CN103606679B - 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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- CN103606679B CN103606679B CN201310485418.1A CN201310485418A CN103606679B CN 103606679 B CN103606679 B CN 103606679B CN 201310485418 A CN201310485418 A CN 201310485418A CN 103606679 B CN103606679 B CN 103606679B
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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
- H01M4/58—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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
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- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
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- H—ELECTRICITY
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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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Abstract
The present invention is the preparation method of a kind of nano carbon electrode composite material, gathers including following step: 1) weigh raw material by following components and mass percentage content: lithium salts 5%～10%, molysite 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 into and put in atmosphere protection tube type vacuum stove after the vacuum drying oven of 60 70 DEG C is dried 10～30 hours, then pass to nitrogen or argon gas, then be passed through methane gas, keep pressure 1.5～2.0Mpa；With laser Supported Pt Nanoparticles or Raney nickel on CNT；3) by step 2) in the product that obtains prepare dispersion powder, and with this dispersion powder of colloidal sol incipient impregnation of phenolic resin P123 high-molecular copolymer ethyl orthosilicate and through being fully condensed, naturally cool to room temperature, i.e. prepare nano carbon electrode composite material.The method can prevent electrode material generation agglomeration, had both reduced cost, and had improved again performance.
Description
Technical field
The invention belongs to battery combination electrode material field, relate to the preparation method of 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 application of Hydrogen Energy.Can vehicle-mounted hydrogen and oxygen fuel cell obtain actual application widely, also have been resolved closely related with this problem.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 the most easily discharges oxygen, brings serious potential safety hazard.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 now.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, especially Development of EV (EV), the key of hybrid electric vehicle (HEV).It can be said that from the lithium ion battery marketization till now, scientist just always searches for the higher positive electrode of cost performance.LiFePO4 low price, specific capacity are high, security performance is good, are preferable anode material for lithium-ion batteries, and the especially 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 the most highly desirable.LiFePO4 wants really to realize application, it is necessary to solve these problems that presently, there are.
The open a kind of Nano sol-gel mould electrode of existing patent CN200410054034.5, its preparation method and application.But in actual use, this method causes electric capacity unstable due to the change of film thickness.Pulp of lithium ion battery solid content is the highest, and viscosity is big, adopts and is difficult in this way make CNT fully dispersed.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, the always core topic of electrochmical power source research field.Simultaneously need to electrode material modification is improved its electric conductivity, thus improve high rate capability, also to keep its high reversible electrochemical capacity and good cyclical stability, and need with low cost.
Summary of the invention
The technical problem to be solved is to provide the preparation method of a kind of nano carbon electrode material, can prevent electrode material generation agglomeration, had both reduced cost, and had improved 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 nano carbon electrode composite material, gathers including following step:
1) raw material is weighed by following components and mass percentage content: lithium salts 5%～10%, molysite 50%～55% and phosphate 30～40%；Described lithium salts is the combination of lithium carbonate, lithium hydroxide, lithium nitrate and lithium phosphate, and its percentage by weight is respectively the 45% of lithium salts gross weight, 25%, 25% and 5%；Described molysite is ferrous oxalate and ferric phosphate, and its percentage by weight is respectively the 70% and 30% of molysite gross weight；Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, and its percentage by weight is respectively the 50% and 50% of phosphate gross weight；Above-mentioned raw materials is added after dispersant the rotating speed ball milling 10～15h with 500～800r/m in ball mill, prepares precursor, add weight is above-mentioned raw materials weight 1%～the 5% of dispersant；
2) precursor of gained is put into and put in atmosphere protection tube type vacuum stove after the vacuum drying oven of 60-70 DEG C is dried 10～30 hours; then pass to nitrogen or argon gas; 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; it is passed through the methane gas that flow is 350～650sccm again, keeps pressure 1.5～2.0Mpa；Also shut off nitrogen or argon gas, constant temperature 90～120min growth CNT and carbon fiber at a temperature of 600～1000 DEG C, it at least contains 18 carbon atoms, described CNT and the length of carbon fiber and a diameter of 10～20nm, and specific surface area is 100-500m2.g-1；Metal platinum or nickel are fixed on the central authorities in laser deposition pond and at the bottom of pond 10～15cm, then the position of 5～8cm in gained CNT and carbon fiber being positioned over laser deposition pond and bottom sedimentation basin, and it is heated to 300～400 DEG C, make CNT be kept in motion under the magnetic agitation of 0.05～0.1T simultaneously, under conditions of-1～-0.5Mpa, by the pulse laser focusing of laser instrument in platinum or nickel surface, platinum or nickle atom is excited to become atomic beam, CNT surface to surrounding sputtering uniform deposition to flowing, i.e. obtain CNT and carbon fiber loaded Pt or Ni catalyst, described catalyst loadings is 100～200 μ g/cm2, the voltage of laser instrument is 260～280V；
3) by step 2) in obtain product be scattered in organic solvent ethanol, transient state drying means is used 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 fully 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 is carried 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; holding pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere are protected, i.e. prepare nano carbon electrode composite material.
Preferably, step 1) described in dispersant be deionized water, absolute ethyl 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, metal platinum or nickel are thick 0.5mm, the disk of diameter 5mm.
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 gas.
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；Described CNT and the length of carbon fiber and a diameter of 15nm, 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 being 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, holding pressure is normal pressure.
Beneficial effect:
Situ growth CNT the most 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 usage amount, have both reduced cost, and have 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 improve high rate capability, the powder granule prepared has a number of nanochannel, add effective affecting acreage and the passage of lithium ion turnover of electrode, make electrode material have the highest 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 beneficially electrolyte and hold storage, ionic conduction and the three-dimensional hierarchical pore structure of 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.
6. the product of gained will not be contaminated, and influence factor is few, and electric conductivity is more preferably.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described.
Embodiment
1
:
1) by following components and mass percentage content weighing raw material: lithium salts 5g, molysite 50g and phosphate 30g；Described lithium salts is the combination of lithium carbonate, lithium hydroxide, lithium nitrate and lithium phosphate, and its percentage by weight is respectively the 45% of lithium salts gross weight, 25%, 25% and 5%；Described molysite is ferrous oxalate and ferric phosphate, and its percentage by weight is respectively the 70% and 30% of molysite gross weight；Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, and its percentage by weight is respectively the 50% and 50% of 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) precursor of gained is put into and put in atmosphere protection tube type vacuum stove after the vacuum drying oven of 60 DEG C is dried 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; it is passed through the methane gas that flow is 350sccm again, keeps pressure at 1.5Mpa；
3) by step 2) in obtain product be scattered in organic solvent ethanol, transient state drying means is used 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 fully 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 is carried 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, holding pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere are protected, i.e. prepare nano carbon electrode composite material.
Using preparation material as positive pole, then with lithium sheet for electrode, U.S. Celgard2400 is barrier film, as electrolyte, is assembled into button cell with 1.0mol L-1LiPF6/EC+DMC [V (EC): V (DMC)=1:1] in the stainless steel glove box of full argon gas.Carrying out constant current constant voltage charge-discharge test on Land-BTL10 (blue electricity) full-automatic battery controlled testing instrument, discharge-rate is respectively 0.5～3C, and charging/discharging voltage scope is 4.5～5.5V.It is 150mAh g-1 at 1C multiplying power discharge capacity.
Record under the pressure of 20 DEG C and 60atm in the hydrogen adsorption capacity of the electrode material that the method prepares is 10min more than or equal to 0.8(gH2/100g).
Testing surface, metal distance such with CNT and carbon fiber can be uniformly distributed and be firmly combined with by guarantee fund's metal particles, meets more preferably electric conductivity (improving 22.5%).
Embodiment
2
:
1) by following components and mass percentage content weighing raw material: lithium salts 10g, molysite 55g and phosphate 40g；Described lithium salts is the combination of lithium carbonate, lithium hydroxide, lithium nitrate and lithium phosphate, and its percentage by weight is respectively the 45% of lithium salts gross weight, 25%, 25% and 5%；Described molysite is ferrous oxalate and ferric phosphate, and its percentage by weight is respectively the 70% and 30% of molysite gross weight；Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, and its percentage by weight is respectively the 50% and 50% of 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) precursor of gained is put into and put in atmosphere protection tube type vacuum stove after the vacuum drying oven of 70 DEG C is dried 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; it is passed through the methane gas that flow is 650sccm again, keeps pressure at 2Mpa；Also shutting off nitrogen, at a temperature of 1000 DEG C, constant temperature 90min grows CNT and carbon fiber, and it at least contains 18 carbon atoms, described CNT and the length of carbon fiber and a diameter of 20nm, and specific surface area is 250m2.g-1；By thickness 0.5mm, the disk metal platinum of diameter 5mm is fixed on the central authorities in laser deposition pond and at 12cm at the bottom of pond, then the position of 7cm in gained CNT and carbon fiber being positioned over laser deposition pond and bottom sedimentation basin, and it is heated to 350 DEG C, make CNT be kept in motion under the magnetic agitation of 0.08T simultaneously, under conditions of-0.7Mpa, by the pulse laser focusing of laser instrument in platinum or nickel surface, pt atom is excited to become atomic beam, CNT surface to surrounding sputtering uniform deposition to flowing, i.e. obtain CNT and carbon fiber loaded Pt catalyst, described catalyst loadings is 150 μ g/cm2, the voltage of laser instrument is 270V；
3) by step 2) in obtain product be scattered in organic solvent ethanol, transient state drying means is used 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 fully 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 is carried 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, holding pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere are protected, i.e. prepare nano carbon electrode composite material.
Using preparation material as positive pole, then with lithium sheet for electrode, U.S. Celgard2400 is barrier film, as electrolyte, is assembled into button cell with 1.0mol L-1LiPF6/EC+DMC [V (EC): V (DMC)=1:1] in the stainless steel glove box of full argon gas.Carrying out constant current constant voltage charge-discharge test on Land-BTL10 (blue electricity) full-automatic battery controlled testing instrument, discharge-rate is respectively 2.5～3.3C, and charging/discharging voltage scope is 5～6V.It is 165mAh g-1 at 1C multiplying power discharge capacity.
Record under the pressure of 20 DEG C and 60atm in the hydrogen adsorption capacity of the electrode material that the method prepares is 10min more than or equal to 0.92(gH2/100g).
Testing surface, metal distance such with CNT and carbon fiber can be uniformly distributed and be firmly combined with by guarantee fund's metal particles, meets more preferably electric conductivity (improving 23%).
Embodiment
3
:
1) by following components and mass percentage content weighing raw material: lithium salts 5g, molysite 50g and phosphate 35g；Described lithium salts is the combination of lithium carbonate, lithium hydroxide, lithium nitrate and lithium phosphate, and its percentage by weight is respectively the 45% of lithium salts gross weight, 25%, 25% and 5%；Described molysite is ferrous oxalate and ferric phosphate, and its percentage by weight is respectively the 70% and 30% of molysite gross weight；Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, and its percentage by weight is respectively the 50% and 50% of 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) precursor of gained is put into and put in atmosphere protection tube type vacuum stove after the vacuum drying oven of 65 DEG C is dried 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; it is passed through the methane gas that flow is 500sccm again, keeps pressure at 1.8Mpa；Also shutting off nitrogen, at a temperature of 800 DEG C, constant temperature 100min grows CNT and carbon fiber, and it at least contains 18 carbon atoms, described CNT and the length of carbon fiber and a diameter of 15nm, and specific surface area is 500m2.g-1；By thickness 0.5mm, the disk metallic nickel of diameter 5mm is fixed on the central authorities in laser deposition pond and at 15cm at the bottom of pond, then the position of 8cm in gained CNT and carbon fiber being positioned over laser deposition pond and bottom sedimentation basin, and it is heated to 400 DEG C, make CNT be kept in motion under the magnetic agitation of 0.1T simultaneously, under conditions of-0.5Mpa, by the pulse laser focusing of laser instrument in platinum or nickel surface, pt atom is excited to become atomic beam, CNT surface to surrounding sputtering uniform deposition to flowing, i.e. obtain CNT and carbon fiber loaded Ni catalyst, described catalyst loadings is 200 μ g/cm2, the voltage of laser instrument is 280V；
3) by step 2) in obtain product be scattered in organic solvent ethanol, transient state drying means is used 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 fully 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 is carried 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, holding pressure is normal pressure; then products therefrom is naturally cooled to room temperature under nitrogen or argon gas atmosphere are protected, i.e. prepare nano carbon electrode composite material.
Using preparation material as positive pole, then with lithium sheet for electrode, U.S. Celgard2400 is barrier film, as electrolyte, is assembled into button cell with 1.0mol L-1LiPF6/EC+DMC [V (EC): V (DMC)=1:1] in the stainless steel glove box of full argon gas.Carrying out constant current constant voltage charge-discharge test on Land-BTL10 (blue electricity) full-automatic battery controlled testing instrument, discharge-rate is respectively 3～3.5C, and charging/discharging voltage scope is 5.5～6.5V.It is 170mAh g-1 at 1C multiplying power discharge capacity.
Record under the pressure of 20 DEG C and 60atm in the hydrogen adsorption capacity of the electrode material that the method prepares is 10min more than or equal to 0.88(gH2/100g).
Testing surface, metal distance such with CNT and carbon fiber can be uniformly distributed and be firmly combined with by guarantee fund's metal particles, meets more preferably electric conductivity (improving 25%).
Step 2 in above-described embodiment) can carry out according to the following step:
The precursor of step 1) gained is put into the vacuum drying oven of 60-70 DEG C is dried after 10～30 hours and puts on the carbon paper in atmosphere protection tube type vacuum stove (this carbon paper be dried at 30～50 DEG C after the hydrochloric acid of 0.1～0.5mol concentration or sulfuric acid soak 5～10 hours 15～20min surface modification treatment), this carbon paper polytetrafluoroethylene (PTFE) is bonded on the porous substrate that aperture is 15～25 μm (such structure can ensure mass-and heat-transfer and waterproof), then pass to nitrogen or argon gas, 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, it is passed through the methane gas that flow is 350～650sccm again, keep pressure 1.5～2.0Mpa；Also shut off nitrogen or argon gas, constant temperature 90～120min growth CNT and carbon fiber at a temperature of 600～1000 DEG C, it at least contains 18 carbon atoms, described CNT and the length of carbon fiber and a diameter of 10～20nm, and specific surface area is 100-500m2.g-1；The mode combining this CNT thus obtained and carbon fiber gaseous oxidation and liquid phase oxidation is purified process；Metal platinum or nickel are fixed on the central authorities in laser deposition pond and at the bottom of pond 10～15cm, then the position of 5～8cm in gained CNT and carbon fiber being positioned over laser deposition pond and bottom sedimentation basin, and it is heated to 300～400 DEG C, make CNT be kept in motion under the magnetic agitation of 0.05～0.1T simultaneously, under conditions of-1～-0.5Mpa, by the pulse laser focusing of laser instrument in platinum or nickel surface, platinum or nickle atom is excited to become atomic beam, CNT surface to surrounding sputtering uniform deposition to flowing, i.e. obtain CNT and carbon fiber loaded Pt or Ni catalyst, described catalyst loadings is 100～200 μ g/cm2, the voltage of laser instrument is 260～280V.
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 possibly also with the technology contents of the disclosure above or are modified as the Equivalent embodiments of equivalent variations.But every without departing from technical solution of the present invention content, any simple modification, equivalent variations and remodeling above example made according to the technical spirit of the present invention, still fall within the protection domain of technical solution of the present invention.
Claims (1)
1. the preparation method of a nano carbon electrode composite material, it is characterised in that include that following step is gathered:
1) weigh raw material by following components and mass percentage content: lithium salts 5%～10%, molysite 50%～55% and phosphate 30～
40%；Described lithium salts is the combination of lithium carbonate, lithium hydroxide, lithium nitrate and lithium phosphate, and its percentage by weight is respectively lithium salts
The 45% of gross weight, 25%, 25% and 5%；Described molysite is ferrous oxalate and ferric phosphate, and its percentage by weight is respectively
The 70% and 30% of molysite gross weight；Described phosphate is ammonium dihydrogen phosphate and ammonium phosphate, and its percentage by weight is respectively phosphoric acid
The 50% and 50% of salt gross weight；Above-mentioned raw materials is added after dispersant the rotating speed ball milling with 500～800r/m in ball mill
10～15h, prepare precursor, add weight is above-mentioned raw materials weight 1%～the 5% of dispersant；
2) by step 1) precursor of gained puts into after being dried 10～30 hours in the vacuum drying oven of 60-70 DEG C and puts into atmosphere protection tube type vacuum
On carbon paper in stove, this carbon paper is at 30～50 DEG C after the hydrochloric acid of 0.1～0.5mol concentration or sulfuric acid soak 5～10 hours
Being dried down the surface modification treatment of 15～20min, this carbon paper polytetrafluoroethylene (PTFE) is bonded in the porous base that aperture is 15～25 μm
On material, such structure can ensure mass-and heat-transfer and waterproof, then pass to nitrogen or argon gas, nitrogen or argon flow amount be 500～
600sccm, is warming up to 500～600 DEG C with the speed of 20～25 DEG C/min, then is passed through the methane that flow is 350～650sccm
Gas, keeps pressure 1.5～2.0Mpa；Also shut off nitrogen or argon gas, constant temperature 90～120min at a temperature of 600～1000 DEG C
Growth CNT and carbon fiber, it at least contains 18 carbon atoms, described CNT and the length of carbon fiber and a diameter of
10～20nm, specific surface area is 100-500m2.g-1；To this CNT thus obtained and carbon fiber gaseous oxidation and liquid
The mode that phase oxidation combines is purified process；Metal platinum or nickel are fixed on laser deposition pond central authorities and distance pond at the bottom of 10～
At 15cm, the position of 5～8cm in then gained CNT and carbon fiber being positioned over laser deposition pond and bottom sedimentation basin,
And be heated to 300～400 DEG C, simultaneously make CNT be kept in motion under the magnetic agitation of 0.05～0.1T ,-1～
Under conditions of-0.5Mpa, by the pulse laser focusing of laser instrument in platinum or nickel surface, platinum or nickle atom is excited to become atomic beam, to
Surrounding sputtering uniform deposition, to the CNT surface of flowing, i.e. obtains CNT and carbon fiber loaded Pt or Ni catalyst,
Described catalyst loadings is 100～200 μ g/cm2, the voltage of laser instrument is 260～280V；
3) by step 2) in the product that obtains be scattered in organic solvent ethanol, use transient state drying means to prepare dispersion powder, and use phenol
This dispersion powder of colloidal sol incipient impregnation of urea formaldehyde-P123 high-molecular copolymer-ethyl orthosilicate is also condensed through abundant, phenolic aldehyde tree
Fat weight content is the 40～50% of colloidal sol gross weight, P123 high-molecular copolymer weight content be colloidal sol gross weight 20～
30%, ethyl orthosilicate weight content is the 30～35% of colloidal sol gross weight；The hot polymerization of phenolic resin is carried out at 100～105 DEG C
20 hours；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, holding pressure is normal pressure, then by products therefrom under nitrogen or argon gas atmosphere are protected from
So it is cooled to room temperature, i.e. prepares nano carbon electrode composite material；
Step 1) described in dispersant be deionized water, absolute ethyl alcohol or acetone；
Step 2) in CNT be the seamless hollow pipe being rolled into by graphite.
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