CN103746118A - Preparation method of nano carbon electrode composite material - Google Patents

Preparation method of nano carbon electrode composite material Download PDF

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CN103746118A
CN103746118A CN201310485413.9A CN201310485413A CN103746118A CN 103746118 A CN103746118 A CN 103746118A CN 201310485413 A CN201310485413 A CN 201310485413A CN 103746118 A CN103746118 A CN 103746118A
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weight
composite material
electrode composite
preparation
nano
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CN103746118B (en
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高虹
李力
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GUIZHOU TELIDA NANO CARBON SCIENCE & TECHNOLOGY Co Ltd
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GUIZHOU TELIDA NANO CARBON SCIENCE & TECHNOLOGY Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a nano carbon electrode composite material. The method comprises the following steps: 1) weighing raw materials according to the following components by the mass percentage: 5%-10% of a catalyst, 5%-10% of a lithium salt, 50%-55% of an iron salt, and 30-40% of phosphate; and after adding a dispersant into the raw materials, carrying out ball milling in a ball mill, and thus obtaining a precursor; 2) putting the obtained precursor in a 60-70 DEG C vacuum oven, drying for 10-30 hours, then putting into a tube type vacuum furnace with atmosphere protection, then introducing nitrogen gas or argon gas, then introducing methane gas, and keeping the pressure at 1.5-2.0 MPa; and 3) preparing a dispersion powder from the product obtained in the step 2), carrying out isopyknic immersion of the dispersion powder with a phenolic resin-P123 macromolecule copolymer-ethyl orthosilicate sol, carrying out full condensation, naturally cooling to the room temperature, and thus obtaining a nano carbon electrode composite material. The method can prevent the electrode material from generating an agglomeration phenomenon, not only reduces the cost, but also improves the performance.

Description

A kind of preparation method of nano carbon electrode composite material
Technical field
The invention belongs to active cell combination electrode material field, relate to a kind of preparation method of nano carbon electrode material.
Background technology
Hydrogen is the cleanest energy, be also a kind of important raw material of industry, but the storage of hydrogen and transportation problem has limited the extensive use of Hydrogen Energy.Can vehicle-mounted hydrogen and oxygen fuel cell obtain practical application widely, also be resolved closely related with this problem.The hydrogen storage material of research and development excellent performance is to solve one of the storage of Hydrogen Energy and critical path of transportation problem.
Cobalt acid lithium shows excellent performance as anode material for lithium-ion batteries in portable type electronic product fields such as mobile phone, Video Camera, notebook computer, digital camera, media players, but, it easily discharges oxygen under higher temperature, brings serious potential safety hazard.Scientific circles and industrial circle generally believe that cobalt acid lithium is not suitable as used for electric vehicle high power, anode material for lithium ion battery with high power capacity now.Meanwhile, because cobalt acid lithium is expensive, for many years lead-acid battery all overwhelming occupied most market.Therefore, searching low cost, high performance positive electrode are needs, the especially Development of EV (EV) that promotes lithium ion battery extensive use, the key of hybrid electric vehicle (HEV).Can say, from the lithium ion battery marketization till now, scientist is just finding the positive electrode that cost performance is higher always.LiFePO4 low price, specific capacity is high, security performance good, is desirable anode material for lithium-ion batteries, and especially the stability under its higher temperature provides safety guarantee to high power, high-capacity battery, is the ideal chose of power battery material.But LiFePO4 conductivity is low, in charge and discharge process, easily there are polarization phenomena, under large electric current high magnification, capacity significantly declines, and performance is not bery desirable.LiFePO4 wants the real application that realizes, and must solve these problems that exist at present.
Existing patent 200410051045.8 is openly that conductive agent and LiFePO4 are as anode material for lithium-ion batteries by CNT (carbon nano-tube).But in actual use, this method of directly doing conductive agent by CNT (carbon nano-tube), CNT (carbon nano-tube) is reunited very serious, because CNT (carbon nano-tube) does not effectively fully contact with LiFePO4, CNT (carbon nano-tube) utilance is low.Patent 200510021505.7 discloses uses CNT (carbon nano-tube) as the manufacture method of conductive agent and pole piece thereof.Pulp of lithium ion battery solid content is very high, and viscosity is large, adopts and is difficult in this way make CNT (carbon nano-tube) abundant
Disperse.Therefore, use at present the method for CNT (carbon nano-tube) can not give full play to its advantage, because CNT (carbon nano-tube) reunion seriously also has to strengthen the consumption of raw material, increased cost simultaneously, reduced the capacity of composite material.
In addition, electrode material is one of key determining chemical power source performance.The research and development of high performance electrode material are the core topic of chemical power source research field always.Need the modification to electrode material to improve its conductivity simultaneously, thereby improve high rate capability, also will keep its high reversible electrochemical capacity and good cyclical stability, and need with low cost.
Summary of the invention
Technical problem to be solved by this invention is, a kind of preparation method of nano carbon electrode material is provided, and can prevent electrode material generation agglomeration, both reduces costs, and improves again performance.The process of electrode material absorption hydrogen obtained by this method can reach balance fast in the short time; Conductivity is high, and internal resistance is little and reduce costs adaptation suitability for industrialized production.
The present invention solves the problems of the technologies described above adopted technical scheme to be:
A preparation method for nano carbon electrode composite material, comprises that following step is poly-:
1) by following component and mass percentage content raw materials weighing: catalyst 5%～10%, lithium salts 5%～10%, molysite 50%～55% and phosphate 30～40%; Described catalyst is the superfine powder of metal Ni, Y, Zr and MgO, is of a size of 500～5000nm, and its percentage by weight is respectively 85%, 5%, 5% and 10% of total catalyst weight; Described lithium salts is the combination of lithium carbonate, lithium hydroxide, lithium nitrate and lithium phosphate, and its percentage by weight is respectively 45%, 25%, 25% and 5% of lithium salts total weight; Described molysite is ferrous oxalate and ferric phosphate, and its percentage by weight is respectively 70% and 30% of molysite total weight; Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, and its percentage by weight is respectively 50% and 50% of phosphate total weight; Above-mentioned raw materials is added after dispersant in ball mill with rotating speed ball milling 10～15h of 500～800r/m, make precursor, the weight that adds dispersant is 1%～5% of above-mentioned raw materials weight;
2) precursor of gained is put into the dry atmosphere protection tube type vacuum stove of putting into after 10～30 hours of vacuum drying oven of 60-70 ℃, then pass into nitrogen or argon gas, nitrogen or argon flow amount are 500～600sccm, with the speed of 20～25 ℃/min, be warming up to 500～600 ℃, pass into again the methane gas that flow is 350～650sccm, keep pressure at 1.5～2.0Mpa; Turn off nitrogen or argon gas simultaneously, constant temperature 90～120min growing nano carbon pipe and carbon fiber at 600～1000 ℃ of temperature, it at least contains 18 carbon atoms, and the length of described CNT (carbon nano-tube) and carbon fiber and diameter are 5～20nm, and specific area is 100-500m2.g-1;
3) by step 2) in the product that obtains be scattered in organic solvent ethanol, adopt transient state drying means to make dispersion powder, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resins-P123 high-molecular copolymer-ethyl orthosilicate and through fully condensation, phenolic resins weight content is 40～50% of colloidal sol total weight, P123 high-molecular copolymer weight content is 20～30% of colloidal sol total weight, and ethyl orthosilicate weight content is 30～35% of colloidal sol total weight; The hot polymerization of phenolic resins carries out 20 hours at 100～105 ℃; Then the product of above-mentioned processing is recovered to nitrogen or argon flow amount; with the speed of 20～25 ℃/min, temperature is adjusted to 600～800 ℃; constant temperature 10～20h; maintenance pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere protection, make nano carbon electrode composite material.
Preferably, the dispersant step 1) is deionized water, absolute ethyl alcohol or acetone.
In above-mentioned arbitrary scheme preferably, step 2) in CNT (carbon nano-tube) be the seamless hollow tube being rolled into by graphite.
In above-mentioned arbitrary scheme preferably, step 2) in CNT (carbon nano-tube) be Single Walled Carbon Nanotube or multiple-wall carbon nanotube.
In above-mentioned arbitrary scheme, preferably, can combine to replace the MgO in step 1) with tin oxide, cupric oxide, vanadium oxide, nickel protoxide, chromium oxide, tungsten oxide or its, its percentage by weight is total catalyst weight 10%.
In above-mentioned arbitrary scheme, preferably, can replace step 2 with helium, neon, CO or CO2 gas) and 3) in nitrogen or argon gas.
In above-mentioned arbitrary scheme, preferably, the drum's speed of rotation in step 1) is 600r/m.
In above-mentioned arbitrary scheme preferably, step 2) in nitrogen or argon flow amount be 550sccm, methane gas flow is 500sccm, keeps pressure at 1.8Mpa; The length of described CNT (carbon nano-tube) and carbon fiber and diameter are 15nm, and specific area is 300-m2.g-1.
In above-mentioned arbitrary scheme preferably, step 3) in phenolic resins hot polymerization at 102 ℃, carry out 20 hours; Then the product of above-mentioned processing is recovered to nitrogen or argon flow amount, with the speed of 20～25 ℃/min, temperature is adjusted to 700 ℃, constant temperature 15h, maintenance pressure is normal pressure.
Beneficial effect:
1. situ growth CNT (carbon nano-tube) of the present invention and carbon fiber, prevented reunion, and CNT (carbon nano-tube) or carbon fiber effectively contact with LiFePO4, reduced CNT (carbon nano-tube) or carbon fiber use amount, both reduced cost, improved again the performance of LiFePO4.
2. can obviously improve the hydrogen storage property of carbon nano-fiber.
3. the present invention compared with prior art, formation has the combination electrode material of good conductivity, thereby raising high rate capability, the powder granule making has the nanochannel of some, increased the effecting reaction area of electrode and the passage of lithium ion turnover, made electrode material have very high reversible electrochemical capacity; Low cost product of the present invention, excellent performance, meets the requirement of electrode material heavy-current discharge, and its preparation method is simple, meets the demand of suitability for industrialized production.
4. there is self-supporting overall structure, without subsequent forming; Have and be beneficial to the three-dimensional hierarchical pore structure that electrolyte holds storage, ionic conduction and storage; Conductivity of composite material is good, internal resistance is little; The regulation and control of composite material texture flexibly.
5. improve ionic conductivity, improved again electronic conductivity.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
1) by following component and mass percentage content raw materials weighing: catalyst 5g, lithium salts 5g, molysite 50g and phosphate 30g; Described catalyst is the superfine powder of metal Ni, Y, Zr and MgO, is of a size of 500nm, and its percentage by weight is respectively 85%, 5%, 5% and 10% of total catalyst weight; Described lithium salts is the combination of lithium carbonate, lithium hydroxide, lithium nitrate and lithium phosphate, and its percentage by weight is respectively 45%, 25%, 25% and 5% of lithium salts total weight; Described molysite is ferrous oxalate and ferric phosphate, and its percentage by weight is respectively 70% and 30% of molysite total weight; Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, and its percentage by weight is respectively 50% and 50% of phosphate total weight; Above-mentioned raw materials is added after dispersant in ball mill with the rotating speed ball milling 15h of 500r/m, make precursor, the weight that adds dispersant is 1% of above-mentioned raw materials weight;
2) precursor of gained is put into the dry atmosphere protection tube type vacuum stove of putting into after 20 hours of vacuum drying oven of 60 ℃, then pass into high pure nitrogen (N2 purity >=99.999%), flow is 500sccm, with the speed of 25 ℃/min, be warming up to 500 ℃, pass into again the methane gas that flow is 350sccm, keep pressure at 1.5Mpa; Turn off nitrogen simultaneously, constant temperature 120min growing nano carbon pipe and carbon fiber at 600 ℃ of temperature, it at least contains 18 carbon atoms, and the length of described CNT (carbon nano-tube) and carbon fiber and diameter are 5nm, and specific area is 100m2.g-1;
3) by step 2) in the product that obtains be scattered in organic solvent ethanol, adopt transient state drying means to make dispersion powder, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resins-P123 high-molecular copolymer-ethyl orthosilicate and through fully condensation, phenolic resins weight content is 40% of colloidal sol total weight, P123 high-molecular copolymer weight content is 20% of colloidal sol total weight, and ethyl orthosilicate weight content is 35% of colloidal sol total weight; The hot polymerization of phenolic resins carries out 20 hours at 105 ℃; Then the product of above-mentioned processing is recovered to nitrogen or argon flow amount; with the speed of 20 ℃/min, temperature is adjusted to 600 ℃, constant temperature 20h, maintenance pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere protection, make nano carbon electrode composite material.
Using preparation material as positive pole, then take lithium sheet as to electrode, U.S. Celgard2400 is barrier film, take 1.0molL-1LiPF6/EC+DMC[V (EC): V (DMC)=1:1] be electrolyte, in being full of the stainless steel glove box of argon gas, be assembled into button cell.On Land-BTL10 (blue electricity) full-automatic battery controlled testing instrument, carry out constant current constant voltage charge-discharge test, discharge-rate is respectively 0.5～3C, and charging/discharging voltage scope is 4.5～5.5V.Under 1C multiplying power, discharge capacity is 150mAhg-1.
The hydrogen adsorption capacity that records the electrode material that the method makes under the pressure of 20 ℃ and 60atm is to be more than or equal to 0.8(gH2/100g in 10min).
Embodiment 2:
1) by following component and mass percentage content raw materials weighing: catalyst 5g, lithium salts 10g, molysite 55g and phosphate 40g; Described catalyst is the superfine powder of metal Ni, Y, Zr and MgO, is of a size of 500nm, and its percentage by weight is respectively 85%, 5%, 5% and 10% of total catalyst weight; Described lithium salts is the combination of lithium carbonate, lithium hydroxide, lithium nitrate and lithium phosphate, and its percentage by weight is respectively 45%, 25%, 25% and 5% of lithium salts total weight; Described molysite is ferrous oxalate and ferric phosphate, and its percentage by weight is respectively 70% and 30% of molysite total weight; Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, and its percentage by weight is respectively 50% and 50% of phosphate total weight; Above-mentioned raw materials is added after dispersant in ball mill with the rotating speed ball milling 10h of 800r/m, make precursor, the weight that adds dispersant is 5% of above-mentioned raw materials weight;
2) precursor of gained is put into the dry atmosphere protection tube type vacuum stove of putting into after 20 hours of vacuum drying oven of 70 ℃, then pass into high pure nitrogen (N2 purity >=99.999%), flow is 600sccm, with the speed of 20 ℃/min, be warming up to 600 ℃, pass into again the methane gas that flow is 650sccm, keep pressure at 2Mpa; Turn off nitrogen simultaneously, constant temperature 90min growing nano carbon pipe and carbon fiber at 1000 ℃ of temperature, it at least contains 18 carbon atoms, and the length of described CNT (carbon nano-tube) and carbon fiber and diameter are 20nm, and specific area is 250m2.g-1;
3) by step 2) in the product that obtains be scattered in organic solvent ethanol, adopt transient state drying means to make dispersion powder, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resins-P123 high-molecular copolymer-ethyl orthosilicate and through fully condensation, phenolic resins weight content is 40% of colloidal sol total weight, P123 high-molecular copolymer weight content is 20% of colloidal sol total weight, and ethyl orthosilicate weight content is 35% of colloidal sol total weight; The hot polymerization of phenolic resins carries out 20 hours at 100 ℃; Then the product of above-mentioned processing is recovered to nitrogen or argon flow amount; with the speed of 20 ℃/min, temperature is adjusted to 800 ℃, constant temperature 10h, maintenance pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere protection, make nano carbon electrode composite material.
Using preparation material as positive pole, then take lithium sheet as to electrode, U.S. Celgard2400 is barrier film, take 1.0molL-1LiPF6/EC+DMC[V (EC): V (DMC)=1:1] be electrolyte, in being full of the stainless steel glove box of argon gas, be assembled into button cell.On Land-BTL10 (blue electricity) full-automatic battery controlled testing instrument, carry out constant current constant voltage charge-discharge test, discharge-rate is respectively 2.5～3.3C, and charging/discharging voltage scope is 5～6V.Under 1C multiplying power, discharge capacity is 165mAhg-1.
The hydrogen adsorption capacity that records the electrode material that the method makes under the pressure of 20 ℃ and 60atm is to be more than or equal to 0.92(gH2/100g in 10min).
Embodiment 3:
1) by following component and mass percentage content raw materials weighing: catalyst 10g, lithium salts 5g, molysite 50g and phosphate 35g; Described catalyst is the superfine powder of metal Ni, Y, Zr and MgO, is of a size of 500nm, and its percentage by weight is respectively 85%, 5%, 5% and 10% of total catalyst weight; Described lithium salts is the combination of lithium carbonate, lithium hydroxide, lithium nitrate and lithium phosphate, and its percentage by weight is respectively 45%, 25%, 25% and 5% of lithium salts total weight; Described molysite is ferrous oxalate and ferric phosphate, and its percentage by weight is respectively 70% and 30% of molysite total weight; Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, and its percentage by weight is respectively 50% and 50% of phosphate total weight; Above-mentioned raw materials is added after dispersant in ball mill with the rotating speed ball milling 10h of 600r/m, make precursor, the weight that adds dispersant is 2.5% of above-mentioned raw materials weight;
2) precursor of gained is put into the dry atmosphere protection tube type vacuum stove of putting into after 20 hours of vacuum drying oven of 65 ℃, then pass into high pure nitrogen (N2 purity >=99.999%), flow is 500sccm, with the speed of 22 ℃/min, be warming up to 550 ℃, pass into again the methane gas that flow is 500sccm, keep pressure at 1.8Mpa; Turn off nitrogen simultaneously, constant temperature 100min growing nano carbon pipe and carbon fiber at 800 ℃ of temperature, it at least contains 18 carbon atoms, and the length of described CNT (carbon nano-tube) and carbon fiber and diameter are 15nm, and specific area is 500m2.g-1;
3) by step 2) in the product that obtains be scattered in organic solvent ethanol, adopt transient state drying means to make dispersion powder, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resins-P123 high-molecular copolymer-ethyl orthosilicate and through fully condensation, phenolic resins weight content is 50% of colloidal sol total weight, P123 high-molecular copolymer weight content is 30% of colloidal sol total weight, and ethyl orthosilicate weight content is 30% of colloidal sol total weight; The hot polymerization of phenolic resins carries out 20 hours at 102 ℃; Then the product of above-mentioned processing is recovered to nitrogen or argon flow amount; with the speed of 22 ℃/min, temperature is adjusted to 700 ℃, constant temperature 15h, maintenance pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere protection, make nano carbon electrode composite material.
Using preparation material as positive pole, then take lithium sheet as to electrode, U.S. Celgard2400 is barrier film, take 1.0molL-1LiPF6/EC+DMC[V (EC): V (DMC)=1:1] be electrolyte, in being full of the stainless steel glove box of argon gas, be assembled into button cell.On Land-BTL10 (blue electricity) full-automatic battery controlled testing instrument, carry out constant current constant voltage charge-discharge test, discharge-rate is respectively 3～3.5C, and charging/discharging voltage scope is 5.5～6.5V.Under 1C multiplying power, discharge capacity is 170mAhg-1.
The hydrogen adsorption capacity that records the electrode material that the method makes under the pressure of 20 ℃ and 60atm is to be more than or equal to 0.88(gH2/100g in 10min).
The catalyst providing in above-described embodiment can be prepared according to the following step:
(1) preparation of solution
The zirconium nitrate aqueous solution that 50ml is contained to 8.5gNi containing the nickel nitrate aqueous solution of 8.5gNi and 50ml containing yttrium nitrate aqueous solution and the 50ml of 5gY, obtains solution A; 15g sodium acid carbonate is made into the 150ml aqueous solution, obtains solution B.
(2) preparation of precipitation
Solution B, in 0 ℃ of speed with about 8ml/min splashes into the solution A under neon strong agitation, is obtained to precipitation, and the speed that is filled with of neon is 100ml/s.
(3) preparation of catalyst
By (2) gained precipitation through deionized water washing, filter, then add the magnesium oxide powder of 10g, fully mix, through 120 ℃ dry 5 hours, the lower 400 ℃ of roastings of argon gas atmosphere made catalyst after 6 hours.
The above, be only preferred embodiment of the present invention, is not the present invention to be done to the restriction of other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection range of technical solution of the present invention.
Finally it should be noted that: above embodiment only, in order to technical scheme of the present invention to be described, is not intended to limit; Although the present invention is had been described in detail with reference to previous embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.

Claims (9)

1. a preparation method for nano carbon electrode composite material, is characterized in that, comprises that following step is poly-:
1) by following component and mass percentage content raw materials weighing: catalyst 5%～10%, lithium salts 5%～10%, molysite 50%～55% and phosphate 30～40%; Described catalyst is the superfine powder of metal Ni, Y, Zr and MgO, is of a size of 500～5000nm, and its percentage by weight is respectively 85%, 5%, 5% and 10% of total catalyst weight; Described lithium salts is the combination of lithium carbonate, lithium hydroxide, lithium nitrate and lithium phosphate, and its percentage by weight is respectively 45%, 25%, 25% and 5% of lithium salts total weight; Described molysite is ferrous oxalate and ferric phosphate, and its percentage by weight is respectively 70% and 30% of molysite total weight; Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, and its percentage by weight is respectively 50% and 50% of phosphate total weight; Above-mentioned raw materials is added after dispersant in ball mill with rotating speed ball milling 10～15h of 500～800r/m, make precursor, the weight that adds dispersant is 1%～5% of above-mentioned raw materials weight;
2) precursor of gained is put into the dry atmosphere protection tube type vacuum stove of putting into after 10～30 hours of vacuum drying oven of 60-70 ℃, then pass into nitrogen or argon gas, nitrogen or argon flow amount are 500～600sccm, with the speed of 20～25 ℃/min, be warming up to 500～600 ℃, pass into again the methane gas that flow is 350～650sccm, keep pressure at 1.5～2.0Mpa; Turn off nitrogen or argon gas simultaneously, constant temperature 90～120min growing nano carbon pipe and carbon fiber at 600～1000 ℃ of temperature, it at least contains 18 carbon atoms, and the length of described CNT (carbon nano-tube) and carbon fiber and diameter are 5～20nm, and specific area is 100-500m2.g-1;
3) by step 2) in the product that obtains be scattered in organic solvent ethanol, adopt transient state drying means to make dispersion powder, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resins-P123 high-molecular copolymer-ethyl orthosilicate and through fully condensation, phenolic resins weight content is 40～50% of colloidal sol total weight, P123 high-molecular copolymer weight content is 20～30% of colloidal sol total weight, and ethyl orthosilicate weight content is 30～35% of colloidal sol total weight; The hot polymerization of phenolic resins carries out 20 hours at 100～105 ℃; Then the product of above-mentioned processing is recovered to nitrogen or argon flow amount; with the speed of 20～25 ℃/min, temperature is adjusted to 600～800 ℃; constant temperature 10～20h; maintenance pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere protection, make nano carbon electrode composite material.
2. the preparation method of nano carbon electrode composite material according to claim 1, is characterized in that step 1) described in dispersant be deionized water, absolute ethyl alcohol or acetone.
3. the preparation method of nano carbon electrode composite material according to claim 1 and 2, is characterized in that step 2) in CNT (carbon nano-tube) be the seamless hollow tube being rolled into by graphite.
4. the preparation method of nano carbon electrode composite material according to claim 3, is characterized in that step 2) in CNT (carbon nano-tube) be Single Walled Carbon Nanotube or multiple-wall carbon nanotube.
5. the preparation method of nano carbon electrode composite material according to claim 4, it is characterized in that, useful tin oxide, cupric oxide, vanadium oxide, nickel protoxide, chromium oxide, tungsten oxide or its combine to replace the MgO in step 1), and its percentage by weight is total catalyst weight 10%.
6. according to the preparation method of the nano carbon electrode composite material described in claim 4 or 5, it is characterized in that, can replace step 2 with helium, neon, CO or CO2 gas) and 3) in nitrogen or argon gas.
7. the preparation method of nano carbon electrode composite material according to claim 1 and 2, is characterized in that, the drum's speed of rotation in step 1) is 600r/m.
8. the preparation method of nano carbon electrode composite material according to claim 7, is characterized in that step 2) in nitrogen or argon flow amount be 550sccm, methane gas flow is 500sccm, keeps pressure at 1.8Mpa; The length of described CNT (carbon nano-tube) and carbon fiber and diameter are 15nm, and specific area is 300-m2.g-1.
9. the preparation method of nano carbon electrode composite material according to claim 8, is characterized in that step 3) in phenolic resins hot polymerization at 102 ℃, carry out 20 hours; Then the product of above-mentioned processing is recovered to nitrogen or argon flow amount, with the speed of 20～25 ℃/min, temperature is adjusted to 700 ℃, constant temperature 15h, maintenance pressure is normal pressure.
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