CN104577124B - The preparation method of lithium battery blended anode material - Google Patents
The preparation method of lithium battery blended anode material Download PDFInfo
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- CN104577124B CN104577124B CN201310478328.XA CN201310478328A CN104577124B CN 104577124 B CN104577124 B CN 104577124B CN 201310478328 A CN201310478328 A CN 201310478328A CN 104577124 B CN104577124 B CN 104577124B
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- fluorocarbons
- lithium battery
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- anode material
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- 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
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 present invention relates to a kind of preparation method of lithium battery blended anode material, it is characterized in：Ag is adulterated in fluorinated carbon material2V4O11Material, the process of the doping include：By fluorocarbons, Ag2V4O11Ball milling in ball mill, which is inserted, with solvent forms mixed slurry；Mixed slurry is dried, dry mixed object is obtained after cooling；After dry mixed object is sieved, lithium battery blended anode material is obtained.The present invention in fluorinated carbon material by being mixed with Ag2V4O11Material, two kinds of materials are mixed by additive, due to Ag2V4O11Material has extraordinary high-rate discharge ability, the problem of compensate for the initial voltage hysteresis of fluorocarbons, effectively improve the discharge performance of fluorocarbons, the big multiplying power discharging of lithium fluorocarbon battery system greatly improved, lithium fluorocarbon battery low-temperature high-current discharge is improved, expands the application of lithium fluorocarbon battery system.
Description
Technical field
The invention belongs to lithium battery material technical field, more particularly to a kind of preparation of lithium battery blended anode 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 application 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, hinder fluorination
The extensive use of carbon material.
The content of the invention
The present invention provides one kind for technical problem present in solution known technology and effectively makes up fluorinated carbon material in itself
The problem of initial voltage hysteresis having, the big multiplying power discharging property of lithium-fluorocarbons battery system is greatly improved, and low temperature is big
Current discharge effect is good, the preparation method for the lithium battery blended anode material having a wide range of application.
The present invention includes following technical scheme：
The preparation method of lithium battery blended anode material, is characterized in：Ag is adulterated in fluorinated carbon material2V4O11Material
Material, the preparation process of the doping include：
Step 1. is according to fluorocarbons：Ag2V4O11：Solvent=1：0.01-0.8：1.5-3 mass ratio, by fluorocarbons,
Ag2V4O11Insert in ball mill with solvent, with 100-500 turns/min rotating speed batch mixing ball milling 12-24h, formed in ball mill mixed
Close slurry；
Mixed slurry is carried out 5-20h drying by step 2. under the conditions of 60 DEG C -120 DEG C, is naturally cooled to room temperature, is done
Dry mixing object；
Step 3. is by the powder after dry mixed object crosses 100-400 mesh sieves in step 2, obtained i.e. as lithium of the present invention electricity
Pond blended anode material.
The present invention can also use following technical measures：
The solvent is one kind in ethanol, ethylene glycol, isopropanol or water.
The ball mill is agate jar, and during ball milling, ball agate mill pearl is placed with agate jar.
The present invention has the advantage that and good effect：
1st, the present invention in fluorinated carbon material by being mixed with Ag2V4O11Material, due to Ag2V4O11It is very good that material has
High-rate discharge ability, the problem of compensate for the initial voltage hysteresis of fluorocarbons, effectively improve the discharge performance of fluorocarbons,
The big multiplying power discharging of lithium-fluorocarbons battery system greatly improved, improve lithium-fluorination carbon battery low-temperature high-current discharge, expand
The big application of lithium-fluorocarbons battery system.
2nd, the present invention is mixed using ball grinding method by additive to two kinds of materials, can be reached good and uniformly be mixed
Effect is closed, the initial discharge voltage lag issues of fluorocarbons is further improved, improves the low temperature performance of fluorocarbons, carry
The high heavy-current discharge performance of lithium-fluorocarbons battery system.
3rd, the present invention is placed with ball agate mill pearl in the material of mechanical milling process, further increases the uniform of mixing material
Property.
Brief description of the drawings
Fig. 1 is that blended anode material is prepared into battery in the embodiment of the present invention 1 and pure fluorinated carbon material is prepared into battery
Discharge curve compares figure；
Fig. 2 is that blended anode material is prepared into battery in the embodiment of the present invention 2 and pure fluorinated carbon material is prepared into 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.
The preparation method of lithium battery blended anode material, adulterates Ag in fluorinated carbon material2V4O11Material, the mistake of doping
Journey includes：
Step 1. is according to fluorocarbons：Ag2V4O11：Solvent=1：0.01-0.8：1.5-3 mass ratio, by fluorocarbons,
Ag2V4O11Insert in ball mill with solvent, with 100-500 turns/min rotating speed batch mixing ball milling 12-24h, formed in ball mill mixed
Close slurry；
Mixed slurry is carried out 5-20h drying by step 2. under the conditions of 60 DEG C -120 DEG C, is naturally cooled to room temperature, is done
Dry mixing object；
Step 3. is by the powder after dry mixed object crosses 100-400 mesh sieves in step 2, obtained i.e. as lithium of the present invention electricity
Pond blended anode material.
The solvent is one kind in ethanol, ethylene glycol, isopropanol or water.
The ball mill is agate jar, and during ball milling, ball agate mill pearl is placed with agate jar.
Embodiment 1：
Step 1. takes 0.2g Ag2V4O11As dopant material, the agate ball as ball mill is together inserted with 4g fluorocarbons
In grinding jar, 6g ethanol is then added, is 1 according to fluorocarbons and ball milling pearl mass ratio：10 ratio is put into agate jar
Ball agate grinds pearl, a diameter of 5-15mm of ball milling pearl, the ball milling mixing under the conditions of 300 turns/min of the material in agate jar
12h, form mixed slurry；Pearl is ground by being put into ball agate, preferably two kinds of materials can be mixed, increase mixed effect.
The mixed slurry that step 2. forms step 1 inserts drying baker, 10h drying is carried out under the conditions of 80 DEG C, after taking-up
25 DEG C of room temperatures are naturally cooled to, obtain the mixing object of drying；
After the mixing object dried in step 2 is crossed 300 mesh sieves by step 3., obtained powder is used as lithium battery of the present invention
Use blended anode material.
Embodiment 2：
Step 1. takes 0.28g Ag2V4O11As dopant material, the agate as ball mill is together inserted with 4g fluorocarbons
In ball grinder, 7g ethanol is then added, is 1 according still further to fluorocarbons and ball milling pearl mass ratio：10 ratio is in agate jar
Ball agate mill pearl is put into, the diameter of ball agate mill pearl is in the range of 5-15mm, and the material in agate jar is in 200 turns/min bars
Ball milling mixing 24h under part, form mixed slurry；
The mixed slurry that step 2. forms step 1 inserts drying baker, 10h drying is carried out under the conditions of 80 DEG C, after taking-up
25 DEG C of room temperatures are naturally cooled to, obtain the mixing object of drying；
After the mixing object dried in step 2 is crossed 200 mesh sieves by step 3., obtained powder is used as lithium battery of the present invention
Blended anode material.
It is used as and bonds as conductive agent, pvdf as positive electrode, SP using blended anode material made of embodiment 1
Agent, according to positive electrode：Conductive agent：Binding agent=84：10：6 mass ratio is uniformly mixed into anode sizing agent and is coated on aluminium foil, and 120
It is dried under the conditions of DEG C, lithium metal carries out the assembling of one group of lithium battery as negative electrode in glove box.Pure fluorination is used again
For carbon as positive electrode, remaining is identical with embodiment 1, carries out another group of lithium battery assembling.Two groups of lithium batteries are carried out simultaneously
Normal temperature shown in Fig. 1, the discharge test under the conditions of 1C, the electric discharge for the lithium battery that the lower curve in Fig. 1 is assembled into for pure fluorocarbons are bent
Line, upper curve are the discharge curve that lithium battery is assembled into using material made of embodiment 1；Substantially observed in figure, pure fluorination
Lithium battery initial voltage made of carbon is 1.7V, and voltage delay is obvious under the conditions of heavy-current discharge；Using mixed in embodiment 1
Close lithium battery made of positive electrode, its initial minimum voltage is 2.0V, lagging voltage be improved significantly, its discharge voltage is put down
Platform is significantly improved, and has embodied Ag2V4O11The good electric conductivity of material；Due to Ag2V4O11Material has 315mA/ in itself
G capacity, and itself there is good electric conductivity, on the premise of the capacity of fluorocarbons is not significantly affected, pole
The big performance for improving fluorinated carbon material.
It is used as and bonds as conductive agent, pvdf as positive electrode, SP using blended anode material made of embodiment 2
Agent, according to positive electrode：Conductive agent：Binding agent=84：10：6 mass ratio is uniformly mixed into anode sizing agent and is coated on aluminium foil, and 120
It is dried under the conditions of DEG C, lithium metal carries out the assembling of one group of lithium battery as negative electrode in glove box.Pure fluorination is used again
For carbon as positive electrode, remaining is identical with embodiment 1, carries out another group of lithium battery assembling.Two groups of lithium batteries are carried out simultaneously
Fig. 2 is shown -10 DEG C, the discharge test under the conditions of 0.1C, the electric discharge for the lithium battery that the lower curve in figure is assembled into for pure fluorocarbons
Curve, upper curve are the discharge curve that lithium battery is assembled into using material made of embodiment 2；Substantially observed in figure, pure fluorine
Lithium battery initial voltage made of changing carbon is 1.81V, and voltage delay is obvious under cryogenic；Using the mixing in embodiment 2
Lithium battery made of positive electrode, its initial minimum voltage are 2.06V, lagging voltage be improved significantly, simultaneously as
Ag2V4O11With good electric conductivity, the improved electric conductivity of fluorinated carbon material, its discharge voltage plateau is set to have substantially
Raising；And adulterate Ag2V4O11The capacity of fluorocarbons afterwards is not affected, and greatly improves the property of fluorinated carbon material
Energy.
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. the preparation method of lithium battery blended anode material, it is characterised in that：Ag is adulterated in fluorinated carbon material2V4O11Material,
The process of the doping includes：
Step 1. is according to fluorocarbons：Ag2V4O11：Solvent=1：0.01-0.8：1.5-3 mass ratio, by fluorocarbons, Ag2V4O11With
Solvent is inserted in ball mill, and with 100-500 turns/min rotating speed batch mixing ball milling 12-24h, mixed slurry is formed in ball mill；
Mixed slurry is carried out 5-20h drying by step 2. under the conditions of 60 DEG C -120 DEG C, naturally cools to room temperature, is obtained drying and is mixed
Compound body；
After the dry mixed object formed in step 2 is crossed 100-400 mesh sieves by step 3., obtained powder is used as lithium battery
Blended anode material.
2. the preparation method of lithium battery blended anode material according to claim 1, it is characterised in that：The solvent is
One kind in ethanol, ethylene glycol, isopropanol or water.
3. the preparation method of lithium battery blended anode material according to claim 1, it is characterised in that：The ball mill
For agate jar, during ball milling, ball agate mill pearl is placed with agate jar.
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| 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 |
| CN106803581A (en) * | 2017-01-24 | 2017-06-06 | 上海空间电源研究所 | Carrier rocket integrated power supply battery, its positive plate active material and preparation method |
| CN109224989A (en) * | 2017-07-11 | 2019-01-18 | 湖北航鹏化学动力科技有限责任公司 | A kind of mixing preparation method of anode for lithium battery material |
| 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 |
| CN110137453A (en) * | 2019-04-26 | 2019-08-16 | 中国航发北京航空材料研究院 | A kind of composite positive pole and the preparation method and application thereof |
| CN112038650A (en) * | 2020-07-28 | 2020-12-04 | 天津力神电池股份有限公司 | Flexible package lithium fluorocarbon primary battery |
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| US7435509B2 (en) * | 2002-09-10 | 2008-10-14 | Uchicago Argonne, Llc | Electrode for a lithium cell |
| CN1913202B (en) * | 2006-05-26 | 2010-07-21 | 南开大学 | Vanadic acid silver electrode material and preparation method and its application |
| CN101807685B (en) * | 2010-04-27 | 2012-01-11 | 青岛科技大学 | Preparation method and application of silver vanadate/vanadium oxide one-dimensional composite nano-electrode material |
| CN102354746A (en) * | 2011-11-11 | 2012-02-15 | 中南大学 | Preparation method for silver vanadate cathode material |
| CN103187557B (en) * | 2013-03-31 | 2015-07-08 | 肖兴立 | Silver vanadate-lithium iron phosphate composite anode material preparation method |
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