CN104577124A - Preparation method of mixed anode material for lithium battery - Google Patents
Preparation method of mixed anode material for lithium battery Download PDFInfo
- Publication number
- CN104577124A CN104577124A CN201310478328.XA CN201310478328A CN104577124A CN 104577124 A CN104577124 A CN 104577124A CN 201310478328 A CN201310478328 A CN 201310478328A CN 104577124 A CN104577124 A CN 104577124A
- Authority
- CN
- China
- Prior art keywords
- lithium battery
- lithium
- preparation
- anode material
- carbon fluoride
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Classifications
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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
-
- 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
-
- 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
-
- 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
-
- 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 a preparation method of a mixed anode material for a lithium battery. The preparation method is characterized by comprising the following steps: doping an Ag2V4O11 material into a carbon fluoride material, wherein the doping process comprises the step of placing carbon fluoride, Ag2V4O11 and a solvent into a ball mill to be milled to form mixed slurry; drying the mixed slurry, and cooling the dried slurry to obtain a dried mixture; screening the dried mixture to obtain the mixed anode material for the lithium battery. According to the preparation method disclosed by the invention, the Ag2V4O11 material is mixed with the carbon fluoride material, the two substances are mixed through an additive, and the Ag2V4O11 material is good in high-rate discharge performance, so that the initial voltage lagging problem of carbon fluoride can be solved, the discharge performance of carbon fluoride can be effectively improved, the high rate discharge of a lithium-carbon fluoride battery system can be greatly improved, the low-temperature heavy current discharge of the lithium-carbon fluoride battery can be improved, and the application range of the lithium-carbon fluoride battery system can be expanded.
Description
Technical field
The invention belongs to lithium battery material technical field, particularly relate to a kind of preparation method of lithium battery blended anode material.
Background technology
Lithium metal primary cell is of a great variety, there is higher specific energy and operating voltage, the comparatively ripe system of current development mainly contains lithium-manganese dioxide battery, lithium-thionyl chloride battery, lithium-sulfur dioxide battery etc., and energy density generally can reach 250-350Wh/kg.In recent years, lithium-fluorocarbons battery receives much concern because having higher energy density.But, due to delayed serious, the large multiplying power discharging property of fluorinated carbon material initial voltage be not very well, the problem such as heat release and expansion, eventually reduce the effect of battery low-temperature high-current discharge, have a strong impact on the large multiplying power discharging property of battery, greatly limit the range of application of lithium-fluorocarbons battery.
Disclose a kind of lithium battery fluorocarbons positive electrode fluorocarbons patent of invention at present, wherein fluorocarbons is fluorographite CF
xwith carbon fluoride nano-tube CF
xmixture; Described fluorographite CF
xwith carbon fluoride nano-tube CF
xmass ratio range be 6:4 to 9.5:0.5.The present invention adopts the mixture of fluorographite and carbon fluoride nano-tube as battery fluorocarbons positive electrode, carbon fluoride nano-tube material is made to be dispersed in around fluorographite particle preferably, effectively eliminate the high agglomeration of carbon fluoride nano-tube material, improving the battery discharge initial stage there is obvious voltage delay phenomenon to some extent, the multiplying power discharging property of lithium-fluorocarbons battery system is increased, but the material due to the present invention's employing is fluoridizes series material, fundamentally do not solve the initial voltage hysteresis that fluorocarbons itself has, be difficult to the discharge-rate significantly improving lithium-fluorocarbons battery, hinder the extensive use of fluorinated carbon material.
Summary of the invention
The present invention provides a kind of delayed problem of initial voltage that fluorinated carbon material itself has that effectively makes up for solving in known technology the technical problem that exists, significantly improve the large multiplying power discharging property of lithium-fluorocarbons battery system, and low-temperature high-current discharge is effective, the preparation method of the lithium battery blended anode material of applied range.
The present invention includes following technical scheme:
The preparation method of lithium battery blended anode material, is characterized in: Ag doped in fluorinated carbon material
2v
4o
11material, the preparation process of described doping comprises:
Step 1. is according to fluorocarbons: Ag
2v
4o
11: the mass ratio of solvent=1:0.01-0.8:1.5-3, by fluorocarbons, Ag
2v
4o
11insert in ball mill with solvent, turn/rotating speed batch mixing ball milling the 12-24h of min with 100-500, in ball mill, form mixed slurry;
Mixed slurry is carried out 5-20h oven dry by step 2. under 60 DEG C of-120 DEG C of conditions, naturally cools to room temperature, obtains dry mixed object;
Step 3. is by after in step 2, dry mixed object crosses 100-400 mesh sieve, and the powder obtained is namely as lithium battery blended anode material of the present invention.
The present invention can also adopt following technical measures:
Described solvent is the one in ethanol, ethylene glycol, isopropyl alcohol or water.
Described ball mill is agate jar, during ball milling, is placed with ball agate mill pearl in agate jar.
The advantage that the present invention has and good effect:
1, the present invention by being mixed with Ag in fluorinated carbon material
2v
4o
11material, due to Ag
2v
4o
11material has extraordinary high-rate discharge ability, compensate for the problem that the initial voltage of fluorocarbons is delayed, effectively improve the discharge performance of fluorocarbons, significantly improve the large multiplying power discharging of lithium-fluorocarbons battery system, improve lithium-fluorocarbons battery low-temperature high-current discharge, expand the range of application of lithium-fluorocarbons battery system.
2, the present invention adopts ball grinding method to be mixed two kinds of materials by additive, good mix uniformly effect can be reached, further improve the initial discharge voltage lag issues of fluorocarbons, improve the low temperature performance of fluorocarbons, improve the heavy-current discharge performance of lithium-fluorocarbons battery system.
3, the present invention is placed with ball agate mill pearl in the material of mechanical milling process, further increases the uniformity of composite material.
Accompanying drawing explanation
Fig. 1 is that in the embodiment of the present invention 1, blended anode material is prepared into the discharge curve comparison diagram that battery and pure fluorinated carbon material are prepared into battery;
Fig. 2 is that in the embodiment of the present invention 2, blended anode material is prepared into the discharge curve comparison diagram that battery and pure fluorinated carbon material are prepared into battery.
Embodiment
For summary of the invention of the present invention, Characteristic can be disclosed further, be also described in detail as follows by reference to the accompanying drawings especially exemplified by following instance.
The preparation method of lithium battery blended anode material, Ag doped in fluorinated carbon material
2v
4o
11material, the process of doping comprises:
Step 1. is according to fluorocarbons: Ag
2v
4o
11: the mass ratio of solvent=1:0.01-0.8:1.5-3, by fluorocarbons, Ag
2v
4o
11insert in ball mill with solvent, turn/rotating speed batch mixing ball milling the 12-24h of min with 100-500, in ball mill, form mixed slurry;
Mixed slurry is carried out 5-20h oven dry by step 2. under 60 DEG C of-120 DEG C of conditions, naturally cools to room temperature, obtains dry mixed object;
Step 3. is by after in step 2, dry mixed object crosses 100-400 mesh sieve, and the powder obtained is namely as lithium battery blended anode material of the present invention.
Described solvent is the one in ethanol, ethylene glycol, isopropyl alcohol or water.
Described ball mill is agate jar, during ball milling, is placed with ball agate mill pearl in agate jar.
Embodiment 1:
Step 1. gets 0.2g Ag
2v
4o
11as dopant material, together insert in the agate jar as ball mill with 4g fluorocarbons, then 6g ethanol is added, the ratio being 1:10 according to fluorocarbons and ball milling pearl mass ratio is put into ball agate and is ground pearl in agate jar, the diameter of ball milling pearl is 5-15mm, material in agate jar is ball milling mixing 12h under 300 turns/min condition, forms mixed slurry; By putting into ball agate mill pearl, better bi-material can be mixed, increasing mixed effect.
The mixed slurry that step 1 is formed by step 2. inserts drying baker, under 80 DEG C of conditions, carry out 10h oven dry, naturally cools to 25 DEG C of room temperatures after taking-up, obtains dry mixing object;
After mixing object dry in step 2 is crossed 300 mesh sieves by step 3., the powder obtained is namely as lithium battery blended anode material of the present invention.
Embodiment 2:
Step 1. gets the Ag of 0.28g
2v
4o
11as dopant material, together insert in the agate jar as ball mill with 4g fluorocarbons, then 7g ethanol is added, the ratio being 1:10 according to fluorocarbons and ball milling pearl mass ratio is again put into ball agate and is ground pearl in agate jar, the diameter of ball agate mill pearl is within the scope of 5-15mm, material in agate jar is ball milling mixing 24h under 200 turns/min condition, forms mixed slurry;
The mixed slurry that step 1 is formed by step 2. inserts drying baker, under 80 DEG C of conditions, carry out 10h oven dry, naturally cools to 25 DEG C of room temperatures after taking-up, obtains dry mixing object;
After mixing object dry in step 2 is crossed 200 mesh sieves by step 3., the powder obtained is namely as the blended anode material of lithium battery of the present invention.
Adopt the blended anode material made of embodiment 1 as positive electrode, SP as conductive agent, pvdf as binding agent, according to positive electrode: conductive agent: the mass ratio of binding agent=84:10:6 is uniformly mixed into anode sizing agent and is coated on aluminium foil, drying is carried out under 120 DEG C of conditions, lithium metal, as negative electrode, carries out the assembling of one group of lithium battery in glove box.Adopt pure fluorocarbons as positive electrode again, all the other are identical with embodiment 1, carry out another group lithium battery assembling.Two groups of lithium batteries carry out the discharge test under normal temperature shown in Fig. 1,1C condition simultaneously, and the lower curve in Fig. 1 is the discharge curve of the lithium battery that pure fluorocarbons is assembled into, upper curve is the discharge curve that the material adopting embodiment 1 to make is assembled into lithium battery; Obviously observe in figure, the lithium battery initial voltage that pure fluorocarbons is made is 1.7V, and under heavy-current discharge condition, voltage delay is obvious; Adopt the lithium battery that the blended anode material in embodiment 1 is made, its initial minimum voltage is 2.0V, lagging voltage be improved significantly, its discharge voltage plateau is significantly improved, and has embodied Ag
2v
4o
11the electric conductivity that material is good; Due to Ag
2v
4o
11material itself has the capacity of 315mA/g, and self has good electric conductivity, under not being subject to the prerequisite of obviously impact, greatly improves the performance of fluorinated carbon material at the capacity of fluorocarbons.
Adopt the blended anode material made of embodiment 2 as positive electrode, SP as conductive agent, pvdf as binding agent, according to positive electrode: conductive agent: the mass ratio of binding agent=84:10:6 is uniformly mixed into anode sizing agent and is coated on aluminium foil, drying is carried out under 120 DEG C of conditions, lithium metal, as negative electrode, carries out the assembling of one group of lithium battery in glove box.Adopt pure fluorocarbons as positive electrode again, all the other are identical with embodiment 1, carry out another group lithium battery assembling.Two groups of lithium batteries to carry out shown in Fig. 2-10 DEG C, discharge test under 0.1C condition simultaneously, and the lower curve in figure is the discharge curve of the lithium battery that pure fluorocarbons is assembled into, upper curve is the discharge curve that the material adopting embodiment 2 to make is assembled into lithium battery; Obviously observe in figure, the lithium battery initial voltage that pure fluorocarbons is made is 1.81V, and voltage delay is obvious under cryogenic; Adopt the lithium battery that the blended anode material in embodiment 2 is made, its initial minimum voltage is 2.06V, lagging voltage be improved significantly, meanwhile, due to Ag
2v
4o
11have good conductivity, the electric conductivity of fluorinated carbon material of improvement, makes its discharge voltage plateau be significantly improved; And Ag doped
2v
4o
11after the capacity of fluorocarbons be not affected, greatly improve the performance of fluorinated carbon material.
Although be described the preferred embodiments of the present invention by reference to the accompanying drawings above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not departing under the ambit that present inventive concept and claim protect, a lot of form can also be made.These all belong within protection scope of the present invention.
Claims (3)
1. the preparation method of lithium battery blended anode material, is characterized in that: Ag doped in fluorinated carbon material
2v
4o
11material, the process of described doping comprises:
Step 1. is according to fluorocarbons: Ag
2v
4o
11: the mass ratio of solvent=1:0.01-0.8:1.5-3, by fluorocarbons, Ag
2v
4o
11insert in ball mill with solvent, turn/rotating speed batch mixing ball milling the 12-24h of min with 100-500, in ball mill, form mixed slurry;
Mixed slurry is carried out 5-20h oven dry by step 2. under 60 DEG C of-120 DEG C of conditions, naturally cools to room temperature, obtains dry mixed object;
After the dry mixed object formed in step 2 is crossed 100-400 mesh sieve by step 3., the powder obtained is namely as lithium battery blended anode material of the present invention.
2. the preparation method of lithium battery blended anode material according to claim 1, is characterized in that: described solvent is the one in ethanol, ethylene glycol, isopropyl alcohol or water.
3. the preparation method of lithium battery blended anode material according to claim 1, is characterized in that: described ball mill is agate jar, during ball milling, is placed with ball agate mill pearl in agate jar.
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|---|---|---|---|
| CN201310478328.XA CN104577124B (en) | 2013-10-14 | 2013-10-14 | The preparation method of lithium battery blended anode material |
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|---|---|---|---|
| CN201310478328.XA CN104577124B (en) | 2013-10-14 | 2013-10-14 | The preparation method of lithium battery blended anode material |
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| CN104577124A true CN104577124A (en) | 2015-04-29 |
| CN104577124B CN104577124B (en) | 2018-01-05 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109873137A (en) * | 2019-02-01 | 2019-06-11 | 贵州梅岭电源有限公司 | A kind of V2O5The preparation method of the fluorocarbons positive electrode of@C modification |
| 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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| CN1913202A (en) * | 2006-05-26 | 2007-02-14 | 南开大学 | Vanadic acid silver electrode material and preparation method and its application |
| CN101807685A (en) * | 2010-04-27 | 2010-08-18 | 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 |
| CN103187557A (en) * | 2013-03-31 | 2013-07-03 | 严建泗 | Silver vanadate-lithium iron phosphate composite anode material preparation method |
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2013
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Patent Citations (5)
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| US20040048156A1 (en) * | 2002-09-10 | 2004-03-11 | The University Of Chicago | Electrode for a lithium cell |
| CN1913202A (en) * | 2006-05-26 | 2007-02-14 | 南开大学 | Vanadic acid silver electrode material and preparation method and its application |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109873137A (en) * | 2019-02-01 | 2019-06-11 | 贵州梅岭电源有限公司 | A kind of V2O5The preparation method of the fluorocarbons positive electrode of@C modification |
| 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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| Publication number | Publication date |
|---|---|
| CN104577124B (en) | 2018-01-05 |
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