CN114639827A - Preparation method of iron-based fluoride composite positive electrode material - Google Patents
Preparation method of iron-based fluoride composite positive electrode material Download PDFInfo
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Abstract
The invention relates to FeF3The preparation method of the/C-based composite cathode material comprises the following steps: preparing a mixed solution of an iron source and a fluorine source; after stirring and reacting, carrying out suction filtration, washing and drying to obtain a precursor; grinding the precursor, and then calcining at 350-450 ℃ for 2-12 h under the atmosphere of inert gas to obtain a fluorine-containing anode material; and (3) ball-milling and uniformly mixing the fluorine-containing positive electrode material and a carbon source, and calcining at a low temperature of 200-300 ℃ for 1-3 h in an inert gas atmosphere to obtain the fluorine-containing positive electrode material. The invention introduces carbon materials to improve the electronic conductance of the material and construct the ferric fluoride composite anode material. The lithium ion battery anode material prepared by the method can improve the charge and discharge capacity and the cycling stability of the battery.
Description
Technical Field
The invention belongs to the technical field of energy storage material preparation, relates to an ion battery anode material, and particularly relates to a preparation method of an iron-based fluoride composite anode material.
Background
In recent years, with the increasing number of the global population, the fossil fuel is increasingly consumed, and the new energy automobile continuously and greatly solves the problems of environmental pollution and energy exhaustion. The key part in the field of new energy automobiles is a power battery which mainly comprises four parts, namely a positive electrode, a negative electrode, electrolyte and a diaphragm. As an energy conversion and storage device, the energy density is closely related to the positive and negative electrode materials of the battery. Among them, the positive electrode material is a main factor limiting the performance of the battery, and also directly determines the cost of the battery.
Firstly, because iron resources are rich, the price is low, the environment is friendly, secondly, fluoride ions have strong electronegativity, and the chemical bond energy of metal fluoride is high, the iron-based fluoride gradually becomes one of the most popular anode materials in recent years due to high specific capacity and high voltage. But the inherent low ionic and electronic conductivity of iron-based fluorides greatly limits the exertion of rate capability.
CN111883770A discloses a composite ferric trifluoride anode material, a preparation method and an application thereof, wherein the synthesis method comprises the following steps: dispersing the treated carbon nanohorn in F-containing ionic liquid, and adding Fe (NO)3)3·9H2Keeping the temperature of O and ethanol at 60-100 ℃, stirring for 5-8 h, centrifuging, washing with acetone, and freeze-drying to obtain the target product. The composite iron-based fluoride obtained by the method has good conductivity and is suitable for large multiplying power;however, this method requires heating, the reaction time is too long, and the fluorine source is expensive, which limits its large-scale application.
CN108682808A discloses a method for coating and modifying a lithium ion battery anode material: dissolving a lithium ion battery anode material in a ferric nitrate solution, then dropwise adding an ammonium bifluoride solution into the solution, generating ferric fluoride trihydrate on the surface of anode material particles at normal temperature, and calcining an obtained product after suction filtration, drying and grinding to obtain the coated lithium ion battery anode material. The iron-based/ternary composite material is a composite of a traditional ternary material and iron-based fluoride, and the charge and discharge energy and the stability are improved. However, the process is complex, needs to prepare ternary materials first and then carry out composite reaction, and is long in time consumption and uneconomical in the whole process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an iron-based fluoride composite positive electrode material which is simple and easy to operate and suitable for mass production, and the iron-based fluoride composite positive electrode material can be used as a positive electrode fluorine-containing material of a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an iron-based fluoride composite positive electrode material comprises the following steps:
1) preparing a mixed solution of an iron source and a fluorine source;
2) after the mixed solution is stirred and reacts, a white solid precursor is obtained through suction filtration, washing and drying;
3) grinding the precursor, and then calcining at 350-450 ℃ for 2-12 h under the atmosphere of inert gas to obtain a black fluorine-containing positive electrode material;
4) and (3) ball-milling and uniformly mixing the fluorine-containing anode material and a carbon source, and then calcining at the low temperature of 200-300 ℃ for 1-3 h in an inert gas atmosphere to obtain the ferric fluoride/carbon anode material.
Specifically, in the above method, in step 1), the iron source includes ferric nitrate nonahydrate and/or ferric chloride hexahydrate; the fluorine source is ammonium fluoride.
Specifically, in the method, in the step 1), the concentration of the iron source in the mixed solution is 0.5-1.5 mol/L, and the concentration of the fluorine source is 2.5-10 mol/L. Preferably, the iron source solution in step (1) is obtained by dissolving an iron source in water, and the concentration in the mixed solution is 0.5-1.5 mol/L, such as 0.5mol/L, 1mol/L, 1.5mol/L, and the like. The fluorine source is dissolved in water, and the concentration of the fluorine source in the mixed solution is 2.5-10 mol/L, such as 3mol/L, 6mol/L, 8mol/L or 10 mol/L. Preferably, the fluorine solution is slowly added to the iron source solution to obtain a mixed solution.
Specifically, in the above method, in the step 2), the stirring manner is: stirring the mixed solution at normal temperature for 0.5-2 h, such as 0.5h, 1h, 1.5h, 2h and the like; the stirring speed is 100 rpm-180 rpm. For example, 100rpm, 120rpm, 150rpm, 160rpm, 170rpm, 180rpm, etc.
Specifically, in the above method, in step 2), the washing solution selected for washing is ethanol and/or water, and after washing, vacuum drying is performed at 60-80 ℃, for example, 60 ℃, 70 ℃, 80 ℃ or the like.
Specifically, in the above method, in step 3) and step 4), the inert gas is one or a mixture of at least two of nitrogen, argon and a mixed hydrogen-argon gas.
Specifically, in the method, in the step 3), the heating rate is 1-10 ℃/min; in the step 4), the heating rate is 1-5 ℃/min.
Specifically, in the method, in the step 4), the carbon source is acetylene black and/or biomass carbon, and the mass ratio of the fluorine-containing cathode material to the carbon source is (4-5): 1, for example, 4:1, 4.2:1, 4.5:1, 4.6:1 or 5: 1. And performing ball milling and mixing on the carbon source and the fluorine-containing anode material at the rotating speed of 300-350 rpm, and performing low-temperature secondary calcination to obtain the carbon-coated iron-based fluoride. The ball milling and mixing time is controlled to be 2-3 h. The fluorine-containing anode material is mixed with a carbon source, the conductivity of the material can be increased through low-temperature secondary calcination, and the carbon source coated on the surface of the iron-based fluoride is firmer, so that the stability of the material in the charge-discharge cycle process is enhanced.
The invention provides the iron-based fluoride composite positive electrode material prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention adopts safe ammonium fluoride as a fluorine source, obtains a precursor by stirring through a normal-temperature liquid phase method, and finally obtains a target product by calcining. The reaction process is more sufficient and mild, the process is simple, the consumed time is short, and the method is suitable for large-scale batch production;
2) the lithium ion battery anode material provided by the invention solves the problems of nickel and cobalt element resource shortage and high price in the existing lithium ion battery industry; according to the invention, a carbon source is introduced to improve the electronic conductivity of the material and construct the ferric fluoride composite anode material. The lithium ion battery anode material prepared by the method can improve the charge and discharge capacity and the cycle stability of the battery;
3) the anode material of the lithium ion battery provided by the invention is an iron-based fluoride composite material; the iron-based fluoride can provide high theoretical specific capacity, and carbon in the electrode material can improve the electronic conductance of the material and buffer the stress change of the material in the charging and discharging processes. Under the voltage window of 2V-4.2V and the current density of 100mA/g, the first cyclic discharge specific capacity is more than 190mAh/g, and the capacity retention rate of 100 cycles is more than 91%.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
In the following examples, all the raw materials used were common commercial products which were directly available. For example, the biomass carbon is purchased from straw biomass carbon and rice hull biomass carbon of Jiangsu Huafeng agricultural bioengineering limited company. Room temperature refers to 25 ± 5 ℃.
Example 1
A preparation method of an iron-based fluoride composite positive electrode material comprises the following steps:
(1) mixing Fe (NO)3)3·9H2Dissolving O in deionized water to obtain 250mL of iron solution, NH4Dissolving F in deionized water to obtain 300mL of fluorine solution, slowly adding the fluorine solution into the iron solution to obtain a mixed solution, and adding Fe (NO) in the mixed solution3)3·9H2O concentration of 1mol/L, NH4The concentration of F is 6 mol/L;
(2) stirring the mixed solution at room temperature for 1h, and controlling the stirring speed to be 120 rpm;
(3) and (3) carrying out suction filtration on the solution after the reaction in the step (2), washing with deionized water, and carrying out vacuum drying on a filter cake at 60 ℃ for 8h to obtain a white precursor. Grinding the precursor into powder, heating to 350 ℃ at the speed of 5 ℃/min from room temperature in an argon atmosphere, preserving heat for 12h, and naturally cooling to obtain ferric fluoride;
(4) and ball-milling and mixing the obtained ferric fluoride powder and acetylene black according to the mass ratio of 4:1, wherein the rotating speed is controlled at 300rpm, and the time is 2.5 h. Then placing the fully mixed substances in a tube furnace, introducing argon, raising the temperature to 200 ℃ at the speed of 2 ℃/min, keeping the temperature for 3 hours, and naturally cooling to obtain the iron-based fluoride composite cathode material (FeF)3/C）。
And (3) testing the battery performance:
the obtained anode material is used as the anode material of the lithium ion battery to carry out electrochemical performance test, and the pole piece ratio is as follows: a positive electrode material: acetylene black: polyvinylidene fluoride PVDF is 8:1:1 (mass ratio), a lithium sheet is used as a reference electrode, ethylene carbonate and diethyl carbonate with the mass of 1:1 are used as solvents in the electrolyte, lithium hexafluorophosphate is used as an additive, and the concentration is 1 mol/L. And preparing a CR2025 button cell. Under the voltage window of 2V-4.2V and the current density of 100mA/g, the first cyclic discharge specific capacity of the battery is 195mAh/g, and the capacity retention rate of 100 cycles is 94%.
Example 2
A preparation method of an iron-based fluoride composite positive electrode material comprises the following steps:
(1) mixing Fe (NO)3)3·9H2Dissolving O in deionized water to obtain 250mL of iron solution, NH4Dissolving F in deionized water to obtain 300mL of fluorine solution, slowly adding the fluorine solution into the iron solution to obtain a mixed solution, and adding Fe (NO) in the mixed solution3)3·9H2O concentration of 0.5mol/L, NH4The concentration of F is 2.5 mol/L;
(2) stirring the mixed solution at room temperature for 1h, wherein the stirring speed is controlled to be 140 rpm;
(3) and (3) carrying out suction filtration on the solution after the reaction in the step (2), washing with ethanol, and carrying out vacuum drying on a filter cake at 60 ℃ for 8h to obtain a white precursor. Grinding the precursor into powder, heating to 380 ℃ at the speed of 5 ℃/min from room temperature in an argon atmosphere, preserving heat for 10h, and naturally cooling to obtain ferric fluoride;
(4) ball-milling and mixing the obtained ferric fluoride powder and straw biomass carbon according to a mass ratio of 4.8:1, controlling the rotating speed at 350rpm for 2 hours, then placing the fully mixed substance in a tubular furnace, introducing nitrogen, raising the temperature to 250 ℃ at a speed of 5 ℃/min, keeping the temperature for 2 hours, and naturally cooling to obtain FeF3and/C. The lithium ion battery positive electrode material is used as a lithium battery positive electrode material. Under the same test conditions of the embodiment 1, the highest specific discharge capacity is 201mAh/g, and the capacity retention rate of 100 cycles is 95%.
Example 3
A preparation method of an iron-based fluoride composite positive electrode material comprises the following steps:
(1) FeCl is added3·6H2Dissolving O in deionized water to obtain 350mL of iron solution, NH4Dissolving F in deionized water to obtain 200mL of fluorine solution, slowly adding the fluorine solution into the iron solution to obtain a mixed solution, and adding FeCl in the mixed solution3·9H2O concentration of 0.5mol/L, NH4The concentration of F is 2.5 mol/L;
(2) stirring the mixed solution at room temperature for 2 hours, wherein the stirring speed is controlled to be 160 rpm;
(3) and (3) carrying out suction filtration on the solution after the reaction in the step (2), washing with deionized water, and carrying out vacuum drying on a filter cake at 80 ℃ for 6h to obtain a white precursor. Grinding the precursor into powder, heating to 400 ℃ at the speed of 8 ℃/min from room temperature in the nitrogen atmosphere, preserving heat for 8h, and naturally cooling to obtain ferric fluoride;
(4) ball-milling and mixing the obtained ferric fluoride powder and straw biomass carbon according to a mass ratio of 4.5:1, controlling the rotating speed at 330rpm for 2.5h, then placing the fully mixed substance in a tubular furnace, introducing hydrogen and argon mixed gas, raising the temperature to 280 ℃ at the speed of 3 ℃/min, keeping the temperature for 2.8h, and naturally cooling to obtain FeF3and/C. Used as a lithium battery cathode material and has the highest specific discharge capacity under the same test conditions as in example 1The capacity retention rate is 91 percent after 150 cycles, and the capacity retention rate is 196 mAh/g.
Example 4
A preparation method of an iron-based fluoride composite positive electrode material comprises the following steps:
(1) mixing Fe (NO)3)3·9H2Dissolving O in deionized water to obtain 250mL of iron solution, NH4Dissolving F in deionized water to obtain 300mL of fluorine solution, slowly adding the fluorine solution into the iron solution to obtain a mixed solution, and adding Fe (NO) in the mixed solution3)3·9H2O concentration of 1mol/L, NH4The concentration of F is 8 mol/L;
(2) stirring the mixed solution at room temperature for 2 hours, wherein the stirring speed is controlled to be 180 rpm;
(3) and (3) carrying out suction filtration on the solution after the reaction in the step (2), washing the solution by using deionized water and ethanol in sequence, and carrying out vacuum drying on a filter cake at 80 ℃ for 6 hours to obtain a white precursor. Grinding the precursor into powder, heating to 450 ℃ at a speed of 10 ℃/min from room temperature in an argon atmosphere, preserving heat for 8h, and naturally cooling to obtain the fluorine-containing lithium ion battery anode material;
(4) ball-milling and mixing the obtained ferric fluoride powder and the rice hull biomass carbon according to the mass ratio of 4.2:1, controlling the rotating speed at 350rpm for 2 hours, then placing the fully mixed substance in a tubular furnace, introducing argon, raising the temperature to 200 ℃ at the speed of 1 ℃/min, keeping the temperature for 3 hours, and naturally cooling to obtain FeF3and/C. The lithium ion battery positive electrode material has the highest specific discharge capacity of 216mAh/g and the capacity retention rate of 95% after 100 cycles under the same test conditions in example 1.
Example 5
A preparation method of an iron-based fluoride composite positive electrode material comprises the following steps:
(1) FeCl is added3·6H2Dissolving O in deionized water to obtain 300mL of iron solution, NH4Dissolving F in deionized water to obtain 300mL of fluorine solution, slowly adding the fluorine solution into the iron solution to obtain a mixed solution, and adding FeCl in the mixed solution3·6H2O concentration of 1.5mol/L, NH4The concentration of F is 10 mol/L;
(2) stirring the mixed solution at room temperature for 0.5h, wherein the stirring speed is controlled to be 180 rpm;
(3) and (3) carrying out suction filtration on the solution after the reaction in the step (2), washing with deionized water, and carrying out vacuum drying on a filter cake at 80 ℃ for 8h to obtain a white precursor. Grinding the precursor into powder, heating to 420 ℃ from room temperature at a speed of 1 ℃/min under the atmosphere of nitrogen, preserving heat for 10h, and naturally cooling to obtain ferric fluoride;
(4) ball-milling and mixing the obtained ferric fluoride powder and acetylene black according to the mass ratio of 4.3:1, controlling the rotating speed at 330rpm for 2.7h, then placing the fully mixed substance in a tube furnace, introducing argon, raising the temperature to 220 ℃ at the speed of 4 ℃/min, keeping the temperature for 3h, and naturally cooling to obtain FeF3and/C. Under the same test conditions of the embodiment 1, the highest specific discharge capacity is 192mAh/g, and the capacity retention rate of 100 cycles is 92%.
Comparative example 1
A preparation method of an iron-based fluoride composite positive electrode material comprises the following steps:
(1) mixing Fe (NO)3)3·9H2Dissolving O in deionized water to obtain 300mL of iron solution, NH4Dissolving F in deionized water to obtain 300mL of fluorine solution, slowly adding the fluorine solution into the iron solution to obtain a mixed solution, and adding Fe (NO) in the mixed solution3)3·9H2O concentration of 1.5mol/L, NH4The concentration of F is 8 mol/L;
(2) the mixed solution was stirred at room temperature for 1 hour with the stirring rate controlled at 180 rpm.
(3) And (3) carrying out suction filtration on the solution after the reaction in the step (2), washing with deionized water, and carrying out vacuum drying on a filter cake at 60 ℃ for 8h to obtain a white precursor. Grinding the precursor into powder, heating to 500 ℃ from room temperature at a speed of 5 ℃/min under the argon atmosphere, preserving heat for 10h, and naturally cooling to obtain ferric fluoride;
(4) ball-milling and mixing the obtained ferric fluoride powder and acetylene black according to the mass ratio of 4:1, controlling the rotating speed at 300rpm for 2.5h, then placing the fully mixed substance in a tube furnace, introducing argon, raising the temperature to 200 ℃ at the speed of 2 ℃/min, keeping the temperature for 3h, and naturally cooling to obtain FeF3/C。
The lithium ion battery positive electrode material has the highest specific discharge capacity of 121mAh/g under the same test conditions of example 1.
Comparative example 2
A preparation method of an iron-based fluoride composite positive electrode material comprises the following steps:
(1) mixing Fe (NO)3)3·9H2Dissolving O in deionized water to obtain 300mL of iron solution, NH4Dissolving F in deionized water to obtain 300mL of fluorine solution, slowly adding the fluorine solution into the iron solution to obtain a mixed solution, and adding Fe (NO) in the mixed solution3)3·9H2O concentration of 0.5mol/L, NH4The concentration of F is 3 mol/L;
(2) stirring the mixed solution at room temperature for 1h, wherein the stirring speed is controlled to be 180 rpm;
(3) and (3) carrying out suction filtration on the solution after the reaction in the step (2), washing with deionized water, and carrying out vacuum drying on a filter cake at 60 ℃ for 8h to obtain a white precursor. Grinding the precursor into powder, heating to 300 ℃ from room temperature at a speed of 5 ℃/min under the argon atmosphere, preserving heat for 10h, and naturally cooling to obtain ferric fluoride;
(4) ball-milling and mixing the obtained ferric fluoride powder and the rice hull biomass carbon according to the mass ratio of 4.8:1, controlling the rotating speed at 350rpm for 2 hours, then placing the fully mixed substance in a tubular furnace, introducing argon, raising the temperature to 250 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and naturally cooling to obtain FeF3/C。
Used as a lithium battery positive electrode material, the highest specific discharge capacity under the same test conditions of example 1 was 89 mAh/g.
Comparative example 3
A preparation method of an iron-based fluoride composite positive electrode material comprises the following steps:
(1) mixing Fe (NO)3)3·9H2Dissolving O in deionized water to obtain 200mL of iron solution, NH4Dissolving F in deionized water to obtain 200mL of fluorine solution, slowly adding the fluorine solution into the iron solution to obtain a mixed solution, and adding Fe (NO) in the mixed solution3)3·9H2O concentration of 1mol/L, NH4The concentration of F is 6 mol/L;
(2) stirring the mixed solution at room temperature for 1h, wherein the stirring speed is controlled to be 180 rpm;
(3) and (3) carrying out suction filtration on the solution after the reaction in the step (2), washing with deionized water, and carrying out vacuum drying on a filter cake at 60 ℃ for 8 hours to obtain a white precursor. Grinding the precursor into powder, heating to 400 ℃ from room temperature at a speed of 5 ℃/min under the argon atmosphere, preserving heat for 8h, and naturally cooling to obtain ferric fluoride;
(4) ball-milling and mixing the obtained ferric fluoride powder and a glucose carbon source according to the mass ratio of 4:1, controlling the rotating speed at 280rpm for 2h, then placing the fully mixed substance in a tube furnace, introducing argon, raising the temperature to 250 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, and naturally cooling to obtain FeF3/C。
The lithium ion battery positive electrode material has the highest specific discharge capacity of 56mAh/g under the same test conditions of example 1.
Comparative example 4
A preparation method of an iron-based fluoride composite positive electrode material comprises the following steps:
(1) FeCl is added3·6H2Dissolving O in deionized water to obtain 300mL of iron solution, NH4Dissolving F in deionized water to obtain 300mL of fluorine solution, slowly adding the fluorine solution into the iron solution to obtain a mixed solution, and adding FeCl in the mixed solution3·6H2O concentration of 0.5mol/L, NH4The concentration of F is 3.5 mol/L;
(2) stirring the mixed solution at room temperature for 1h, wherein the stirring speed is controlled to be 180 rpm;
(3) and (3) carrying out suction filtration on the solution after the reaction in the step (2), washing with deionized water, and carrying out vacuum drying on a filter cake at 60 ℃ for 8h to obtain a white precursor. Grinding the precursor into powder, heating to 400 ℃ from room temperature at a speed of 5 ℃/min under the argon atmosphere, preserving heat for 8h, and naturally cooling to obtain the ferric fluoride.
The ferric fluoride is directly used as the lithium battery positive electrode material, the highest specific discharge capacity is 39mAh/g under the same test condition of the embodiment 1, and the capacity retention rate of 40 cycles of circulation is 47%.
Combining the above examples and comparative examples, it can be seen that: according to the FeF3/C anode material provided by the invention, safe ammonium fluoride is used as a fluorine source, a precursor is obtained by stirring through a normal-temperature liquid phase method, and a target product is obtained by secondary calcination. The reaction process is more sufficient and mild, the process is simple, the consumed time is short, and the method is suitable for large-scale batch production. The obtained material has the advantages of high reversible specific capacity and good cycle stability when being used as the anode material of the lithium ion battery. The comparative example did not adopt the scheme of the present invention, and thus the excellent effects of the present invention could not be obtained.
The applicant states that the present invention is illustrated by the above examples to show the detailed method of the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be carried out. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. The preparation method of the iron-based fluoride composite positive electrode material is characterized by comprising the following steps of:
1) preparing a mixed solution of an iron source and a fluorine source;
2) stirring the mixed solution for reaction, and then carrying out suction filtration, washing and drying to obtain a precursor;
3) grinding the precursor, and then calcining at 350-450 ℃ for 2-12 h under the atmosphere of inert gas to obtain a fluorine-containing anode material;
4) and (3) ball-milling and uniformly mixing the fluorine-containing positive electrode material and a carbon source, and calcining at a low temperature of 200-300 ℃ for 1-3 h in an inert gas atmosphere to obtain the fluorine-containing positive electrode material.
2. The method for preparing the iron-based fluoride composite positive electrode material according to claim 1, wherein, in the step 1), the iron source comprises iron nitrate nonahydrate and/or iron chloride hexahydrate; the fluorine source is ammonium fluoride.
3. The method for preparing the iron-based fluoride composite positive electrode material according to claim 2, wherein in the step 1), the concentration of the iron source in the mixed solution is 0.5-1.5 mol/L, and the concentration of the fluorine source is 2.5-10 mol/L.
4. The preparation method of the iron-based fluoride composite positive electrode material according to claim 1, wherein in the step 2), the stirring reaction time is 0.5-2 h, and the stirring speed is 100-180 rpm.
5. The method for preparing the iron-based fluoride composite positive electrode material according to claim 4, wherein in the step 2), the washing solution selected in the washing is ethanol and/or water, and the iron-based fluoride composite positive electrode material is dried in vacuum at 60-80 ℃ after being washed.
6. The method for preparing the iron-based fluoride composite positive electrode material according to claim 1, wherein the inert gas in the steps 3) and 4) is one or a mixture of at least two of nitrogen, argon and a hydrogen-argon mixture.
7. The preparation method of the iron-based fluoride composite positive electrode material according to claim 1, wherein in the step 3), the temperature rise rate is 1 ℃/min to 10 ℃/min; in the step 4), the heating rate is 1-5 ℃/min.
8. The preparation method of the iron-based fluoride composite positive electrode material according to claim 1, wherein in the step 4), the carbon source is acetylene black and/or biomass carbon, and the mass ratio of the fluorine-containing positive electrode material to the carbon source is (4-5): 1.
9. The iron-based fluoride composite positive electrode material prepared by the method of any one of claims 1 to 8.
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| CN103151522A (en) * | 2013-02-28 | 2013-06-12 | 湘潭大学 | Mixed crystal form ferric fluoride cathode material and preparation method thereof |
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| CN106025182A (en) * | 2016-08-03 | 2016-10-12 | 广东工业大学 | Titanium and chromium doped iron fluoride-carbon nanometer composite positive electrode material, and preparation method and application thereof |
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| CN106450179A (en) * | 2016-09-14 | 2017-02-22 | 湘潭大学 | Preparation method of titanium-doping ferric fluoride positive electrode material |
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