CN115010113B - Fluorocarbon material and application thereof, and lithium battery - Google Patents

Fluorocarbon material and application thereof, and lithium battery Download PDF

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Publication number
CN115010113B
CN115010113B CN202210726263.5A CN202210726263A CN115010113B CN 115010113 B CN115010113 B CN 115010113B CN 202210726263 A CN202210726263 A CN 202210726263A CN 115010113 B CN115010113 B CN 115010113B
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lithium battery
discharge
fluorocarbon
furnace
carbon
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CN115010113A (en
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李烨
刘超
杨敏
李明书
张鹏
陈少云
焦文慧
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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    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 relates to the technical field of lithium battery anode materials, in particular to a carbon fluoride material, an application thereof and a lithium battery. The preparation process is simple, and the prepared carbon fluoride material with excellent performance has the advantages of micron-sized particle size, higher discharge platform, excellent multiplying power performance and low-temperature performance, and can be used as an electrode material of a lithium battery.

Description

Fluorocarbon material and application thereof, and lithium battery
Technical Field
The invention relates to the technical field of lithium battery anode materials, in particular to a fluorocarbon material and application thereof, and a lithium battery.
Background
The fluorocarbon material is an important derivative of the carbon material, has extremely low surface energy and excellent chemical stability and thermal stability, and has a theoretical specific capacity of 865mAh/g as a positive electrode material of a lithium battery under the condition of a fluorocarbon ratio of 1, so that the fluorocarbon material has important application in the fields of solid lubrication, corrosion resistance, pollution resistance, lithium batteries and the like.
The lithium/fluorocarbon battery is the primary battery with the highest specific energy in the prior art, the theoretical specific energy is 2180Wh/kg, and the lithium/fluorocarbon battery also has the characteristics of stable voltage, wide working temperature, small self-discharge, long service life and the like, and is considered as one of the most potential batteries. The working temperature range of the lithium/carbon fluoride battery is-60 ℃ to 180 ℃, and the extreme environment requirements of aerospace and the like can be met.
However, because of the strong covalent nature of the c—f bond, the conductivity of the fluorocarbon is poor, and the surface energy of the fluorocarbon is low, and the permeability with the electrolyte is poor, so that polarization is easily caused when the fluorocarbon is used as an electrode, resulting in poor rate performance of the lithium/fluorocarbon battery, lower discharge plateau, far from its theoretical discharge plateau, and inability to meet the discharge requirements of high power, high rate and low temperature environment.
Disclosure of Invention
Aiming at the problem that the lithium/carbon fluoride battery in the prior art cannot meet the discharge requirements of high power, high multiplying power and low temperature environment, the invention provides a carbon fluoride material and application thereof, and a lithium battery.
In a first aspect, the invention provides a method for preparing a fluorocarbon material, comprising the steps of mixing a carbon source and an activating agent, placing the mixture in a heating furnace, heating the mixture in a protective gas atmosphere for reaction, washing the mixture, drying the mixture to obtain an intermediate product, and heating the intermediate product and fluorine-containing gas for reaction to obtain the fluorocarbon material.
Further, the carbon source is one or more of carbon fiber, bamboo charcoal, coke and carbon nanotube.
Further, the activator is one or more of phosphoric acid, zinc chloride, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, water vapor and carbon dioxide.
Further, the mass ratio of the carbon source to the activator is 1:a, wherein a is more than 0 and less than or equal to 100.
Further, the shielding gas is nitrogen.
Further, the heating reaction temperature of the carbon source and the activator is 300-1500 ℃, and the reaction time is less than or equal to 100 hours.
Further, the heating reaction temperature of the intermediate product and the fluorine-containing gas is less than or equal to 600 ℃, and the reaction time is less than or equal to 50 hours.
In a second aspect, the invention provides an application of the prepared fluorocarbon material in a positive electrode material of a lithium battery.
In a third aspect, the present invention provides a lithium battery positive electrode material prepared from the prepared fluorocarbon material.
In a fourth aspect, the invention provides a lithium battery, comprising the lithium battery anode material prepared by the method.
The preparation method has the beneficial effects that the preparation process is simple, the prepared carbon fluoride material with excellent performance is micron-sized, has a higher discharge platform and excellent multiplying power performance and low-temperature performance, and can be used as an electrode material of a lithium battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is an X-ray diffraction pattern of a fluorocarbon material prepared according to example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of a fluorocarbon material prepared according to example 1 of the present invention.
FIG. 3 is an infrared spectrum of a fluorocarbon material prepared in example 1 of the present invention.
Fig. 4 is a graph showing discharge performance of the lithium battery manufactured in example 4 according to the embodiment of the present invention.
Fig. 5 is a graph showing discharge performance of a lithium battery prepared in example 5 according to an embodiment of the present invention.
Fig. 6 is a graph showing discharge performance of a lithium battery fabricated in comparative example 1 according to the embodiment of the present invention.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
Mixing 10g of carbon fiber and 60g of zinc chloride, grinding uniformly, calcining for 4 hours at 600 ℃ under the protection of nitrogen atmosphere in a tube furnace, cooling to room temperature along with the furnace, adding water for washing, filtering, and drying the obtained filter residues to obtain the precursor activated carbon. Subsequently, the obtained precursor activated carbon was placed in a tube furnace, fluorine gas of 20% by volume concentration was introduced, and the reaction was carried out at 240℃for 6 hours. After the reaction is finished, nitrogen is introduced for replacement, the mixture is cooled to room temperature along with a furnace, and the obtained product is the activated modified carbon fluoride material. Example 1 the X-ray diffraction pattern of the resulting fluorocarbon material is shown in figure 1. Example 1 a scanning electron microscope image of the resulting fluorocarbon material is shown in fig. 2. The infrared spectrum of the fluorocarbon material prepared in example 1 is shown in fig. 3. As can be seen from the above characterization data, the fluorocarbon material was successfully synthesized.
Example 2
10g of carbon fiber is placed in a tube furnace, the temperature is raised to 1000 ℃, nitrogen and steam are introduced, the water steam is 100g, the calcination is carried out for 2 hours, then the furnace is cooled to room temperature, the product is washed by adding water, suction filtration is carried out, and the obtained filter residue is dried, thus obtaining the precursor activated carbon. Subsequently, the obtained precursor activated carbon was placed in a tube furnace, fluorine gas was introduced at a concentration of 3% by volume, and the reaction was carried out at 220℃for 10 hours. After the reaction is finished, nitrogen is introduced for replacement, the mixture is cooled to room temperature along with a furnace, and the obtained product is the activated modified carbon fluoride material.
Example 3
Mixing 100g of carbon fiber and 2000g of potassium hydroxide, directly stirring and mixing, calcining for 10 hours at 700 ℃ under the protection of nitrogen atmosphere in a tube furnace, cooling to room temperature along with the furnace, adding water into the product for washing, carrying out suction filtration, and drying the obtained filter residues to obtain the precursor activated carbon. The resulting carbon precursor was then placed in a tube furnace, 1% by volume fluorine gas was introduced, and reacted at 350 ℃ for 36 hours. After the reaction is finished, nitrogen is introduced for replacement, the mixture is cooled to room temperature along with a furnace, and the obtained product is the activated modified carbon fluoride material.
Example 4
Mixing the activated and modified fluorocarbon material prepared in the example 1 serving as a positive electrode material with conductive carbon black and PVDF (polyvinylidene fluoride) according to the ratio of 80:10:10 into N-methylpyrrolidone, grinding into paste, and coating the paste on an aluminum foil; vacuum drying at 120deg.C for 12 hr, and cutting into electrode sheet with diameter of 12 mm; the weighed electrode plate is made into an anode, lithium metal is used as a cathode, a polyethylene microporous membrane is used as a diaphragm, and 1M LiClO is used 4 (DME+PC) is used as electrolyte, and the electrolyte is assembled into a lithium battery for discharge performance evaluation, and a discharge performance diagram of the lithium battery is shown in FIG. 4.
Example 5
The lithium battery was assembled in a glove box filled with argon gas to evaluate discharge performance using the activated and modified fluorocarbon material prepared in example 2 as a positive electrode material, and the discharge performance of the lithium battery was shown in fig. 5.
Comparative example 1
The carbon fiber of example 1 was used as a raw material, placed in a tube furnace, and 20% by volume of fluorine gas was introduced to react for 6 hours at 350 ℃. After the reaction, nitrogen is introduced for replacement, the obtained product is cooled to room temperature along with the furnace, the fluorocarbon is used as a positive electrode material, and the rest materials are assembled into a lithium battery in a glove box filled with argon for discharge performance evaluation, wherein the materials are selected from the same materials as those in example 4.
The electrochemical performance of the lithium battery of example 4 was tested, and as shown in fig. 4, at a rate of 50mA/g at normal temperature, a specific discharge capacity of more than 1.5V was 769.1mAh/g, and the discharge plateau reached 2.74V, with a higher discharge plateau; under the discharge current of 4A/g at normal temperature, the discharge specific capacity of more than 1.5V reaches 580.63mAh/g, the discharge platform is 2.32V, and has excellent multiplying power performance; the specific discharge capacity of more than 1.5V can reach 478.9mAh/g under the current of 50mA/g at the temperature of minus 40 ℃, the discharge platform is 2.43V, and the low-temperature performance is excellent.
The electrochemical performance test is carried out on the lithium battery of the example 5, and the result is shown in figure 5, the discharge specific capacity of more than 1.5V is 763.5mAh/g under the multiplying power of 50mA/g at normal temperature, the discharge platform reaches 3.11V, and the discharge platform is higher; under the discharge current of 4A/g at normal temperature, the discharge specific capacity of more than 1.5V reaches 611.2mAh/g, the discharge platform is 2.62V, and has excellent multiplying power performance; the specific discharge capacity of more than 1.5V can reach 600.9mAh/g under the current of 50mA/g at the temperature of minus 40 ℃, the discharge platform is 2.59V, and the low-temperature performance is excellent.
The lithium battery of comparative example 1 was subjected to electrochemical performance test, and as shown in FIG. 6, a specific discharge capacity of 788.2mAh/g at a constant temperature of 50mA/g was set to a discharge plateau of 2.51V at a constant temperature of 1.5V or higher; however, under the discharge current of 4A/g at normal temperature, the specific discharge capacity of more than 1.5V is only 0.8mAh/g; the specific discharge capacity of more than 1.5V is only 237.3mAh/g under the current of 50mA/g at the temperature of minus 40 ℃ and the low temperature and high rate performance are extremely poor.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.

Claims (1)

1. A method for preparing a fluorocarbon material, comprising the steps of: mixing 10g of carbon fiber and 60g of zinc chloride, grinding uniformly, calcining for 4 hours at 600 ℃ under the protection of nitrogen atmosphere in a tube furnace, cooling to room temperature along with the furnace, adding water for washing, filtering, and drying the obtained filter residues to obtain precursor activated carbon; and then placing the obtained precursor activated carbon into a tube furnace, introducing fluorine gas with the volume concentration of 20%, reacting for 6 hours at 240 ℃, introducing nitrogen for replacement after the reaction is finished, and cooling to room temperature along with the furnace to obtain the product, namely the activated modified carbon fluoride material.
CN202210726263.5A 2022-06-24 2022-06-24 Fluorocarbon material and application thereof, and lithium battery Active CN115010113B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103626130A (en) * 2012-08-27 2014-03-12 切弗朗菲利浦化学公司 Vapor phase preparation of fluorided solid oxides
CN104150479A (en) * 2014-07-17 2014-11-19 大连理工大学 Preparation method of doped high-specific-surface-area activated carbon
CN106672939A (en) * 2016-12-05 2017-05-17 四川大学 Fluorinated graphene with large surface area and high thermal stability and preparation method thereof
CN109461923A (en) * 2018-11-13 2019-03-12 山东重山光电材料股份有限公司 A kind of lithium primary battery compound fluorocarbons positive electrode and its preparation method and application
JP2019091558A (en) * 2017-11-13 2019-06-13 大陽日酸株式会社 Manufacturing method of positive electrode active material
CN110935717A (en) * 2019-12-16 2020-03-31 金海华 Modification method of high-alumina fly ash

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103626130A (en) * 2012-08-27 2014-03-12 切弗朗菲利浦化学公司 Vapor phase preparation of fluorided solid oxides
CN104150479A (en) * 2014-07-17 2014-11-19 大连理工大学 Preparation method of doped high-specific-surface-area activated carbon
CN106672939A (en) * 2016-12-05 2017-05-17 四川大学 Fluorinated graphene with large surface area and high thermal stability and preparation method thereof
JP2019091558A (en) * 2017-11-13 2019-06-13 大陽日酸株式会社 Manufacturing method of positive electrode active material
CN109461923A (en) * 2018-11-13 2019-03-12 山东重山光电材料股份有限公司 A kind of lithium primary battery compound fluorocarbons positive electrode and its preparation method and application
CN110935717A (en) * 2019-12-16 2020-03-31 金海华 Modification method of high-alumina fly ash

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