CN106531455A - Composite electrode material with adding of polypyrrole compound rare earth modified barium nitrate - Google Patents

Composite electrode material with adding of polypyrrole compound rare earth modified barium nitrate Download PDF

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Publication number
CN106531455A
CN106531455A CN201610929780.7A CN201610929780A CN106531455A CN 106531455 A CN106531455 A CN 106531455A CN 201610929780 A CN201610929780 A CN 201610929780A CN 106531455 A CN106531455 A CN 106531455A
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parts
electrode material
barium nitrate
minutes
polypyrrole
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CN201610929780.7A
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鲍启兵
刘芳
俞泽涛
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Anhui Jiangwei Precision Manufacturing Co Ltd
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Anhui Jiangwei Precision Manufacturing Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/48Conductive polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses a composite electrode material with the adding of polypyrrole compound rare earth modified barium nitrate. The composite electrode material is formed by the following materials of, by weight, 10 to 12 parts of multi-wall carbon nanotubes, 1.5-1.6 parts of sodium dodecyl sulfate, an appropriate amount of deionized water, an appropriate amount of absolute ethanol, 10 to 12 parts of polyaniline, an appropriate amount of chloroform, 14 to 15 parts of polyethylene oxide, 12 to 13 parts of DL-camphor sulfonic acid, 1.2-1.4 parts of polyethylene glycol-6000, 3-4 parts of polypyrrole, 3-4 parts of barium nitrate, 2-3 parts of lanthanum nitrate, and 9-10 parts of citric acid. The electrode material prepared by the invention has the advantages of excellent electrochemical performance, fast charging and discharging, and no pollution and safety, the process is convenient for industrial control, and an assembled super capacitor has the advantages of good stability and a long service life.

Description

A kind of addition polypyrrole compounds the combination electrode material of rare earth modified barium nitrate
Technical field
The present invention relates to capacitor technology field, more particularly to a kind of addition polypyrrole compounds answering for rare earth modified barium nitrate Composite electrode material.
Background technology
Ultracapacitor also known as electrochemical capacitor, with power density it is big, have extended cycle life, easy maintenance and cost The features such as relative moderate.Ultracapacitor is with the energy density bigger than traditional dielectric capacitor and the power higher than battery Density, has broad application prospects in fields such as emergency power supply, hybrid power, digital product, telecommunications.CNT since Since 1991 are found, due to excellent mechanical property, thermal property, electric conductivity, and scientist's research is become Focus.CNT is preferable composite addition phase, with up to more than 1000 draw ratio, simultaneously because sp2 Orbital hybridization forms a large amount of delocalization p electronics, and electric conductivity is excellent.Electricity of the polyaniline as ultracapacitor electric conductive polymer The advantages of pole material, environmental stability, high conductivity due to being readily synthesized, good, application it has been widely studied.However, poly- The shortcomings of aniline is because of change in volume big and poor cycle charging/discharge capability, limits which in electrode of super capacitor material Application in terms of material.These problems can be solved by polyaniline is merged with c-based nanomaterial, so as to realize electrification Learn the synergism of double layer capacitor and fake capacitance capacitor.Therefore, the nano-carbon material of bigger serface and satisfactory electrical conductivity It is used as support material to obtain the combination electrode of high-performance and long circulation life.
《Carbon nano-tube/poly aniline/Graphene composite nanometer carbon paper and its electrochemical capacitor performance》Pass through vacuum in one text The method of sucking filtration prepares carbon nanotube paper, and a volt-ampere electrochemicial oxidation is circulated to which, with the electrochemicial oxidation Carbon nanotube paper based on, using electrochemical polymer deposition polyaniline, subsequently adsorb Graphene, prepare with sandwich Carbon nano-tube/poly aniline/Graphene the composite nanometer carbon paper of sandwich structure, the compound carbon paper have good capacitance characteristic, big Current charge-discharge electrical characteristics and good stable circulation performance.But operating procedure is complicated, it is difficult to control the structure of extrusion coating paper, with As for being difficult to improve its specific surface area, the raising of specific capacitance is limited;And as the carbon produced in actual production process is received Mitron can all remain the catalyst impurities of a part, and some amorphous carbon, and the presence of these impurity limits carbon nanometer The use of pipe, using sour purifying carbon nano-tube in article, eliminates most of amorphous carbon and gold while nitration mixture process Metal particles, but processing procedure is loaded down with trivial details, it is seriously polluted, while some functional groups are have also been introduced, the presence pair of these functional groups The structure of CNT causes certain destruction, so as to produce certain impact to performance, limits its performance;To sum up institute State, need certain improvement to be carried out to process meanses such that it is able to which prepared operation is controllable, and electric conductivity is strong, specific surface area is big, ratio is electric Hold big electrode material for super capacitor, meet the demand of development in science and technology.
The content of the invention
The object of the invention is exactly for the defect for making up prior art, there is provided a kind of addition polypyrrole compounds rare earth modified nitre The combination electrode material of sour barium.
The present invention is achieved by the following technical solutions:
A kind of addition polypyrrole compounds the combination electrode material of rare earth modified barium nitrate, is prepared by the raw materials in:It is many Wall carbon nano tube 10-12, sodium lauryl sulphate 1.5-1.6, appropriate deionized water, appropriate dehydrated alcohol, polyaniline 10-12, Appropriate chloroform, polyethylene glycol oxide 14-15, DL camphorsulfonic acid 12-13, PEG-4000 1.2-1.4, polypyrrole 3-4, nitre Sour barium 3-4, Lanthanum (III) nitrate 2-3, citric acid 9-10.
A kind of addition polypyrrole compounds the combination electrode material of rare earth modified barium nitrate, is prepared by following concrete grammar Form:
(1)Multi-walled carbon nano-tubes is placed on into graphite crucible stove, is placed in graphitizing furnace, evacuation is carried out to which, with 10-15 DEG C/ Min is warming up to 2800 DEG C, is incubated 20-20 hours, and natural cooling obtains graphitized carbon nano pipe;By above-mentioned graphitized carbon nano Pipe is dissolved in the 25-30 times of deionized water measured with the speed ball milling 90-120 minutes of 200-300 turn/part, addition in being put into ball mill Sodium lauryl sulphate, after ultrasonic 20-30 minutes be spray-dried, obtain modified carbon nano-tube;
(2)Barium nitrate, Lanthanum (III) nitrate are dissolved in the 2-3 times of deionized water measured, citric acid are added, after dispersed with stirring, is added poly- second two Alcohol -6000, stir 30-40 minutes, heat 3-4 hours, filter after the completion of reaction in 80 DEG C of water-baths, drying, by the powder for obtaining Body calcines 60-90 minutes at 800-850 DEG C, obtains modified RE doping barium nitrate, then mixes with polypyrrole, add total amount 2- The dehydrated alcohol of 3 times of amounts, ultrasonic disperse 30-40 minutes, is vacuum dried 10-12 hours at 50-70 DEG C, obtains modified filler;
(3)Polyaniline is dissolved in the chloroform of 100 times of amounts, DL camphorsulfonic acid is added, with 300-400 rev/min under room temperature Speed stirs 12-14 hours, is subsequently adding step(1)Step(2)The product for obtaining, ultrasonic disperse add which after 20-30 minutes Remaining residual componentss, continue the speed stirring 10-12 hours with 300-400 rev/min, obtain spinning liquid;
(4)Spinning liquid is drawn in syringe and spinning liquid is collected on collector metallic nickel using electrostatic spinning technique, control Spinning solution flow processed is 0.2-0.3ml/h, and voltage is 15-20kV, and spinning distance is 8-14cm, and spinning process 5-6 hour is formed Composite fibre electrode material with certain thickness network structure.
It is an advantage of the invention that:The present invention carries out the method for high temperature graphitization process to reach purification first to CNT Effect, there is evaporation in metallic catalyst, CNT will not be destroyed simultaneously graphited, while degree of crystallinity and leading Electrically improve;Then the CNT after graphitization, polyaniline, polyethylene glycol oxide etc. net has been made into using electrostatic spinning technique The composite cellulosic membrane of network structure, causes the fiber of preparation thinner by controlling spinning distance, spinning flow etc., enhances which and compare table Area, so that electrolyte ion diffusional resistance diminishes, charge transferring channel is more unobstructed, thus shows more preferable capacitive character Can, specific capacitance is improve, and good cyclical stability is shown using ultracapacitor made by this electrode material, while Process is simple, is easy to Industry Control.
The present invention obtains lanthanum modified barium nitrate by a series of PROCESS FOR TREATMENT, then compounds with polypyrrole, and formation has The modified filler of good dielectric properties, is added in the preparation of the membranaceous electrode material of fiber, and rare earth ion is in polypyrrole and polyphenyl Function served as bridge is played between amine, electric charge transfer is smoothly transmitted therebetween, be conducive to materials conductive network Formed, improve its electrical conductivity;Electrode material excellent electrochemical performance made by the present invention, discharge and recharge are rapid, safety non-pollution, and Technique is easy to Industry Control, the ultracapacitor good cycling stability being assembled into which, long service life.
Specific embodiment
A kind of addition polypyrrole compounds the combination electrode material of rare earth modified barium nitrate, by following weight portion(Kilogram)Original Material is made:Multi-walled carbon nano-tubes 10, sodium lauryl sulphate 1.5, appropriate deionized water, appropriate dehydrated alcohol, polyaniline 10, chlorine Imitative appropriate, polyethylene glycol oxide 14, DL camphorsulfonic acid 12, PEG-4000 1.2, polypyrrole 3, barium nitrate 3, Lanthanum (III) nitrate 2, Citric acid 9.
According to claims 1, a kind of addition polypyrrole compounds the combination electrode material of rare earth modified barium nitrate, by Following concrete grammar is prepared from:
(1)Multi-walled carbon nano-tubes is placed on into graphite crucible stove, is placed in graphitizing furnace, evacuation is carried out to which, with 10 DEG C/min 2800 DEG C are warming up to, 20 hours are incubated, natural cooling obtains graphitized carbon nano pipe;Above-mentioned graphitized carbon nano pipe is put into With the speed ball milling 90 minutes of 200 turns/part in ball mill, addition is dissolved in the sodium lauryl sulphate of the deionized waters of 25 times of amounts, Ultrasound was spray-dried after 20 minutes, obtained modified carbon nano-tube;
(2)Barium nitrate, Lanthanum (III) nitrate are dissolved in the deionized water of 2 times of amounts, citric acid are added, after dispersed with stirring, is added poly- second two Alcohol -6000, stir 30 minutes, heat 3 hours in 80 DEG C of water-baths, filter after the completion of reaction, and the powder body for obtaining is existed by drying 800 DEG C are calcined 60 minutes, are obtained modified RE doping barium nitrate, are then mixed with polypyrrole, add the anhydrous second of 2 times of amounts of total amount Alcohol, ultrasonic disperse 30 minutes are vacuum dried 10 hours at 50 DEG C, obtain modified filler;
(3)Polyaniline is dissolved in the chloroform of 100 times of amounts, DL camphorsulfonic acid is added, with 300 revs/min of speed under room temperature Stirring 12 hours, is subsequently adding step(1)Step(2)The product for obtaining, ultrasonic disperse add remaining residual components after 20 minutes, Continue to stir 10 hours with 300 revs/min of speed, obtain spinning liquid;
(4)Spinning liquid is drawn in syringe and spinning liquid is collected on collector metallic nickel using electrostatic spinning technique, control Spinning solution flow processed is 0.2ml/h, and voltage is 15kV, and spinning distance is 8cm, and spinning process 5 hours, formation have certain thickness Network structure composite fibre electrode material.
Teflon septum is immersed in polyvinyl alcohol-sulfogel electrolyte, keep 20 minutes, after taking-up Under room temperature natural evaporation be dried, then using made by the embodiment collect composite cellulosic membrane metallic nickel as electrode material with Polyvinyl alcohol-sulphuric acid barrier film is stacked together by sandwich structure, and which is packaged with mylar, obtains super capacitor Device.Cyclic voltamogram curve when scanning speed is 5 mV s 1, potential region 0.8-0.2 V obtains super capacitor The specific capacitance of device is 96F/g, and after 1 000 cycle charge discharge electrical testings, specific capacitance remains to be remained above 90%.

Claims (2)

1. a kind of addition polypyrrole compounds the combination electrode material of rare earth modified barium nitrate, it is characterised in that by following weight portion Raw material make:Multi-walled carbon nano-tubes 10-12, sodium lauryl sulphate 1.5-1.6, appropriate deionized water, appropriate dehydrated alcohol, Polyaniline 10-12, appropriate chloroform, polyethylene glycol oxide 14-15, DL camphorsulfonic acid 12-13, PEG-4000 1.2-1.4, Polypyrrole 3-4, barium nitrate 3-4, Lanthanum (III) nitrate 2-3, citric acid 9-10.
2. according to claims 1, a kind of addition polypyrrole compounds the combination electrode material of rare earth modified barium nitrate, and which is special Levy and be, be prepared from by following concrete grammar:
(1)Multi-walled carbon nano-tubes is placed on into graphite crucible stove, is placed in graphitizing furnace, evacuation is carried out to which, with 10-15 DEG C/ Min is warming up to 2800 DEG C, is incubated 20-20 hours, and natural cooling obtains graphitized carbon nano pipe;By above-mentioned graphitized carbon nano Pipe is dissolved in the 25-30 times of deionized water measured with the speed ball milling 90-120 minutes of 200-300 turn/part, addition in being put into ball mill Sodium lauryl sulphate, after ultrasonic 20-30 minutes be spray-dried, obtain modified carbon nano-tube;
(2)Barium nitrate, Lanthanum (III) nitrate are dissolved in the 2-3 times of deionized water measured, citric acid are added, after dispersed with stirring, is added poly- second two Alcohol -6000, stir 30-40 minutes, heat 3-4 hours, filter after the completion of reaction in 80 DEG C of water-baths, drying, by the powder for obtaining Body calcines 60-90 minutes at 800-850 DEG C, obtains modified RE doping barium nitrate, then mixes with polypyrrole, add total amount 2- The dehydrated alcohol of 3 times of amounts, ultrasonic disperse 30-40 minutes, is vacuum dried 10-12 hours at 50-70 DEG C, obtains modified filler;
(3)Polyaniline is dissolved in the chloroform of 100 times of amounts, DL camphorsulfonic acid is added, with 300-400 rev/min under room temperature Speed stirs 12-14 hours, is subsequently adding step(1)Step(2)The product for obtaining, ultrasonic disperse add which after 20-30 minutes Remaining residual componentss, continue the speed stirring 10-12 hours with 300-400 rev/min, obtain spinning liquid;
(4)Spinning liquid is drawn in syringe and spinning liquid is collected on collector metallic nickel using electrostatic spinning technique, control Spinning solution flow processed is 0.2-0.3ml/h, and voltage is 15-20kV, and spinning distance is 8-14cm, and spinning process 5-6 hour is formed Composite fibre electrode material with certain thickness network structure.
CN201610929780.7A 2016-10-31 2016-10-31 Composite electrode material with adding of polypyrrole compound rare earth modified barium nitrate Pending CN106531455A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107365496A (en) * 2017-04-03 2017-11-21 新沂市中诺新材料科技有限公司 A kind of Performances of Novel Nano-Porous meter level La SnO2/ PANI composite conducting material synthetic methods

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101130431A (en) * 2006-08-23 2008-02-27 中国科学院金属研究所 Method for purifying nano carbon fiber of multi-wall carbon nano-tube
CN102634016A (en) * 2012-04-05 2012-08-15 南昌航空大学 Preparation method of neodymium-lanthanum-doped barium ferrite-polyrrole composite microwave absorbent
CN105977043A (en) * 2016-04-07 2016-09-28 铜陵泰力电子有限公司 Supercapacitor electrode material added with modified lignite and preparation method thereof
CN105977020A (en) * 2016-06-21 2016-09-28 闽江学院 Fiber capacitor and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101130431A (en) * 2006-08-23 2008-02-27 中国科学院金属研究所 Method for purifying nano carbon fiber of multi-wall carbon nano-tube
CN102634016A (en) * 2012-04-05 2012-08-15 南昌航空大学 Preparation method of neodymium-lanthanum-doped barium ferrite-polyrrole composite microwave absorbent
CN105977043A (en) * 2016-04-07 2016-09-28 铜陵泰力电子有限公司 Supercapacitor electrode material added with modified lignite and preparation method thereof
CN105977020A (en) * 2016-06-21 2016-09-28 闽江学院 Fiber capacitor and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107365496A (en) * 2017-04-03 2017-11-21 新沂市中诺新材料科技有限公司 A kind of Performances of Novel Nano-Porous meter level La SnO2/ PANI composite conducting material synthetic methods

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