CN104577107B - A kind of surface modification method of fluorinated carbon material - Google Patents

A kind of surface modification method of fluorinated carbon material Download PDF

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CN104577107B
CN104577107B CN201310478262.4A CN201310478262A CN104577107B CN 104577107 B CN104577107 B CN 104577107B CN 201310478262 A CN201310478262 A CN 201310478262A CN 104577107 B CN104577107 B CN 104577107B
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fluorocarbons
carbon material
nanometer copper
mix powder
fluorinated carbon
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CN104577107A (en
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丁飞
孙文彬
张晶
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CETC 18 Research Institute
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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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture

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  • Engineering & Computer Science (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a kind of surface modification method of fluorinated carbon material, step includes：(1) Nanometer Copper and fluorocarbons are mixed, mixed slurry is formed after adding solvent ball milling；(2) mixed slurry is dried, and forms mixture；(3) mixture is sieved, obtain mix powder；(4) mix powder is inserted in atmosphere furnace and calcined；(5) the mix powder after calcining is taken out, after being down to room temperature, sieving, that is, forms the fluorinated carbon material modified through Nanometer Copper.The present invention in fluorocarbons with good conductive nanometer copper by mixing, after the calcining of inert atmosphere high temperature, Nanometer Copper reacts in fluorination carbon surface, hence it is evident that improves fluorocarbons voltage delay phenomenon, and big multiplying power discharging and cryogenic property all improve a lot；Fluorocarbons has the performance of big multiplying power discharging, low-temperature high-current discharge as the lithium fluorocarbon battery system that positive electrode is fabricated to after the surface modification prepared by the present invention, expands the application of lithium fluorocarbon battery system.

Description

A kind of surface modification method of fluorinated carbon material
Technical field
The invention belongs to anode material of lithium battery technical field, more particularly to a kind of surface modification side of fluorinated carbon material Method.
Background technology
Metal lithium primary battery species is various, has higher ratio energy and operating voltage, the more maturation of development at present System mainly has lithium-manganese dioxide battery, lithium-thionyl chloride battery, lithium-sulfur dioxide battery etc., and energy density can typically reach To 250-350Wh/kg.In recent years, lithium-fluorination carbon battery receives much concern because with higher energy density.But due to fluorine Change carbon material initial voltage and lag the problems such as serious, big multiplying power discharging property is not fine, heat release and expansion, eventually reduce The effect of battery low-temperature high-current discharge, the big multiplying power discharging property of battery is had a strong impact on, greatly limit lithium-fluorine Change the technology development of carbon battery.
A kind of lithium battery fluorocarbons positive electrode fluorocarbons patent of invention is disclosed at present, and wherein fluorocarbons is fluorination Graphite C FXWith carbon fluoride nano-tube CFXMixture；The fluorographite CFXWith carbon fluoride nano-tube CFXMass ratio model Enclose for 6:4 to 9.5:0.5.The present invention is using the mixture of fluorographite and carbon fluoride nano-tube as battery fluorocarbons positive pole Material, carbon fluoride nano-tube material is preferably dispersed in around fluorographite particle, effectively eliminate carbon fluoride nano-tube material The high agglomeration of material, improve battery discharge and obvious voltage delay phenomenon occurred initial stage, to lithium-fluorocarbons battery system Multiplying power discharging property increases, but because the material that the present invention uses is fluorination series material, does not solve fluorine fundamentally Change the initial voltage hysteresis that carbon has in itself, it is difficult to greatly improve the discharge-rate of lithium-fluorination carbon battery, have impact on fluorination The extensive use of carbon material.
The content of the invention
The present invention carries to solve the voltage delay that technical problem present in known technology provides effectively reduction fluorocarbons The surface modification method of the big multiplying power discharging property of high fluorocarbons and a kind of fluorinated carbon material of cryogenic property.
The present invention includes following technical scheme：
A kind of surface modification method of fluorinated carbon material, is characterized in：Including following preparation process：
Step 1. is by Nanometer Copper：Fluorocarbons=0.001-0.4：The material of 1 mass ratio, which is inserted in ball mill, to be mixed, then in ball Fluorocarbons is compared with quality in grinding machine：Solvent=1：1-2 ratio adds solvent；With 100-600 turns/min rotating speed batch mixing ball milling 12-24h, adding in mechanical milling process has ball agate to grind pearl, forms mixed slurry；The ball mill is agate jar；It is described molten Agent is ethanol；
Step 2. takes out mixed slurry, and the 10-20h that dried in the air in room temperature environment is dried, and forms mixture；
After mixture in step 2 is crossed 100-400 mesh sieves by step 3., mix powder is obtained；
Step 4. inserts mix powder in atmosphere furnace, and under inert atmosphere, atmosphere furnace is with 3-15 DEG C/min speed liter Temperature carries out 1-24h calcinings to 300-500 DEG C of constant temperature in constant temperature to mix powder；
Step 5. takes out the mix powder after calcining, after being down to room temperature with 2-15 DEG C/min speed, crosses 100-300 mesh Sieve, that is, form the fluorinated carbon material modified through Nanometer Copper.
The present invention can also use following technical measures：
The inert atmosphere is nitrogen or argon gas.
The a diameter of 10-100nm of Nanometer Copper.
The present invention has the advantage that and good effect：
1st, the present invention in fluorocarbons with good conductive nanometer copper by mixing, the calcining of inert atmosphere high temperature Afterwards, Nanometer Copper reacts in fluorination carbon surface, hence it is evident that improve fluorocarbons voltage delay phenomenon, and big multiplying power discharging and low Warm nature can all improve a lot；Lithium-fluorination that fluorocarbons is fabricated to as positive electrode after the surface modification prepared by the present invention Carbon battery system has the performance of big multiplying power discharging, low-temperature high-current discharge, and expand lithium-fluorocarbons battery system applies model Enclose.
2nd, the present invention is placed with ball agate mill pearl in the material of mechanical milling process so that the mixing of fluorocarbons and Nanometer Copper is more Uniformly.
Brief description of the drawings
Fig. 1 is that battery prepared by the fluorinated carbon material after being modified in the embodiment of the present invention 1 is prepared with pure fluorinated carbon material Battery discharge curve compares figure；
Fig. 2 is that battery prepared by the fluorinated carbon material after being modified in the embodiment of the present invention 2 is prepared with pure fluorinated carbon material Battery discharge curve compares figure.
Embodiment
Further to disclose the invention, features and effects of the present invention, enter especially exemplified by following instance and with reference to accompanying drawing Row describes in detail as follows.
A kind of surface modification method of fluorinated carbon material, is characterized in：Including following preparation process：
Step 1. is by Nanometer Copper：Fluorocarbons=0.001-0.4：The material of 1 mass ratio, which is inserted in ball mill, to be mixed, then in ball Fluorocarbons is compared with quality in grinding machine：Solvent=1：1-2 ratio adds solvent；With 100-600 turns/min rotating speed batch mixing ball milling 12-24h, form mixed slurry；
Step 2. takes out mixed slurry, and the 10-20h that dried in the air in room temperature environment is dried, and forms mixture；
After mixture in step 2 is crossed 100-400 mesh sieves by step 3., mix powder is obtained；
Step 4. inserts mix powder in atmosphere furnace, and under inert atmosphere, atmosphere furnace is with 3-15 DEG C/min speed liter Temperature carries out 1-24h calcinings to 300-500 DEG C of constant temperature in constant temperature to mix powder；
Step 5. takes out the mix powder after calcining, after being down to room temperature with 2-15 DEG C/min speed, crosses 100-300 mesh Sieve, that is, form the fluorinated carbon material modified through Nanometer Copper.
The solvent is a kind of in ethanol, ethylene glycol, isopropanol or water.
The inert atmosphere is nitrogen or argon gas.
Being added in mechanical milling process in the step 1 has ball agate to grind pearl.
Ball mill in the step 1 is agate jar.
The a diameter of 10-100nm of Nanometer Copper.
Embodiment 1：
Step 1. takes a diameter of 10-100nm of 0.2g Nanometer Copper, and 4g fluorocarbons is added in agate jar and mixed, then 6g ethanol is added, it is 1 to grind pearl mass ratio according to fluorocarbons and ball agate：10 ratio is put into ball agate mill in agate jar Pearl, ball agate grind a diameter of 5-15mm of pearl, material ball milling mixing 12h under the conditions of 300 turns/min in agate jar, are formed Mixed slurry；By ball milling, preferably Nanometer Copper and fluorocarbons can be mixed, improve mixed effect.
Step 2. takes out the mixed slurry that step 1 is formed, and the 10h that dried in the air in room temperature environment is dried, and forms mixture；
After mixture in step 2 is crossed 300 mesh sieves by step 3., mix powder is obtained；
Step 4. inserts mix powder in atmosphere furnace, and under nitrogen atmosphere, atmosphere furnace is warming up to 5 DEG C/min speed 450 DEG C of constant temperature, 5h is calcined to mix powder in constant temperature；
Step 5. takes out the mix powder after calcining, after being cooled to 25 DEG C of room temperatures according to 2 DEG C/min speed, crosses 300 Mesh sieve, that is, form the fluorinated carbon material that the present invention modifies through Nanometer Copper.
Embodiment 2：
Step 1. takes a diameter of 20-40nm of 0.4g Nanometer Copper, and 10g fluorocarbons is added in agate jar and mixed, then 14g ethanol is added, it is 1 to grind pearl mass ratio according to fluorocarbons and ball agate：15 ratio is put into ball agate in agate jar Pearl is ground, ball agate grinds a diameter of 5-15mm of pearl, material ball milling mixing 12h, shape under the conditions of 200 turns/min in agate jar Into mixed slurry；By ball milling, preferably Nanometer Copper and fluorocarbons can be mixed, add mixed effect.
Step 2. takes out the mixed slurry that step 1 is formed, and the 10h that dried in the air in room temperature environment is dried, and forms mixture；
After mixture in step 2 is crossed 300 mesh sieves by step 3., mix powder is obtained；
Step 4. inserts mix powder in atmosphere furnace, and under argon gas atmosphere, atmosphere furnace is warming up to 5 DEG C/min speed 450 DEG C of constant temperature, 5h is calcined to mix powder in constant temperature；
Step 5. takes out the mix powder after calcining, after being cooled to 25 DEG C of room temperatures according to 10 DEG C/min speed, crosses 300 Mesh sieve, that is, form the fluorinated carbon material that the present invention modifies through Nanometer Copper.
Using the fluorinated carbon material through Nanometer Copper modification made of embodiment 1 as positive electrode, SP as conductive agent, Pvdf compares positive electrode as binding agent according to quality：Conductive agent：Binding agent=84：10：6 ratio is uniform in ball mill It is mixed into anode sizing agent to be coated on aluminium foil, is dried under the conditions of 120 DEG C；Lithium metal is carried out as negative electrode in glove box The assembling of one group of lithium battery.Again using pure fluorocarbons as positive electrode, remaining is identical with embodiment 1, carries out another group Lithium battery assembles.Two groups of lithium batteries carry out the discharge test under the conditions of 25 DEG C of normal temperature, 0.1C shown in Fig. 1 simultaneously, the lower song in Fig. 1 Line is the discharge curve for the lithium battery that pure fluorocarbons is assembled into, upper curve is to be assembled into lithium electricity using material made of embodiment 1 The discharge curve in pond；Substantially observed in Fig. 1, lithium battery initial voltage made of pure fluorocarbons is 2.30V, and uses embodiment Lithium battery made of blended anode material in 1, its initial minimum voltage are 2.49V, lagging voltage be improved significantly, and Battery made of fluorinated carbon material after being modified using Nanometer Copper, discharge voltage plateau, which there has also been, to be significantly improved, its voltage delay Problem and voltage platform all be improved significantly, greatly improve the discharge performance of battery.
Using the fluorinated carbon material through Nanometer Copper modification made of embodiment 2 as positive electrode, SP as conductive agent, Pvdf compares positive electrode as binding agent according to quality：Conductive agent：Binding agent=84：10：6 ratio is uniform in ball mill It is mixed into anode sizing agent to be coated on aluminium foil, is dried under the conditions of 120 DEG C；Lithium metal is carried out as negative electrode in glove box The assembling of one group of lithium battery.Again using pure fluorocarbons as positive electrode, remaining is identical with embodiment 2, carries out another group Lithium battery assembles.Two groups of lithium batteries carry out the discharge test under the conditions of 25 DEG C of normal temperature, 1C shown in Fig. 2 simultaneously, the lower curve in Fig. 2 Discharge curve, the upper curve for the lithium battery being assembled into for pure fluorocarbons are to be assembled into lithium battery using material made of embodiment 2 Discharge curve；Substantially observed in Fig. 2, lithium battery initial voltage made of pure fluorocarbons is 1.8V or so, is put in high current Under the conditions of electricity, voltage delay is obvious；Using lithium battery made of the blended anode material in embodiment 2, its initial minimum voltage Higher than 2.0V, lagging voltage be improved significantly, embodied the fluorocarbons by Nanometer Copper modification, its electric conductivity and electric discharge Platform is significantly improved, discharge performance be improved significantly.
Although the preferred embodiments of the present invention are described above in conjunction with accompanying drawing, the invention is not limited in upper The embodiment stated, above-mentioned embodiment is only schematical, be not it is restricted, this area it is common Technical staff in the case of present inventive concept and scope of the claimed protection is not departed from, may be used also under the enlightenment of the present invention By make it is many in the form of.These are belonged within protection scope of the present invention.

Claims (3)

  1. A kind of 1. surface modification method of fluorinated carbon material, it is characterised in that：Including following preparation process：
    Step 1. is by Nanometer Copper：Fluorocarbons=0.001-0.4：The material of 1 mass ratio, which is inserted in ball mill, to be mixed, then in ball mill In fluorocarbons compared with quality：Solvent=1：1-2 ratio adds solvent；With 100-600 turns/min rotating speed batch mixing ball milling 12- 24h, adding in mechanical milling process has ball agate to grind pearl, forms mixed slurry；The ball mill is agate jar；The solvent is Ethanol；
    Step 2. takes out mixed slurry, and the 10-20h that dried in the air in room temperature environment is dried, and forms mixture；
    After mixture in step 2 is crossed 100-400 mesh sieves by step 3., mix powder is obtained；
    Step 4. inserts mix powder in atmosphere furnace, and under inert atmosphere, atmosphere furnace is warming up to 3-15 DEG C/min speed 300-500 DEG C of constant temperature, 1-24h calcinings are carried out to mix powder in constant temperature；
    Step 5. takes out the mix powder after calcining, after being down to room temperature with 2-15 DEG C/min speed, crosses 100-300 mesh sieves, i.e., Form the fluorinated carbon material modified through Nanometer Copper.
  2. A kind of 2. surface modification method of fluorinated carbon material according to claim 1, it is characterised in that：The inert atmosphere For nitrogen or argon gas.
  3. A kind of 3. surface modification method of fluorinated carbon material according to claim 1, it is characterised in that：The Nanometer Copper is straight Footpath is 10-100nm.
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CN105655588B (en) * 2016-04-08 2017-12-15 北京工业大学 A kind of silica modified fluorinated carbon material and preparation method
CN106229511A (en) * 2016-10-13 2016-12-14 江苏超电新能源科技发展有限公司 Surface modifying method of a kind of fluorinated carbon material and products thereof and application
CN106384812B (en) * 2016-10-13 2019-01-04 江苏超电新能源科技发展有限公司 A kind of modified fluorinated carbon material in surface and its method and application
CN107910521B (en) * 2017-11-10 2021-03-16 北京工业大学 Ruthenium-modified carbon fluoride material, preparation and application
CN107968205A (en) * 2017-12-06 2018-04-27 贵州梅岭电源有限公司 A kind of method of the modified fluorinated carbon positive electrode of chemical reduction method
CN108929745B (en) * 2018-08-17 2021-05-07 深圳南科新材科技有限公司 Wear-resistant additive, preparation method and application thereof, and lubricating oil containing wear-resistant additive
CN109659515A (en) * 2018-11-23 2019-04-19 贵州梅岭电源有限公司 A kind of preparation method of the fluorination carbon electrode material of Ag C modification
CN109390551A (en) * 2018-11-23 2019-02-26 贵州梅岭电源有限公司 A kind of preparation method of nanometer-material-modified fluorination carbon electrode material
CN109698365A (en) * 2018-12-05 2019-04-30 上海空间电源研究所 A kind of lithium metal battery with elastic buffer structure
CN109873137B (en) * 2019-02-01 2019-12-20 贵州梅岭电源有限公司 V-shaped groove2O5Preparation method of @ C modified carbon fluoride cathode material
CN112186139B (en) * 2019-07-04 2023-01-06 上海大学 Single-metal atom point modified carbon fluoride anode material and preparation method thereof
CN114400305A (en) * 2021-12-14 2022-04-26 中国电子科技集团公司第十八研究所 Thermal battery high-voltage spherical carbon fluoride anode material and preparation method thereof

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CN102628115A (en) * 2012-04-01 2012-08-08 昆明理工大学 Preparation method of carbon nano tube enhanced copper-based composite material

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