CN112701286A - Ferric fluoride/carbon composite positive electrode material, preparation method thereof and lithium ion battery - Google Patents
Ferric fluoride/carbon composite positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention discloses an iron fluoride/carbon composite positive electrode material, a preparation method thereof and a lithium ion battery. The method comprises the following steps: (1) preparing a precursor by reacting the steam of the fluorine source and the steam of the carbon-containing organic matter with the iron source; (2) and carrying out heat treatment on the precursor to obtain the ferric fluoride/carbon composite anode material. The invention utilizes gas phase reaction to introduce fluorine source and carbon source, controls the morphology of the powder and obtains the high-performance ferric fluoride anode material. The lithium ion battery anode material provided by the invention has the advantages of high reversible specific capacity and good cycle stability.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, relates to a lithium ion battery anode material, and particularly relates to an iron fluoride/carbon composite anode material, a preparation method thereof and a lithium ion battery.
Background
With the rapid development of new energy automobiles, the lithium ion battery industry has entered a rapid development stage. The key materials influencing the performance of the lithium ion battery mainly comprise a positive electrode material, a negative electrode material, electrolyte and the like. The positive electrode material is a main factor which currently limits the performance of the battery and also a main factor which accounts for the higher cost of the lithium ion battery, and is close to 40%.
Iron fluoride has advantages of high specific capacity, high voltage, and abundant natural resources, and has gradually become one of the most interesting positive electrode materials in recent years. However, the ionic bonding property of metal fluoride causes poor electronic conductivity and ionic diffusion, and the electrochemical performance still needs to be further improved.
CN202010820328.3 discloses a composite ferric trifluoride anode material, a preparation method and application thereof. The synthesis method comprises the following steps: formed of carbon nanohorns and Fe (NO)3)3·9H2FeF synthesized by liquid phase synthesis of O3·0.33H2O-carbon nanohorn composite material for improving FeF3The conductivity is not good.
CN202010443374.6 discloses an iron-based fluoride particle, its preparation method and application. The obtained material comprises a porous octahedral carbon skeleton and ferric fluoride dispersed in the porous octahedral carbon skeleton, and the preparation method comprises the following steps: 1) respectively dispersing ferric salt and terephthalic acid in a solvent, and carrying out solvothermal reaction to obtain Fe-MOF; 2) mixing Fe-MOF and NH4And F is uniformly mixed and then placed in a protective atmosphere to carry out co-pyrolysis reaction, or Fe-MOF is added into a reaction kettle containing HF solution and placed above the liquid level, and heating is carried out to carry out fluorination reaction, so that the iron-based fluoride particles are obtained. The iron-based fluoride particles are porous octahedral and FeF3The carbon nano-particles are uniformly distributed in highly graphitized three-dimensional porous carbon, and the conductivity is high.
Jea Li et al fluorinate Fe by Using HF2O3Method of preparing/C precursor to obtain carbon-coated FeF3A material. The obtained material has a particle size of about 60nm, is beneficial to the full infiltration of electrolyte, and when used as the anode material of a lithium ion battery, the particle size is 20mA g-1The first discharge specific capacity is 166.4mAh g under the current density-1And the discharge capacity after 100 cycles is 126.3mAh g-1(Li J,Fu L,Xu Z,et al.Electrochimica Acta,2018,281:88-98.)。
However, the reversible specific capacity and the cycle performance of the electrode material obtained by the scheme are to be improved.
Therefore, the development of a lithium ion battery cathode material with better performance is of great significance to the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the ferric fluoride/carbon composite cathode material, the preparation method thereof and the lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an iron fluoride/carbon composite positive electrode material, the method comprising:
(1) preparing a precursor by reacting the steam of the fluorine source and the steam of the carbon-containing organic matter with the iron source;
(2) and carrying out heat treatment on the precursor to obtain the ferric fluoride/carbon composite anode material.
According to the method, the fluorine source and the carbon source are introduced by utilizing the gas phase, atomic-level mixing can be realized, the uniformity degree is high, fluorine source steam directly reacts with the iron source, the reaction process is more sufficient and mild, heat is uniformly released in the reaction process, and the powder morphology is more controllable; the decomposition of the carbon-containing organic matter and the synthesis of the ferric fluoride are carried out synchronously, the growth of crystal grains of the material is hindered in the reaction process, the in-situ compounding of the carbon can be realized, the electronic conductivity of the material is improved, and the performance of the material is improved.
The preparation method provided by the invention is simple in process and suitable for large-scale preparation.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, the fluorine source of step (1) comprises hydrofluoric acid.
Preferably, the mass fraction of the hydrofluoric acid in the step (1) is 40% -50%, such as 40%, 42%, 43%, 45%, 47%, 50% or the like.
Preferably, the carbon-containing organic of step (1) comprises toluene and/or octafluorotoluene.
Preferably, the iron source of step (1) comprises ferrocene.
Preferably, the molar ratio of Fe in the iron source to F in the fluorine source in step (1) is 1 (0.5-6), such as 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5 or 1:6, etc.
Preferably, the molar ratio of Fe in the iron source in step (1) to carbon in the organic carbon source is 1 (0.1-2), such as 1:0.1, 1:0.3, 1:0.5, 1:0.7, 1:0.8, 1:1, 1:1.2, 1:1.5 or 1:2.
Preferably, the reaction of step (1) is carried out under an atmosphere of a protective gas.
Preferably, the shielding gas comprises any one of nitrogen, argon or helium or a combination of at least two thereof.
As a preferred technical scheme of the method, the step (1) is realized by the following steps:
placing an iron source, a fluorine source and carbon-containing organic matters into a closed reaction container, heating to convert the fluorine source and the carbon-containing organic matters into a steam state, and further reacting with the iron source;
the closed reaction vessel is divided into at least two mutually independent subareas by a porous partition plate, the subarea in which the iron source is placed in the closed reaction vessel is marked as a first subarea, and the fluorine source and the carbon-containing organic matter are placed in other subareas except the first subarea. The closed reaction vessel having such a structure can be regarded as a non-contact closed reaction vessel.
Preferably, the porous separator has a pore size of less than 100nm, such as 98nm, 95nm, 90nm, 85nm, 80nm, 70nm, 60nm, 50nm, or 30nm, and the like.
Preferably, airtight reaction vessel is hierarchical formula reation kettle, porous baffle divides into upper strata region and lower floor region with reation kettle, the upper strata region is arranged in to the iron source, fluorine source and carbon-containing organic matter are located the region of lower floor.
It is understood that the reaction vessel is divided into an upper layer region and a lower layer region by the porous partition, and the reaction vessel can be further subdivided by further arranging the porous partition, and the present invention is not particularly limited as long as at least two regions are ensured to be distributed vertically.
The reaction kettle is divided into an upper layer and a lower layer through the porous partition plate, so that solid-liquid separation can be realized.
Preferably, the heating temperature is 90-150 ℃, such as 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 120 ℃, 125 ℃, 130 ℃, 140 ℃ or 150 ℃.
Preferably, the heating time is 2-15h, such as 2h, 3h, 4h, 6h, 8h, 9h, 10h, 11h, 12h, 13h or 15h, etc.
Preferably, the heat treatment of step (2) is performed under an atmosphere of a protective gas.
Preferably, the shielding gas comprises any one of nitrogen, argon or helium or a combination of at least two thereof.
Preferably, the temperature of the heat treatment in step (2) is 150-.
Preferably, the heating rate of the heat treatment in step (2) is 1-30 deg.C/min, such as 1 deg.C/min, 3 deg.C/min, 5 deg.C/min, 8 deg.C/min, 10 deg.C/min, 15 deg.C/min, 20 deg.C/min, 25 deg.C/min, or 30 deg.C/min.
Preferably, the heat treatment in step (2) has a holding time of 1-10h, such as 1.5h, 2h, 3h, 4h, 5h, 6h, 8h, 9h or 10 h.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) placing reaction raw materials in a closed layered reaction kettle, wherein the layered reaction kettle comprises an upper layer and a lower layer which are separated by a porous partition plate, the reaction raw materials comprise an iron source, a fluorine source and carbon-containing organic matters, the iron source is placed in the upper layer, and the lower layer is the fluorine source and the carbon-containing organic matters;
the inner container of the layered reaction kettle is made of polytetrafluoroethylene, the outer shell of the layered reaction kettle is made of stainless steel, and the aperture of the porous partition plate is smaller than 100 nm;
the iron source is ferrocene, the fluorine source is hydrofluoric acid, and the carbon-containing organic matter is toluene and/or octafluorotoluene; the molar ratio of the ferrocene to the hydrofluoric acid is 1 (0.5-6); the mol ratio of the ferrocene to the carbon in the toluene and/or the octafluorotoluene is 1 (0.1-2);
(2) filling a closed layered reaction kettle with protective gas, heating at 90-150 ℃ for reaction for 2-15h, and collecting powder after reaction;
(3) the obtained powder is subjected to heat treatment in the atmosphere of protective gas, the temperature is raised to 150-400 ℃ at the speed of 1-30 ℃/min for heat treatment for 1-10h, and FeF is obtained after cooling3And C, a positive electrode material.
The optimized technical scheme uses a layered reaction kettle, introduces a fluorine source and a carbon source by utilizing gas phase reaction, controls the morphology of powder, compounds a carbon material in situ and improves the electronic conductance of the material.
In a second aspect, the invention provides an iron fluoride/carbon composite cathode material prepared according to the method of the first aspect.
The ferric fluoride/carbon composite anode material provided by the invention solves the problems of nickel and cobalt element resource shortage, high price and the like in the lithium ion battery industry.
In a third aspect, the present invention provides a lithium ion battery, which includes the iron fluoride/carbon composite cathode material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, the fluorine source and the carbon source are introduced by utilizing the gas phase, atomic-level mixing can be realized, the uniformity degree is high, fluorine source steam directly reacts with the iron source, the reaction process is more sufficient and mild, heat is uniformly released in the reaction process, and the powder morphology is more controllable; the decomposition of the carbon-containing organic matter and the synthesis of the ferric fluoride are carried out synchronously, the growth of crystal grains of the material is hindered in the reaction process, the in-situ compounding of the carbon can be realized, the electronic conductivity of the material is improved, and the performance of the material is improved.
(2) The preparation method provided by the invention is simple in process and suitable for large-scale preparation.
(3) The anode material of the lithium ion battery provided by the invention is FeF3/C composite positive electrode material. Wherein, carbon can improve the electronic conductance of the material in the electrode material, and the stress change of the buffer material in the charging and discharging processes. The obtained material has the advantages of high specific capacity, good cycling stability and the like. Under the voltage window of 1.5-4.5V and the current density of 100mA/g, the first cycle discharge specific capacity is more than 200mAh/g, and the capacity retention rate of 200 cycles is more than 90%.
Drawings
FIG. 1 is a schematic structural diagram of a closed reaction kettle.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The mass fraction of hydrofluoric acid used in the examples of the present invention was 40%.
The device adopted in the embodiment of the invention is a closed reaction kettle, the structural schematic diagram is shown in figure 1, and the reaction kettle is divided into an upper layer and a lower layer by a porous partition plate (the aperture is 50 nm).
Example 1
The embodiment provides an iron fluoride/carbon composite cathode material and a preparation method thereof, and the preparation method specifically comprises the following steps:
(1) placing ferrocene in the upper layer of a closed reaction kettle, wherein the lower layer is hydrofluoric acid and methylbenzene; wherein the molar ratio of the ferrocene to the hydrofluoric acid is 1: 3; the molar ratio of ferrocene to carbon in toluene was 1: 0.5.
(2) Filling argon into the closed reaction kettle, heating at 120 ℃ for reaction for 10 hours, and collecting powder after reaction;
(3) carrying out heat treatment on the obtained powder in an argon atmosphere, heating to 250 ℃ at the speed of 5 ℃/min for heat treatment for 4h, and cooling to obtain FeF3And C, a positive electrode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF (mass ratio) 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 1.5-4.5V and the current density of 100mA/g, the first cyclic discharge specific capacity is 221mAh/g, and the capacity retention rate of 200 cycles is 94%.
Example 2
The embodiment provides an iron fluoride/carbon composite cathode material and a preparation method thereof, and the preparation method specifically comprises the following steps:
(1) placing ferrocene in the upper layer of a closed reaction kettle, wherein the lower layer is hydrofluoric acid and octafluorotoluene; wherein the molar ratio of the ferrocene to the hydrofluoric acid is 1: 0.5; the molar ratio of ferrocene to carbon in octafluorotoluene is 1:2.
(2) Filling nitrogen into the closed reaction kettle, heating at 90 ℃ for reaction for 15 hours, and collecting powder after reaction;
(3) carrying out heat treatment on the obtained powder in a nitrogen atmosphere, heating to 150 ℃ at the speed of 1 ℃/min for heat treatment for 10h, and cooling to obtain FeF3And C, a positive electrode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF (mass ratio) 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 1.5-4.5V and the current density of 100mA/g, the first cyclic discharge specific capacity is 201mAh/g, and the capacity retention rate of 200 cycles is 91%.
Example 3
The embodiment provides an iron fluoride/carbon composite cathode material and a preparation method thereof, and the preparation method specifically comprises the following steps:
(1) placing ferrocene in the upper layer of a closed reaction kettle, wherein the lower layer is hydrofluoric acid and methylbenzene; wherein the molar ratio of the ferrocene to the hydrofluoric acid is 1: 6; the molar ratio of ferrocene to carbon in toluene and/or octafluorotoluene is 1: 0.1.
(2) Filling helium into the closed reaction kettle, heating at the temperature of 150 ℃ for reaction for 2 hours, and collecting powder after the reaction;
(3) carrying out heat treatment on the obtained powder in helium atmosphere, heating to 150 ℃ at the speed of 30 ℃/min for heat treatment for 1h, and cooling to obtain FeF3And C, a positive electrode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF (mass ratio) 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 1.5-4.5V and the current density of 100mA/g, the first cyclic discharge specific capacity is 204mAh/g, and the capacity retention rate of 200 cycles is 91%.
Example 4
The embodiment provides an iron fluoride/carbon composite cathode material and a preparation method thereof, and the preparation method specifically comprises the following steps:
(1) placing ferrocene in the upper layer of a closed reaction kettle, wherein the lower layer is hydrofluoric acid, methylbenzene and octafluoromethylbenzene; wherein the molar ratio of the ferrocene to the hydrofluoric acid is 1: 1; the molar ratio of ferrocene to carbon in toluene and octafluorotoluene was 1:1.
(2) Filling nitrogen into the closed reaction kettle, heating at 100 ℃ for reaction for 4 hours, and collecting powder after reaction;
(3) carrying out heat treatment on the obtained powder in an argon atmosphere, heating to 200 ℃ at the speed of 10 ℃/min for heat treatment for 2h, and cooling to obtain FeF3And C, a positive electrode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF (mass ratio) 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 1.5-4.5V and the current density of 100mA/g, the first cyclic discharge specific capacity is 213mAh/g, and the capacity retention rate of 200 cycles is 91%.
Example 5
The embodiment provides an iron fluoride/carbon composite cathode material and a preparation method thereof, and the preparation method specifically comprises the following steps:
(1) placing ferrocene in the upper layer of a closed reaction kettle, wherein the lower layer is hydrofluoric acid and methylbenzene; wherein the molar ratio of the ferrocene to the hydrofluoric acid is 1: 2; the molar ratio of ferrocene to carbon in toluene was 1:1.
(2) Filling argon into the closed reaction kettle, heating at 115 ℃ for reaction for 8 hours, and collecting powder after reaction;
(3) carrying out heat treatment on the obtained powder in helium atmosphere, heating to 300 ℃ at the speed of 15 ℃/min for heat treatment for 2h, and cooling to obtain FeF3And C, a positive electrode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF (mass ratio) 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 1.5-4.5V and the current density of 100mA/g, the first cyclic discharge specific capacity is 210mAh/g, and the capacity retention rate of 200 cycles is 90%.
Comparative example 1
(1) Placing ferrocene in the upper layer of a closed reaction kettle, wherein the lower layer is hydrofluoric acid; wherein the molar ratio of the ferrocene to the hydrofluoric acid is 1:3.
(2) Filling argon into the closed reaction kettle, carrying out heat treatment reaction at the temperature of 120 ℃ for 10 hours, and collecting powder after the reaction;
(3) carrying out heat treatment on the obtained powder in an argon atmosphere, heating to 250 ℃ at the speed of 5 ℃/min for heat treatment for 4h, and cooling to obtain FeF3And C, a positive electrode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF (mass ratio) 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 1.5-4.5V and the current density of 100mA/g, the first cyclic discharge specific capacity is 185mAh/g, and the capacity retention rate of 200 cycles is 71%.
Comparative example 2
(1) Mixing ferrocene, hydrofluoric acid and toluene, and placing the mixture in a closed reaction kettle; wherein the molar ratio of the ferrocene to the hydrofluoric acid is 1: 3; the molar ratio of ferrocene to carbon in toluene was 1: 0.5.
(2) Filling argon into the closed reaction kettle, carrying out heat treatment reaction at the temperature of 120 ℃ for 10 hours, and collecting powder after the reaction;
(3) carrying out heat treatment on the obtained powder in an argon atmosphere, heating to 250 ℃ at the speed of 5 ℃/min for heat treatment for 4h, and cooling to obtain FeF3And C, a positive electrode material.
The obtained anode material is used as the anode material of the lithium ion battery for electrochemical performance test, and the pole piece ratio is that the anode material: acetylene black: PVDF (mass ratio) 90:5: 5. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 1.5-4.5V and the current density of 100mA/g, the first cyclic discharge specific capacity is 175mAh/g, and the capacity retention rate of 200 cycles is 70%.
By combining the above examples and comparative examples, the FeF provided by the present invention3the/C anode material adopts the non-contact closed reaction kettle, utilizes the iron source, the fluorine source and the steam of the carbon-containing organic matter to react, the fluorine source steam directly reacts with the iron source, the reaction process is more sufficient and mild, the heat is uniformly released in the reaction process, and the powder morphology is more controllable; the decomposition of carbon-containing organic matter and the synthesis of ferric fluoride are carried out synchronously, the growth of crystal grains of the material is hindered in the reaction process, the in-situ compounding of carbon can be realized, and the electronic conductivity of the material is improved. 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 effects of the present invention could not be obtained.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of an iron fluoride/carbon composite cathode material is characterized by comprising the following steps:
(1) preparing a precursor by reacting the steam of the fluorine source and the steam of the carbon-containing organic matter with the iron source;
(2) and carrying out heat treatment on the precursor to obtain the ferric fluoride/carbon composite anode material.
2. The method of claim 1, wherein step (1) the fluorine source comprises hydrofluoric acid;
preferably, the mass fraction of the hydrofluoric acid in the step (1) is 40-50%;
preferably, the carbon-containing organic matter of step (1) comprises toluene and/or octafluorotoluene;
preferably, the iron source of step (1) comprises ferrocene.
3. The method according to claim 1 or 2, wherein the molar ratio of Fe in the iron source to F in the fluorine source in step (1) is 1 (0.5-6);
preferably, the molar ratio of Fe in the iron source to carbon in the organic carbon source in the step (1) is 1 (0.1-2);
preferably, the reaction of step (1) is carried out under an atmosphere of a protective gas;
preferably, the shielding gas comprises any one of nitrogen, argon or helium or a combination of at least two thereof.
4. A method according to any one of claims 1-3, characterized in that step (1) is carried out by:
placing an iron source, a fluorine source and carbon-containing organic matters into a closed reaction container, heating to convert the fluorine source and the carbon-containing organic matters into a steam state, and further reacting with the iron source;
the closed reaction vessel is divided into at least two mutually independent subareas by a porous partition plate, the subarea in which the iron source is placed in the closed reaction vessel is marked as a first subarea, and the fluorine source and the carbon-containing organic matter are placed in other subareas except the first subarea.
5. The method of claim 4, wherein the porous separator has a pore size of less than 100 nm;
preferably, airtight reaction vessel is hierarchical formula reation kettle, porous baffle divides into upper strata region and lower floor region with reation kettle, the upper strata region is arranged in to the iron source, fluorine source and carbon-containing organic matter are located the region of lower floor.
6. The method of claim 4 or 5, wherein the temperature of the heating is 90-150 ℃;
preferably, the heating time is 2-15 h.
7. The method according to any one of claims 1 to 6, wherein the heat treatment of step (2) is performed under an atmosphere of a protective gas;
preferably, the shielding gas comprises any one of nitrogen, argon or helium or a combination of at least two thereof;
preferably, the temperature of the heat treatment in the step (2) is 150-400 ℃;
preferably, the heating rate of the heat treatment in the step (2) is 1-30 ℃/min;
preferably, the heat treatment of the step (2) has the holding time of 1-10 h.
8. The method according to any one of claims 1-7, characterized in that the method comprises the steps of:
(1) placing reaction raw materials in a closed layered reaction kettle, wherein the layered reaction kettle comprises an upper layer and a lower layer which are separated by a porous partition plate, the reaction raw materials comprise an iron source, a fluorine source and carbon-containing organic matters, the iron source is placed in the upper layer, and the lower layer is the fluorine source and the carbon-containing organic matters;
the inner container of the layered reaction kettle is made of polytetrafluoroethylene, the outer shell of the layered reaction kettle is made of stainless steel, and the aperture of the porous partition plate is smaller than 100 nm;
the iron source is ferrocene, the fluorine source is hydrofluoric acid, and the carbon-containing organic matter is toluene and/or octafluorotoluene; the molar ratio of the ferrocene to the hydrofluoric acid is 1 (0.5-6); the mol ratio of the ferrocene to the carbon in the toluene and/or the octafluorotoluene is 1 (0.1-2);
(2) filling a closed layered reaction kettle with protective gas, heating at 90-150 ℃ for reaction for 2-15h, and collecting powder after reaction;
(3) heat treating the obtained powder in protective gas atmosphere at a rate of 1-30 deg.C/minHeating to 150 ℃ and 400 ℃ for 1-10h, cooling to obtain FeF3And C, a positive electrode material.
9. An iron fluoride/carbon composite positive electrode material prepared according to the method of any one of claims 1 to 8.
10. A lithium ion battery comprising the iron fluoride/carbon composite positive electrode material according to claim 9.
Priority Applications (2)
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| CN113394394A (en) * | 2021-05-20 | 2021-09-14 | 华中科技大学 | Bimetallic fluoride, preparation method thereof and application thereof in lithium-free anode |
| CN114447324A (en) * | 2021-12-29 | 2022-05-06 | 湖北卓熙氟化股份有限公司 | Preparation method of battery-grade anhydrous ferric trifluoride |
| CN114447318A (en) * | 2021-12-22 | 2022-05-06 | 西安理工大学 | Preparation method for synthesizing iron trifluoride carbon anode material by gas phase fluorination |
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| CN116477667B (en) * | 2023-04-26 | 2024-03-22 | 南京工业大学 | Asphalt-based carbon-coated nano lithium iron fluoride battery anode material and preparation method and application thereof |
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| CN100511775C (en) * | 2005-01-26 | 2009-07-08 | 中国科学院金属研究所 | Modified method for lithium ion cell negative electrode material |
| CN102945961A (en) * | 2012-12-05 | 2013-02-27 | 吉林大学 | Preparation method of high-performance positive FeF3 composite material for lithium ion batteries |
| US9446966B2 (en) * | 2013-03-21 | 2016-09-20 | Quantumscape Corporation | Method for forming metal fluoride material |
| CN106356528A (en) * | 2015-07-18 | 2017-01-25 | 宁波大学 | Ferric fluoride electrode material for energy storage and preparation method thereof |
| US10770721B2 (en) * | 2017-04-10 | 2020-09-08 | Global Graphene Group, Inc. | Lithium metal secondary battery containing anode-protecting polymer layer and manufacturing method |
| CN107634224B (en) * | 2017-09-14 | 2020-11-27 | 辽宁兰晶科技有限公司 | Preparation method of fluorinated multi-walled carbon nanotube containing outer wall of iron fluoride intercalation substance |
| CN107658461B (en) * | 2017-10-18 | 2020-06-12 | 中南大学 | Method for preparing ferric fluoride/carbon composite material by taking organic iron compound as raw material |
| CN109786698A (en) * | 2018-12-29 | 2019-05-21 | 湖南中科星城石墨有限公司 | A kind of nucleocapsid structure lithium ion battery cathode material and preparation method thereof coated using inorganic extending carbon material as shell |
| CN111370661A (en) * | 2020-03-10 | 2020-07-03 | 协鑫高新材料科技有限公司 | Method for preparing lithium ion battery anode material and precursor thereof by high-temperature high-pressure steam pretreatment |
| CN111682171B (en) * | 2020-05-22 | 2021-09-28 | 华南师范大学 | Iron-based fluoride particle and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113394394A (en) * | 2021-05-20 | 2021-09-14 | 华中科技大学 | Bimetallic fluoride, preparation method thereof and application thereof in lithium-free anode |
| CN113394394B (en) * | 2021-05-20 | 2022-06-21 | 华中科技大学 | Bimetal fluoride, preparation method thereof and application thereof in lithium-free anode |
| CN114447318A (en) * | 2021-12-22 | 2022-05-06 | 西安理工大学 | Preparation method for synthesizing iron trifluoride carbon anode material by gas phase fluorination |
| CN114447324A (en) * | 2021-12-29 | 2022-05-06 | 湖北卓熙氟化股份有限公司 | Preparation method of battery-grade anhydrous ferric trifluoride |
| CN114447324B (en) * | 2021-12-29 | 2024-03-12 | 湖北卓熙氟化股份有限公司 | Preparation method of battery-grade anhydrous ferric trifluoride |
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