CN104733186A - Preparation method of negative electrode material with good charge and discharge performance - Google Patents
Preparation method of negative electrode material with good charge and discharge performance Download PDFInfo
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- CN104733186A CN104733186A CN201310718574.8A CN201310718574A CN104733186A CN 104733186 A CN104733186 A CN 104733186A CN 201310718574 A CN201310718574 A CN 201310718574A CN 104733186 A CN104733186 A CN 104733186A
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- manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method of a negative electrode material with good charge and discharge performance. The method is characterized by comprising the following steps: 1, sulfur/carbon composite material production; 2, ultrasonic treatment; 3, washing; 4, drying. The sulfur/carbon composite material has a high specific area and high electronic conductivity, so that a device can have good capacity and rate performance; ingredients are economical and environment friendly, an active material, namely sulfur which is high in content can be loaded, the energy density of a cell can be increased, and the cycling performance of the cell can be effectively improved as a result of an inherent enormous surface absorption effect of a carbon material; a manganese material has the remarkable advantages of being environment friendly and wide in electrochemical work window, so that the electrode material of a manganese-based super-capacitor is safer and more convenient to use, the preparation process is simple, the cost is low, and the material is suitable for industrial production.
Description
Technical field
The invention belongs to electrode material manufacture technology field, be specifically related to a kind of preparation method of negative material of good charge-discharge performance.
Background technology
Negative pole refers to one end that current potential in power supply (electromotive force) is lower.In primary cell, refer to the electrode of oxidation, in cell reaction, write on the left side.From physical angle, be the pole that in circuit, electronics flows out.And negative material, then refer in battery the raw material forming negative pole, negative material common at present has carbon negative pole material, tin base cathode material, lithium-containing transition metal nitride negative material, alloy type negative material and nanoscale negative material.
Electrode material at present for ultracapacitor mainly contains carbon, transition metal oxide and conducting polymer.The electrode material for super capacitor that material with carbon element is current research and is most widely used, it mainly comprises activated carbon, activated carbon fiber, carbon nano-tube and Graphene etc.Wherein, active carbon material, owing to having stable useful life, cheap price and large-scale industrial production basis, is widely adopted in current ultracapacitor commodity.But active carbon material ratio is easier to oxidized, cause Carbon-based supercapacitor internal resistance comparatively large, high frequency characteristics is poor, and the conductivity of active carbon material is poor.Many defects allow it be difficult to meet the active demand to ultracapacitor high-energy, high power density such as electric automobile.Conducting polymer has the shortcoming of cyclical stability difference.This just needs scientific research personnel to find more suitably new material.
Manganese dioxide class material, there is cheap, environmentally friendly and that electrochemical operation window is wide remarkable advantage, the more important thing is, manganese dioxide based super capacitor can adopt neutral electrolyte solution (aqueous solution etc. as sodium sulphate, potassium chloride), and strong acid and strong base electrolyte must be adopted unlike other metal oxides or Carbon-based supercapacitor, this makes the assembling of manganese dioxide based super capacitor and uses safer, more convenient.At present, the method preparing manganese oxide mainly contains: hydro thermal method, colloidal sol-gel method, template, phonochemistry method, oxidation-reduction method and high-temperature decomposition etc.Made the manganese oxide nanometer material of various pattern by above method, however due to these material porositys low, without flourishing electron conduction path, performance is not high.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of negative material of good charge-discharge performance, make device can have good capacity and high rate performance; Improve the energy density of battery, and the huge adsorption interaction energy of material with carbon element itself effectively improves the cycle performance of battery; The electrode material of manganese based super capacitor is used safer, more convenient, preparation technology is simple, and cost is low, is suitable for suitability for industrialized production.
The technical scheme that the present invention takes is:
A preparation method for the negative material of good charge-discharge performance, is characterized in that, comprises the steps:
(1) sulphur/carbon composite processed: material with carbon element and Cosan are put into zirconium dioxide ball grinder according to weight ratio 1:10, after ball grinder is injected high purity inert gas, control rotational speed of ball-mill is 300-350 rev/min, ball milling 2-2.5h;
(2) ultrasonic process: it is in the manganese containing materials aqueous solution of 20-25% that sulphur/carbon composite is added mass concentration, then it is 800-2000 watt every square centimeter at power, frequency is in the ultrasonic reactor of 50-100 KHz, and control temperature is ultrasonic process 4-6h at 40-50 DEG C;
(3) wash: in the organic solvent be dispersed in the composite material after ultrasonic process, add ammonium persulfate aqueous solution and adjust pH=2-3, control temperature is 60-70 DEG C, stirring reaction 3-4h, then centrifugation, and washing, makes it disperse completely equably;
(4) dry: at 155-180 DEG C of roasting 3-4h under mixed gas protected containing hydrogen reduction, to obtain containing manganese porous sulphur carbon/manganese oxide nano composite material.
Manganese containing materials in above-mentioned steps (2) is the mixture that potassium permanganate and manganese carbonate form according to mol ratio 2:1.
Organic solvent in above-mentioned steps (3) to be volume ratio be 3: 1 chloroform and acetone mixture.
The preparation method of the negative material of a kind of good charge-discharge performance according to claim 1, is characterized in that, in above-mentioned steps (4) is the mist that hydrogen and argon gas form according to mol ratio 2:1 containing hydrogen reduction mist.
Beneficial effect of the present invention is:
1, sulphur/carbon composite provided by the invention have high specific area and and electronic conductivity, thus make device can have good capacity and high rate performance;
2, raw material economics environmental protection, can the active material sulphur of load high-load, improves the energy density of battery, and the huge adsorption interaction energy of material with carbon element itself effectively improves the cycle performance of battery;
3, manganese material has environment friendly and the wide remarkable advantage of electrochemical operation window, the electrode material of manganese based super capacitor is used safer, more convenient, and preparation technology is simple, and cost is low, is suitable for suitability for industrialized production.
Embodiment
Embodiment 1
A preparation method for the negative material of good charge-discharge performance, is characterized in that, comprises the steps:
(1) sulphur/carbon composite processed: material with carbon element and Cosan are put into zirconium dioxide ball grinder according to weight ratio 1:10, after ball grinder is injected high purity inert gas, controlling rotational speed of ball-mill is 300 revs/min, ball milling 2.5h;
(2) ultrasonic process: sulphur/carbon composite add mass concentration be 20% potassium permanganate and the manganese containing materials aqueous solution that forms according to mol ratio 2:1 of manganese carbonate in, then it is 2000 watts every square centimeter at power, frequency is in the ultrasonic reactor of 100 KHz, and control temperature is ultrasonic process 6h at 40 DEG C;
(3) wash: the volume ratio that the composite material after ultrasonic process is dispersed in be 3: 1 chloroform and acetone composition organic solvent in, add ammonium persulfate aqueous solution adjust pH=2-3, control temperature is 60 DEG C, stirring reaction 4h, then centrifugation, washing, makes it disperse completely equably;
(4) dry: hydrogen and argon gas form according to mol ratio 2:1 mixed gas protected containing hydrogen reduction under at 160 DEG C of roasting 4h, obtain containing manganese porous sulphur carbon/manganese oxide nano composite material.
Embodiment 2
A preparation method for the negative material of good charge-discharge performance, is characterized in that, comprises the steps:
(1) sulphur/carbon composite processed: material with carbon element and Cosan are put into zirconium dioxide ball grinder according to weight ratio 1:10, after ball grinder is injected high purity inert gas, controlling rotational speed of ball-mill is 350 revs/min, ball milling 2h;
(2) ultrasonic process: sulphur/carbon composite add mass concentration be 25% potassium permanganate and the manganese containing materials aqueous solution that forms according to mol ratio 2:1 of manganese carbonate in, then it is 2000 watts every square centimeter at power, frequency is in the ultrasonic reactor of 100 KHz, and control temperature is ultrasonic process 4h at 50 DEG C;
(3) wash: the volume ratio that the composite material after ultrasonic process is dispersed in be 3: 1 chloroform and acetone composition organic solvent in, add ammonium persulfate aqueous solution adjust pH=2-3, control temperature is 70 DEG C, stirring reaction 3h, then centrifugation, washing, makes it disperse completely equably;
(4) dry: hydrogen and argon gas form according to mol ratio 2:1 mixed gas protected containing hydrogen reduction under at 180 DEG C of roasting 3h, obtain containing manganese porous sulphur carbon/manganese oxide nano composite material.
Claims (4)
1. a preparation method for the negative material of good charge-discharge performance, is characterized in that, comprises the steps:
(1) sulphur/carbon composite processed: material with carbon element and Cosan are put into zirconium dioxide ball grinder according to weight ratio 1:10, after ball grinder is injected high purity inert gas, control rotational speed of ball-mill is 300-350 rev/min, ball milling 2-2.5h;
(2) ultrasonic process: it is in the manganese containing materials aqueous solution of 20-25% that sulphur/carbon composite is added mass concentration, then it is 800-2000 watt every square centimeter at power, frequency is in the ultrasonic reactor of 50-100 KHz, and control temperature is ultrasonic process 4-6h at 40-50 DEG C;
(3) wash: in the organic solvent be dispersed in the composite material after ultrasonic process, add ammonium persulfate aqueous solution and adjust pH=2-3, control temperature is 60-70 DEG C, stirring reaction 3-4h, then centrifugation, and washing, makes it disperse completely equably;
(4) dry: at 155-180 DEG C of roasting 3-4h under mixed gas protected containing hydrogen reduction, to obtain containing manganese porous sulphur carbon/manganese oxide nano composite material.
2. the preparation method of the negative material of a kind of good charge-discharge performance according to claim 1, is characterized in that, the manganese containing materials in described step (2) is the mixture that potassium permanganate and manganese carbonate form according to mol ratio 2:1.
3. the preparation method of the negative material of a kind of good charge-discharge performance according to claim 1, is characterized in that, the organic solvent in described step (3) to be volume ratio be 3: 1 chloroform and acetone mixture.
4. the preparation method of the negative material of a kind of good charge-discharge performance according to claim 1, is characterized in that, 4, in described step be the mist that hydrogen and argon gas form according to mol ratio 2:1 containing hydrogen reduction mist.
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| CN201310718574.8A CN104733186A (en) | 2013-12-24 | 2013-12-24 | Preparation method of negative electrode material with good charge and discharge performance |
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| CN201310718574.8A CN104733186A (en) | 2013-12-24 | 2013-12-24 | Preparation method of negative electrode material with good charge and discharge performance |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159234A (en) * | 2016-08-25 | 2016-11-23 | 广东工业大学 | Manganese dioxide carbon coated sulfur composite and preparation method thereof, lithium-sulfur cell |
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- 2013-12-24 CN CN201310718574.8A patent/CN104733186A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159234A (en) * | 2016-08-25 | 2016-11-23 | 广东工业大学 | Manganese dioxide carbon coated sulfur composite and preparation method thereof, lithium-sulfur cell |
| CN106159234B (en) * | 2016-08-25 | 2018-11-02 | 广东工业大学 | Manganese dioxide carbon coated sulphur composite material and preparation method, lithium-sulfur cell |
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Application publication date: 20150624 |