CN101840792B - Hybrid super capacitor and manufacture method thereof - Google Patents

Hybrid super capacitor and manufacture method thereof Download PDF

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CN101840792B
CN101840792B CN2009100796693A CN200910079669A CN101840792B CN 101840792 B CN101840792 B CN 101840792B CN 2009100796693 A CN2009100796693 A CN 2009100796693A CN 200910079669 A CN200910079669 A CN 200910079669A CN 101840792 B CN101840792 B CN 101840792B
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tio
super capacitor
binding agent
nano
hybrid super
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CN2009100796693A
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CN101840792A (en
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李景虹
王强
吕小军
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清华大学
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    • 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

Abstract

The invention discloses a hybrid super capacitor and a manufacture method thereof, belonging to novel energy storage elements and the technical field of manufacture thereof. A negative active material of the hybrid super capacitor is one or more of polymorphs TiO2-B of nano TiO2 or TiO2, and a positive active material thereof is one or more of carbon nano tube, carbon nano fiber, graphite, conductive carbon black, nickel hydroxide, manganese hydrate or molybdenum hydroxide. The hybrid super capacitor manufactures electrodes by adopting positive and negative active materials, a binder and a conductive agent as raw materials, and assemblies the electrodes into a simulative battery in a glove box so as to manufacture the hybrid super capacitor. The manufacture method provided by the invention has adjustability, simple manufacture process and easy operation, and the assembled hybrid super capacitor has the characteristics of high capacitance, low potential, stable performance, charge and discharge with large current, long cycle life, low cost, easy implementation for mechanized and large-scale production and the like.

Description

A kind of hybrid super capacitor and preparation method thereof
Technical field
The present invention relates to belong to novel energy storage unit and preparing technical field thereof, particularly a kind of hybrid super capacitor and preparation method thereof.
Background technology
Hybrid super capacitor is a kind of novel energy storage unit between ultracapacitor and battery.Compare with traditional ultracapacitor, it has higher energy density: compare with battery, have higher power density.Hybrid super capacitor has following characteristics: the power density that (1) is higher, and the high energy pulse environment particularly in big electric current application scenario can satisfy power requirement better; (2) the charge and discharge cycles time very short, much smaller than charging and discharging required time of circulation of battery; (3) can use for a long time, need not safeguard; (4) wideer operating temperature range, can be in-45~85 ℃ scope operate as normal.In sum, this novel energy storage device has very excellent charging and discharging cycle performance, has used the mixed type technology, has overcome the defective of conventional batteries and ultracapacitor.Hybrid super capacitor is backward relatively in China's research level, mainly concentrate on the Primary Study of water system electrode material, cell voltage is low, the cycle performance instability, the organic electrolyte system hybrid super capacitor can make these performances increase substantially, the therefore necessary research work of actively developing in this respect.
Seek suitable negative material and be the key of exploitation organic system hybrid super capacitor, but from abundant lithium ion battery negative material, select to have the specific capacity height, current potential is low, stable performance high current charge-discharge, the TiO that has extended cycle life 2Monodimension nanometer material meets the optimal selection of all conditions just.Although had much about TiO 2The report of monodimension nanometer material preparation, but these methods substantially only are applicable to preparation single shape TiO 2, how to realize TiO and seldom relate to 2The regulation and control of pattern and dimension.And with TiO 2Nano thread structure is as the negative material of hybrid super capacitor, and is rare especially.
Summary of the invention
The purpose of this invention is to provide a kind of hybrid super capacitor and preparation method thereof.
A kind of hybrid super capacitor comprises positive pole and negative pole, it is characterized in that, described negative active core-shell material is a nano-TiO 2Or TiO 2Polymorph TiO 2Among-the B one or more, described positive electrode active materials are one or more in carbon nano-tube, carbon nano-fiber, graphite, conductive black, nickel hydroxide, manganous hydroxide or the molybdenum hydroxide.
A kind of preparation method of hybrid super capacitor is characterized in that, this method step is as follows,
(1) Zheng Ji preparation: with positive electrode active materials, binding agent and conductive agent are raw material, wherein, positive electrode active materials is a carbon nano-tube, carbon nano-fiber, graphite, conductive black, nickel hydroxide, in manganous hydroxide or the molybdenum hydroxide one or more, binding agent is the Kynoar emulsion, conductive agent is graphite or acetylene black, each raw material by the quality percentage composition is, positive electrode active materials: 50%~85%, binding agent: 5%~15%, conductive agent 5%~40%, with positive electrode active materials and conductive agent, fully ground and mixed becomes uniform powder in mortar, drip binding agent Kynoar emulsion, after thing to be mixed becomes glue, it evenly is coated on the aluminium foil collector electrode dry 4h~12h under 80 ℃~120 ℃ with scraper, depress to electrode, make positive pole at 12MPa~18MPa pressure then;
(2) preparation of negative pole: with negative active core-shell material, binding agent and conductive agent is raw material, and wherein, negative active core-shell material is a nano-TiO 2Or TiO 2Polymorph TiO 2Among-the B one or more, binding agent is the Kynoar emulsion, conductive agent is graphite or acetylene black, each raw material by the quality percentage composition is, negative active core-shell material: 50%~85%, binding agent: 5%~15%, conductive agent 5%~40%, with negative active core-shell material and conductive agent, fully ground and mixed becomes uniform powder in mortar, drip binding agent Kynoar emulsion, after thing to be mixed becomes glue, it evenly is coated on the aluminium foil collector electrode dry 4h~12h under 80 ℃~120 ℃ with scraper, depress to electrode, make negative pole at 12MPa~18MPa pressure then;
(3) assembling of ultracapacitor: positive pole, negative pole, barrier film and electrolyte are assembled into simulated battery in being full of the glove box of argon gas, with positive plate, barrier film and negative plate are packed in the lithium-battery mold successively, splash into 8~10 electrolyte, at last with die sealing, wherein, barrier film is a capillary polypropylene, and electrolyte is the LiPF of 1mol/L 6At ethylene carbonate, the mixed solution in diethyl carbonate and the dimethyl carbonate, wherein, and ethylene carbonate, the volume ratio of diethyl carbonate and dimethyl carbonate is 1: 1: 1.
Described negative active core-shell material nano-TiO 2The preparation method be, according to TiO 2Nano powder: the ratio of the NaOH aqueous solution=1g: 30mL, with TiO 2Nano powder is scattered in the NaOH aqueous solution that concentration is 10mol/L, fully fully stir behind the cosolvent of stirring or adding and NaOH aqueous solution equal volume, cosolvent is an absolute ethyl alcohol, a kind of in anhydrous glycerol or the ethylenediamine, the gained suspension-turbid liquid is transferred in the water heating kettle of polytetrafluoroethylliner liner, seal tight kettle cover, in 160 ℃~200 ℃ baking oven, reacted 12~36 hours, take out reactor natural cooling in air, by hydrochloric acid solution and the deionized water cyclic washing precipitation of suction filtration with 0.05~0.2mol/L, pH value to eluate is 7, at last product being contained in porcelain increases in the pot, 300 ℃~450 ℃ were heated 2~6 hours in Muffle furnace, naturally cool to normal temperature, obtain TiO 2Nano wire, TiO 2Nanotube, TiO 2Nanometer sheet, TiO 2Nanocrystalline or TiO 2Nano particle.
Beneficial effect of the present invention is: manufacture method provided by the invention has adjustable, preparation flow is simple, processing ease, but the hybrid super capacitor model of assembling has that specific capacity height, current potential are low, the stable performance high current charge-discharge, have extended cycle life, with low cost, mechanization large-scale production characteristics such as realization easily.
Description of drawings
Fig. 1 is the 10C stable state charging and discharging curve of hybrid super capacitor, carbon back ultracapacitor;
Fig. 2 is the 10C cyclic curve of hybrid super capacitor, carbon back ultracapacitor.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing:
Embodiment 1
A kind of hybrid super capacitor comprises positive pole and negative pole, and described negative active core-shell material is TiO 2Nano wire, described positive electrode active materials are carbon nano-tube.
A kind of preparation method of hybrid super capacitor, this method step is as follows,
(1) preparation of positive electrode active materials carbon nano-tube, method are to adopt iron-containing catalyst (Fe/Al 2O 3), with ethene is carbon source, in the poly-group of nanometer bed reaction device, prepare carbon nano-tube, experimental technique [Y.Wang, F.Wei, G.H.Luo, H.Yu, G.S.Gu, Chem.Phys.Lett.2002,364,568.]: in the reactor 10g iron-containing catalyst under 82 3K temperature in hydrogen atmosphere reductase 12 h, feed nitrogen and ethene mist then, wherein, nitrogen is 2: 3 with the volume of ethylene ratio, begin reaction, continue logical nitrogen cool to room temperature under the 823K temperature behind the reaction 5h, collect product and carry out the purifying of carbon nano-tube, purification step is, at first carbon nano-tube is soaked in HNO 3And H 2SO 4In the solution, wherein, HNO 3With H 2SO 4Volume ratio be 1: 3, soak to filter behind the 48h and clean, fully be filtered to the pH value of pH value and deionized water when identical with deionized water then, in 100 ℃ of air, dry, obtain carbon nano-tube;
(2) Zheng Ji preparation: with positive electrode active materials, binding agent and conductive agent are raw material, wherein, positive electrode active materials is the carbon nano-tube of step (1) preparation, binding agent is the Kynoar emulsion, conductive agent is an acetylene black, each raw material by the quality percentage composition is, positive electrode active materials: 80%, binding agent: 10%, conductive agent 10%, will be as the carbon nano-tube of positive electrode active materials with as the acetylene black of conductive agent, fully ground and mixed becomes uniform powder in mortar, drip binding agent Kynoar emulsion, after thing to be mixed becomes glue, it evenly is coated on the aluminium foil collector electrode dry 8h under 100 ℃ with scraper, depress to electrode at 15MPa pressure then, make positive pole;
(3) negative active core-shell material TiO 2The preparation method of nano wire is, according to TiO 2Nano powder: the ratio of the NaOH aqueous solution=1g: 30mL, with the TiO of 2g 2Nano powder is scattered in the NaOH aqueous solution that 30mL concentration is 10mol/L, adding 30mL fully stirs after as the absolute ethyl alcohol of cosolvent, the gained suspension-turbid liquid is transferred in the water heating kettle of polytetrafluoroethylliner liner, seal tight kettle cover, reaction is 18 hours in 180 ℃ baking oven, take out reactor natural cooling in air, by hydrochloric acid solution and the deionized water cyclic washing precipitation of suction filtration with 0.1mol/L, pH value to eluate is 7, at last product being contained in porcelain increases in the pot, 350 ℃ were heated 4 hours in Muffle furnace, and natural cooling obtains TiO 2Nano wire;
Add different cosolvent, can obtain different TiO 2Nanostructure, when adopting pure aquatic system (promptly not having cosolvent), nanometer sheet structure for random distribution of sizes, when adopting ethylenediamine as cosolvent, for a large amount of overlong nanowires constitutes, its length reaches several microns, and diameter is about 20~50nm, if when the cosolvent absolute ethyl alcohol was changed to anhydrous glycerol, that obtain no longer was TiO 2Nano wire, but TiO 2Nanotube;
(4) preparation of negative pole: with negative active core-shell material, binding agent and conductive agent is raw material, and wherein, negative active core-shell material is the TiO of step (3) preparation 2Nano wire, binding agent are the Kynoar emulsion, and conductive agent is an acetylene black, and each raw material by the quality percentage composition is negative active core-shell material: binding agent 80%: conductive agent 10%: 10%, and will be as the TiO of negative active core-shell material 2Nano wire and as the acetylene black of conductive agent, fully ground and mixed becomes uniform powder in mortar, drip binding agent Kynoar emulsion, after thing to be mixed becomes glue, with scraper it evenly is coated on the aluminium foil collector electrode, dry 8h under 100 ℃ depresses to electrode at 15MPa pressure then, makes negative pole;
(5) assembling of ultracapacitor: positive pole, negative pole, barrier film and electrolyte are assembled into simulated battery in being full of the glove box of argon gas, with positive plate, barrier film and negative plate are packed in the lithium-battery mold successively, splash into 8~10 electrolyte, at last with die sealing, wherein, barrier film is a capillary polypropylene, and electrolyte is the LiPF of 1mol/L 6At ethylene carbonate, the mixed solution in diethyl carbonate and the dimethyl carbonate, wherein, and ethylene carbonate, the volume ratio of diethyl carbonate and dimethyl carbonate is 1: 1: 1.
The TiO that present embodiment is synthetic 2The product size of nano wire and carbon nano-tube and the sign of pattern are at Hitachi H-800 transmission electron microscope (TEM), carry out on high transmission resolution Electronic Speculum (HRTEM) of JEOL-2010F and the JSM-7401E field emission scanning electron microscope (FESEM).Electronic Speculum result shows: the structure of the nano wire that is synthesized is a homogeneous.Through calculating, obtaining corresponding interplanar distance is 0.65nm, this and TiO 2The interplanar distance of (001) crystal face of-B is on all four, illustrates that nanometer rods is along (001) direction different growth.
The electrochemical properties of battery carries out the cyclic voltammetric test on the CHI-802B electrochemical workstation, voltage scan range is 2.8-0.0V, sweep speed is from 20mV/s to 120mV/s, the result shows: very unconspicuous redox peak appears in hybrid super capacitor, from the redox electric current, hybrid super capacitor has still provided comparatively desirable capacitance.
Adopt the Roofer battery test system at room temperature to charge and discharge with the multiplying power of 10C, in the 2.8-0.0V scope to the charge/discharge capacity of sample, cycle life and capability retention are tested, test result is seen Fig. 1 and Fig. 2, Fig. 1 is a hybrid super capacitor, (a is the 10C stable state charging and discharging curve of hybrid super capacitor to the 10C stable state charging and discharging curve of carbon back ultracapacitor, b is the 10C stable state charging and discharging curve of carbon back ultracapacitor), Fig. 2 is a hybrid super capacitor, the 10C cyclic curve of carbon back ultracapacitor (a is the 10C cyclic curve of hybrid super capacitor, and b is the 10C cyclic curve of carbon back ultracapacitor).
The result shows that this is anodal with the carbon nano-tube, TiO 2Nano wire is a negative pole, the novel hybrid super capacitor that adopts lithium-ion battery electrolytes to assemble out, by utilizing carbon nanotube electrode conductivity and suitable pore-size distribution preferably, in electrode/electrolyte Electrostatic Absorption taking place at the interface stores a large amount of electric charges, impel TiO 2Nano line electrode can carry out corresponding faraday's reaction unobstructedly in comparatively wide potential window, keep its excellent capacitive property.Based on the total weight of active material, under the multiplying power condition of 10C, the specific energy of hybrid super capacitor is 12.5Wh/kg, doubles the specific energy of carbon back ultracapacitor, has also kept good cyclical stability simultaneously.Along with the raising of potential window, improved the power density and the energy density of hybrid super capacitor to a certain extent, especially under bigger current density, more have superiority.
Embodiment 2
A kind of hybrid super capacitor comprises positive pole and negative pole, and described negative active core-shell material is TiO 2Nanotube, described positive electrode active materials are conductive black.
A kind of preparation method of hybrid super capacitor, this method step is as follows,
(1) Zheng Ji preparation: with positive electrode active materials, binding agent and conductive agent are raw material, wherein, positive electrode active materials is a conductive black, binding agent is the Kynoar emulsion, conductive agent is a graphite, each raw material by the quality percentage composition is, positive electrode active materials: 70%, binding agent: 15%, conductive agent: 15%, will be as the conductive black of positive electrode active materials with as the graphite of conductive agent, fully ground and mixed becomes uniform powder in mortar, drip binding agent Kynoar emulsion, after thing to be mixed becomes glue, it evenly is coated on the aluminium foil collector electrode dry 10h under 80 ℃ with scraper, depress to electrode at 18MPa pressure then, make positive pole;
(2) negative active core-shell material TiO 2The preparation method of nanotube is, according to TiO 2Nano powder: the ratio of the NaOH aqueous solution=1g: 30mL, with the TiO of 2g 2Nano powder is scattered in the NaOH aqueous solution that 30mL concentration is 10mol/L, adding 30mL fully stirs after as the anhydrous glycerol of cosolvent, the gained suspension-turbid liquid is transferred in the water heating kettle of polytetrafluoroethylliner liner, seal tight kettle cover, reaction is 16 hours in 200 ℃ baking oven, take out reactor natural cooling in air, by hydrochloric acid solution and the deionized water cyclic washing precipitation of suction filtration with 0.1mol/L, pH value to eluate is 7, at last product being contained in porcelain increases in the pot, 400 ℃ were heated 3.5 hours in Muffle furnace, and natural cooling obtains TiO 2Nanotube;
(3) preparation of negative pole: with negative active core-shell material, binding agent and conductive agent is raw material, and wherein, negative active core-shell material is the TiO of step (2) preparation 2Nanotube, binding agent are the Kynoar emulsion, and conductive agent is a graphite, and each raw material by the quality percentage composition is negative active core-shell material: binding agent 70%: conductive agent 15%: 15%, and will be as the TiO of negative active core-shell material 2Nanotube and as the graphite of conductive agent, fully ground and mixed becomes uniform powder in mortar, drip binding agent Kynoar emulsion, after thing to be mixed becomes glue, with scraper it evenly is coated on the aluminium foil collector electrode, dry 10h under 80 ℃ depresses to electrode at 18MPa pressure then, makes negative pole;
(5) assembling of ultracapacitor: positive pole, negative pole, barrier film and electrolyte are assembled into simulated battery in being full of the glove box of argon gas, with positive plate, barrier film and negative plate are packed in the lithium-battery mold successively, splash into 8~10 electrolyte, at last with die sealing, wherein, barrier film is a capillary polypropylene, and electrolyte is the LiPF of 1mol/L 6At ethylene carbonate, the mixed solution in diethyl carbonate and the dimethyl carbonate, wherein, and ethylene carbonate, the volume ratio of diethyl carbonate and dimethyl carbonate is 1: 1: 1.
Ultracapacitor electrochemical properties on the CHI-802B electrochemical workstation, carry out cyclic voltammetric test, voltage scan range is 2.8-0.0V, sweep speed is from 20mV/s to 120mV/s, the result shows: very unconspicuous redox peak appears in hybrid super capacitor, from the redox electric current, hybrid super capacitor has still provided comparatively desirable capacitance.Adopt the Roofer battery test system at room temperature to charge and discharge with the multiplying power of 10C, to the charge/discharge capacity of sample, cycle life and capability retention are tested in the 2.8-0.0V scope, and the result shows: this is anodal with the conductive black, TiO 2Nanotube is a negative pole, and the novel hybrid super capacitor that adopts lithium-ion battery electrolytes to assemble out than the specific energy height of carbon back ultracapacitor, has also been kept good cyclical stability simultaneously.Along with the raising of potential window, improved the power density and the energy density of hybrid super capacitor to a certain extent, especially under bigger current density, more have superiority.

Claims (2)

1. the preparation method of a hybrid super capacitor is characterized in that, this method step is as follows,
(1) Zheng Ji preparation: with positive electrode active materials, binding agent and conductive agent are raw material, wherein, positive electrode active materials is a carbon nano-tube, carbon nano-fiber, graphite, conductive black, nickel hydroxide, in manganous hydroxide or the molybdenum hydroxide one or more, binding agent is the Kynoar emulsion, conductive agent is graphite or acetylene black, each raw material by the quality percentage composition is, positive electrode active materials: 50%~85%, binding agent: 5%~15%, conductive agent 5%~40%, with positive electrode active materials and conductive agent, fully ground and mixed becomes uniform powder in mortar, drip binding agent Kynoar emulsion, after thing to be mixed becomes glue, it evenly is coated on the aluminium foil collector electrode dry 4h~12h under 80 ℃~120 ℃ with scraper, depress to electrode, make positive pole at 12MPa~18MPa pressure then;
(2) preparation of negative pole: with negative active core-shell material, binding agent and conductive agent is raw material, and wherein, negative active core-shell material is a nano-TiO 2Or TiO 2Polymorph TiO 2Among-the B one or more, binding agent is the Kynoar emulsion, conductive agent is graphite or acetylene black, each raw material by the quality percentage composition is, negative active core-shell material: 50%~85%, binding agent: 5%~15%, conductive agent 5%~40%, with negative active core-shell material and conductive agent, fully ground and mixed becomes uniform powder in mortar, drip binding agent Kynoar emulsion, after thing to be mixed becomes glue, it evenly is coated on the aluminium foil collector electrode dry 4h~12h under 80 ℃~120 ℃ with scraper, depress to electrode, make negative pole at 12MPa~18MPa pressure then;
(3) assembling of ultracapacitor: positive pole, negative pole, barrier film and electrolyte are assembled into simulated battery in being full of the glove box of argon gas, with positive plate, barrier film and negative plate are packed in the lithium-battery mold successively, splash into 8~10 electrolyte, at last with die sealing, wherein, barrier film is a capillary polypropylene, and electrolyte is the LiPF of 1mol/L 6At ethylene carbonate, the mixed solution in diethyl carbonate and the dimethyl carbonate, wherein, and ethylene carbonate, the volume ratio of diethyl carbonate and dimethyl carbonate is 1: 1: 1.
2. the preparation method of a kind of hybrid super capacitor according to claim 1 is characterized in that, described negative active core-shell material nano-TiO 2The preparation method be, according to TiO 2Nano powder: the ratio of the NaOH aqueous solution=1g: 30mL, with TiO 2Nano powder is scattered in the NaOH aqueous solution that concentration is 10mol/L, fully fully stir behind the cosolvent of stirring or adding and NaOH aqueous solution equal volume, cosolvent is an absolute ethyl alcohol, a kind of in anhydrous glycerol or the ethylenediamine, the gained suspension-turbid liquid is transferred in the water heating kettle of polytetrafluoroethylliner liner, seal tight kettle cover, in 160 ℃~200 ℃ baking oven, reacted 12~36 hours, take out reactor natural cooling in air, by hydrochloric acid solution and the deionized water cyclic washing precipitation of suction filtration with 0.05~0.2mol/L, pH value to eluate is 7, at last product being contained in porcelain increases in the pot, 300 ℃~450 ℃ were heated 2~6 hours in Muffle furnace, naturally cool to normal temperature, obtain TiO 2Nano wire, TiO 2Nanotube, TiO 2Nanometer sheet, TiO 2Nanocrystalline or TiO 2Nano particle.
CN2009100796693A 2009-03-16 2009-03-16 Hybrid super capacitor and manufacture method thereof CN101840792B (en)

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