CN101038816A - Method for preparing porous carbon/nano metal oxide composite material - Google Patents
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- CN101038816A CN101038816A CNA2007100720731A CN200710072073A CN101038816A CN 101038816 A CN101038816 A CN 101038816A CN A2007100720731 A CNA2007100720731 A CN A2007100720731A CN 200710072073 A CN200710072073 A CN 200710072073A CN 101038816 A CN101038816 A CN 101038816A
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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
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- 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 relates to a method for preparing a lacunaris carbon/nanometer oxide composite material used in an ultra capacitor electrode. The prepared material is capable of evenly dispersing a nanometer oxide into a lacunaris carbon substrate. When the ultra capacitor electrode is prepared by the material, with a combination of a double-electric-layer capacitor and a metal oxide pseudocapacitance, the electrode can has a higher unit capacitor and a carbon framework can provide a favorable conductive passage for nanometer metal oxide particles dipersed in the carbon framework to reduce an equivalent internal resistance of the capacitor, thereby the capacitor has a high power and power density.
Description
(1) technical field
The present invention relates to the chemical material preparation field, be specifically related to a kind of preparation method of porous carbon/nano metal oxide composite material.
(2) background technology
Ultracapacitor is a kind of novel energy-storing element, because the advantage that has quick storage, releases energy, therefore can be as the stand-by power supply of electronic systems such as computer, flash of light in the industrial equipment and igniter also have wide practical use at the aspects such as AC-battery power source of High-Power Microwave and laser weapon and electric automobile.The structural property of electrode material plays a decisive role to the performance of ultracapacitor.At present, the research of electrode material for super capacitor mainly concentrates on aspects such as activated carbon, carbon nano-tube, transition metal oxide and organic conductive polymer.Carbon electrode material is cheap, and preparation technology is simple, but specific capacitance is lower by (50～100F/g), and metal oxide electrode material is representative (RuO with the ruthenium oxide hydration
2.xH
2O), the redox reversible that takes place by the surface reacts the storage that realizes energy, its specific capacitance (720F/g) is much larger than the ratio electric capacity of carbon electrode, but the expensive price of noble metal has limited its application prospect, the conductive polymer electrodes material also reacts by surface oxidation reduction realizes store energy, also have higher specific capacitance (＞200F/g) and characteristics that can fast charging and discharging, but conducting polymer is unstable properties in long-term charge and discharge process, the phenomenon of volumetric expansion or contraction can take place in charge and discharge process, and its research at present still is in the exploration stage.
Combination electrode material can be realized the reasonable balance of material property and cost as a kind of novel electrode material for super capacitor, and has the not available premium properties of unitary electrode material, and application prospect is very wide.Thereby be subjected to paying close attention to widely.Now have: C/RuO at the composite electrode material for super capacitor that grinds
2,, C/lrO
2, C/V
2O
5Deng.The preparation of present nanocarbon/metal oxide electrode mainly is to adopt the sol impregnation method, promptly prepare metal oxide sol earlier, add fine grain carbon then, fully stirring makes colloidal sol evenly distribute at carbon surface, again colloidal sol is heat-treated [Li Jing etc., the progress of composite electrode material for super capacitor, material Leader after the filtration, 2005,19 (8): 13].The dispersion in carbon base body of the metal oxide of preparation one side is inhomogeneous like this, is gathered into bulky grain at carbon surface easily on the other hand in heat treated process, thereby can reduces the specific capacity of material.Nano-metal-oxide is evenly dispersed in the carbon base body, is the main developing direction of preparation high power, high-energy-density nanocarbon/metal oxide super capacitor electrode material thereby utilize the characteristics of burning object height fake capacitance and active carbon high-specific surface area and good electrical conductivity fully.
(3) summary of the invention
The object of the invention provides a kind of gathering that can suppress nano-metal-oxide, it is evenly disperseed on the porous carbon surface, porous carbon can provide the favorable conductive passage for nano-metal-oxide simultaneously, thereby makes to have the preparation method of the porous carbon/nano oxide combination electrode material that is used for ultracapacitor of high energy density and power density with the ultracapacitor of this material preparation.
Consisting of of porous carbon/nano oxide composite of the present invention: porous carbon: 5%～95%, be preferably 30%～50%, nano-oxide: 5%～95% is preferably 50%～70%, wherein nano-oxide is: transition metal Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pa or Ru, oxide in a kind of or at least two kinds.
The preparation method of porous carbon/nano metal oxide of the present invention comprises the steps:
(1) stable dispersions of preparation inorganic nano-particle
Hydroxide, carbonate or other oxide precursor nano particles of above-mentioned transition metal are evenly spread in the aqueous solution by surfactant, the stable dispersions of preparation inorganic nano-particle, wherein the weight ratio of nano particle is 1%～70%, is preferably 20%～50%; Particle diameter is 5～1000nm, is preferably 5～100nm.Can buy by commercial means, perhaps according to disclosed bibliographical information preparation [Jongnam Park, et al ultra-large-scale synthesis of monodisperse nanocrystal, Nature Materials, 2004,3:891; Guo Liqin etc., the preparation of nano-nickel oxide and application thereof, Chemical Engineer, 2006,130 (7): 28]
(2) preparation carbon precursor solution
Described carbon precursor solution is the aqueous solution, the phenol/formaldehyde aqueous solution that contains the resorcin/formaldehyde mixing of proper catalyst, and perhaps phenolic resins, poly furfuryl alcohol, sucrose, pitch etc. are dissolved in the solution of making in the organic solvent.
Above-mentioned resorcin/formaldehyde or phenol/formaldehyde mixture content are 30%～70% (weight), and catalyst is common acid or alkali, comprises Na
2CO
3, NaOH, H
2SO
4, HNO
3Deng, phenol: the aldehyde mol ratio is 0.5～5: 1, is preferably 2～3: 1.The weight content of carbon matrix precursor is 10%～90% in other carbon precursor solution, is preferably 40～70%.
(3) the carbon precursor solution (B) that makes of the stable dispersions (A) of the inorganic nano-particle that step (1) is made and step (2) is by weight 1: 1～20, be preferably 1: 1～5 mixing, under ℃ condition of room temperature～200, be preferably 100～200 ℃, aging 1 hour～10 days, be preferably 1 hour～10 hours, mixture is fully solidified.
(4) mixture after the curing that step (3) is made is 600 ℃～900 ℃ carbonizations, be preferably 600～800 ℃, carburizing atmosphere is nitrogen or argon gas, carbonization time is 0.5～10 hour, be preferably 2～4 hours, metal carbonate, hydroxide or other oxide precursor nano particles decompose the generation metal oxide nanoparticles simultaneously in the process of carbonization, and are evenly dispersed in the duct of porous carbon, thus preparation porous carbon/nano oxide composite.
(5) the described porous carbon/nano metal oxide material of step (4) is evenly mixed with adhesive and conductive filler and be coated on the collector electrode preparation electrode of super capacitor wherein.The porous carbon/nano metal oxide material; 70wt%～85wt%; Adhesive 2%～5%; Conductive filler 15%～30%, adhesive are polytetrafluoroethylene or cellulose; Conductive filler is conductive carbon black, electrically conductive graphite or carbon nano-tube.
The present invention can be used for the preparation of the polarizing electrode of ultracapacitor, the porous carbon/nano metal oxide material is evenly mixed and is coated on the collector electrode making with adhesive and conductive filler.The polarizing electrode material rate is the porous carbon/nano metal oxide material; 70wt%～85wt%; Adhesive 2%～5%; Conductive filler 15%～30%.Adhesive can be selected polytetrafluoroethylene or cellulose for use; Conductive filler is conductive carbon black, electrically conductive graphite or carbon nano-tube.The inventive method is introduced the nano-metal-oxide presoma in the preparation process of porous carbon, can suppress the gathering of nano-metal-oxide on the one hand, it is evenly disperseed on the porous carbon surface, porous carbon can provide the favorable conductive passage for nano-metal-oxide on the other hand, and therefore the ultracapacitor with this material preparation has high energy density and power density.
The beneficial effect of patent of the present invention has:
Prior art mostly is active carbon or the activated carbon fiber that utilizes high-specific surface area, forms electric double layer with stored energy on its surface, or utilizes the pseudo capacitance principle of metal oxide to carry out energy storage.Therefore there are problems such as the low or electrode material conductance of specific capacity is low.The present invention proposes to introduce the nano-metal-oxide presoma in the preparation process of porous carbon, and it is dispersed in the carbon base body solution, prepare in the process of porous carbon in the heating carbonization, the nano-metal-oxide presoma decomposes generation gas on the one hand, in the porous carbon matrix, make gas passage, the nano-metal-oxide of generation is exposed in the unlimited duct, surrounded by carbon matrix precursor owing to the nano-metal-oxide presoma on the other hand, so the nano-metal-oxide that generates can not assembled, thereby improve the ratio electric capacity of material; Last carbon skeleton can also provide the favorable conductive passage for the nano-metal-oxide particle that is dispersed in wherein, reduces the equivalent resistance of capacitor.Therefore can significantly improve the energy density and the power density of ultracapacitor by the enforcement of this patent.This method technology is simple simultaneously, cost is low, be easy to commercialization.
(4) embodiment
The present invention is further illustrated below in conjunction with specific embodiment:
Embodiment 1:
(A) preparation of porous carbon/nano metal oxide
Mixture (30wt%) with resorcin/formaldehyde (mol ratio 1: 2), colloidal sol (average grain diameter 5nm with nano-sized nickel hydroxide, 1wt%) mixed by weight 1: 1, the aqueous solution by adding 1N NaOH and the aqueous solution of nitric acid of 1N are adjusted to 8 with the pH value of mixture.Mixed liquor in aged at room temperature 10 days, is formed resorcinol-formaldehyde-gel/nano-sized nickel hydroxide composite material.Under blanket of nitrogen, this composite material is heated to 850 ℃ and keep carrying out in 1 hour carbonization, make nano-sized nickel hydroxide resolve into nano-nickel oxide simultaneously, thereby preparation porous carbon/nano nickel oxide composite material, prepared material is listed in table 1 with the content that thermogravimetry records nano-nickel oxide.
(B) preparation of electrode and performance test
Be mixed into paste by following composition: porous carbon/nano nickel oxide composite material 80wt%, conductive carbon black 10wt%, polytetrafluoroethylene (PTFE) 5wt%, distilled water 5wt%.Porous carbon/nano nickel oxide and the conductive carbon black mode by mechanical oscillation is fully mixed, add distilled water and PTFE emulsion successively, make it even while adding by mechanical agitation, collector adopts foaming metal nickel, the electrode lug adopts metallic nickel platinum, and lug adopts the spot welding mode to be connected with collector; With above-mentioned mixed cream by hand or mechanical system be coated with prior sanction well and in the collector of soldering polar ear, to be coated with pole piece that cream finishes 110 ℃ of vacuumizes 10 hours, electrode (1cm is made in pole piece compacting after will drying on the hydraulic press behind the burr through paring off the edge then
2).Polypropylene diaphragm is inserted between two identical electrodes and with clip compresses.After 30%KOH electrolyte injecting electrode, use platinum comparative electrode and SCE reference electrode under the constant current conditions of 0.0～0.8V voltage range, 1mA, carry out cyclic voltammetry with the scanning digit rate of 1mV/s and measure.Can calculate specific capacitance with the electric current in the cyclic voltammetry divided by the quality that scans digit rate and electrode active material.After charging is finished, opened a way for 1 second, obtain interior resistance R by electric current and voltage drop Δ V before will opening a way according to Δ V=RI, gained the results are shown in table 1.
Embodiment 2:
With the mixture (50wt%) of resorcin/formaldehyde (mol ratio 2: 1) and with neopelex is colloidal sol (the average grain diameter 100nm of surfactant stabilized nano cobalt carbonate, 1wt%) mixed by weight 1: 10, the aqueous solution by adding 1N nitric acid is adjusted to 5 with the pH value of mixture.Concentrate mixed liquor and wore out 2 days formation resorcinol-formaldehyde-gel/nano-calcium carbonate cobalt composite material at 100 ℃.Under blanket of nitrogen, this composite material is heated to 800 ℃ and keep carrying out in 1 hour carbonization, make the nano-calcium carbonate cobalt resolve into nanometer cobalt oxide simultaneously, thereby preparation porous carbon/nano cobalt oxide composite material, prepared material is listed in table 1 with the content that thermogravimetry records nanometer cobalt oxide, the preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
Embodiment 3:
(average grain diameter 1000nm 1wt%) mixed by weight 1: 20, and the aqueous solution by adding 1N sodium carbonate is adjusted to 8 with the pH value of mixture with the mixture (30wt%) of phenol/formaldehyde (mol ratio 5: 1) and the colloidal sol of nanometer manganous hydroxide.Concentrate mixed liquor and wore out three days formation P-F-gel/nanometer manganous hydroxide composite material at 85 ℃.Under blanket of nitrogen, this composite material is heated to 900 ℃ and keep carrying out in 1 hour carbonization, make the nanometer manganous hydroxide resolve into nano manganese oxide simultaneously, thereby preparation porous carbon/nano manganese oxide composite material, prepared material records nano manganese oxide content with thermogravimetry and lists in table 1, the preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
Embodiment 4:
Phenolic resins is dissolved in solution (10wt%) that ethanol makes and is colloidal sol (the average grain diameter 50nm of the stable hydroxide the Liao Dynasty of surfactant with ten hexamethyl trimethylammonium bromides, 10wt%) mixed by weight 1: 1, concentrate mixed liquor and wore out 1 hour formation phenolic resins-aeroge/nanometer hydroxide ruthenium composite material at 200 ℃.Under blanket of nitrogen, this composite material is heated to 600 ℃ and keep carrying out in 4 hours carbonization, make nanometer hydroxide ruthenium resolve into nano oxidized ruthenium simultaneously, thereby preparation porous carbon/nano ruthenium-oxide composite material, prepared material is listed in table 1 with the content that thermogravimetry records nano oxidized ruthenium, the preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
Embodiment 5:
Pitch is dissolved in solution (90wt%) that oxolane makes and is colloidal sol (the average grain diameter 50nm of surfactant stabilized nano carbonic acid molybdenum with ten hexamethyl trimethylammonium bromides, 30wt%) mixed by weight 1: 1, mixed liquor was worn out 3 days at 85 ℃, form pitch/nano-calcium carbonate molybdenum composite material.Under blanket of nitrogen, this composite material is heated to 800 ℃ and keep carrying out in 4 hours carbonization, make the nano-calcium carbonate molybdenum resolve into nano oxidized molybdenum simultaneously, thereby preparation porous carbon/nano molybdenum oxide composite material, prepared material is listed in table 1 with the content that thermogravimetry records nano oxidized molybdenum, the preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
Embodiment 6:
Poly furfuryl alcohol is dissolved in solution (50wt%) that oxolane makes and is colloidal sol (the average grain diameter 50nm of the stable manganese carbonate of surfactant with polyethylene glycol, 10wt%) mixed by weight 1: 1, mixed liquor was worn out 3 days at 85 ℃, form poly furfuryl alcohol/nano-calcium carbonate manganese composite material.Under blanket of nitrogen, this composite material is heated to 800 ℃ and keep carrying out in 4 hours carbonization, make nano-calcium carbonate manganese resolve into nano manganese oxide simultaneously, thereby preparation porous carbon/nano manganese oxide composite material, prepared material is listed in table 1 with the content that thermogravimetry records nano manganese oxide, the preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
Embodiment 7:
Pitch is dissolved in solution (50wt%) that oxolane makes and is colloidal sol (the average grain diameter 50nm of the stable nickelous carbonate of surfactant with polyethylene glycol, 20wt%) mixed by weight 1: 10, mixed liquor was solidified 1 day at 200 ℃, form pitch/nano-calcium carbonate nickel composite material.Under blanket of nitrogen, this composite material is heated to 800 ℃ and keep carrying out in 4 hours carbonization, make nano-calcium carbonate nickel resolve into nano-nickel oxide simultaneously, thereby preparation porous carbon/nano nickel oxide composite material, prepared material is listed in table 1 with the content that thermogravimetry records nano-nickel oxide, the preparation of electrode and method of testing are with embodiment 1, and measured result is listed in table 1.
The content of table 1 nano-oxide and test result
| Embodiment | The content wt% of nano-oxide | Specific capacitance F/g | Interior resistance Ω |
| Embodiment 1 | 5.0 | 110 | 0.24 |
| Embodiment 2 | 22.5 | 135 | 0.38 |
| Embodiment 3 | 40.6 | 240 | 0.34 |
| Embodiment 4 | 39.2 | 620 | 0.25 |
| Embodiment 5 | 17.8 | 265 | 0.34 |
| Embodiment 6 | 8.9 | 257 | 0.21 |
| Embodiment 7 | 95 | 278 | 0.39 |
Claims (8)
1, a kind of preparation method of porous carbon/nano metal oxide composite material is characterized in that:
(A) preparation transition metal hydroxide, carbonate or the stable dispersion liquid of other oxide precursor nano particles;
(B) preparation carbon precursor solution;
(C) dispersion liquid that the nano particle of above-mentioned (A) step preparation is stable fully mixes with carbon precursor solution that (B) step prepares nano particle is dispersed in the carbon precursor solution fully;
(D) mixture solidified of step (C) gained is prepared the carbon precursor composites of hydroxide, carbonate or other oxide precursor nano particles of transition metal;
(E) the carbon precursor of the coated inorganic nano particle by carbonization (D) step preparation, and transition metal hydroxide, carbonate or other oxide precursor nano particles are decomposed, obtain product.
2, the preparation method of a kind of porous carbon/nano metal oxide composite material according to claim 1 is characterized in that described nano-oxide is: transition metal Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pa or Ru, oxide in a kind of or at least two kinds mixture.
3, the preparation method of a kind of porous carbon/nano metal oxide composite material according to claim 1, it is characterized in that: described preparation transition metal hydroxide, carbonate or the stable dispersion liquid of other oxide precursor nano particles are with transition metal Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, the hydroxide among Pa or the Ru, a kind of in carbonate or other oxide precursor nano particles or at least two kinds are distributed in the aqueous solution by surfactant equably, wherein the weight ratio of nano particle is 1%～70%, is preferably 20%～50%; Particle diameter is 5～1000nm, is preferably 5～100nm.
4, the preparation method of a kind of porous carbon/nano metal oxide composite material according to claim 1, it is characterized in that: described carbon precursor solution is that the aqueous solution, the phenol/formaldehyde aqueous solution, phenolic resins, poly furfuryl alcohol, sucrose or the pitch that contain the resorcin/formaldehyde mixing of catalyst are dissolved in the solution of making in the organic solvent, wherein benzenediol/formaldehyde or phenol/formaldehyde mixture content are 30%～70%, phenol: the aldehyde mol ratio is 0.5～5: 1, the weight content of carbon matrix precursor is 10%～90% in other carbon precursor solution, and described catalyst is Na
2CO
3, NaOH, H
2SO
4Or HNO
3
5, the preparation method of a kind of porous carbon/nano metal oxide composite material according to claim 1 is characterized in that: the stable dispersions of transition metal hydroxide, carbonate or other oxide precursor nano particles is than 1: 1～20 with carbon precursor solution weight.
6, the preparation method of a kind of porous carbon/nano metal oxide composite material according to claim 5 is characterized in that: the stable dispersions of transition metal hydroxide, carbonate nanoparticle or other oxide precursor nano particles and carbon precursor solution weight for than be preferably 1: 1～5.
7, the preparation method of a kind of porous carbon/nano metal oxide composite material according to claim 1, it is characterized in that: described curing temperature is room temperature～200 ℃, be preferably 100～200 ℃, the time is 1 hour～10 days, is preferably 1 hour～10 hours.
8, the preparation method of a kind of porous carbon/nano metal oxide composite material according to claim 4, it is characterized in that: described carbonization decomposition temperature is 600 ℃～900 ℃, be preferably 600～800 ℃, carburizing atmosphere is nitrogen or argon gas, carbonization time is 0.5～10 hour, is preferably 2～4 hours.
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