CN110875475A - Method for preparing high-specific-energy carbon fluoride anode material by gas-phase fluoridation of fruit shell carbon - Google Patents

Method for preparing high-specific-energy carbon fluoride anode material by gas-phase fluoridation of fruit shell carbon Download PDF

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CN110875475A
CN110875475A CN201811026672.4A CN201811026672A CN110875475A CN 110875475 A CN110875475 A CN 110875475A CN 201811026672 A CN201811026672 A CN 201811026672A CN 110875475 A CN110875475 A CN 110875475A
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gas
carbon
shells
shell carbon
reaction
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冯奕钰
彭聪
封伟
李瑀
李泽宇
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Tianjin University
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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
    • H01M4/582—Halogenides
    • 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
    • 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
    • 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

The invention discloses a method for preparing a high-specific-energy carbon fluoride anode material by gas-phase fluoridation of shell carbon. The technical scheme provided by the invention is simple and effective to operate, the carbon fluoride material with the yield reaching several grams or even hundred grams is provided to meet the requirement of high specific energy of the lithium primary battery, and the discharge voltage and specific energy of the prepared carbon fluoride material are higher than those of a commercial graphite fluoride material.

Description

Method for preparing high-specific-energy carbon fluoride anode material by gas-phase fluoridation of fruit shell carbon
Technical Field
The invention relates to the technical field of carbon fluoride materials used for lithium primary batteries, in particular to a method for preparing a high-specific-energy carbon fluoride anode material by gas-phase fluorinated shell carbon.
Background
Fluorination of carbon materials is a process by which a pi bond in a carbon layer is broken and bonds with carbon atoms to form a C-F bond, which can be manifestedThe surface polarity, electric conductivity, adsorption capacity and capacitance of the carbon material are improved remarkably. The carbon fluoride material has unique physical and chemical characteristics, and thus is one of the international research hotspots for a novel carbon-based material with high technology, high performance and high benefit. In particular, the carbon fluoride has important application prospect in the field of the positive electrode of the high-energy lithium primary battery. Compared with other lithium primary batteries, the lithium/carbon fluoride battery has the advantages of large specific capacity, stable voltage, wide working temperature range, long service life and the like. The high-end civil instrument and military equipment such as military mobile radio station, guided missile ignition system of wide application in portable electronic equipment, chip storage power, implanted medical equipment etc.. The discharge voltage of the current commercialized graphite fluoride material is generally 2.5-2.6V (vs. Li)+/Li), well below the theoretical calculation. This is due to sp3Fluorine-carbon bonds in graphite fluoride in a hybrid configuration show covalence, only 55% of chemical energy of the graphite fluoride can be utilized, and the rest energy is released in the form of heat energy, so that a large amount of heat energy is released. Therefore, how to regulate and control the bond formation of the fluorocarbon bond of the carbon fluoride material is the key for improving the discharge voltage of the carbon fluoride material. The shell charcoal (black granular) is biomass charcoal obtained by high-temperature carbonization of shells such as high-quality coconut shells, apricot shells, peach shells, walnut shells, jujube shells and the like. Generally, the high temperature and degree of fluorination will result in a small amount of reformation and collapse of the pore structure of the original material without affecting the overall structural integrity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing a carbon fluoride anode material with high specific energy by using gas-phase fluorinated fruit shell carbon, namely, the carbon fluoride anode material is prepared by using the gas-phase fluorinated fruit shell carbon. The method is simple and effective to operate. The prepared carbon fluoride material has higher discharge voltage and specific energy than commercial graphite fluoride materials, and provides the carbon fluoride material with the yield reaching several grams or even hundreds of grams so as to meet the requirement of high specific energy of the lithium primary battery.
The technical purpose of the invention is realized by the following technical scheme.
A method for preparing carbon fluoride anode material with high specific energy by gas phase fluorination of shell carbon comprises the steps of placing dried shell carbon in a reaction device, pumping to a vacuum environment for maintaining, heating to 100-400 ℃ for heat preservation, introducing mixed gas of fluorine gas and inert protective gas as reaction gas for reaction, and obtaining carbon fluoride.
In the above technical solution, in the mixed gas of fluorine gas and inert protective gas, the volume percentage of fluorine gas is 1 to 30%, preferably 10 to 20%, and the inert protective gas is nitrogen gas, helium gas or argon gas.
In the above technical scheme, when the reaction is carried out by introducing the reaction gas, the reaction temperature is 100-400 ℃, preferably 200-300 ℃, and the reaction time is 1-10 hours, preferably 4-8 hours.
In the technical scheme, the shell carbon is dried before use to remove moisture, for example, the shell carbon is dried for 1 to 12 hours at a temperature of between 80 and 150 ℃ in a vacuum drying oven, and is preferably dried for 4 to 10 hours at a temperature of between 100 and 120 ℃.
In the technical scheme, the temperature is maintained for 10-60 min, preferably 200-300 ℃ when the temperature is heated to 200-400 ℃, and the temperature maintaining time is 20-40 min.
In the technical scheme, the dried husk carbon is placed in a reaction device and is pumped to a vacuum environment and maintained in the whole reaction process, when the vacuum pumping is started, the pressure is pumped to be below-0.1 MPa, such as-0.1-0.5 MPa, and when reaction gas is introduced, the gauge pressure is maintained to be-0.03-0.1 MPa; after the reaction is finished, extracting the mixed gas of the fluorine gas and the inert protective gas out of the reaction device, introducing the inert protective gas into the reaction device until the gauge pressure is zero (namely, one atmosphere pressure is restored), and naturally cooling to the room temperature of 20-25 ℃, thus opening the reaction device.
In the technical scheme, the shell charcoal is prepared by taking shells such as coconut shells, apricot shells, peach shells, walnut shells, jujube shells and the like as raw materials and carbonizing the shells at high temperature.
In the technical scheme, the shell carbon is prepared according to the following method: firstly, drying the shells to ensure that the moisture is removed, for example, drying the shells for 2-12h at 80-150 ℃ in a vacuum drying oven, then putting the dried shells into a muffle furnace for carbonization, heating the shells to 800-1200 ℃ from the room temperature of 20-25 ℃ at the heating rate of 1-5 ℃ per minute, and preserving the temperature for 1-5 h, wherein the carbonization atmosphere is inert protective gas, such as nitrogen, helium or argon, and the introduction speed is 30-50 ml/min.
In the technical scheme, the shell carbon is ball-milled into powder and then fluorinated, and the particle size of the shell carbon is 40-200 meshes, preferably 100-200 meshes after ball milling.
Compared with the prior art, the method for preparing the carbon fluoride cathode material by adopting the gas-phase fluorinated shell carbon has the advantages of simple and effective operation, wide raw materials, higher discharge voltage and specific energy of the prepared carbon fluoride material than that of a commercial graphite fluoride material (purchased from Sigma company, the atomic ratio of fluorine to carbon is 0.9:1, namely the molar ratio), and capability of providing the carbon fluoride material with the yield reaching several grams or even hundred grams so as to meet the requirement on high specific energy of a lithium primary battery.
Drawings
FIG. 1 is SEM photographs of a pre-fluorination (a) and a post-fluorination (b) using macadamia nut shell carbon in the present invention.
FIG. 2 is an XPS plot of carbon fluoride materials prepared according to examples of the present invention.
FIG. 3 is a graph showing the discharge curve at 0.05C of the carbon fluoride material prepared in the example of the present invention for a positive electrode material of a lithium primary battery.
Detailed description of the preferred embodiments
The technical solution of the present invention is illustrated below by specific examples, which are not intended to limit the scope of the present invention. Commercial graphite fluoride material available from sigma, with a 0.9:1 atomic ratio of fluorine to carbon, i.e. molar ratio.
Example 1
(1) Putting 0.8g of macadamia nut shells into a vacuum drying oven to be dried for 6 hours at 120 ℃ to ensure that no water exists completely;
(2) putting 0.72g of macadamia nut shells in the step (1) into an atmosphere muffle furnace for carbonization, and keeping the temperature at 800 ℃ for 1h at the nitrogen rate of 50 ml/min;
(3) putting 0.3g of the shell carbon prepared in the step (2) into a reaction kettle, pumping to vacuum, heating the reaction kettle to 200 ℃, preserving heat for 10min, pumping to vacuum, introducing a mixed gas of 20% fluorine gas and nitrogen gas to-0.03 MPa, and reacting for 4h to obtain carbon fluoride;
(4) the fluorocarbon in (3) is prepared according to the following steps: carbon black: binder (PVDF) ═ 8: 1: 1, uniformly coating the ground slurry on a carbon-attached aluminum foil, and placing the carbon-attached aluminum foil in a blast oven for drying for 12 hours. And (5) placing the dried material in a vacuum drying oven, and performing vacuum drying for 8 hours. And finally, cutting and weighing the anode material electrode plates to 10.4mg,10.3mg and 9.3 mg.
Example 2
(1) Placing 0.5g of coconut shell into a vacuum drying oven to be dried for 2 hours at the temperature of 150 ℃ to ensure that no water exists completely;
(2) putting 0.42g of coconut shells in the step (1) into an atmosphere muffle furnace for carbonization, and keeping the temperature at 1200 ℃ for 3h at the argon speed of 50 ml/min;
(3) putting 0.3g of the shell carbon prepared in the step (2) into a reaction kettle, pumping to vacuum, heating the reaction kettle to 300 ℃, preserving the temperature for 20min, pumping to vacuum, introducing 10% of mixed gas of fluorine gas and nitrogen gas to 0.03MPa, and reacting for 4h to obtain carbon fluoride;
(4) the fluorocarbon in (3) is prepared according to the following steps: carbon black: binder (PVDF) ═ 8: 1: 1, uniformly coating the ground slurry on a carbon-attached aluminum foil, and placing the carbon-attached aluminum foil in a blast oven for drying for 12 hours. And (5) placing the dried material in a vacuum drying oven, and performing vacuum drying for 8 hours. And finally, cutting and weighing the electrode plates of the anode material to 7.2mg,7.3mg and 7.3 mg.
Example 3
(1) Putting 0.5g of apricot shells into a vacuum drying oven, and drying for 8 hours at 120 ℃ to ensure that no water exists completely;
(2) putting 0.43g of coconut shells in the step (1) into an atmosphere muffle furnace for carbonization, and keeping the temperature at 800 ℃ for 1h at the nitrogen rate of 30 ml/min;
(3) putting 0.3g of the shell carbon prepared in the step (2) into a reaction kettle, pumping to vacuum, heating the reaction kettle to 150 ℃, preserving the temperature for 60min, pumping to vacuum, introducing 5% of mixed gas of fluorine gas and nitrogen gas to 0Mpa, and reacting for 8h to obtain carbon fluoride;
(4) the fluorocarbon in (3) is prepared according to the following steps: carbon black: binder (PVDF) ═ 8: 1: 1, uniformly coating the ground slurry on a carbon-attached aluminum foil, and placing the carbon-attached aluminum foil in a blast oven for drying for 12 hours. And (5) placing the dried material in a vacuum drying oven, and performing vacuum drying for 8 hours. And finally, cutting and weighing the anode material electrode plates to 10.4mg,10.3mg and 10.3 mg.
Example 4
(1) Putting 0.8g of peanut shells into a vacuum drying oven, and drying for 2 hours at 150 ℃ to ensure that no water exists completely;
(2) putting 0.73g of coconut shells in the step (1) into an atmosphere muffle furnace for carbonization, and keeping the temperature at 1000 ℃ for 3 hours at the argon rate of 40 ml/min;
(3) putting 0.2g of the shell carbon prepared in the step (2) into a reaction kettle, vacuumizing the reaction kettle, heating the reaction kettle to 100 ℃, preserving the temperature for 30min, vacuumizing the reaction kettle, introducing a 2% mixed gas of fluorine gas and nitrogen gas to 0.1Mpa, and reacting for 5h to obtain carbon fluoride;
(4) the fluorocarbon in (3) is prepared according to the following steps: carbon black: binder (PVDF) ═ 8: 1: 1, uniformly coating the ground slurry on a carbon-attached aluminum foil, and placing the carbon-attached aluminum foil in a blast oven for drying for 12 hours. And (5) placing the dried material in a vacuum drying oven, and performing vacuum drying for 8 hours. And finally, cutting and weighing the electrode plates of the anode material to 9.4mg,9.3mg and 9.3 mg.
As shown in the attached figure 1, the shapes of the shell carbon of the macadamia nut before (a) fluorination and after (b) fluorination are not changed obviously, and the original shapes can be basically maintained. XPS test is performed on the carbon fluoride material prepared by the invention, as shown in figure 2, the measured characteristic peak is subjected to peak separation, the 290eV position is a C-F covalent bond (the highest peak), and the other two peaks (the two peaks next to the highest peak) respectively correspond to CF2And CF3(the ratio of the C-F covalent bond to the three covalent bonds is 0.7-0.9, the sum of the integral areas of the three characteristic peaks after peak splitting is used as a denominator, and the integral area of the C-F covalent bond characteristic peak is used as a molecule), which indicates that the fluorinated carbon material is obtained after fluorination; tests show that the atomic ratio of fluorine to carbon in the carbon fluoride material prepared by the invention is more than 0.95, such as 0.95-0.99.
The carbon fluoride material, carbon black and a binder (PVDF) prepared by the technical scheme of the invention are prepared according to the following steps of carbon fluoride: carbon black: binder (PVDF) ═ 8: 1: 1, uniformly coating the ground slurry on a carbon-attached aluminum foil, and placing the carbon-attached aluminum foil in a blast oven for drying for 12 hours. And (3) placing the dried material in a vacuum drying oven, drying for 8 hours in vacuum, taking the dried material as an anode material electrode plate, adopting a lithium primary battery structure, wherein a test instrument is a blue-electricity system, electrolyte is 1M LiBF4 solution, solvent is PC and DME with equal volume ratio, and discharge current is 10 mA/g. Tests show that the highest voltage of a lithium primary battery adopting the carbon fluoride material prepared by the invention can reach 3.14V and reach 2.8-3.14V, the specific capacity is 760-940mAh.g < -1 >, the highest specific energy can reach 2600Wh/Kg and reach 2400-2600 Wh/Kg, the commercial graphite fluoride as the lithium primary battery anode material has electrochemical performance, the voltage is 2.5-2.6V, and the highest specific energy can reach 2100Wh/Kg, and the performance of the fluorocarbon material prepared by the invention is about 17 percent higher than that of commercial graphite fluoride, namely the carbon fluoride material prepared by the technical scheme of the invention is applied to the lithium primary battery anode material.
The preparation of the carbon fluoride material can be realized by adjusting the process parameters according to the content of the invention, and the carbon fluoride material shows basically consistent performance with the invention through tests. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

1. A method for preparing a carbon fluoride anode material with high specific energy by gas phase fluorination of shell carbon is characterized in that dried shell carbon is placed in a reaction device and pumped to a vacuum environment for maintaining, after heating to 100-400 ℃ for heat preservation, mixed gas of fluorine gas and inert protective gas is introduced as reaction gas for reaction, so that carbon fluoride is obtained.
2. The method for preparing the high specific energy fluorocarbon anode material from the gas-phase fluorinated shell carbon according to claim 1, wherein the dried shell carbon is placed in a reaction device and is vacuumized to a vacuum environment and maintained in the whole reaction process, the gauge pressure is reduced to below-0.1 MPa when the vacuumization is started, and the gauge pressure is maintained to be-0.03 to-0.1 MPa when the reaction gas is introduced; and after the reaction is finished, extracting the mixed gas of the fluorine gas and the inert protective gas out of the reaction device, introducing the inert protective gas into the reaction device until the gauge pressure is zero, and naturally cooling to the room temperature of 20-25 ℃.
3. The method for preparing the high specific energy fluorocarbon anode material by gas phase fluorination of shell carbon as claimed in claim 1 or 2, wherein the volume percentage of fluorine gas in the mixed gas of fluorine gas and inert shielding gas is 1-30%, preferably 10-20%, and the inert shielding gas is nitrogen, helium or argon.
4. The method for preparing the high-specific-energy carbon fluoride anode material by gas-phase fluorinated shell carbon according to claim 1 or 2, wherein the reaction is carried out by introducing a reaction gas, the reaction temperature is 100-400 ℃, preferably 200-300 ℃, and the reaction time is 1-10 hours, preferably 4-8 hours.
5. The method for preparing the high-specific-energy carbon fluoride anode material from the gas-phase fluorinated fruit shell carbon according to claim 1 or 2, wherein the fruit shell carbon is prepared by carbonizing shells such as coconut shells, apricot shells, peach shells, walnut shells and jujube shells at high temperature.
6. The method for preparing the high-specific-energy carbon fluoride anode material by gas-phase fluorinated shell carbon according to claim 1 or 2, characterized in that the shell carbon is subjected to fluorination after being ball-milled into powder, and the particle size of the shell carbon after ball-milling is 40-200 meshes, preferably 100-200 meshes.
7. The method for preparing the high specific energy fluorocarbon anode material by gas phase fluorination shell carbon as claimed in claim 1 or 2, wherein the shell carbon is dried before use, such as dried in a vacuum drying oven at 80-150 ℃ for 1-12 h, preferably at 100-120 ℃ for 4-10 h.
8. The method for preparing the high-specific-energy carbon fluoride cathode material from the gas-phase fluorinated shell carbon according to claim 5, wherein the shell carbon is prepared according to the following method: firstly, drying the shells to ensure that the moisture is removed, for example, drying the shells for 2-12h at 80-150 ℃ in a vacuum drying oven, then putting the dried shells into a muffle furnace for carbonization, heating the shells to 800-1200 ℃ from the room temperature of 20-25 ℃ at the heating rate of 1-5 ℃ per minute, and preserving the temperature for 1-5 h, wherein the carbonization atmosphere is inert protective gas, such as nitrogen, helium or argon, and the introduction speed is 30-50 ml/min.
9. The fluorocarbon positive electrode material of claim 1 or 2, wherein the atomic ratio of fluorine to carbon is 0.95 or more, e.g. 0.95 to 0.99, and the covalent bond of C-F is C-F, CF2And CF3The ratio of the three covalent bonds is 0.7-0.9.
10. A lithium primary cell using the fluorocarbon positive electrode material prepared by the method as set forth in claim 1 or 2, wherein the voltage of the lithium primary cell can be up to 3.14V, which is in the range of 2.8-3.14V, the specific capacity is 760-940mah.g-1, and the specific energy is up to 2600Wh/Kg, which is in the range of 2400-2600 Wh/Kg.
CN201811026672.4A 2018-09-04 2018-09-04 Method for preparing high-specific-energy carbon fluoride anode material by gas-phase fluoridation of fruit shell carbon Pending CN110875475A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114148998A (en) * 2021-12-06 2022-03-08 电子科技大学长三角研究院(湖州) Accurate fluorinated ginkgo leaf, purification method and functional application of lithium primary battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101486456A (en) * 2008-01-17 2009-07-22 杨先金 Industrial novel method for synthesizing fluorizated petroleum coke
CN102730664A (en) * 2012-07-04 2012-10-17 四川大学 Carbon nano-tube with fluorine-containing surface and preparation method thereof
CN106744800A (en) * 2016-12-23 2017-05-31 中国工程物理研究院激光聚变研究中心 The method that sodium-ion battery electrode carbon material is prepared using peanut shell
CN106941178A (en) * 2017-05-12 2017-07-11 厦门希弗新能源科技有限公司 A kind of fluorocarbons and its preparation method and application
CN107082424A (en) * 2017-05-12 2017-08-22 厦门希弗新能源科技有限公司 A kind of fluorinated graphene and its preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101486456A (en) * 2008-01-17 2009-07-22 杨先金 Industrial novel method for synthesizing fluorizated petroleum coke
CN102730664A (en) * 2012-07-04 2012-10-17 四川大学 Carbon nano-tube with fluorine-containing surface and preparation method thereof
CN106744800A (en) * 2016-12-23 2017-05-31 中国工程物理研究院激光聚变研究中心 The method that sodium-ion battery electrode carbon material is prepared using peanut shell
CN106941178A (en) * 2017-05-12 2017-07-11 厦门希弗新能源科技有限公司 A kind of fluorocarbons and its preparation method and application
CN107082424A (en) * 2017-05-12 2017-08-22 厦门希弗新能源科技有限公司 A kind of fluorinated graphene and its preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114148998A (en) * 2021-12-06 2022-03-08 电子科技大学长三角研究院(湖州) Accurate fluorinated ginkgo leaf, purification method and functional application of lithium primary battery
CN114148998B (en) * 2021-12-06 2023-08-04 电子科技大学长三角研究院(湖州) Precise fluorinated ginkgo leaf, purification method and functional application of lithium primary battery

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Application publication date: 20200310