperature increase rate during sintering is 5 ℃/min.
Preferably, the preparation method of the anode material ferric pyrophosphate comprises the following specific steps:
(1) preheating pyrophosphoric acid, dissolving pyrophosphoric acid in alcohol to form a pyrophosphoric acid solution, adding an alcoholic solution of ferric chloride to form a reaction system, stirring for reaction for 10min ~ 30min, carrying out solid-liquid separation, washing, and drying to obtain an iron pyrophosphate compound;
(2) and (2) taking the ferric pyrophosphate compound obtained in the step (1) under an inert gas atmosphere, and sintering at 400 ~ 600 ℃ and 600 ℃ for 4 ~ 6 h.
Preferably, the temperature of the preheating is 70 ~ 100 deg.C, preferably 75 ~ 95 deg.C.
Preferably, the preheating time is 0.5 ~ 12h, preferably 1 ~ 2 h.
Preferably, in the reaction system, the initial concentration of the pyrophosphoric acid is 0.001 ~ 2mol/L, preferably 0.01 ~ 0.1.1 mol/L.
Preferably, the washing is with water. Washing with water can remove impurities, and if washing with an organic solvent, residues can be generated, thereby resulting in impure phases of the product.
Preferably, the drying temperature is 50 ~ 250 ℃, preferably 70 ~ 150 ℃, and the drying time is 2h ~ 10h, preferably 3h ~ 8 h.
The invention has the beneficial effects that:
(1) the preparation method creatively synthesizes the ferric pyrophosphate material, directly adopts less-than-selected pyrophosphoric acid as a raw material, combines the pyrophosphoric acid with iron metal ions to obtain the ferric pyrophosphate as the cathode material, and provides a new way for synthesizing the ferric pyrophosphate;
(2) the ferric pyrophosphate material prepared by the method can be applied to the field of energy storage, can be applied to ferric pyrophosphate of an energy storage material for the first case, has excellent electrochemical performance, and develops a prospect for the field of new energy storage materials.
Drawings
FIG. 1 is an SEM photograph of an anode material ferric pyrophosphate prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of iron pyrophosphate as a negative electrode material prepared in example 1 of the present invention;
fig. 3 is a graph showing electrochemical properties of the anode material ferric pyrophosphate prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
The embodiment comprises the following steps:
(1) in order to conveniently weigh the pyrophosphoric acid condensed into a solid state, firstly preheating the pyrophosphoric acid in a forced air drying oven at 80 ℃ for 2 hours, and then sucking 1.9775g (10 mmol) of pyrophosphoric acid by using a syringe and adding the pyrophosphoric acid into 100mL of ethanol solution (with the water content of 0.5%) to obtain a pyrophosphate solution; 2.7802g (10 mmol) of ferrous sulfate heptahydrate is weighed, dissolved in 100mL of ethanol solution (the water content is 0.5 percent), added with the pyrophosphate solution, directly mixed and stirred at room temperature for reaction for 10 minutes to generate precipitate; centrifuging and washing for three times; drying in an oven at 80 ℃ for 12h to obtain a ferric pyrophosphate compound;
(2) and (2) under the protection of inert gas, heating the ferric pyrophosphate compound obtained in the step (1) to 500 ℃ (the heating rate is 5 ℃/min), and sintering for 5h to obtain the cathode material ferric pyrophosphate.
The negative electrode material ferric pyrophosphate prepared in this example was taken to perform electron microscope scanning, and the result is shown in fig. 1, specifically, three electron microscope images with different magnifications in the figure are non-uniform block-shaped, rough surface, and the size is 20 ~ 50 μm.
The negative electrode material ferric pyrophosphate prepared in the example is taken for X-ray diffraction measurement, the result is shown in figure 2, the standard PDF card of the X-ray diffraction composite ferric pyrophosphate can be seen, and the explanation phase is pure phase ferric pyrophosphate and has good and obvious sharp peak type.
Taking the anode material pyrophosphate iron phosphate prepared in the embodiment as an active substance, weighing the materials according to the ratio of the active substance to acetylene black to PVDF =8:1:1, mixing, after uniformly mixing, dropwise adding a proper amount of n-methylpyrrolidone (NMP) to prepare slurry with a certain viscosity, uniformly coating the slurry on an aluminum foil, drying, then cutting into 12mm round pieces as a current collector, putting the prototype current collector into a 2030 type button battery under the protection of argon in a glove box, taking metal lithium as a cathode piece, taking a Celgard type polyethylene film as a diaphragm, and taking 1mol/L LiPF6Dissolving in mixture of Ethyl Carbonate (EC) and dimethyl carbonate (DMC) as electrolyte (EC: DMC =1:1 (v/v)), mounting 2032 type coin cell, mounting coin cell, and testing electrochemical performance by blue electric testAnd (4) testing a system, activating for three circles under the small multiplying power of 0.1C, and then performing charge-discharge cycle testing under the condition of 1C.
The electrochemical performance test result is shown in fig. 3, in the graph, the curve is divided into two y axes, the left arrow indicates a cycle capacity curve of the battery, the cycle capacity curve indicates the capacity performance of the battery, and the right arrow indicates a cycle coulombic efficiency curve of the battery, so that the coulombic efficiency of the battery in each cycle period can be clearly expressed.
As shown in fig. 3, after activation at a rate of 0.1C, the first charge specific capacity is 607.9mAh/g, the first discharge specific capacity is 807.1mAh/g, the first efficiency is 75.3%, and after 1C is cycled to 100 cycles, the charge specific capacity is 378.3mAh/g, the discharge specific capacity is 379.3mAh/g, and the coulombic efficiency is 99.7%, which indicates that the battery assembled by the electrode prepared from the obtained negative electrode material has good electrochemical performance. (general battery test first activated three times at 0.1C low rate, then tested at 1C rate for normal cycle)
As can be further seen from fig. 3, the battery has locally better capacity and cycle performance, and the reason that the capacity curve begins to decline and rise is that the capacity of the negative electrode material generally has the phenomenon of forming an SEI film to reversely rise, and the capacity is stably maintained at less than about 400 in the later period, which proves that the material has good electrochemical performance, and the coulombic efficiency is basically maintained at more than 99% in the later period, which proves that the material has good coulombic efficiency.
Example 2
The embodiment comprises the following steps:
(1) in order to conveniently weigh the pyrophosphoric acid condensed into a solid state, firstly preheating the pyrophosphoric acid in a forced air drying oven at 80 ℃ for 2h, and then sucking 1.9775g (10 mmol) of pyrophosphoric acid by using a syringe and adding the pyrophosphoric acid into 100mL of ethylene glycol (the water content is 0%) to obtain a pyrophosphoric acid solution; 8.3406g (30 mmol) of ferrous sulfate heptahydrate is weighed, dissolved in 100mL of glycol (the water content is 0 percent), added with pyrophosphoric acid solution, directly mixed and stirred at room temperature for reaction for 10 minutes to generate precipitate; centrifuging and washing for three times; drying in an oven at 100 ℃ for 12h to obtain a ferric pyrophosphate compound;
(2) and (2) under the protection of inert gas, heating the ferric pyrophosphate compound obtained in the step (1) to 500 ℃ (the heating rate is 5 ℃/min), and sintering for 5h to obtain the cathode material ferric pyrophosphate.
The electrochemical performance test method of this example is the same as that of example 1
The cathode material ferric pyrophosphate prepared in the embodiment is used for scanning by an electron microscope, and a sample is detected to be in an uneven stone shape, the surface of the sample is rough, and the size of the sample is 10 ~ 50 μm.
The anode material ferric pyrophosphate prepared in the embodiment is taken for X-ray diffraction measurement, and detection shows that the prepared material is pure-phase ferric pyrophosphate and no other impurities are generated
The cathode material ferric pyrophosphate prepared in the embodiment is taken to carry out electrochemical performance detection, and through detection, activation is carried out at a multiplying power of 0.1C, the first charging specific capacity is 620mAh/g, the first discharging specific capacity is 756mAh/g, the first efficiency is 82%, after 1C is circulated to 100 circles, the charging specific capacity is 390mAh/g, the discharging specific capacity is 394mAh/g, and the coulombic efficiency is 98.9%, which indicates that a battery assembled by an electrode prepared from the obtained cathode material has good electrochemical performance.
Example 3
The embodiment comprises the following steps:
(1) in order to conveniently weigh the pyrophosphoric acid condensed into a solid state, firstly preheating the pyrophosphoric acid in a forced air drying oven at 80 ℃ for 2 hours, and then sucking 3.9550g (20 mmol) of pyrophosphoric acid by using a syringe and adding the pyrophosphoric acid into 100mL of ethanol solution (with the water content of 0.5%) to obtain a pyrophosphate solution; 2.7802g (10 mmol) of ferrous sulfate heptahydrate is weighed, dissolved in 100mL of ethanol solution (the water content is 0.5 percent), added with pyrophosphoric acid solution, directly mixed and stirred at room temperature for reaction for 10 minutes to generate precipitate; centrifuging and washing for three times; drying in an oven at 100 ℃ for 12h to obtain a ferric pyrophosphate compound;
(2) under the protection of inert gas, heating the ferric pyrophosphate compound obtained in the step (1) to 400 ℃ (the heating rate is 5 ℃/min), and sintering for 5h to obtain the cathode material ferric pyrophosphate.
The electrochemical performance test method of this example is the same as that of example 1
The cathode material ferric pyrophosphate prepared in the embodiment is used for scanning by an electron microscope, and a sample is detected to be in an uneven stone shape, the surface of the sample is rough, and the size of the sample is 10 ~ 50 μm.
The anode material ferric pyrophosphate prepared in the embodiment is taken for X-ray diffraction measurement, and detection shows that the prepared material is pure-phase ferric pyrophosphate and no other impurities are generated. The cathode material ferric pyrophosphate prepared in the embodiment is taken to carry out electrochemical performance detection, and through detection, activation is carried out at a multiplying power of 0.1C, the first charging specific capacity is 596mAh/g, the first discharging specific capacity is 740mAh/g, the first efficiency is 80%, after 1C is circulated to 100 circles, the charging specific capacity is 356mAh/g, the discharging specific capacity is 558mAh/g, and the coulombic efficiency is 99.4%, which indicates that a battery assembled by an electrode prepared from the obtained cathode material has good electrochemical performance. The above description is only an example of the present invention, and is not intended to limit the present invention, and it is obvious to those skilled in the art that various modifications and variations can be made in the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of ferric pyrophosphate serving as a negative electrode material is characterized by comprising the following steps of firstly, taking alcohol as a solvent, and taking soluble ferric salt and pyrophosphoric acid as raw materials to react to prepare a ferric pyrophosphate compound; and then sintering the ferric pyrophosphate compound in an inert gas atmosphere to obtain the ferric pyrophosphate serving as the anode material.
2. The method for preparing ferric pyrophosphate as the anode material of claim 1, wherein the alcohol is selected from one or more of methanol, ethanol, ethylene glycol and isopropanol, and the water content in the alcohol is not more than 1%.
3. The preparation method of the anode material ferric pyrophosphate according to claim 1 or 2, wherein the amount ratio of the iron element in the soluble ferric salt to the pyrophosphoric acid is 1:0.5 ~ 3, and preferably, the soluble ferric salt is selected from one or more of ferrous chloride, ferrous sulfate, ferrous oxalate and their hydrates.
4. The method for preparing ferric pyrophosphate serving as a cathode material of any one of claims 1 to 3, wherein the reaction temperature is 0 ~ 80 ℃, and preferably the reaction time is 0.05 ~ 12h, and preferably 0.1 ~ 1 h.
5. The method for preparing the anode material ferric pyrophosphate according to any one of claims 1-4, wherein the sintering temperature is 400 ~ 600 ℃, preferably the sintering time is 2 ~ 10h, and preferably the heating rate during sintering is 5 ℃/min.
6. The preparation method of the anode material ferric pyrophosphate of any one of claims 1-5, characterized by comprising the following specific steps:
(1) preheating pyrophosphoric acid, dissolving pyrophosphoric acid in alcohol to form a pyrophosphoric acid solution, adding an alcoholic solution of ferric chloride to form a reaction system, stirring for reaction for 10min ~ 30min, carrying out solid-liquid separation, washing, and drying to obtain an iron pyrophosphate compound;
(2) and (2) taking the ferric pyrophosphate compound obtained in the step (1) under an inert gas atmosphere, and sintering at 400 ~ 600 ℃ and 600 ℃ for 4 ~ 6 h.
7. The preparation method of the anode material ferric pyrophosphate according to claim 6, wherein the preheating temperature is 70 ~ 100 ℃, preferably the preheating time is 0.5 ~ 12h, and the preheating time is preferably 1 ~ 2 h.
8. The method for producing ferric pyrophosphate as an anode material according to claim 6 or 7, wherein the initial concentration of the pyrophosphoric acid in the reaction system is 0.001 ~ 2mol/L, preferably 0.01 ~ 0.1.1 mol/L.
9. The method for preparing ferric pyrophosphate as an anode material according to any one of claims 6 to 8, wherein said washing is washing with water.
10. The method for preparing ferric pyrophosphate serving as an anode material according to any one of claims 6 to 9, wherein the drying temperature is 50 ~ 250 ℃ and the drying time is 2h ~ 10 h.
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CN117125687A (en) * | 2021-05-31 | 2023-11-28 | 福建师范大学 | Method for circularly regenerating iron phosphate for lithium battery from positive lithium iron phosphate of waste lithium battery |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101363079A (en) * | 2007-08-10 | 2009-02-11 | 有研稀土新材料股份有限公司 | Smelting method of iron rich mengite rare-earth mine |
CN104662717A (en) * | 2013-09-04 | 2015-05-27 | 株式会社Lg化学 | Transition metal-pyrophosphate anode active material, manufacturing method therefor, and lithium secondary battery or hybrid capacitor comprising same |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101363079A (en) * | 2007-08-10 | 2009-02-11 | 有研稀土新材料股份有限公司 | Smelting method of iron rich mengite rare-earth mine |
CN104662717A (en) * | 2013-09-04 | 2015-05-27 | 株式会社Lg化学 | Transition metal-pyrophosphate anode active material, manufacturing method therefor, and lithium secondary battery or hybrid capacitor comprising same |
Non-Patent Citations (1)
Title |
---|
佚名: "《化学词典》", 30 September 1989 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117125687A (en) * | 2021-05-31 | 2023-11-28 | 福建师范大学 | Method for circularly regenerating iron phosphate for lithium battery from positive lithium iron phosphate of waste lithium battery |
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Application publication date: 20191220 |