CN114634172A - Preparation method of carbon fluoride material - Google Patents

Preparation method of carbon fluoride material Download PDF

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Publication number
CN114634172A
CN114634172A CN202210224005.7A CN202210224005A CN114634172A CN 114634172 A CN114634172 A CN 114634172A CN 202210224005 A CN202210224005 A CN 202210224005A CN 114634172 A CN114634172 A CN 114634172A
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China
Prior art keywords
carbon
carbon fluoride
producing
microwave
fluoride
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CN202210224005.7A
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Chinese (zh)
Inventor
杨敏
陈少云
刘超
李烨
李明书
张鹏
方治文
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Shandong Zhongshan Photoelectric Material Co ltd
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Shandong Zhongshan Photoelectric Material Co ltd
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Priority to CN202210224005.7A priority Critical patent/CN114634172A/en
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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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/10—Carbon fluorides, e.g. [CF]nor [C2F]n
    • 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
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/5835—Comprising fluorine or fluoride salts

Abstract

The invention relates to the technical field of lithium carbon fluoride batteries, in particular to a preparation method of a carbon fluoride material, which comprises the following steps: (1) pretreating a carbon material under microwave to obtain a material A; (2) adding ammonia water into the material A for soaking, filtering and drying to obtain a material B; (3) placing the material B into a reactor, and carrying out microwave treatment under the protective gas atmosphere to obtain a material C; (4) the material C is placed in a reactor and is fed with a gas containing F2Heating the mixed gas for reaction to obtain the finished product. The carbon fluoride material prepared by the invention has high discharge rate, simple preparation process and low cost.

Description

Preparation method of carbon fluoride material
Technical Field
The invention relates to the technical field of lithium fluorocarbon batteries, in particular to a preparation method of a carbon fluoride material.
Background
The carbon fluoride material is an excellent battery active material, and the carbon fluoride material can be combined with a nonaqueous electrolyte to prepare a novel battery with high energy density, high energy output power, long storage period and high safety performance, wherein the energy of the battery is 6-9 times that of zinc and alkaline batteries, and lithium carbon fluoride batteries using the carbon fluoride material as an active material have been produced in batches in Japan, and are used for radio transmitters, measuring equipment, observation balloons, fishing buoys and illumination, electronic watches, calculators and other aspects. The carbon fluoride material takes a carbon material as a basic raw material, and the variety of the carbon fluoride material is determined by the diversity of the carbon material. Graphite fluoride is widely applied, and carbon fluoride fibers, carbon fluoride coke, carbon fluoride nanotubes, graphene fluoride and the like are also applied; novel carbon materials such as nano carbon materials, composite carbon materials and the like developed by researchers such as graphdiyne, carbon quantum dots, template carbon and the like can be prepared into corresponding carbon fluoride materials through fluorination reaction.
The carbon material and fluorine-containing gas react under the high temperature condition (300-600 ℃) to obtain the carbon fluoride material; the other method is a low-temperature fluorination method, wherein the carbon material is firstly reacted with a catalyst to form an interlayer compound and then reacted with a fluorine-containing reagent at a low temperature (100-200 ℃) to form the carbon fluoride material. The carbon fluoride materials prepared by the two methods are directly used for lithium carbon fluoride batteries, most of the lithium carbon fluoride batteries have poor rate performance and need to be modified correspondingly.
The prior art mainly improves the rate capability of the material through two aspects:
1. the method comprises the following steps of carrying out surface coating, chemical reduction or introduction of other active materials on a finished product of the carbon fluoride material, and the like, so that the overall conductivity of the material is improved, and the rate performance of the material is improved, for example, a V2O5@ C modified carbon fluoride anode material is disclosed in the patent number CN201910103600.3, and the carbon fluoride material improves the voltage hysteresis phenomenon of carbon fluoride and greatly improves the rate performance; patent No. CN201711272530.1 discloses a chemical reduction method modified fluorocarbon anode material, which improves the initial discharge voltage hysteresis and rate discharge performance of a lithium fluorocarbon battery; patent No. CN201710621698.2 discloses an asphalt carbon-coated carbon fluoride positive electrode material, which improves the interface bonding force between coated carbon and carbon fluoride, improves the carbon coating effect on the surface of carbon fluoride, and overcomes the common problem of replacing the specific capacity of carbon fluoride with high rate performance; patent No. cn201510641793.x discloses a polypyrrole-coated carbon fluoride positive electrode material, in which polypyrrole is uniformly coated on the surface of carbon fluoride particles, so that a dense and stable polypyrrole film is formed on the surface of the carbon fluoride particles, and the conductivity of the material is improved. The method disclosed in the above patent mostly introduces a substance which can only provide conductivity and cannot provide discharge capacity, and has an influence on the discharge capacity of the material;
2. in a mode of adopting a composite carbon source material, for example, patent No. CN202010048761.X discloses carbon fluoride prepared by mixing and sintering a soft carbon material and a graphite material, and the material can realize discharge under the current of 10A/g; patent No. CN202010048060.6 discloses a carbon fluoride material prepared by sintering a mixture of hard carbon and soft carbon, which can realize discharge at a current of 30A/g. The patent realizes the direct preparation of carbon fluoride capable of discharging at high rate, but needs high-temperature sintering of two different types of carbon materials, has high sintering temperature requirement, and has extremely high equipment requirement and production energy consumption and harsh preparation process when being applied to industry.
Disclosure of Invention
Aiming at the problems of low discharge rate, harsh preparation process and the like in the prior art, the invention provides the preparation method of the carbon fluoride material, and the prepared carbon fluoride material has high discharge rate, simple preparation process and low cost.
The invention provides a preparation method of a carbon fluoride material, which comprises the following steps:
(1) pretreating a carbon material under microwave to obtain a material A;
(2) adding ammonia water into the material A for soaking, filtering and drying to obtain a material B;
(3) placing the material B into a reactor, and carrying out microwave treatment under the protective gas atmosphere to obtain a material C;
(4) the material C is placed in a reactor and is fed with a gas containing F2Mixed gas of (2), heatingAnd reacting to obtain a finished product.
Further, the carbon material is one of graphite, carbon fiber and coke.
Further, the carbon material in the step (1) is pretreated by microwave in an oxygen-containing atmosphere.
Further, the microwave pretreatment conditions in the step (1) are as follows: the microwave power is 100-1000 w, and the processing time is 1-60 min.
Further, in the step (2), the ratio of the material A to the ammonia water is as follows: 1-4 ml of ammonia water is used for soaking every 1g of the material A for 0.5-4 h.
Further, in the step (2), the drying temperature is 60-180 ℃.
Further, in the step (3), the microwave treatment process comprises: the microwave power is 100-1000 w, and the processing time is 1-60 min.
Further, the protective gas in the step (3) is one of nitrogen, argon and helium.
Further, step (4) contains F2The mixed gas of (A) is F2And N2Wherein F is2The volume fraction of the catalyst is 5-20%, the heating reaction temperature is 100-350 ℃, and the reaction time is 1-6 h.
The principle of the invention is as follows: according to the method, a carbon material is subjected to microwave treatment in an aerobic atmosphere, a trace amount of oxygen-containing groups are introduced into the carbon material, and partial surface etching is formed, so that the chemical reaction activity of the carbon material is improved; and then the ammonia water molecule wedge-shaped structure is utilized to be inserted into the carbon material interlayer, and the carbon material interlayer structure is adjusted through microwave rapid treatment. The reaction activity of the carbon material after adjustment is increased, the fluorination temperature is reduced, the bond energy of the formed carbon fluoride product is reduced, the conductivity is improved, the interlayer spacing is improved, and an effective ion transmission channel can be provided, so that the high power performance is integrally improved.
The invention has the beneficial effects that:
(1) the preparation process is simple and convenient for industrial production;
(2) the preparation method does not contain a high-temperature heating step, has low energy consumption, cheap and easily obtained ammonia water and low overall cost;
(3) the preparation method only uses ammonia water for treating the carbon material, no other strong acid, strong oxidant and the like are introduced, and the filtered ammonia water is easy to recycle and has small overall process pollution;
(4) the carbon fluoride material prepared by the invention can realize 4A/g current discharge when being applied to the lithium carbon fluoride battery.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is an SEM photograph of graphite fluoride obtained in example 1 of the present invention.
FIG. 2 is a graph showing the discharge performance at 25 ℃ and current density of 4A/g of button cells prepared from graphite fluoride prepared in example 2 according to the embodiment of the present invention.
FIG. 3 is a graph showing the discharge performance at 25 ℃ and 4A/g current density of a button cell prepared from the fluorinated carbon fiber obtained in example 4 according to the embodiment of the present invention.
FIG. 4 is a graph showing the discharge performance at 25 ℃ at 4A/g current density of a button cell prepared from the fluorinated coke obtained in example 5 according to the embodiment of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
Example 1
Weighing 20g of graphite powder, and carrying out air atmospherePerforming microwave treatment for 60min under the power of 1000w in the enclosure; putting the treated graphite powder into a container, adding 80ml of ammonia water (AR) to soak for 2 hours, filtering after soaking, putting a filter cake into an oven, and drying at 180 ℃; microwave treating the dried material for 60min under the protection of nitrogen atmosphere and the power of 1000w, then putting the material into a reactor, and introducing F2、N2A mixture of gases in which F2The medium volume fraction is 15 percent, and the graphite fluoride is obtained by fluorination reaction for 4 hours at 100 ℃.
Example 2
Weighing 20g of graphite powder, and carrying out microwave treatment for 20min under the power of 100w in the air atmosphere; putting the treated graphite powder into a container, adding 20ml of ammonia water (AR) to soak for 0.5h, filtering after soaking, putting a filter cake into an oven, and drying at 80 ℃; microwave treating the dried material for 1min under 100w power under the protection of argon atmosphere, then putting the material into a reactor, and introducing F2、N2A mixture of gases in which F2The volume fraction of the graphite is 5 percent, and the graphite fluoride is obtained by fluorination reaction for 1h at 350 ℃.
Example 3
Weighing 20g of graphite powder, and carrying out microwave treatment for 1min at the power of 700w in the air atmosphere; putting the treated graphite powder into a container, adding 40ml of ammonia water (AR) to soak for 4 hours, filtering after soaking, putting a filter cake into an oven, and drying at 90 ℃; microwave treating the dried material for 40min under the protection of helium atmosphere and 600w power, putting the material into a reactor, and introducing F2、N2Mixed gas of F2The volume fraction of the graphite is 20 percent, and the graphite fluoride is obtained by fluorination reaction for 6 hours at 280 ℃.
Example 4
Weighing 500g of carbon fiber, and performing microwave treatment for 30min under the power of 500w in the air atmosphere; putting the treated graphite powder into a container, adding 1000ml of ammonia water (AR) to soak for 3h, filtering after soaking, putting a filter cake into an oven, and drying at 100 ℃; microwave treating the dried material for 40min under the protection of nitrogen atmosphere and 600w power, then putting the material into a reactor, and introducing F2、N2A mixture of gases in which F2The medium volume fraction is 15 percent, and the fluorinated carbon fiber is obtained by fluorination reaction for 4 hours at 300 ℃.
Example 5
Weighing 20g of coke, and carrying out microwave treatment for 20min at a power of 200w in an air atmosphere; putting the treated graphite powder into a container, adding 60ml of ammonia water (AR) to soak for 2 hours, filtering after soaking, putting a filter cake into an oven, and drying at 90 ℃; microwave treating the dried material for 50min at 700w under the protection of nitrogen atmosphere, putting the material into a reactor, and introducing F2、N2A mixture of gases in which F2The medium volume fraction is 15 percent, and the fluorinated coke is obtained by fluorination reaction for 6h at 250 ℃.
FIG. 1 shows an SEM image of the graphite fluoride obtained in example 1, with the desired particle size.
The carbon fluoride materials prepared in the examples 2, 4 and 5 were prepared into button cells, and constant current discharge tests were performed at a temperature of 25 ℃ and a current density of 4A/g, and the results are shown in FIGS. 2, 3 and 4, and the carbon fluoride materials prepared by the method of the present invention all had a discharge plateau of more than 2V at a current density of 4A/g.
Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention.

Claims (9)

1. A method for producing a carbon fluoride material, characterized by comprising the steps of:
(1) pretreating a carbon material under microwave to obtain a material A;
(2) adding ammonia water into the material A for soaking, filtering and drying to obtain a material B;
(3) placing the material B into a reactor, and carrying out microwave treatment under the protective gas atmosphere to obtain a material C;
(4) the material C is placed in a reactor and is fed with a gas containing F2Heating the mixed gas for reaction to obtain the finished product.
2. The method for producing a carbon fluoride material according to claim 1, wherein the carbon material is one of graphite, carbon fiber and coke.
3. The method for producing a fluorinated carbon material according to claim 1, wherein the carbon material in the step (1) is subjected to microwave pretreatment in an oxygen-containing atmosphere.
4. The method for producing a carbon fluoride material according to claim 1, wherein the microwave pretreatment in the step (1) is performed under the following conditions: the microwave power is 100-1000 w, and the processing time is 1-60 min.
5. The method for producing a fluorinated carbon material according to claim 1, wherein in the step (2), the ratio of the amount of the material A to the amount of the aqueous ammonia is: 1-4 ml of ammonia water is used for soaking every 1g of the material A for 0.5-4 h.
6. The method for producing a carbon fluoride material as claimed in claim 1, wherein the drying temperature in the step (2) is 60 to 180 ℃.
7. The method for producing a carbon fluoride material according to claim 1, wherein in the step (3), the microwave treatment comprises: the microwave power is 100-1000 w, and the processing time is 1-60 min.
8. The method for producing a fluorinated carbon material as claimed in claim 1, wherein the protective gas in the step (3) is one of nitrogen, argon and helium.
9. The method for producing a fluorinated carbon material according to claim 1, wherein the F is contained in the step (4)2The mixed gas of (A) is F2And N2Wherein F is2The volume fraction of the catalyst is 5-20%, the heating reaction temperature is 100-350 ℃, and the reaction time is 1-6 h.
CN202210224005.7A 2022-03-07 2022-03-07 Preparation method of carbon fluoride material Pending CN114634172A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5869708A (en) * 1981-10-19 1983-04-26 Kawasaki Steel Corp Method for improving oxidation resistance of carbon material
RU2170701C2 (en) * 1999-10-18 2001-07-20 ГУП "Ангарский электролизный химический комбинат" Method of preparing fluorinated caron
CN102390826A (en) * 2011-07-14 2012-03-28 华东理工大学 Carbon aerogel surface modification method
CN105800603A (en) * 2016-04-22 2016-07-27 华侨大学 Method for quickly preparing high-quality graphene
CN105883745A (en) * 2016-04-07 2016-08-24 严瑾 Fluorinated graphite and preparation method thereof
CN109179374A (en) * 2018-08-17 2019-01-11 山东重山光电材料股份有限公司 A kind of method of low temperature preparation fluorinated carbon material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5869708A (en) * 1981-10-19 1983-04-26 Kawasaki Steel Corp Method for improving oxidation resistance of carbon material
RU2170701C2 (en) * 1999-10-18 2001-07-20 ГУП "Ангарский электролизный химический комбинат" Method of preparing fluorinated caron
CN102390826A (en) * 2011-07-14 2012-03-28 华东理工大学 Carbon aerogel surface modification method
CN105883745A (en) * 2016-04-07 2016-08-24 严瑾 Fluorinated graphite and preparation method thereof
CN105800603A (en) * 2016-04-22 2016-07-27 华侨大学 Method for quickly preparing high-quality graphene
CN109179374A (en) * 2018-08-17 2019-01-11 山东重山光电材料股份有限公司 A kind of method of low temperature preparation fluorinated carbon material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张祥功;黄瑞霞;吴军;: "改性氟化碳材料结构与电性能的研究" *

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