CN103746118B - A kind of preparation method of nano carbon electrode composite material - Google Patents
A kind of preparation method of nano carbon electrode composite material Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
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- 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
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Abstract
The preparation method that the invention discloses a kind of nano carbon electrode composite material, gathers including following step: 1) weigh raw material by following components and mass percentage content: catalyst 5%～10%, lithium salts 5%～10%, iron salt 50%～55% and phosphate 30～40%；Above-mentioned raw materials is added after dispersant ball milling in ball mill, prepares precursor；2) precursor of gained is put in the vacuum drying oven of 60-70 DEG C and put in atmosphere protection tube type vacuum stove after dry 10～30 hours, then pass to nitrogen or argon, then pass into methane gas, keep pressure at 1.5～2.0Mpa；3) by step 2) the prepared dispersion powder of the middle product obtained, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resin-P123 high-molecular copolymer-ethyl orthosilicate and through abundant condensation, naturally cool to room temperature, namely prepare nano carbon electrode composite material.The method can prevent electrode material generation agglomeration, had both reduced cost, improves again performance.
Description
Technical field
The invention belongs to active cell combination electrode material field, the preparation method relating to a kind of nano carbon electrode material.
Background technology
Hydrogen is the cleanest energy, is also a kind of important raw material of industry, but the storage of hydrogen and transportation problem limit the extensive use of Hydrogen Energy.Can vehicle-mounted hydrogen and oxygen fuel cell obtain practical application widely, also obtain solution with this problem closely related.The hydrogen storage material of research and development excellent performance is one of the storage solving Hydrogen Energy critical path with transportation problem.
Cobalt acid lithium shows the performance of excellence 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 at relatively high temperatures, brings serious potential safety hazard.Present scientific circles and industrial circle generally believe that cobalt acid lithium is not suitable as high power used for electric vehicle, anode material for lithium ion battery with high power capacity.Simultaneously as cobalt acid lithium is expensive, lead-acid battery all overwhelmings occupy most market for many years.Therefore, find low cost, high performance positive electrode is to promote the wide variety of needs of lithium ion battery, the especially key of Development of EV (EV), hybrid electric vehicle (HEV).It can be said that from the lithium ion battery marketization till now, scientist just always searches for the positive electrode that cost performance is higher.LiFePO4 low price, specific capacity are high, security performance is good, are 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 electrical conductivity is low, polarization phenomena easily occurring in charge and discharge process, under big electric current high magnification, capacity significantly declines, and performance is not highly desirable.LiFePO4 wants really to realize application, it is necessary to solve these problems that presently, there are.
The existing open CNT of patent 200410051045.8 is that conductive agent and LiFePO4 are as anode material for lithium-ion batteries.But in actual use, the method that this direct CNT does conductive agent, CNT is reunited very serious, because CNT is not effectively fully contacted with LiFePO4, CNT utilization rate is low.Patent 200510021505.7 discloses the use of the CNT manufacture method as conductive agent and pole piece thereof.Pulp of lithium ion battery solid content is very high, and viscosity is big, adopts and is difficult in this way make CNT abundant
Dispersion.Therefore, the method for currently used CNT can not give full play to its advantage, simultaneously because CNT is reunited seriously also has to strengthen the consumption of raw material, adds cost, reduces the capacity of composite.
It addition, electrode material is one of key determining electrochmical power source performance.The research and development of high performance electrode material, are always up the core topic of electrochmical power source research field.Improve its electric conductivity simultaneously need to electrode material is modifiied, thus improving high rate capability, also keeping its high reversible electrochemical capacity and good cyclical stability, and needing with low cost.
Summary of the invention
The preparation method that the technical problem to be solved is to provide a kind of nano carbon electrode material, can prevent electrode material generation agglomeration, both reduce cost, improve again performance.The process of electrode material obtained by this method absorption hydrogen can be rapidly achieved balance in the short time；Electric conductivity is high, and internal resistance is little and reduces cost, adapts to industrialized production.
The present invention solves that above-mentioned technical problem be the technical scheme is that
The preparation method of a kind of nano carbon electrode composite material, gathers including following step:
1) raw material is weighed by following components and mass percentage content: catalyst 5%～10%, lithium salts 5%～10%, iron salt 50%～55% and phosphate 30～40%；Described catalyst is the superfine powder of W metal, Y, Zr and MgO, is of a size of 500～5000nm, 85%, 5%, 5% and the 10% of its percentage by weight respectively total catalyst weight；Described lithium salts is the combination of lithium carbonate, Lithium hydrate, lithium nitrate and lithium phosphate, its percentage by weight respectively the 45% of lithium salts gross weight, 25%, 25% and 5%；Described iron salt is Ferrox. and iron phosphate, the 70% and 30% of its percentage by weight respectively iron salt gross weight；Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, the 50% and 50% of its percentage by weight respectively phosphate gross weight；Above-mentioned raw materials is added after dispersant in ball mill with the rotating speed ball milling 10～15h of 500～800r/m, prepare precursor, add weight is above-mentioned raw materials weight the 1%～5% of dispersant；
2) being put into by the precursor of gained in the vacuum drying oven of 60-70 DEG C puts in atmosphere protection tube type vacuum stove after dry 10～30 hours; then pass to nitrogen or argon; nitrogen or argon flow amount are 500～600sccm; it is warming up to 500～600 DEG C with the speed of 20～25 DEG C/min; pass into the methane gas that flow is 350～650sccm again, keep pressure at 1.5～2.0Mpa；Also shutting off nitrogen or argon, at 600～1000 DEG C of temperature, constant temperature 90～120min grows CNT and carbon fiber, and it at least contains 18 carbon atoms, the length of described CNT and carbon fiber and diameter is 5～20nm, and specific surface area is 100-500m2.g-1；
3) by step 2) in obtain product be scattered in organic solvent ethanol, transient state drying means is adopted to prepare dispersion powder, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resin-P123 high-molecular copolymer-ethyl orthosilicate and through abundant condensation, phenolic resin weight content is the 40～50% of colloidal sol gross weight, P123 high-molecular copolymer weight content is the 20～30% of colloidal sol gross weight, and ethyl orthosilicate weight content is the 30～35% of colloidal sol gross weight；The hot polymerization of phenolic resin carries out 20 hours at 100～105 DEG C；Then the product of above-mentioned process is recovered nitrogen or argon flow amount; with the speed of 20～25 DEG C/min, temperature is adjusted to 600～800 DEG C; constant temperature 10～20h; maintenance pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere are protected, namely prepare nano carbon electrode composite material.
Preferably, step 1) described in dispersant be deionized water, dehydrated alcohol or acetone.
In any of the above-described scheme preferably, step 2) in CNT be the seamless hollow pipe being rolled into by graphite.
In any of the above-described scheme preferably, step 2) in CNT be SWNT or multiple-wall carbon nanotube.
In any of the above-described scheme preferably, can replacing the MgO in step 1) with stannum oxide, copper oxide, vanadium oxide, nickel protoxide, chromium oxide, tungsten oxide or its combination, its percentage by weight is the 10% of total catalyst weight.
In any of the above-described scheme preferably, step 2 can be replaced with helium, neon, CO or CO2 gas) and 3) in nitrogen or argon.
In any of the above-described scheme preferably, the drum's speed of rotation in step 1) is 600r/m.
In any of the above-described 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 and carbon fiber and diameter are 15nm, and specific surface area is 300-m2.g-1.
In any of the above-described scheme preferably, step 3) in phenolic resin hot polymerization carry out at 102 DEG C 20 hours；Then the product of above-mentioned process recovering nitrogen or argon flow amount, with the speed of 20～25 DEG C/min, temperature is adjusted to 700 DEG C, constant temperature 15h, maintenance pressure is normal pressure.
Beneficial effect:
1. situ growth CNT of the present invention and carbon fiber, it is therefore prevented that reuniting, CNT or carbon fiber effectively contact with LiFePO4, reduce CNT or carbon fiber makes consumption, both reduced cost, improve again the performance of LiFePO4.
2. can significantly improve the hydrogen storage property of carbon nano-fiber.
3. the present invention is compared with prior art, form the combination electrode material with good conductivity, thus improving high rate capability, the powder granule prepared has a number of nanochannel, add the effective affecting acreage of electrode and the passage of lithium ion turnover, make electrode material have significantly high reversible electrochemical capacity；The low cost product of the present invention, excellent performance, meet the requirement of electrode material heavy-current discharge, its preparation method is simple, meets the demand of industrialized production.
4. there is self-supporting overall structure, it is not necessary to subsequent forming；There is the three-dimensional hierarchical pore structure being beneficial to electrolyte appearance storage, ionic conduction and storage；Conductivity of composite material is good, internal resistance is little；The regulation and control of composite texture are flexibly.
5. improve ionic conductivity, improve again electronic conductivity.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described.
Embodiment 1:
1) raw material is weighed by following components and mass percentage content: catalyst 5g, lithium salts 5g, iron salt 50g and phosphate 30g；Described catalyst is the superfine powder of W metal, Y, Zr and MgO, is of a size of 500nm, 85%, 5%, 5% and the 10% of its percentage by weight respectively total catalyst weight；Described lithium salts is the combination of lithium carbonate, Lithium hydrate, lithium nitrate and lithium phosphate, its percentage by weight respectively the 45% of lithium salts gross weight, 25%, 25% and 5%；Described iron salt is Ferrox. and iron phosphate, the 70% and 30% of its percentage by weight respectively iron salt gross weight；Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, the 50% and 50% of its percentage by weight respectively phosphate gross weight；Above-mentioned raw materials is added after dispersant in ball mill with the rotating speed ball milling 15h of 500r/m, prepare precursor, add weight is above-mentioned raw materials weight the 1% of dispersant；
2) being put into by the precursor of gained in the vacuum drying oven of 60 DEG C puts in atmosphere protection tube type vacuum stove after dry 20 hours; then pass to high pure nitrogen (N2 purity >=99.999%); flow is 500sccm; it is warming up to 500 DEG C with the speed of 25 DEG C/min; pass into the methane gas that flow is 350sccm again, keep pressure at 1.5Mpa；Also shutting off nitrogen, at 600 DEG C of temperature, constant temperature 120min grows CNT and carbon fiber, and it at least contains 18 carbon atoms, the length of described CNT and carbon fiber and diameter is 5nm, and specific surface area is 100m2.g-1；
3) by step 2) in obtain product be scattered in organic solvent ethanol, transient state drying means is adopted to prepare dispersion powder, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resin-P123 high-molecular copolymer-ethyl orthosilicate and through abundant condensation, phenolic resin weight content is the 40% of colloidal sol gross weight, P123 high-molecular copolymer weight content is the 20% of colloidal sol gross weight, and ethyl orthosilicate weight content is the 35% of colloidal sol gross weight；The hot polymerization of phenolic resin carries out 20 hours at 105 DEG C；Then the product of above-mentioned process is recovered nitrogen or argon flow amount; with the speed of 20 DEG C/min, temperature is adjusted to 600 DEG C, constant temperature 20h, maintenance pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere are protected, namely prepare nano carbon electrode composite material.
Using the material of preparation as positive pole, then with lithium sheet for electrode, U.S. Celgard2400 is barrier film, for electrolyte, is assembled into button cell with 1.0mol L-1LiPF6/EC+DMC [V (EC): V (DMC)=1:1] in the rustless steel glove box of full argon.Carrying out constant current constant voltage charge-discharge test on Land-BTL10 (blue electricity) full-automatic battery controlled testing instrument, discharge-rate is 0.5～3C respectively, and charging/discharging voltage ranges for 4.5～5.5V.It is 150mAh g-1 at 1C multiplying power discharge capacity.
The hydrogen adsorption ability recording the electrode material that the method prepares under 20 DEG C of pressure with 60atm is be more than or equal to 0.8(gH2/100g in 10min).
Embodiment 2:
1) raw material is weighed by following components and mass percentage content: catalyst 5g, lithium salts 10g, iron salt 55g and phosphate 40g；Described catalyst is the superfine powder of W metal, Y, Zr and MgO, is of a size of 500nm, 85%, 5%, 5% and the 10% of its percentage by weight respectively total catalyst weight；Described lithium salts is the combination of lithium carbonate, Lithium hydrate, lithium nitrate and lithium phosphate, its percentage by weight respectively the 45% of lithium salts gross weight, 25%, 25% and 5%；Described iron salt is Ferrox. and iron phosphate, the 70% and 30% of its percentage by weight respectively iron salt gross weight；Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, the 50% and 50% of its percentage by weight respectively phosphate gross weight；Above-mentioned raw materials is added after dispersant in ball mill with the rotating speed ball milling 10h of 800r/m, prepare precursor, add weight is above-mentioned raw materials weight the 5% of dispersant；
2) being put into by the precursor of gained in the vacuum drying oven of 70 DEG C puts in atmosphere protection tube type vacuum stove after dry 20 hours; then pass to high pure nitrogen (N2 purity >=99.999%); flow is 600sccm; it is warming up to 600 DEG C with the speed of 20 DEG C/min; pass into the methane gas that flow is 650sccm again, keep pressure at 2Mpa；Also shutting off nitrogen, at 1000 DEG C of temperature, constant temperature 90min grows CNT and carbon fiber, and it at least contains 18 carbon atoms, the length of described CNT and carbon fiber and diameter is 20nm, and specific surface area is 250m2.g-1；
3) by step 2) in obtain product be scattered in organic solvent ethanol, transient state drying means is adopted to prepare dispersion powder, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resin-P123 high-molecular copolymer-ethyl orthosilicate and through abundant condensation, phenolic resin weight content is the 40% of colloidal sol gross weight, P123 high-molecular copolymer weight content is the 20% of colloidal sol gross weight, and ethyl orthosilicate weight content is the 35% of colloidal sol gross weight；The hot polymerization of phenolic resin carries out 20 hours at 100 DEG C；Then the product of above-mentioned process is recovered nitrogen or argon flow amount; with the speed of 20 DEG C/min, temperature is adjusted to 800 DEG C, constant temperature 10h, maintenance pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere are protected, namely prepare nano carbon electrode composite material.
Using the material of preparation as positive pole, then with lithium sheet for electrode, U.S. Celgard2400 is barrier film, for electrolyte, is assembled into button cell with 1.0mol L-1LiPF6/EC+DMC [V (EC): V (DMC)=1:1] in the rustless steel glove box of full argon.Carrying out constant current constant voltage charge-discharge test on Land-BTL10 (blue electricity) full-automatic battery controlled testing instrument, discharge-rate is 2.5～3.3C respectively, and charging/discharging voltage ranges for 5～6V.It is 165mAh g-1 at 1C multiplying power discharge capacity.
The hydrogen adsorption ability recording the electrode material that the method prepares under 20 DEG C of pressure with 60atm is be more than or equal to 0.92(gH2/100g in 10min).
Embodiment 3:
1) raw material is weighed by following components and mass percentage content: catalyst 10g, lithium salts 5g, iron salt 50g and phosphate 35g；Described catalyst is the superfine powder of W metal, Y, Zr and MgO, is of a size of 500nm, 85%, 5%, 5% and the 10% of its percentage by weight respectively total catalyst weight；Described lithium salts is the combination of lithium carbonate, Lithium hydrate, lithium nitrate and lithium phosphate, its percentage by weight respectively the 45% of lithium salts gross weight, 25%, 25% and 5%；Described iron salt is Ferrox. and iron phosphate, the 70% and 30% of its percentage by weight respectively iron salt gross weight；Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, the 50% and 50% of its percentage by weight respectively phosphate gross weight；Above-mentioned raw materials is added after dispersant in ball mill with the rotating speed ball milling 10h of 600r/m, prepare precursor, add weight is above-mentioned raw materials weight the 2.5% of dispersant；
2) being put into by the precursor of gained in the vacuum drying oven of 65 DEG C puts in atmosphere protection tube type vacuum stove after dry 20 hours; then pass to high pure nitrogen (N2 purity >=99.999%); flow is 500sccm; it is warming up to 550 DEG C with the speed of 22 DEG C/min; pass into the methane gas that flow is 500sccm again, keep pressure at 1.8Mpa；Also shutting off nitrogen, at 800 DEG C of temperature, constant temperature 100min grows CNT and carbon fiber, and it at least contains 18 carbon atoms, the length of described CNT and carbon fiber and diameter is 15nm, and specific surface area is 500m2.g-1；
3) by step 2) in obtain product be scattered in organic solvent ethanol, transient state drying means is adopted to prepare dispersion powder, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resin-P123 high-molecular copolymer-ethyl orthosilicate and through abundant condensation, phenolic resin weight content is the 50% of colloidal sol gross weight, P123 high-molecular copolymer weight content is the 30% of colloidal sol gross weight, and ethyl orthosilicate weight content is the 30% of colloidal sol gross weight；The hot polymerization of phenolic resin carries out 20 hours at 102 DEG C；Then the product of above-mentioned process is recovered nitrogen or argon flow amount; with the speed of 22 DEG C/min, temperature is adjusted to 700 DEG C, constant temperature 15h, maintenance pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere are protected, namely prepare nano carbon electrode composite material.
Using the material of preparation as positive pole, then with lithium sheet for electrode, U.S. Celgard2400 is barrier film, for electrolyte, is assembled into button cell with 1.0mol L-1LiPF6/EC+DMC [V (EC): V (DMC)=1:1] in the rustless steel glove box of full argon.Carrying out constant current constant voltage charge-discharge test on Land-BTL10 (blue electricity) full-automatic battery controlled testing instrument, discharge-rate is 3～3.5C respectively, and charging/discharging voltage ranges for 5.5～6.5V.It is 170mAh g-1 at 1C multiplying power discharge capacity.
The hydrogen adsorption ability recording the electrode material that the method prepares under 20 DEG C of pressure with 60atm is be more than or equal to 0.88(gH2/100g in 10min).
The catalyst provided in above-described embodiment can be prepared according to the following step:
(1) preparation of solution
By the 50ml nickel nitrate aqueous solution containing 8.5gNi with the 50ml yttrium nitrate aqueous solution containing 5gY and the 50ml zirconium nitrate aqueous solution containing 8.5gNi, obtain solution A；15g sodium bicarbonate is made into 150ml aqueous solution, obtains solution B.
(2) preparation precipitated
Solution B being instilled, in the solution A under neon strong agitation, to obtain precipitation with the speed of about 8ml/min at 0 DEG C, the speed that is filled with of neon is 100ml/s.
(3) preparation of catalyst
Precipitating (2) gained through deionized water wash, filtration, be subsequently adding the magnesium oxide powder of 10g, be sufficiently mixed uniformly, dry 5 hours through 120 DEG C, the lower 400 DEG C of roastings of argon gas atmosphere prepared catalyst after 6 hours.
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention makees other form, and any those skilled in the art are changed or be modified as the Equivalent embodiments of equivalent variations possibly also with the technology contents of the disclosure above.But every without departing from technical solution of the present invention content, according to any simple modification, equivalent variations and remodeling that above example is made by the technical spirit of the present invention, still fall within the protection domain of technical solution of the present invention.
Last it is noted that above example is only in order to illustrate technical scheme, it is not intended to limit；Although the present invention being described in detail with reference to previous embodiment, it will be understood by those within the art that: the technical scheme described in foregoing embodiments still can be modified by it, or wherein portion of techniques feature is carried out equivalent replacement；And these amendments 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 (3)
1. the preparation method of a nano carbon electrode composite material, it is characterised in that include following step and gather:
1) raw material is weighed by following components and mass percentage content: catalyst 5%～10%, lithium salts 5%～10%, iron salt 50%～55% and phosphate 30～40%；Described lithium salts is the combination of lithium carbonate, Lithium hydrate, lithium nitrate and lithium phosphate, its percentage by weight respectively the 45% of lithium salts gross weight, 25%, 25% and 5%；Described iron salt is Ferrox. and iron phosphate, the 70% and 30% of its percentage by weight respectively iron salt gross weight；Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, the 50% and 50% of its percentage by weight respectively phosphate gross weight；Above-mentioned raw materials is added after dispersant in ball mill with the rotating speed ball milling 10～15h of 600r/m, prepare precursor, add weight is above-mentioned raw materials weight the 1%～5% of dispersant；Described catalyst is prepared according to the following step:
(1) preparation of solution
By the 50ml nickel nitrate aqueous solution containing 8.5gNi with the 50ml yttrium nitrate aqueous solution containing 5gY and the 50ml zirconium nitrate aqueous solution containing 8.5gZr, obtain solution A；15g sodium bicarbonate is made into 150ml aqueous solution, obtains solution B；
(2) preparation precipitated
Solution B being instilled, in the solution A under neon strong agitation, to obtain precipitation with the speed of about 8ml/min at 0 DEG C, the speed that is filled with of neon is 100ml/s；
(3) preparation of catalyst
Precipitating (2) gained through deionized water wash, filtration, be subsequently adding the magnesium oxide powder of 10g, be sufficiently mixed uniformly, dry 5 hours through 120 DEG C, the lower 400 DEG C of roastings of argon gas atmosphere prepared catalyst after 6 hours；
2) being put into by the precursor of gained in the vacuum drying oven of 60-70 DEG C puts in atmosphere protection tube type vacuum stove after dry 10～30 hours; then pass to nitrogen or argon; nitrogen or argon flow amount are 550sccm; it is warming up to 500～600 DEG C with the speed of 20～25 DEG C/min; pass into the methane gas that flow is 500sccm again, keep pressure at 1.8Mpa；Also shutting off nitrogen or argon, at 600～1000 DEG C of temperature, constant temperature 90～120min grows CNT and carbon fiber, and it at least contains 18 carbon atoms, the length of described CNT and carbon fiber and diameter is 15nm, and specific surface area is 300m2.g-1；
3) by step 2) in obtain product be scattered in organic solvent ethanol, transient state drying means is adopted to prepare dispersion powder, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resin-P123 high-molecular copolymer-ethyl orthosilicate and through abundant condensation, phenolic resin weight content is the 40～50% of colloidal sol gross weight, P123 high-molecular copolymer weight content is the 20～30% of colloidal sol gross weight, and ethyl orthosilicate weight content is the 30～35% of colloidal sol gross weight；The hot polymerization of phenolic resin carries out 20 hours at 102 DEG C；Then the product of above-mentioned process is recovered nitrogen or argon flow amount; with the speed of 20～25 DEG C/min, temperature is adjusted to 700 DEG C, constant temperature 15h, maintenance pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere are protected, namely prepare nano carbon electrode composite material；
Step 1) described in dispersant be deionized water, dehydrated alcohol or acetone；
Step 2) in CNT be the seamless hollow pipe being rolled into by graphite.
2. the preparation method of nano carbon electrode composite material according to claim 1, it is characterised in that step 2) in CNT be SWNT or multiple-wall carbon nanotube.
3. the preparation method of nano carbon electrode composite material according to claim 1, it is characterised in that available helium, neon, CO or CO2Gas replaces step 2) and 3) in nitrogen or argon.
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