CN100382214C - A composite carbon-based electrode material for super capacitor and method for making same - Google Patents
A composite carbon-based electrode material for super capacitor and method for making same Download PDFInfo
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Abstract
The present invention discloses a composite carbon-based electrode material for a super capacitor and a preparation method thereof. The material is composed of nanometer metal, nanometer metal composite oxide, activated carbon and nanometer carbon fibers. The present invention effectively utilizes the activated carbon with high specific surface area and the nanometer carbon fibers to provide the super capacitor with a double electric layer capacitor. The present invention combines Faraday quasi-capacitance provided by the nanometer metal oxide and simultaneously utilizes the high conductivity of the nanometer carbon fibers and the nanometer metal and nanometer synergistic effect to improve the capacity density and the power density of the electrode material to obtain the super capacitor with high energy density and power density. The present invention has the advantage of low cost and can be applied to commerce easily.
Description
Technical field
The present invention relates to a kind of electrode of super capacitor active material and preparation method thereof that is used for, belong to material science, relate in particular to technical field of electrochemistry.
Technical background
In the world, the energy more and more is subjected to people's great attention as one of pillar industry of human modern civilization.Meanwhile, the various exhaust gas discharging that the energy produced, the environmental problem that the greenhouse effect that cause cause have become the focus that the whole world is paid close attention to the most, also are deep day by day socialization problems.Rugged environment pollutes, and has brought serious threat not only for the mankind and biological existence space, and can stay infinite hidden danger to the generation after generation of descendants.Global scientist and knowledgeable people call upon States one after another government and branch of industry are researching and developing new forms of energy energetically, when accelerating to solve energy crisis, and the environment of must preserving our planet, protection human existence space.At this urgent problem; beginning western developed country from the eighties, to take the lead in seeking with efficient, energy-conservation, low public hazards be final goal; research and development cleanings, novel power supply efficiently; wherein the ultracapacitor energy storage system unifies " green technology " with the energy mutually with environmental protection; the practicability of quickening the ultracapacitor energy storage system is positive feasible strategies to the environment of preserving our planet, air conservation and greenhouse effect, relates to the human society significant problem and has strategic importance for the solution energy, these two of environment.
Ultracapacitor (Super capacitor) is a kind of novel energy device that occurs in recent years, it is a kind of a kind of novel energy device between rechargeable battery and capacitor, have the dual-use function of electric capacity and battery concurrently, its power density is far above common batteries (10 times～100 times), energy density is far above conventional physical electric capacity (＞100 times), compare with battery with ordinary capacitor, it is little that ultracapacitor has a volume, capacity is big, charging rate is fast, have extended cycle life, the discharge power height, working temperature wide (25 ℃～85 ℃), good reliability and advantage such as with low cost, therefore probably develop into a kind of novel from now on, efficiently, practical energy accumulating device, thereby at the energy, communication, power electronics, all there is very wide application prospect in fields such as national defence, as: portable instrument equipment, the data accumulating storage system, electric car power supply, aspects such as emergent back-up source.
In recent years, ultracapacitor is as a kind of energy storage device of excellent performance, becomes the U.S., Japan, Russia and European developed country at one of focus of material, electric power, electronics, physics, chemical multidisciplinary crossing domain research.Main goal in research is the required low-cost electrode material of the fine and close energy of preparation high-energy-density and high power density, and the electrolyte body based material of operating voltage height, stable electrochemical property, conductivity height and long service life, and prepare the ultracapacitor that can be used for dynamical system (comprising back-up source and electric motor car etc.) renewable energy system of high power density, high capacity density and stable performance on this basis.
Electrode is the core part of capacitor, and its structure, character play decisive influence to the performance of double electric layer capacitor.Electrode material can be divided three classes: metal oxide, high molecular polymer and carbon-based electrode material.
Owing to adopt metal oxide and high molecular polymer electrochemical capacitor as electrode material, its electrode-electric separate pseudo capacitance that the matter interface produced will much larger than the electric double layer capacitance of material with carbon element (～900F/g), thereby extremely researcher's concern.But adopt metal oxide containing precious metals or conducting polymer as electrode material because of it, the production cost height, simultaneously itself in use chemical stability is poor than carbon-based material.Therefore, the research direction for electrochemical capacitor is mainly the chemical stability that reduces production costs and improve material.
Active carbon because have porous, big specific area, porosity height, chemical stability is good, with low cost and characteristics such as long service life, electrode material as double electric layer capacitor, can obtain high energy density and power density, therefore at present mostly with active carbon as polarizing electrode.But active carbon itself exists capacity density and the lower shortcoming of conductivity, has limited ultracapacitor in many application that require the high-energy-density field, and the capacity density that therefore improves electrode material becomes one of present urgency key issue to be solved.
In order further to improve the performance of carbon-based electrode material, by surface modification and various novel preparation process the carbon-based electrode material is carried out a large amount of research work, mainly comprised active carbon, activated carbon fiber, carbon gel, CNT (carbon nano-tube), vitreous carbon, carbon fiber, high-density graphite and the resulting foam of pyrolyzed-polymer matrix etc.
Present research for active carbon obtains the specific area maximum and can reach 3000m
2More than/the g, but its capacity density do not present simply with the increase of specific area and increases progressively, and this and its porosity and pore-size distribution are closely related, wherein in micropore (2nm～50nm) shared ratio is one of key factor of its amount of capacity of decision.But in fact micropore in the active carbon (＜2nm) proportion is bigger, because electrolyte can not soak into wherein, thereby this a part of micropore can not form electric double layer and storage power, so the existence of this a part of micropore is for not contribution of the capacity density that improves material.For example for present common specific area＞2000m
2The active carbon electrode material of/g, the utilance of its specific surface usually＜30%, its capacity density is general＜210F/g, is generally＜100F/g.Therefore increasing specific surface area and to control pore-size distribution be the important channel of improving the active carbon electrode material capacitance.
Be easy to get owing to carbon-based material is cheap simultaneously, the surface easily formations=C=O ,-OH and-COOH etc. has the functional group of activity, thereby generation pseudo capacitance, by capacitance that pseudo capacitance produced 10 times～100 times of electric double layer capacitance often, even it is higher, therefore improve the pseudo capacitance in the carbon-based material, can increase substantially super capacitor capacity density.
Though carbon-based electrode material category and preparation method thereof is a lot, in US6198623, utilize the self-supporting electrode material of the carbon fiber of high-specific surface area as Amatucci and Glenn G. as ultracapacitor, though having the micropore prosperity, this electrode material is easy to the advantage that electrolyte soaks into, but because the conductivity of carbon fiber itself is with respect to metallic nickel equal difference, simultaneously because therefore main electric double layer capacitance and a small amount of pseudo capacitance storage power of relying on exist the relatively poor and lower shortcoming of energy density of conductivity; The expensive grade of assistant rattan described a kind of electrode material that is used for battery or ultracapacitor in Japan Patent JP008890/2001 and Chinese patent application CN1379497A, carbonaceous materials such as employing acetylene black are conductive agent, utilize the particulate conductive powder to stick to the surface of carbonaceous material, form the active material powder mixture, in the mixture because of not introducing metal oxide, thereby this electrode material mainly comes storage power with electric double layer energy storage mechanism and a spot of pseudo capacitance, finally causes the energy density of electrode material to be limited in lower level; Tang Minhong etc. disclose a kind of processing method of activated carbon in Chinese patent application CN1404082A, mainly be that metal ion is carried out underpotential deposition with the form of solion at activated carbon surface, to provide pseudo capacitance to improve its energy density, and because ion concentration is lower, make metal ion lower at the deposition of activated carbon surface, finally cause by the pseudo capacitance that underpotential deposition produced of metal ion lowlyer, this method exists long processing period, the more high shortcoming of cost simultaneously; A kind of electrode material for super capacitor is disclosed among the Chinese patent application CN1357899A, this material is made up of carbon nano-tube and metal oxide, because high conductivity, high-specific surface area, the high microporosity of carbon nano-tube, with compound high energy density and the power density of obtaining of burning, but carbon nano-tube costs an arm and a leg, and has the too high problem of production cost.
From above analysis as can be known, carbon nano-tube, metal oxide containing precious metals and metal oxide containing precious metals composite carbon base electrode material though higher capacity density and power density are arranged, because its cost is higher, still do not possess commercial application value at present.Therefore the composite carbon base electrode material of developing low-cost high capacity density becomes the capacity density of present raising ultracapacitor, and the effective way that is implemented in the widespread commercial application of renewable energy resources field and dynamical system.
Summary of the invention
Technology of the present invention is dealt with problems and is: a kind of composite carbon base electrode material that is used for ultracapacitor and preparation method thereof is provided, and it has high energy density and power density, and the commerce that is easy to low cost is used.
Technical solution of the present invention is: a kind of composite carbon base electrode material that is used for ultracapacitor, its component and content are: nano metal 1%～30%, nano-metal-oxide 0.1%～95%, active carbon 0.1%～95%, 0.1%～95% carbon nano-fiber more than are mass percent.
Principle of the present invention is: nano metal and active carbon and carbon nano-fiber form combination electrode material, the introducing of nano metal has improved the electric conductivity of carbon-based electrode material on the one hand, the formation of the three-dimensional network skeleton of carbon nano-fiber has formed more middle micropore diameter and large aperture on the other hand, help the infiltration of electrolyte, improved the effective ratio area of active carbon and nano metal and carbon nano-fiber itself, form the little electric capacity of more electric double layer, improve the capacity density of combination electrode material; Itself has higher specific surface area active carbon, nano-metal-oxide is compound with it, on the basis of original electric double layer energy storage, by the nanometer cooperative effect, increased the specific area of basis material greatly, improved capacity density, the Faraday effect of while nano-metal-oxide surface and body phase thereof, the high conductivity of nano metal and carbon nano-fiber in addition, make metal oxide in charging and discharging process, can export and obtain electronics quickly, guaranteed the quick storage and the release of energy, make high rate during charging-discharging ground to significantly improving, improve the capacitance of combination electrode material significantly.
Above-mentioned nano metal mass fraction is preferably in 1%～20% scope, the mass fraction of nano-oxide preferably is controlled at 0.5%～55%, the control of activated carbon mass fraction is preferred 0.5%～95%, the control of carbon nano-fiber mass fraction preferred 0.5%～95%.
Nano metal in above-mentioned is one or more among Al or Li or Zn or Cu or Ni or Tl or Ti or Fe or the Pb; Nano-metal-oxide is Li
2O or Al
2O
3, or Fe
2O
3, or NiO or ZrO
2, or TiO
2, or MnO
2, or V
2O
5, or Co
3O
4, or WO
3, or Li
1-xNa
xMnO
2 -yl
y, or LiCoO
2In one or more, Co wherein can be by replacements such as Mn, Ni, Fe; The material of above-mentioned active carbon is the absorbent charcoal material of wooden nitre or shell or paper pulp or sugar or ring or stone tar or coal tar or pitch coke or its analog etc., also can partly or entirely wait with carbon aerogels and carbon nano-tube to replace; Carbon nano-fiber is the phenolic resins base nano carbon fibre.
The preparation method of above-mentioned active carbon material is: with wooden nitre; or shell; or paper pulp; or sugar; or ring; or stone tar; or coal tar; or in pitch coke or its analog one or more etc. be raw material; with carbon dioxide; or steam; or potassium hydroxide; or NaOH; or calcium chloride; or potassium sulfide; or phosphoric acid; or in sulfuric acid or the zinc dichloride one or more are activator; in 600 ℃～950 ℃ temperature ranges; preferred range is 600 ℃～850 ℃; under inert atmosphere protection; activation processing 0.5h～8h; the preferred activation processing time is 1h～5h, and washes; oven dry; pulverize; ball milling; the active carbon with high specific surface area that sieves etc. and to obtain after the processing.
Above-mentioned basic demand to carbon nano-fiber is specific area＞100m
2/ g, the specific area of micro content＜5%,
The basic demand of prepared active carbon is that specific area is 50m among the present invention
2/ g～4000m
2/ g, further preferred specific area is 100m
2/ g～2500m
2/ g, density is 0.7g/cm
3～1.2g/cm
3, middle micropore＞30%, granularity is controlled in 0.1 μ m～100 mu m ranges.
The ratio of the molal quantity of the active group on above-mentioned active carbon and carbon nano-fiber surface and its carbon molal quantity is 0.1～2.5%.
Above-mentioned nano metal can be particle or fiber, and particle size range is 1nm～10 μ m, and further preferred particle size range is 10nm～100nm, and the granularity of nano-metal-oxide is controlled in 0.1 μ m～100 mu m ranges.
The present invention is because it has bigger specific area, when according to the Faraday effect stored energy, can be because of cationic a large amount of consumption in the nano-metal-oxide, and form " passivating film " that is similar in the lithium ion battery at composite material surface, the retardance cation is moved into and is moved out, and causes the decline of energy storage density.Therefore need take adequate measures to reduce cationic consumption in the nano-metal-oxide, main surface of adopting organic substance to coat active carbon and carbon nano-fiber among the present invention, make it become ion conductor, the organic substance that coats can adopt polyacrylic acid, polyacrylate, polyethylene glycol etc., to reduce " passivating film " thickness in active carbon and the formation of carbon nano-fiber surface, thereby cationic consumption in the minimizing nano-metal-oxide, the energy storage density of raising combination electrode material.
Be used for the composite carbon base electrode preparation methods of ultracapacitor among the present invention, it is characterized in that: comprise following process steps:
(1) with nano metal oxide materials with immersions such as 1%～10% polyacrylic acid, polyacrylate, polyethylene glycol, drying, the back of sieving are stand-by;
(2) with the described active carbon of claim 6, Nano carbon fibers peacekeeping nano-metal-oxide, mass ratio is (0.1～95): (0.1～95): (0.1～95), place mixer, on planetary ball mill, mix, form uniform mixture, rotating speed 400rpm～800rpm, ball milling time 10min～30min repeats 2～4 times and promptly gets uniform carbon back mixture;
(3) with above-mentioned steps (2) gained mixture and nano metal powder, mass ratio is (80～99): (1～20), place mixer, on planetary ball mill, mix, form uniform mixture, rotating speed 400rpm～800rpm, ball milling time 10min～30min repeats 2～4 times and promptly gets uniform nano combined carbon back mixture; Mixing through planetary ball mill makes each component mix, and the less relatively nano-metal particle of particle diameter adheres to the bigger particle surface of carbon-based material, forms comparatively orderly mixed state, promptly obtains nano combined carbon-based electrode material.
The nano combined carbon-based electrode material of above-mentioned preparation, during the assembling ultracapacitor, electrolytical selecting for use also is an important factors.In order to obtain higher capacity density and power density, electrolyte selects for use the organic electrolyte that contains lithium salts to be advisable, as tetraethyl tetrafluoro boric acid amine-lithium perchlorate (lithium hexafluoro phosphate, LiBF4)-propene carbonate (ethylene carbonate-carbonic acid diethyl ester) etc., electrolyte concentration is controlled at 0.5mol/L～5mol/L, and preferable range is 1mol/L～2.5mol/L.
The advantage that the present invention compared with prior art has is: prior art mostly is active carbon or the carbon fiber that utilizes high-specific surface area, form electric double layer with storage power on its surface, or utilize the pseudo capacitance principle of the compound active carbon electrode material of metal oxide containing precious metals such as metal oxide ruthenium-oxide to carry out energy storage, obtain high capacity density and high power density, but exist the electrode material conductivity low and the specific area utilance is low and shortcoming such as cost height, finally cause the energy density of ultracapacitor and power density to be limited in a very limited level; The present invention utilizes preparation active carbon with high specific surface area such as low-cost raw material petroleum coke again, its high-specific surface area and the low-cost advantage that is easy to get have been kept, introduce the electric conductivity that cheap nano metal improves carbon-based material, reduce the internal resistance of electrode material, introduce the low-cost nano-oxide and the carbon nano-fiber of wide material sources simultaneously, on the basis of the effective ratio area that improves the carbon-based electrode material, utilize the nanometer cooperative effect on nano carbon-base material surface and nano-metal-oxide surface, form nano combined carbon-based electrode material, when keeping the electric double layer capacitance that high-specific surface area produced, by the nano-metal-oxide surface pseudo capacitance mutually huge with body, increase substantially the capacity density and the power density of ultracapacitor, and gained composite carbon base electrode lower cost for material, be easy to obtain, be beneficial to commercial applications.
Embodiment
Embodiment 1
At first being raw material with the petroleum coke, is activator with potassium hydroxide, NaOH, with raw material and activator mix; in 800 ℃ of temperature ranges, in the atmosphere protection high temperature stove, under inert atmosphere protection; activation processing 3h through washing, oven dry and pulverizing, obtains active carbon again.The nano NiO powder is soaked with 1% polyacrylic acid, drying, sieve after, promptly get the nano-powder that surperficial quilt coats.Be that (granule size is that 1nm～100nm), mass fraction are that 20% NiO powder (granule size is 10nm～1 μ m), mass fraction are that (granularity is 0.1 μ m～100 μ m, and specific area is 1500m for 45% active carbon for 5% Al powder by mass fraction then
2About/g, density is 0.7g/cm
3About, middle micropore＞30%), mass fraction is carbon nano-fiber (specific area＞100m of 30%
2/ g, the specific area of micro content＜5%) weighing respectively, wherein the ratio of the molal quantity of the active group on active carbon and carbon nano-fiber surface and its carbon molal quantity is 0.1%～2.5%.At first nano-metal-oxide, active carbon and carbon nano-fiber are placed in the mixer, on planetary ball mill (XQM-4L, Nanjing Kexi Inst. of Experiment Instrument), by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, obtain mixture of powders, then nano metal powder and this mixture of powders are placed mixer, by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, thus obtain the nano combined carbon-based electrode material of target.
Embodiment 2
At first being raw material with the petroleum coke, is activator with potassium hydroxide, NaOH, with raw material and activator mix; in 600 ℃ of temperature ranges, in the atmosphere protection high temperature stove, under inert atmosphere protection; activation processing 3h through washing, oven dry and pulverizing, obtains active carbon again.With nanometer MnO
2Powder soaks with 5% polypropylene ammonium, drying, sieve after, promptly get the nano-powder that surperficial quilt coats.Be that (granule size is that 1nm～100nm), mass fraction are 55% MnO for 5% Ni powder by mass fraction then
2Powder (granule size is 10nm～1 μ m), mass fraction are that (granularity is 0.1 μ m～100 μ m, and specific area is 1000m for 20% active carbon
2About/g, density is 0.76g/cm
3About, middle micropore＞30%), mass fraction is carbon nano-fiber (specific area＞100m of 20%
2/ g, the specific area of micro content＜5%) weighing respectively, wherein the ratio of the molal quantity of the active group on active carbon and carbon nano-fiber surface and its carbon molal quantity is 0.1%～2.5%.At first nano-metal-oxide, active carbon and carbon nano-fiber are placed in the mixer, on planetary ball mill (XQM-4L, Nanjing Kexi Inst. of Experiment Instrument), by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, obtain mixture of powders, then nano metal powder and this mixture of powders are placed mixer, by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, thus obtain the nano combined carbon-based electrode material of target.
Embodiment 3
At first being raw material with natural gum, is activator with potassium hydroxide, NaOH, with raw material and activator mix; in 900 ℃ of temperature ranges, in the atmosphere protection high temperature stove, under inert atmosphere protection; activation processing 3h through washing, oven dry and pulverizing, obtains active carbon again.With nanometer LiCoO
2Powder soaks with 10% polyacrylic acid, drying, sieve after, promptly get the nano-powder that surperficial quilt coats.Be that (granule size is that 1nm～100nm), mass fraction are 5% LiCoO for 20% Cu powder by mass fraction then
2Powder (granule size is 10nm～1 μ m), mass fraction are that (granularity is 0.1 μ m～100 μ m, and specific area is 500m for 5% active carbon
2About/g, density is 1.1g/cm
3About, middle micropore＞30%), mass fraction is carbon nano-fiber (specific area＞100m of 70%
2/ g, the specific area of micro content＜5%)) weighing respectively, wherein the ratio of the molal quantity of the active group on active carbon and carbon nano-fiber surface and its carbon molal quantity is 0.1%～2.5%.At first nano-metal-oxide, active carbon and carbon nano-fiber are placed in the mixer, on planetary ball mill (XQM-4L, Nanjing Kexi Inst. of Experiment Instrument), by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, obtain mixture of powders, then nano metal powder and this mixture of powders are placed mixer, by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, thus obtain the nano combined carbon-based electrode material of target.
Embodiment 4
Being raw material with the shell at first, is activator with the potassium sulfide, and with raw material and activator mix, in 600 ℃ of temperature ranges, in the atmosphere protection high temperature stove, under inert atmosphere protection, activation processing 3h through washing, oven dry and pulverizing, obtains active carbon again.With nanometer Al
2O
3Powder soaks with 5% polyacrylic acid, drying, sieve after, promptly get the nano-powder that surperficial quilt coats.Be that (granule size is that 1nm～100nm), mass fraction are 25% Al for 10% Zn powder by mass fraction then
2O
3Powder (granule size is 10nm～1 μ m), mass fraction are that (granularity is 0.1 μ m～100 μ m, and specific area is 300m for 60% active carbon
2About/g, density is 1.2g/cm
3About, middle micropore＞30%)), mass fraction is carbon nano-fiber (specific area＞100m of 5%
2/ g, the specific area of micro content＜5%) weighing respectively, wherein the ratio of the molal quantity of the active group on active carbon and carbon nano-fiber surface and its carbon molal quantity is 0.1%～2.5%.At first nano-metal-oxide, active carbon and carbon nano-fiber are placed in the mixer, on planetary ball mill (XQM-4L, Nanjing Kexi Inst. of Experiment Instrument), by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, obtain mixture of powders, then nano metal powder and this mixture of powders are placed mixer, by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, thus obtain the nano combined carbon-based electrode material of target.
Embodiment 5
At first being raw material with phenolic resins, is activator with potassium hydroxide, NaOH, with raw material and activator mix; in 900 ℃ of temperature ranges, in the atmosphere protection high temperature stove, under inert atmosphere protection; activation processing 3h through washing, oven dry and pulverizing, obtains active carbon again.With nanometer LiCoO
2Powder soaks with 10% polyacrylic acid, drying, sieve after, promptly get the nano-powder that surperficial quilt coats.Be that (granule size is that 1nm～100nm), mass fraction are 1% LiCoO for 1% Fe powder by mass fraction then
2Powder (granule size is 10nm～1 μ mm), mass fraction are that (granularity is 0.1 μ m～100 μ m, and specific area is 2000m for 3% active carbon
2About/g, density is 0.9g/cm
3About, middle micropore＞30%)), mass fraction is carbon nano-fiber (specific area＞100m of 95%
2/ g, the specific area of micro content＜5%) weighing respectively, wherein the ratio of the molal quantity of the active group on active carbon and carbon nano-fiber surface and its carbon molal quantity is 0.1%～2.5%.At first nano-metal-oxide, active carbon and carbon nano-fiber are placed in the mixer, on planetary ball mill (XQM-4L, Nanjing Kexi Inst. of Experiment Instrument), by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, obtain mixture of powders, then nano metal powder and this mixture of powders are placed mixer, by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, thus obtain the nano combined carbon-based electrode material of target.
Embodiment 6
Obtain active carbon by embodiment 5.With nanometer Li
2The O powder soaks with 5% polyacrylic acid, drying, sieve after, promptly get the nano-powder that surperficial quilt coats.Be that (granule size is that 1nm～100nm), mass fraction are 1% Li for 1% Ni powder by mass fraction then
2O powder (granule size is 10nm～1 μ m), mass fraction are that (granularity is 0.1 μ m～100 μ m, and specific area is 2000m for 95% active carbon
2About/g, density is 0.9g/cm
3About, middle micropore＞30%)), mass fraction is carbon nano-fiber (specific area＞100m of 3%
2/ g, the specific area of micro content＜5%) weighing respectively, wherein the ratio of the molal quantity of the active group on active carbon and carbon nano-fiber surface and its carbon molal quantity is 0.1%～2.5%.At first nano-metal-oxide, active carbon and carbon nano-fiber are placed in the mixer, on planetary ball mill (XQM-4L, Nanjing Kexi Inst. of Experiment Instrument), by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, obtain mixture of powders, then nano metal powder and this mixture of powders are placed mixer, by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, thus obtain the nano combined carbon-based electrode material of target.
Embodiment 7
Obtain active carbon by embodiment 1.The nano NiO powder is soaked with 5% polyethylene glycol, drying, sieve after, promptly get the nano-powder that surperficial quilt coats.The weighing mass fraction is that (granule size is that 1nm～100nm), mass fraction are that 3% NiO powder (granule size is 10nm～1 μ m), mass fraction are 7% TiO for 10% Ni powder then
2Powder (granule size is 10nm～1 μ m), mass fraction are that (granularity is 0.1 μ m～100 μ m, and specific area is 2000m for 0.5% active carbon
2About/g, density is 0.9g/cm
3About, middle micropore＞30%)), mass fraction is carbon nano-fiber (specific area＞100m of 79.5%
2/ g, the specific area of micro content＜5%), wherein the ratio of the molal quantity of the active group on active carbon and carbon nano-fiber surface and its carbon molal quantity is 0.1%～2.5%.At first nano-metal-oxide, active carbon and carbon nano-fiber are placed in the mixer, on planetary ball mill (XQM-4L, Nanjing Kexi Inst. of Experiment Instrument), by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, obtain mixture of powders, then nano metal powder and this mixture of powders are placed mixer, by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, thus obtain the nano combined carbon-based electrode material of target.
Embodiment 8
Obtain active carbon by embodiment 3.The nano NiO powder is soaked with 5% ammonium polyacrylate, drying, sieve after, promptly get the nano-powder that surperficial quilt coats.Be that (granule size is that 1nm～100nm), mass fraction are that 1.9% NiO powder (granule size is 10nm～1 μ m), mass fraction are 1% LiCoO for 0.1% Al powder by mass fraction then
2Powder (granule size is 10nm～1 μ m), mass fraction are 2% MnO
2Powder (granule size is 10nm～1 μ m), mass fraction are that (granularity is 0.1 μ m～100 μ m, and specific area is 1500m for 94.5% activated carbon
2About/g, density is 0.7g/cm
3About, middle micropore＞30%), mass fraction is carbon nano-fiber (specific area＞100m of 0.5%
2/ g, the specific area of micro content＜5%) weighing respectively, wherein the ratio of the molal quantity of the active group on active carbon and carbon nano-fiber surface and its carbon molal quantity is 0.1%～2.5%.At first nano-metal-oxide, active carbon and carbon nano-fiber are placed in the mixer, on planetary ball mill (XQM-4L, Nanjing Kexi Inst. of Experiment Instrument), by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, obtain mixture of powders, then nano metal powder and this mixture of powders are placed mixer, by revolution and rotation, speed is 600rpm, ball milling three times, each 20 minutes, thus obtain the nano combined carbon-based electrode material of target.
Embodiment 9
Obtain active carbon by embodiment 4.With nanometer MnO
2Powder soaks with 5% ammonium polyacrylate, drying, sieve after, promptly get the nano-powder that surperficial quilt coats.Be that (granule size is that 1nm～100nm), mass fraction are that (granule size is that 1nm～100nm), mass fraction are that (granule size is that 1nm～100nm), mass fraction are 10% MnO for 5% Cu powder for 3% Zn powder for 2% Fe powder by mass fraction then
2Powder (granule size is 10nm～1 μ m), mass fraction are that (granularity is 0.1 μ m～100 μ m, and specific area is 300m for 79.5% activated carbon
2About/g, density is 1.2g/cm
3About, middle micropore＞30%)), mass fraction is carbon nano-fiber (specific area＞100m of 0.5%
2/ g, the specific area of micro content＜5%) weighing respectively of ratio, wherein the ratio of the molal quantity of the active group on active carbon and carbon nano-fiber surface and its carbon molal quantity is 0.1%～2.5%.At first nano-metal-oxide, active carbon and carbon nano-fiber are placed in the mixer, on planetary ball mill (XQM-4L, Nanjing Kexi Inst. of Experiment Instrument), by revolution and rotation, speed is 800rpm, twice of ball milling, each 20 minutes, obtain mixture of powders, then nano metal powder and this mixture of powders are placed mixer, by revolution and rotation, speed is 800rpm, ball milling 2 times, each 20 minutes, thus obtain the nano combined carbon-based electrode material of target.
Embodiment 10
Obtain active carbon by embodiment 5.The nano NiO powder is soaked with 5% ammonium polyacrylate, drying, sieve after, promptly get the nano-powder that surperficial quilt coats.Be that (granule size is that 1nm～100nm), mass fraction are that (granule size is that 1nm～100nm), mass fraction are that 10% NiO powder (granule size is 10nm～1 μ m), mass fraction are that (granularity is 0.1 μ m～100 μ m, and specific area is 2000m for 0.1% activated carbon for 4% Ni powder for 1% Al powder by mass fraction then
2About/g, density is 0.9g/cm
3About, middle micropore＞30%)), mass fraction is carbon nano-fiber (specific area＞100m of 84.9%
2/ g, the specific area of micro content＜5%) weighing respectively, wherein the ratio of the molal quantity of the active group on active carbon and carbon nano-fiber surface and its carbon molal quantity is 0.1%～2.5%.At first nano-metal-oxide, active carbon and carbon nano-fiber are placed in the mixer, on planetary ball mill (XQM-4L, Nanjing Kexi Inst. of Experiment Instrument), by revolution and rotation, speed is 400rpm, ball milling four times, each 10 minutes, obtain mixture of powders, then nano metal powder and this mixture of powders are placed mixer, by revolution and rotation, speed is 400rpm, ball milling 4 times, each 10 minutes, thus obtain the nano combined carbon-based electrode material of target.
Claims (20)
1. composite carbon base electrode material that is used for ultracapacitor, it is characterized in that: its component and content are: nano metal 1%～30%, nano-metal-oxide 0.1%～95%, active carbon 0.1%～95%, 0.1%～95% carbon nano-fiber more than are mass percent.
2. the composite carbon base electrode material that is used for ultracapacitor according to claim 1, it is characterized in that: wherein: nano metal 1%～20%, nano-metal-oxide 0.5%～55%, active carbon 0.5%～95%, 0.5%～95% carbon nano-fiber more than are mass percent.
3. the composite carbon base electrode material that is used for ultracapacitor according to claim 1 and 2 is characterized in that: described nano metal is one or more among Al or Li or Zn or Cu or Ni or Tl or Ti or Fe or the Pb.
4. the composite carbon base electrode material that is used for ultracapacitor according to claim 1 and 2, it is characterized in that: described nano-metal-oxide is Li
2O or Al
2O
3, or Fe
2O
3, or NiO or ZrO
2, or TiO
2, or MnO
2, or V
2O
5, or Co
3O
4, or WO
3, or Li
1-xNa
xMnO
2-yI
y, LiCoO
2In one or more, Co wherein can be replaced by Mn, Ni, Fe.
5. the composite carbon base electrode material that is used for ultracapacitor according to claim 1 and 2, it is characterized in that: described carbon nano-fiber is the phenolic resins base nano carbon fibre.
6. the composite carbon base electrode material that is used for ultracapacitor according to claim 1 and 2; it is characterized in that: described absorbent charcoal material is with wooden nitre; or shell; or paper pulp; or sugar; or ring; or stone tar; or coal tar; or in the pitch coke one or more are raw material; with carbon dioxide; or steam; or potassium hydroxide; or NaOH; or calcium chloride; or potassium sulfide; or phosphoric acid; or in sulfuric acid or the zinc dichloride one or more are activator; in 600 ℃～950 ℃ temperature ranges; under inert atmosphere protection; activation processing 0.5h～8h, and wash; oven dry; pulverize; ball milling; the active carbon with high specific surface area that sieves and obtain after handling.
7. the composite carbon base electrode material that is used for ultracapacitor according to claim 6 is characterized in that: wherein the activating treatment temperature scope is 600 ℃～850 ℃, and the activation processing time is 1h～5h.
8. the composite carbon base electrode material that is used for ultracapacitor according to claim 1 and 2, it is characterized in that: the specific area of described active carbon is 50m
2/ g～4000m
2/ g, density is 0.7g/cm
3～1.2g/cm
3
9. the composite carbon base electrode material that is used for ultracapacitor according to claim 6, it is characterized in that: the specific area of wherein said active carbon is 50m
2/ g～4000m
2/ g, density is 0.7g/cm
3～1.2g/cm
3
10. the composite carbon base electrode material that is used for ultracapacitor according to claim 8, it is characterized in that: the wherein density of wherein said active carbon is 0.7g/cm
3～1.2g/cm
3, middle micropore＞30%.
11. the composite carbon base electrode material that is used for ultracapacitor according to claim 9, it is characterized in that: the wherein density of wherein said active carbon is 0.7g/cm
3～1.2g/cm
3, middle micropore＞30%.
12. the composite carbon base electrode material that is used for ultracapacitor according to claim 1 and 2 is characterized in that: the specific area＞100m of described carbon nano-fiber
2/ g, the specific area of micro content＜5%.
13. the composite carbon base electrode material that is used for ultracapacitor according to claim 1 and 2, it is characterized in that: the ratio of carbon molal quantity is 0.1～2.5% in the molal quantity of the active group on described active carbon and carbon nano-fiber surface and active carbon and the carbon nano-fiber.
14. the composite carbon base electrode material that is used for ultracapacitor according to claim 1 and 2 is characterized in that: the particle size range of described nano metal is 1nm～10 μ m.
15. the composite carbon base electrode material that is used for ultracapacitor according to claim 14, it is characterized in that: wherein the particle size range of nano metal is 10nm～100nm.
16. the composite carbon base electrode material that is used for ultracapacitor according to claim 1 and 2 is characterized in that: the particle size range of nano-metal-oxide is 1nm～5 μ m.
17. the composite carbon base electrode material that is used for ultracapacitor according to claim 16 is characterized in that: wherein the particle size range of nano-metal-oxide is 10nm～1 μ m.
18. the composite carbon base electrode material that is used for ultracapacitor according to claim 1 and 2, it is characterized in that: granularity of activated carbon is in 0.1 μ m～100 mu m ranges.
19. the composite carbon base electrode material that is used for ultracapacitor according to claim 1 and 2 is characterized in that: adopt organic substance that the nano-metal-oxide surface is coated before forming combination electrode material.
20. preparation claim 1 or the 2 described methods that are used for the composite carbon base electrode material of ultracapacitor is characterized in that: comprise following process steps:
(1) with nano metal oxide materials with 1%～10% polyacrylic acid, or polyacrylate, or immersion such as polyethylene glycol, drying, the back of sieving are stand-by;
(2) with the described active carbon of claim 6, Nano carbon fibers peacekeeping nano-metal-oxide, mass ratio is (0.1～95): (0.1～95): (0.1～95), place mixer, on planetary ball mill, mix, form uniform mixture, rotating speed 400min～800rpm, ball milling time 10min～30min repeats 2～4 times and promptly gets uniform carbon back mixture;
(3) with above-mentioned steps (2) gained mixture and nano metal powder, mass ratio is (80～99): (1～20), place mixer, on planetary ball mill, mix, form uniform mixture, rotating speed 400rpm～800rpm, ball milling time 10min～30min repeats 2～4 times and promptly gets uniform nano combined carbon back mixture; Mixing through planetary ball mill makes each component mix, and the less relatively nano-metal particle of particle diameter adheres to the bigger particle surface of carbon-based material, forms comparatively orderly mixed state, promptly obtains nano combined carbon-based electrode material.
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