CN105261744B - A kind of preparation method of porous vanadium Mn oxide negative material - Google Patents
A kind of preparation method of porous vanadium Mn oxide negative material Download PDFInfo
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- CN105261744B CN105261744B CN201510605995.9A CN201510605995A CN105261744B CN 105261744 B CN105261744 B CN 105261744B CN 201510605995 A CN201510605995 A CN 201510605995A CN 105261744 B CN105261744 B CN 105261744B
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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- 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
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Abstract
A kind of preparation method of porous vanadium Mn oxide negative material, comprises the following steps：（1）It is 1 that vanadium source, manganese source are pressed into v element, manganese element, two oxalic acid hydrates, citric acid mol ratio with two oxalic acid hydrates, citric acid:1:2:1~3 ratio, add in deionized water and form solution, the concentration for controlling manganese ion in solution is 0.5~1 mol/L；（2）The solution of gained is placed in the water-bath with ultrasonic agitation device, ultrasonic agitation 36 h of reaction, forms colloidal sol；（3）The colloidal sol of gained is put into 80~120 DEG C of baking ovens and dries 2~6 h, obtains gel；（4）By the gel of gained in protective atmosphere, at 200~500 DEG C, after being calcined 2~10 h, room temperature is cooled to the furnace,.Course of reaction of the present invention is simple, is easy to industrialization control, and prepared vanadium Mn oxide has loose structure, is advantageous to lithium ion deintercalation, has good gram volume and cycle performance.
Description
Technical field
The present invention relates to a kind of preparation side of the porous vanadium Mn oxide negative material as lithium ion battery negative material
Method.
Background technology
Lithium ion battery is expected to replace traditional fossil energy in various fields with its significant advantage, applied to large-scale dynamic
In power battery, energy-storage battery, perplex global energy and environment problem at present so as to alleviate.Research and develop high performance lithium-ion electric
Pond electrode material, which turns into, meets one of growing vital task of lithium ion battery with high energy density demand.
Lithium-ion negative pole is the chief component of lithium ion battery, mainly graphite cathode commercialized at present, but its
Theoretical specific capacity is low（372 mAh/g）.Although it has the advantages that cheap, abundance, safe, as anode holds
The continuous improvement of amount, graphite can not meet the needs of negative pole.
Common metal negative pole all has crystal structure at present, and structure easily changes influence circulation after circulation.
The A of CN 103864045 disclose a kind of freeze-drying and prepare duct shape lithium ion battery negative material vanadium phosphate
Method, specifically include following steps：It is 1 by a mole metering ratio:1:3 vanadium source, phosphorus source and reducing agent are soluble in water, stir
To homogeneous solution；Resulting solution is transferred in vacuum freezing drying oven by the homogeneous solution of gained, -40 DEG C, 15
Pa is freeze-dried to obtaining the presoma dry powder of vanadium phosphate.Ground, tabletting, presoma is placed in pipe type sintering furnace, Yu Fei
Oxidizing atmosphere 6 h of lower 750 DEG C of sintering, are cooled to room temperature and obtain vanadium phosphate negative material.The method freeze-drying power consumption is higher,
And gram volume is relatively low first.
The A of CN 103972506 disclose a kind of preparation method of nano-sheet lithium ion battery negative material vanadyl phosphate,
Comprise the following steps：（1）Using vanadium source, phosphorus source and reducing agent as raw material, according to phosphate anion in vanadium ion, phosphorus source in vanadium source and
The mol ratio 1 of reducing agent:1:1~5, it is dissolved in deionized water；（2）By step（1）Middle gained mixed solution is placed in 70~90 DEG C
The h of stirred in water bath 1~6 obtain uniform solution；（3）By step（2）Solution, colloidal sol or the suspension regulation pH to 6 of middle gained
~9；（4）By step（3）Solution, colloidal sol or the suspension of middle gained are placed in pyrolytic tank, at 150~350 DEG C be pyrolyzed 10~
30 h；（5）By step（4）Products therefrom is filtered, and vanadyl phosphate presoma is dried to obtain in 80~120 DEG C；（6）By step（5）
Gained vanadyl phosphate presoma 100~400 DEG C of 1~10 h of sintering under non-reducing atmosphere, are cooled to room temperature, obtain phosphoric acid oxygen
Vanadium.This negative pole preparation process is complicated, and capacity is close with metavanadic acid manganese, and sintering temperature is higher.
At present, have no that related amorphous metal oxide makees the invention research of negative pole.
The content of the invention
The technical problems to be solved by the invention are, in view of the shortcomings of the prior art, there is provided a kind of porous vanadium Mn oxide
The preparation method of negative material, the material prepared by this method have regular loose structure, can bring good gram volume
With cycle performance.
The technical solution adopted for the present invention to solve the technical problems is：A kind of system of porous vanadium Mn oxide negative material
Preparation Method, comprise the following steps：
（1）Vanadium source, manganese source and two oxalic acid hydrates, citric acid are rubbed by v element, manganese element, two oxalic acid hydrates, citric acid
You are than being 1:1:2:1~3 ratio, add in deionized water and form solution, the concentration for controlling manganese ion in solution is 0.5~1
mol/L；
（2）By step（1）The solution of gained is placed in the water-bath with ultrasonic agitation device, ultrasonic agitation reaction 3-6
h（It is preferred that 4-5 h）, form colloidal sol；
（3）By step（2）The colloidal sol of gained, which is put into 80~120 DEG C of baking ovens, dries 2~6 h, obtains gel；
（4）By step（3）The gel of gained is in protective atmosphere, at 200~500 DEG C, after being calcined 2~10 h, with stove
Room temperature is cooled to, obtains porous vanadium Mn oxide negative material.
Further, step（1）In, described vanadium source is ammonium metavanadate, vanadyl oxalate, vanadic anhydride or their mixing
Thing.The introducing of vanadium root can prevent Mn oxide from forming crystal structure, to improve its performance.
Further, step（1）In, described manganese source is in four acetate hydrate manganese, Manganous sulfate monohydrate, two oxalic acid hydrate manganese
One or more of mixtures.
Further, step（2）In, ultrasonic frequency is 20~40 kHz, and the speed of stirring is 50~400 r/min.
Further, step（2）In, the bath temperature of water-bath is 70~90 DEG C.
Further, step（4）In, the protective atmosphere be argon gas, nitrogen, hydrogen, carbon dioxide, carbon monoxide or hydrogen/
It is argon-mixed；The volumetric concentration of the hydrogen/argon-mixed middle hydrogen is 2~8 %.
The present invention mixes formation amorphous metal oxide at a certain temperature with manganese ion using vanadic acid root, using without fixed
The cycle performance of shape structural improvement material.The negative material of preparation discharges the mAh/g of gram volume 1024 first, 300 mA/g electric currents
Under discharge first the mAh/g of gram volume 407, capability retention is up to 100 % after circulation 50 times.
Building-up process of the present invention is simple, and condition is easily controllable, and obtained negative material cycle performance is excellent.
Brief description of the drawings
Fig. 1 is the SEM figures of the porous vanadium manganese negative material obtained by embodiment 1；
Fig. 2 is discharge curve of the porous vanadium manganese negative material under different current densities obtained by embodiment 1；
Fig. 3 is cyclic curve of the porous vanadium manganese negative material under 300 mA/g current densities obtained by embodiment 1.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
（1）Weigh the g of ammonium metavanadate 11.70（0.1mol）, the g of four acetate hydrate manganese 24.51（0.1mol）, two oxalic acid hydrates
25.32 g（0.2mol）, the g of citric acid 38.42（0.2mol）, it is added in 150 mL deionized waters and forms solution, manganese in solution
The concentration of ion is 0.67 mol/L；
（2）By step（1）The solution of gained is placed in the water-bath with ultrasonic agitation device, ultrasonic agitation reaction
4.5h, it is 30 kHz to control supersonic frequency, and the speed of stirring is 200 r/min, 80 DEG C of bath temperature, forms colloidal sol；
（3）By step（2）The colloidal sol of gained, which is put into 110 DEG C of baking ovens, dries 5 h, obtains gel；
（4）By step（3）The gel of gained is in argon gas atmosphere, at 400 DEG C, after being calcined 6 h, cools to room with the furnace
Temperature, obtain porous vanadium Mn oxide negative material.
The SEM figures of porous vanadium manganese negative material obtained by the present embodiment as shown in figure 1, understand, material tool as shown in Figure 1
There is porous pattern.
The assembling of battery：The porous vanadium manganese negative material obtained by 0.40 g is weighed, 0.05 g acetylene blacks is added and makees conductive agent
With 0.05 g NMP（1-METHYLPYRROLIDONE）Make binding agent, be coated in after well mixed on copper foil and negative plate is made, in vacuum hand
It is barrier film with Celgard 2300 using metal lithium sheet as positive pole in casing, 1mol/L LiPF6/EC:DMC（Volume ratio 1:1）For
Electrolyte, it can be assembled into CR2025 button cell.
By battery in 0.05~3 V voltage ranges, its charge/discharge capacity and high rate performance are surveyed, under 30 mA/g electric currents
The gram volume that discharges first is 1024 mAh/g, and the gram volume that discharged first under 300 mA/g electric currents is 407.3 mAh/g, is circulated 50 times
Capability retention is 100% afterwards（See Fig. 2 and Fig. 3）.
Embodiment 2
（1）Weigh the g of vanadyl oxalate 12.25（0.05mol）, the g of vanadic anhydride 9.1（0.05mol）, two oxalic acid hydrates
The g of manganese 8.95（0.05 mol）, the g of Manganous sulfate monohydrate 8.45（0.05 mol）, the g of two oxalic acid hydrate 25.32（0.2 mol）,
The g of citric acid 19.12（0.1 mol）, it is added in 100 mL deionized waters and forms solution, the concentration of manganese ion is 1 in solution
mol/L；
（2）By step（1）The solution of gained is placed in the water-bath with ultrasonic agitation device, ultrasonic agitation 4 h of reaction,
It is 20 kHz to control supersonic frequency, and the speed of stirring is 50 r/min, 70 DEG C of bath temperature, forms colloidal sol；
（3）By step（2）The colloidal sol of gained, which is put into 80 DEG C of baking ovens, dries 6 h, obtains gel；
（4）By step（3）The gel of gained is in argon gas atmosphere, at 200 DEG C, after being calcined 10 h, cools to room with the furnace
Temperature, obtain porous vanadium Mn oxide negative material.
The assembling of battery：The porous vanadium manganese negative material obtained by 0.40 g is weighed, 0.05 g acetylene blacks is added and makees conductive agent
With 0.05 g NMP（1-METHYLPYRROLIDONE）Make binding agent, be coated in after well mixed on copper foil and negative plate is made, in vacuum hand
It is barrier film with Celgard 2300 using metal lithium sheet as positive pole in casing, 1mol/L LiPF6/EC:DMC（Volume ratio 1:1）For
Electrolyte, it can be assembled into CR2025 button cell.
By battery in 0.05~3 V voltage ranges, its charge/discharge capacity and high rate performance are surveyed, under 30 mA/g electric currents
The gram volume that discharges first is 1008.4 mAh/g, and the gram volume that discharged first under 300 mA/g electric currents is 380.3 mAh/g, circulation 50
Capability retention is 98% after secondary.
Embodiment 3
（1）Weigh the g of vanadyl oxalate 24.50（0.1 mol）, the g of Manganous sulfate monohydrate 16.90（0.1 mol）, two hydrations
The g of oxalic acid 25.32（0.2 mol）, the g of citric acid 57.36（0.3 mol）, it is added in 200 mL deionized waters and forms solution, it is molten
The concentration of manganese ion is 0.5 mol/L in liquid；
（2）By step（1）The solution of gained is placed in the water-bath with ultrasonic agitation device, ultrasonic agitation 5 h of reaction,
It is 40 kHz to control supersonic frequency, and the speed of stirring is 400 r/min, 90 DEG C of bath temperature, forms colloidal sol；
（3）By step（2）The colloidal sol of gained, which is put into 120 DEG C of baking ovens, dries 2 h, obtains gel；
（4）By step（3）The gel of gained is in hydrogen/argon-mixed（Hydrogen volume concentration is 5%）In, at 500 DEG C, roasting
After burning 2 h, room temperature is cooled to the furnace, obtain porous vanadium Mn oxide negative material.
The assembling of battery：The porous vanadium manganese negative material obtained by 0.40 g is weighed, 0.05 g acetylene blacks is added and makees conductive agent
With 0.05 g NMP（1-METHYLPYRROLIDONE）Make binding agent, be coated in after well mixed on copper foil and negative plate is made, in vacuum hand
It is barrier film with Celgard 2300 using metal lithium sheet as positive pole in casing, 1mol/L LiPF6/EC:DMC（Volume ratio 1:1）For
Electrolyte, it can be assembled into CR2025 button cell.
By battery in 0.05~3V voltage ranges, its charge/discharge capacity and high rate performance are surveyed, it is first under 30 mA/g electric currents
Secondary electric discharge gram volume is 980.5 mAh/g, and the gram volume that discharged first under 300 mA/g electric currents is 353.1 mAh/g, is circulated 50 times
Capability retention is 95% afterwards.
Claims (7)
1. a kind of preparation method of porous vanadium Mn oxide negative material, it is characterised in that comprise the following steps：
（1）By vanadium source, manganese source with two oxalic acid hydrates, citric acid by v element, manganese element, two oxalic acid hydrates, citric acid mol ratio
For 1:1:2:1~3 ratio, add in deionized water and form solution, the concentration for controlling manganese ion in solution is 0.5~1 mol/L；
（2）By step（1）The solution of gained is placed in the water-bath with ultrasonic agitation device, ultrasonic agitation reaction 3-6 h, shape
Into colloidal sol；
（3）By step（2）The colloidal sol of gained, which is put into 80~120 DEG C of baking ovens, dries 2~6 h, obtains gel；
（4）By step（3）The gel of gained is in protective atmosphere, at 200~500 DEG C, after being calcined 2~10 h, and furnace cooling
To room temperature, porous vanadium Mn oxide negative material is obtained.
2. the preparation method of porous vanadium Mn oxide negative material according to claim 1, it is characterised in that step（1）
In, described vanadium source is ammonium metavanadate, vanadyl oxalate, vanadic anhydride or their mixture.
3. the preparation method of porous vanadium Mn oxide negative material according to claim 1 or 2, it is characterised in that step
（1）In, described manganese source is one or more of mixing in four acetate hydrate manganese, Manganous sulfate monohydrate, two oxalic acid hydrate manganese
Thing.
4. the preparation method of porous vanadium Mn oxide negative material according to claim 1 or 2, it is characterised in that step
（2）In, ultrasonic frequency is 20~40 kHz, and the speed of stirring is 50~400 r/min.
5. the preparation method of porous vanadium Mn oxide negative material according to claim 1 or 2, it is characterised in that step
（2）In, the bath temperature of water-bath is 70~90 DEG C.
6. the preparation method of porous vanadium Mn oxide negative material according to claim 1 or 2, it is characterised in that step
（4）In, the protective atmosphere is argon gas, nitrogen, hydrogen, carbon dioxide, carbon monoxide or hydrogen/argon-mixed.
7. the preparation method of porous vanadium Mn oxide negative material according to claim 6, it is characterised in that the hydrogen/
The volumetric concentration of argon-mixed middle hydrogen is 2~8 %.
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| CN106684359B (en) * | 2017-01-19 | 2019-05-10 | 电子科技大学 | Different-shape Co (VO3)2-Mn(VO3)2And its preparation method and application |
| CN107394128B (en) * | 2017-06-19 | 2021-04-06 | 厦门大学 | Lithium ion battery cathode material and preparation method thereof |
| CN111204811B (en) * | 2020-01-13 | 2021-05-07 | 中国科学技术大学 | Preparation method of vanadium-based spinel material and preparation method of battery anode |
| CN112322953A (en) * | 2020-12-07 | 2021-02-05 | 湖南众鑫新材料科技股份有限公司 | Nitrided ferrovanadium alloy and preparation method thereof |
| CN112575239A (en) * | 2020-12-08 | 2021-03-30 | 湖南众鑫新材料科技股份有限公司 | Preparation method of high-quality low-cost nitrided ferrovanadium |
| CN114229901B (en) * | 2021-12-17 | 2024-05-07 | 华南协同创新研究院 | Transition metal vanadate material and preparation method and application thereof |
| CN116060019B (en) * | 2023-03-15 | 2024-05-21 | 天津大学 | Supported multi-metal oxide series catalyst and preparation method and application thereof |
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| CN104269529B (en) * | 2014-09-23 | 2016-05-11 | 中南大学 | A kind of preparation method of lithium ion battery negative material boric acid vanadium |
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