CN104638275A - Carbon material and production method thereof, electrochemical battery, deoxidation device, and refrigerator adopting the same - Google Patents
Carbon material and production method thereof, electrochemical battery, deoxidation device, and refrigerator adopting the same Download PDFInfo
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides carbon materials capable of conducting large current. The carbon material is characterized in that carbon filters are provided, and comprises column-shaped structures, which are partially replaced by the nitrogen atoms, and formed by overlapping the carbon compound layers having the grapheme skeletons. The grapheme skeletons of the carbon compound layers are inclined at an angle in a range from 5degrees to 80degrees with respect to the axis of the column-shaped structures.
Description
Technical field
Present embodiment relate to material with carbon element and manufacture method thereof, use material with carbon element electrochemical cell and subtract oxygen device and refrigerator.
Background technology
At present, be well known that the material with carbon element with nitrogen-atoms aliquot replacement becomes the oxygen reduction catalyst of fuel cell etc.Wherein, the carbon particle at least partially containing nanoshell structure is well known that, the C catalyst formed with threadiness.Threadiness is conducive to the diffusion of the gas of fuel and the water of generation.But the active site of the C catalyst of existing maintenance fibre-like morphology is few, therefore there is the problem can not introducing sufficient electric current.
Prior art document
Patent documentation
Patent documentation 1: JP 2009-208061 publication
Summary of the invention
The problem that invention will solve
Therefore, be to provide can the material with carbon element of conducting big current in the invention of execution mode.
For solving the means of problem
The feature of the material with carbon element of execution mode is, containing carbon fiber, described carbon fiber has column structure, described column structure is that carbon compound that replaced by nitrogen-atoms by a part for contained carbon atom, that have Graphene skeleton is laminated, the Graphene skeleton face of carbon compound relative to the axis of a cylinder direction of column structure with the angular slope of more than 5 degree less than 80 degree.
Embodiment
Below, with reference to accompanying drawing, execution mode is described as required.The material with carbon element of execution mode is preferably containing carbon fiber, described carbon fiber has the stacked column structure of the carbon compound with Graphene skeleton of the structure that the part that comprises carbon atom has been replaced by nitrogen-atoms, the Graphene skeleton face of carbon compound relative to the axis of a cylinder direction of column structure with the angular slope of more than 5 degree less than 80 degree.
The material with carbon element 10 of present embodiment is as shown in the concept map of Fig. 1, and the material with carbon element of execution mode has the closely stacked columnar structures of carbon compound 11 10.A part for the carbon atom of the Graphene skeleton of carbon compound is replaced by nitrogen-atoms at least partially, or carbon atom and oxygen atoms bond.Symbol 13 ' represents the concept map of the lateral side regions 13 of amplifying columnar structures.The feature in the Graphene skeleton face (hreinafter referred to as Graphene face) of the carbon compound 11 of the lateral side regions 13 ' of columnar structures is to have the Graphene face being distributed in the angular slope between 5 degree ~ 80 degree relative to axis of a cylinder direction 12.Below the symbol in Graphene face is also designated as 11.Graphene face is the line segment of the symbol 11 in the concept map of Fig. 1, according to line segment with relative to the angle of the known Graphene face of the angle of axis of a cylinder relative to axis of a cylinder direction 12.As the parts with columnar structures 10, carbon fiber can be enumerated.
If comprise columnar structures, then in material with carbon element, the material such as oxygen, hydrogen or water easily spreads, and can carry out with the action of high electric current.In general cast carbon fiber, Graphene face walks abreast and symmetrical substantially relative to axis of a cylinder, but the Graphene face 11 of the carbon fiber of execution mode tilts relative to axis of a cylinder.Graphene face relative to axis of a cylinder direction 12 with more than 5 degree 80 degree to have a down dip, there is a large amount of active graphene edge in the end of columnar structures 10, and the contact area each other in Graphene face 11 becomes large, column structure can stably keep.If tilt to be greater than 80 degree, then Graphene contact area diminishes, the unstable and frangibility of column structure.In addition, if tilt to be less than 5 degree, then active graphene edge reduces.Be more preferably more than 10 degree less than 60 degree.
The Graphene face 11 of post side such as can be observed by following method particularly relative to the inclination in axis of a cylinder direction 12.Utilize transmission electron microscope (TEM:Transmission Electron Microscope) to amplify 4,000,000 times, the mode of shining upon the angle that can confirm Graphene face 11 at central part with axis of a cylinder direction 12 is taken.In the TEM image of column structure, never the region of carbon compound is to the surface of the carbon compound of column and then to inner, little by little dark-coloured change weighs, even if therefore the graphene-structured of column most surface is mixed and disorderly, as shown in Figure 10 ~ Figure 12, also can according to deep or light change from photographic images specific go out axis of a cylinder direction 12.In addition, from the image confirming axis of a cylinder direction of more low range, and can compare with the axis of a cylinder direction obtained according to above-mentioned deep or light change, confirm.At this, the layer of the grid of coincidence 10 × 10 pieces on the image taken the amplification concept map of the material with carbon element as Fig. 2, the Graphene face 11 that mensuration overlaps with the intersection point of graticule or distance intersection point is nearest and the angle in axis of a cylinder direction 12.Also, after the photographic images of TEM can being converted as the concept map of Fig. 2, the angle of Graphene face 11 relative to axis of a cylinder direction 12 is measured.To there is from figure upper right in fig. 2 towards lower-left with the axis of a cylinder direction 12 that thick line represents, represent Graphene face 11 with fine rule.And, the Graphene face 11 of the goniometry object of a part is represented in fig. 2 with thick line.The mensuration of angle is carried out at the position that preferably can not identify at the difference measured, Graphene.In addition, as the concept map of Fig. 1, camera site preferably by carbon fiber trisection along its length, in the central authorities in the region of this trisection.At this moment, the central point of each shooting area preferably can taken with the position that straight line connects.In the angle of the Graphene face 11 of each area test relative to axis of a cylinder direction 12, more than at least 5% less than 95%, preferably meet more than 5 degree less than 80 degree, the more preferably scope of more than 10 degree less than 60 degree.If the Graphene face 11 meeting above-mentioned angular range is very few, then Graphene reduce and not preferred.Therefore, the Graphene face 11 more preferably meeting above-mentioned angular range is more than 40%.In addition, if the Graphene face 11 meeting above-mentioned angular range is too much, then the stability of the column structure of carbon fiber likely reduces and not preferred.Therefore, the Graphene face 11 more preferably meeting above-mentioned angular range is less than 90%.
The diameter preferably 30 ~ 500nm of the columnar structures 10 of the material with carbon element of present embodiment.If be less than 30nm, then hinder the diffusion carrying out the material reacted using material with carbon element as catalyst.If be greater than 500nm, then active site diminishes.Be more preferably 100nm ~ 300nm.The length in the axis of a cylinder direction 12 of material with carbon element preferably comprises more than 1 μm less than 10 μm.
From the viewpoint of the increase active site of catalyst, the diffusivity excellence of material, comprise the open-ended situation of the columnar structures 10 of present embodiment, there is the situation of recess preferred end.The recess of columnar structures 10 can be confirmed by TEM image.
In addition, the carbon compound 11 of the columnar structures 10 of preferred implementation has closely overlapping structure.So-called closely overlapping laminated arrangement, columnar structures 11 or carbon fiber are being amplified in the TEM image of 4,000,000 times, the region in Graphene face 11 can confirmed, area shared by Graphene face 11 is more than 50%, to have in Graphene face 11 more than 50% part overlapping with other Graphene face 11.If Graphene is closely overlapping state, then there is constitutionally stable advantage.
The schematic diagram of Fig. 3 represents the example of the metal comprised in the atomic structure of carbon compound 11 and material with carbon element etc.A part of carbon atom of Graphene skeleton 21 is replaced by nitrogen-atoms.In addition, a part of carbon atom of the skeleton of Graphene skeleton 21 and oxygen atom also can bondings.Material with carbon element is sometimes also containing metallic 22, metal ion 23 or phosphorus compound 24 etc.Can also containing the compound of the form with or without displacement in carbon compound 11.
A part for the carbon atom of the Graphene skeleton 21 of carbon compound 11 is replaced by nitrogen-atoms.The displacement typoiogical classification of nitrogen-atoms is quaternary nitrogen, pyridine nitrogen, pyrroles's pyridone nitrogen, nitrogen with oxygen bonding.
Nitrogen-atoms is more than 0.1atom% below 30atom% to the replacement amount preferred nitrogen atom of carbon atom relative to carbon atom.If nitrogen replacement amount is fewer than this lower limit, then catalyst activity is little, not preferably.In addition, if nitrogen replacement amount is larger than this higher limit, then graphene-structured is at random, and resistance increases thus, not preferably.More preferably more than 3atom%, below 20atom%.
A part of carbon atom bonding of the Graphene skeleton 21 of oxygen atom carburet thing 11.If containing oxygen atom in Graphene skeleton 21, the impact of the caused long term deterioration such as after oxygen reduction catalyst manufacture oxygen molecule can be reduced.The speciation of oxygen atom and carbon atom comprises ether type, ketone type, alcohol type, phenolic, carboxylic acid type etc.In addition, oxygen atom is contained in phosphorus compound sometimes, is sometimes also contained in material with carbon element as metal oxide.
The preferred oxygen atom of import volume of oxygen atom is more than 5atom% below 100atom% relative to carbon atom.If the import volume of oxygen atom is fewer than this lower limit, then for oxygen, the variation of catalyst activity increases.In addition, if the import volume of oxygen atom is larger than this higher limit, then resistance increases, and increases simultaneously, easily cause the obstruction of the oxygen diffusion being called overflow phenomena to the compatibility of water.
The material with carbon element of present embodiment also can comprise metallic 22 or its ion 23.In this situation, metal is preferably selected from more than one of iron, cobalt and manganese etc.The size of metallic is such as more than 1nm below 10nm.If containing these metallics or metal ion, during making oxygen reduction catalyst, graphitization is easily carried out, and therefore the durability of oxygen reduction catalyst improves further.In addition, by the interelectric interaction of metal and Graphene, the activity of catalyst improves.The amount of metallic atom is preferably below the 1atom% of carbon atom.If more than 1atom%, then metal ion enters dielectric film and hinders the possibility of electric charge movement to increase.
Also platinum particles can be contained in the material with carbon element of present embodiment.When using platinum particles, the material with carbon element of execution mode becomes the carrier of platinum.It is such as the size of the particle diameter usually used as oxygen reduction catalyst use of more than 1nm below 10nm that the size of platinum particles can use.Because nitrogen-atoms is replaced, therefore make platinum particles reduce, the Graphene simultaneously as the attachment site of platinum particles becomes many, therefore, it is possible to not easily depart from.As long as add the platinum relative to more than material with carbon element 0.1wt%, even if minute quantity just can improve activity.In addition, in material with carbon element, import by prior the oxygen suppressing carbon corrosion, can prevent platinum from departing from from carrier further, the use amount of platinum can be suppressed.
As execution mode material with carbon element contained by phosphorus compound 24, can enumerate in monophosphate (monophosphate), few phosphoric acid (oligophosphate) and polyphosphoric acid (polyphosphate) more than one.Phosphorus compound is contained between the outside or inside of carbon fiber.Preferably utilize the existence of phosphorus compound to catch free radical, the deterioration of material with carbon element can be prevented thus.According to XPS, by being derived from peak that 132.0 ~ 133.0eV of few phosphoric acid, the 132.6 ~ 133.3eV being derived from few phosphoric acid and the pyrophosphate be condensed into by 2 molecule orthophosphoric acid and the electronics of 2p track of 134.0 ~ 134.5eV that is derived from polyphosphate release energy and can knowing the existence of phosphorus compound.
The amount of each atom comprised in material with carbon element can use x-ray photoelectron power spectrum (XPS:X-ray photoelectron spectroscopy) to measure.As XPS device, such as use PHI Inc. Quantum-2000, x-ray source uses monocrystalline light splitting AlK alpha ray, power output 40W, analyzed area is diameter 200 μm, passes through energy: Wide Scan-187.85eV (1.60eV/ step), Narrow Scan-58.70eV (0.125eV/ step), use Ar+ simultaneously, e-as in electrostatic and rifle, with geometry: θ=45 ° (θ: the angle between specimen surface and detector) carries out.In order to prevent charging, conductivity band etc. is adopted to be energized to mensuration sample as required.
Below, the manufacture method of the material with carbon element of present embodiment is described.
For the material with carbon element of execution mode, the carbon fiber with the structure of Graphene face overlap contains metallic, preferably has the operation that metallic is dissolved, an operation part for carbon atom being replaced after operation by nitrogen-atoms.
And, make a part for carbon atom preferably in containing the acid solution of potassium permanganate, be carried out oxidation processes to carbon fiber by the operation that nitrogen-atoms is replaced, after oxidation processes, carry out processing, heating with hydrazine or ammonia.When above-mentioned oxidation processes, metallic dissolves.
Because the carbon fiber with the closely overlapping structure in Graphene face 11 contains metallic, so preferably use metallic as catalyst, supply methane, hydrogen and argon gas etc., make the method for carbon fiber by CVD (Chemical Vapor Deposition: chemical vapour deposition (CVD)) legal system.As metallic, preferred iron or cobalt, nickel, wherein, more preferably iron.As the diameter of metallic, preferred 30nm ~ 500nm.Can according to the diameter of the diameter control carbon fiber of metallic.If metallic is too small, then produce carbon nano-tube, if metallic is excessive, be difficult to the control carrying out particle diameter, not preferably.
As with the operation of a nitrogen-atoms displacement carbon atom part, preferably with potassium permanganate etc., the carbon atom of carbon fiber is oxidized, then processes with hydrazine or ammonia.In acid solution, preferably add potassium permanganate carry out to the oxidation of carbon atom with potassium permanganate etc.The concentration of acid be applicable to, processing time and treatment temperature change according to each condition.An example as the condition be applicable to is the mixture of 1 mole, sulfuric acid, 0.02 mole, nitric acid, 0.05 mole, potassium permanganate, from 0 DEG C, slowly promote the oxidation processes that temperature carries out carbon fiber.Now, metallic also dissolves.Preferably carry out the process with hydrazine or ammonia after with potassium permanganate process.Can enumerate with the process of hydrazine or ammonia: in the gas phase or on oxides coating or spraying hydrazine or ammonia, more than 70 DEG C, less than 150 DEG C (about 80 DEG C) heat the process of about 1 hour or in the aqueous dispersions of oxide, add hydrazine or ammonia and heat etc.In addition, also can by these treatment combinations.In addition, preferably hydrazine or the ammonia high temperature at 400 DEG C ~ 1100 DEG C is processed.Preferred process temperature is more than 700 DEG C less than 900 DEG C.More preferably in containing the gas of ammonia, high-temperature process is carried out.When in the feed containing very many oxygen atoms, if containing hydrogen, then oxygen amount can be controlled in right amount, thus preferably.After this operation, carbon fiber cuts off the bonding between carbon atom by oxidation processes, produces recess in the end of cut-off carbon fiber.
In addition, when the high-temperature process of above-mentioned 400 DEG C ~ 1100 DEG C, also polymer with nitrogen, nitrogen containing metal compound or phosphorus compound can be contained.As long as carry out high-temperature process to the mixture of these compounds and hydrazine handled thing.Metal contained in these compounds exists as metal ion in material with carbon element.Can enumerate such as polymer with nitrogen: melamine resin, guanamine resin, benzoguanamine resin, carbamide resin, polyacrylonitrile, polyaniline, polyphenyl diamines etc.As nitrogen containing metal compound, the compound of preferred iron or cobalt, can enumerate such as: FePC, Cobalt Phthalocyanine, PORPHYRIN IRON, Cobalt Porphyrin etc.Also mixed-metal compounds in thing can be sintered.As metallic compound, such as, there are ferric sulfate, cobaltous sulfate, iron chloride, cobalt chloride etc.As phosphorus compound, can enumerate: triphenylphosphine, phosphazene derivative, phosphoric acid, polyphosphoric acid etc.
When nano platinum particle is imported material with carbon element, by dispersed carbon material in the aqueous solution that makes chloroplatinic acid, with reducing agent reduction platinum ions such as sodium borohydrides, generate nano platinum particle and carry out.
Preferably the material with carbon element of execution mode is used for electrochemical cell.Fig. 4 is the concept map of the cross section structure of the electrochemical cell 30 representing present embodiment.31 is positive pole, and 33 is negative pole, and 32 is electrolyte, is clamped by positive pole 31 and negative pole 33.31 are connected with external circuit 34 with 33.Preferably by making positive pole 31 or the material with carbon element as high activated catalyst of negative pole 33 containing execution mode, improve the performance of electrochemical cell.
Preferably the electrochemical cell of present embodiment is used for fuel cell.By this material with carbon element being used for oxygen reduction catalyst or the carrier of positive pole, high-power fuel cell can be provided.
Preferably the electrochemical cell of present embodiment is used for the lithium rechargeable battery that negative pole contains this material with carbon element and silicon particle.Silicon particle enters lithium ion and forms jumbo secondary cell, but cycle characteristics is poor.This material with carbon element in nitrogen battery with replaced Graphene can stably keep silicon particle, significantly can improve cycle characteristics.As silicon particle, the silicon nano of preferred diameter 2nm ~ 300nm.The weight rate of this material with carbon element in the total of this material with carbon element and silicon particle is preferably 1% ~ 50%.More preferably 3% ~ 40%.Negative pole can also contain conductive auxiliary agent.Conductive auxiliary agent is by the powder that forms of at least one conductive material being selected from carbon, copper, tin, zinc, nickel, silver.
The execution mode possessing the electrochemical cell 30 of execution mode can be enumerated and subtract oxygen device.Fig. 5 is the concept map subtracting oxygen device 40 of the electrochemical cell 30 possessing execution mode.Subtract oxygen device 40 also have electrochemical cell 30 and with electrochemical cell 30 separate subtract oxygen container 41.Positive pole 31 side of electrochemical cell 30 is provided with positive pole zone 42, negative pole 33 side is provided with anode chamber 43, by the cell reaction of the water of the side of the positive electrode of electrochemical cell and the oxygen reduction reaction of negative side, anode chamber 43 can be made to become and subtract oxygen condition.Positive pole zone 42 also can to atmosphere opening.Be explained, the formation subtracting oxygen device 40 of Fig. 5 only represents basic formation, except illustrated formation, can also add the door of taking-up and the function etc. for high-efficiency operation.By adopting the electrode possessing highly active catalyst in the electrode subtracting oxygen device 40, can be formed efficiently and subtracting oxygen condition.Oxygen condition good material is subtracted when preferably putting into preservation in advance in anode chamber 43.
As the execution mode subtracting oxygen device possessing execution mode, refrigerator can be enumerated.Fig. 6 is the concept map of the refrigerator with the refrigerating chamber 51 subtracting oxygen device possessing execution mode.As refrigerating chamber 51, preference is as thin dish room.Dredge dish and fruit sometimes by being formed as subtracting oxygen condition and not easily corrupt.The electrochemical cell of execution mode also can enumerate the form etc. that the oxygen concentration for cell culture apparatus regulates except refrigerator.
Below, the present invention is specifically described by embodiment.
(embodiment 1)
Using the iron granules of diameter 100 ~ 400nm as catalyst, under methane, hydrogen, argon gas stream, make by hot CVD the carbon nano-fiber that diameter is 100 ~ 400nm.Then, carbon nano-fiber reaction in the mixed solvent of 1 mole, sulfuric acid with 0.15 mole, nitric acid, under 0.04 mole, potassium permanganate exists, oxidation is made.By the oxide of gained in hydrazine heated in water solution, filter.By the powder of gained under argon gas stream, 800 DEG C of heating, obtain material with carbon element.In the XPS of material with carbon element measures, observe relative to carbon number, nitrogen-atoms is 4%, and oxygen atom is 3%, and manganese atom is 0.05%.Fig. 7 represents the photo of the scanning electron microscope (SEM) of the material with carbon element of gained.Sometimes see column structure and see recess in the end of column structure.In addition, Fig. 8 and Fig. 9 represents the photo of the transmission electron microscope (TEM) of the material with carbon element of gained.Observe the form that column structure and column structure become coiled type.
Figure 10 ~ Figure 12 represents the powerful TEM photo of column structure thing 10.Observe Graphene face 11 known, the Graphene mask of post side 13 has the Graphene face being distributed in the inclination between 5 degree ~ 80 degree relative to axis of a cylinder direction 12.For the ease of understanding, in TEM photo, demonstrate white boost line.
The material with carbon element of gained is dispersed in after in ethanol/water, coats on rotational circle plate-like glass-carbon electrode, use the device of Figure 13 to measure oxygen reduction activity.The device of Figure 13 is the device 60 for studying oxygen reduction activity.The device of Figure 13 is made up of flask 61, sulfuric acid solution 62, oxygen introduction part 63, rotational circle plate-like glass-carbon electrode 64, oxygen reduction catalyst 65, carbon polarity 66, silver/silver chloride electrode 67, motor 68, potentiostat 69, measures the catalyst activity of the electrode of embodiment with this device in oxygen.The curve chart of Figure 14 is the curve chart of the result gathering embodiment and comparative example.As Figure 14 71 experiment curv shown in, in the motor speed of 900rpm, be 0.07mg and under oxygen at catalytic amount, when current potential is 0V (relative to silver/silver chloride electrode), in the guiding to negative potential side, observe the reduction current of 0.26mA, be high activity.72 of Figure 14 is the experiment curv be replaced into by oxygen 63 in the nitrogen of nitrogen.
(comparative example 1)
Use graphite to replace carbon nano-fiber as raw material, in addition, operate similarly to Example 1 and make material with carbon element.Figure 15 represents the photo of the scanning electron microscope (SEM) of the material with carbon element of gained.For the aggregate of plate-like structure.Operate similarly to Example 1 and measure the oxygen reduction activity of the material with carbon element of gained.As shown in the experiment curv of 73 in Figure 14, in the motor speed of 900rpm, be 0.07mg and under oxygen at catalytic amount, when current potential is 0V (for silver/silver chloride electrode), the reduction current of 0.1mA is only observed in the guiding of negative potential side, low with embodiment 1 phase specific activity.Oxygen 63 is being replaced into the experiment curv in the nitrogen of nitrogen by 74 of Figure 14.
(comparative example 2)
As raw material, use Graphene face and axis of a cylinder direction almost parallel, diameter is the carbon nano-fiber (multilayer carbon nanotube) (Graphene that Graphene face is less than 5 ° relative to the angle of axis of a cylinder is more than 80% of photographic images face) of 50 ~ 70nm, in addition, operate similarly to Example 1 and make material with carbon element.Iron Pt microparticles as catalyst, is made by the thermal cvd of acetylene by the carbon nano-fiber of this comparative example.The oxygen reduction activity of the material with carbon element of gained is low with embodiment 1 phase specific activity, is less than 1/2.
(embodiment 2)
Except making except potassium permanganate is 1.5 times of embodiment 1, operates similarly to Example 1 and make material with carbon element.Observe relative to carbon number in the XPS of material with carbon element measures, nitrogen-atoms is 5%, and oxygen atom is 4%, and manganese atom is 0.05%.The hydrogen reduction electric current of the material with carbon element of gained is about 1.5 times of embodiment 1, high activity more.
(embodiment 3)
Sodium borohydride is made the Pt microparticles of the carbon material supported 0.2wt% diameter 1 ~ 3nm obtained in embodiment 1 in chloroplatinic acid aqueous solution as reducing agent.The hydrogen reduction of the catalyst of gained starts current potential and embodiment 1 is in a ratio of positive side, and the magnitude of current is also than embodiment more than 1, is more high activity.In addition, even if after 1.0V ~ 1.5V current potential repeatable operation 500 times, reducing about about 10% of initial current value, is stable.
(comparative example 3)
Except the material with carbon element obtained except using comparative example 1, operating similarly to Example 3, making platinum supported catalyst.Oxygen reduction activity in the same manner as in Example 3, but 1.0V ~ 1.5V current potential repeatedly 500 times time, be reduced to about half from initial current value.
(embodiment 4)
Anode catalyst uses the material with carbon element obtained in embodiment 1 to make cell of fuel cell.Form the oxygen-reducing catalyst layer being mixed with oxygen reduction catalyst, carbon fiber, perfluorinated sulfonic acid ion exchange membrane on the gas diffusion.The load capacity of oxygen reduction catalyst is set as 5mg/cm
2.In the hydro-oxidation catalyst of negative side, use TEC10E30E (Tanaka's noble metal Inc.), dielectric film uses NRE211CS (E.I.Du Pont Company's system).The platinum amount of negative side is 0.05mg/cm
2.Positive pole and negative pole is integrated by thermo-compressed with dielectric film.Make it again to contact the carbon paper making fuel cell unit as gas diffusion layers.Negative side supply humidity to this cell of fuel cell is the hydrogen of 100%RH, is the air of 100%RH to side of the positive electrode supply humidity.Then, in electronics load device, electrochemical reaction is produced.The cell of fuel cell obtained is high-output power, and it is also good to start the cycle characteristics stopped.
(comparative example 4)
Except using the material with carbon element of gained in comparative example 1, operating similarly to Example 3, making cell of fuel cell.The cell of fuel cell of gained is compared with embodiment 3, and power output is less.
(embodiment 5)
In cathode catalyst, use the material with carbon element obtained in embodiment 2 to make subtract oxygen unit.Form the oxygen-reducing catalyst layer being mixed with oxygen reduction catalyst, carbon fiber, perfluorinated sulfonic acid ion exchange membrane on the gas diffusion.The load capacity of oxygen reduction catalyst is 5mg/cm
2.Positive pole uses indium oxide hydrolyst, and load capacity is 1mg/cm
2.Dielectric film uses NRE211CS (E.I.Du Pont Company's system).By negative pole and positive pole integrated with dielectric film by thermo-compressed.Contact with the carbon paper as gas diffusion layers again and make and subtract oxygen unit.To the side of the positive electrode feed fluid water that this subtracts oxygen unit, the airtight spatial joins of negative side and 10L, with 0.1A/cm
2current density operate, make the oxygen concentration in airtight space be reduced to 15%.Thereafter, import extraneous gas and recover oxygen concentration.The operation cycle characteristic subtracting oxygen unit obtained is also good.
(comparative example 5)
Except the material with carbon element obtained in use comparative example 1, operate similarly to Example 4, make and subtract oxygen unit.What obtain subtracts oxygen unit with 0.1A/cm
2current density running time, need high voltage, fast more than 2 times of degradation speed.
(embodiment 6)
Negative pole uses the material with carbon element that obtains of embodiment 1 and makes Dehumidifying element.Form the oxygen-reducing catalyst layer being mixed with oxygen reduction catalyst, carbon fiber, perfluorinated sulfonic acid ion exchange membrane on the gas diffusion.The load capacity of oxygen reduction catalyst is 5mg/cm
2.Positive pole uses indium oxide, and dielectric film uses NRE211CS (E.I.Du Pont Company's system).By negative pole and positive pole integrated with dielectric film by thermo-compressed.Contact with the carbon paper as gas diffusion layers again, make Dehumidifying element.The spatial joins of the side of the positive electrode of this Dehumidifying element and the airtight of 10L, with 0.02A/cm
2current density operate, make the relative humidity in airtight space be reduced to 30%.Thereafter, the air importing relative humidity 80% recovers relative humidity.The operation cycle characteristic of the Dehumidifying element obtained is also good.
(embodiment 7)
Negative pole uses in embodiment 1 material with carbon element that obtains and makes lithium rechargeable battery.
Make tetraethoxysilane 20g, ethanol 50g is in ice bath and mix in beaker.Then, in this solution, by the material with carbon element 5g obtained in the Si particle 5g of average grain diameter 60nm and embodiment 1 with 5% ammoniacal liquor 120g mix.Be uniformly mixed 3 hours in the oil bath of 80 DEG C after, stir and be cooled to room temperature, obtain coating solution.
On collector body Copper Foil, with scraper plate blade applicator with the above-mentioned coating solution of the condition in 50 μm, gap coating pasty state, in an atmosphere 150 DEG C of dryings 1 hour.After drying, regulate thickness with roll squeezer, be formed as thickness 15 μm.On this film, utilize sputtering method to form the carbon film of thickness 1 μm as conductive layer again, obtain lithium ion secondary battery cathode.
Above-mentioned negative pole, LiPON solid electrolyte and metal Li paper tinsel reference electrode is used to form lithium rechargeable battery.Measure the discharge capacity after the charging of initial discharge capacity and 50 circulations, electric discharge, undertaken by the sustainment rate calculating discharge capacity.Design load for benchmark, is set as 1200mAh/g with effective active material Si by discharge capacity.First, under 25 DEG C of environment, charge under constant current and constant voltage condition, until current value be 0.2C, magnitude of voltage is 0.02V, when current value is reduced to 0.05C, stops charging.Then, be discharge under the condition of 0.2C, until become relative to the voltage of metal Li at current value
1.5V, measures the initial discharge capacity of 0.2C.Be explained, so-called 1C refers to the current value that can be full of electricity in 1 hour.In addition, charging and discharging all carries out under the environment of 25 DEG C.Then, with the above-mentioned discharge and recharge that the charge/discharge rates of 0.2C circulates for 50 times repeatedly.Discharge capacity when obtaining 50 discharge and recharges repeatedly with percentage is relative to the ratio of the initial discharge capacity of 0.2C.Capacity dimension holdup is more than 95%, and cycle characteristics is excellent.
(comparative example 6)
Except the material with carbon element obtained in use comparative example 2, operate similarly to Example 7, make lithium rechargeable battery.The capacity dimension holdup of the lithium rechargeable battery obtained is less than 50%, and cycle characteristics is poor.
Describe several execution mode of the present invention, but these execution modes are pointed out as an example, do not mean that restriction scope of invention.These new execution modes can be implemented by other various mode, can carry out various omission, displacement, change without departing from the spirit and scope of the invention.These execution modes and distortion thereof are contained in scope of invention and aim, and are contained in the scope of invention described in claims and equivalence thereof.
Accompanying drawing explanation
Fig. 1 is the concept map of the material with carbon element of execution mode;
Fig. 2 is the amplification concept map of the material with carbon element of execution mode;
Fig. 3 is the schematic diagram of the atomic structure of the material with carbon element comprising execution mode;
Fig. 4 is the concept map employing the electrochemical cell of the material with carbon element of execution mode at negative or positive electrode;
Fig. 5 is the concept map subtracting oxygen device of execution mode;
Fig. 6 is the concept map of the refrigerator of execution mode;
Fig. 7 is scanning electron microscope (SEM) photo of the material with carbon element of embodiment 1;
Fig. 8 is transmission electron microscope (TEM) photo of the material with carbon element of embodiment 1;
Fig. 9 is transmission electron microscope (TEM) photo at other position of material with carbon element of embodiment 1;
Figure 10 is transmission electron microscope (TEM) the high magnification photo of the material with carbon element of embodiment 1;
Figure 11 is transmission electron microscope (TEM) the high magnification photo at other position of material with carbon element of embodiment 1;
Figure 12 is transmission electron microscope (TEM) the high magnification photo at the other position of material with carbon element of embodiment 1;
Figure 13 is the schematic diagram of the device of oxygen reduction activity for checking material with carbon element;
Figure 14 is the experiment curv of the oxygen reduction activity of the material with carbon element of embodiment 1 and comparative example 1;
Figure 15 is scanning electron microscope (SEM) photo of the material with carbon element of comparative example 1.
Symbol description
10: columnar structures, 11: Graphene face, 12: axis of a cylinder direction, 13: column face, 21: single-layer graphene, 22: phosphorus compound, 23: metallic or metal ion, 30: electrochemical cell, 31: positive pole, 32: electrolyte, 33: negative pole, 34: external circuit, 40: subtract oxygen device, 41: subtract oxygen container, 42: positive pole zone, 43: anode chamber, 50: refrigerator, 51: refrigerating chamber (vegetable compartment), 60: for checking the device of oxygen reduction activity, 61: flask, 62: sulfuric acid solution, 63: oxygen, 64: rotational circle plate-like glass-carbon electrode, 65: oxygen reduction catalyst, 66: carbon polarity, 67: silver/silver chloride electrode, 68: motor, 69: potentiostat, 71: the experiment curv in the oxygen of the material with carbon element of embodiment 1, 72: the experiment curv in the nitrogen of the material with carbon element of embodiment 1, 73: the experiment curv in the oxygen of the material with carbon element of comparative example 1, 74: the experiment curv in the nitrogen of the material with carbon element of comparative example 1
Claims (15)
1. material with carbon element, is characterized in that,
Containing columnar structures, described columnar structures is that carbon compound that replaced by nitrogen-atoms by a part for contained carbon atom, that have Graphene skeleton is laminated, the Graphene skeleton face of described carbon compound relative to the axis of a cylinder direction of column structure with the angular slope of more than 5 degree less than 80 degree.
2. material with carbon element as claimed in claim 1, is characterized in that,
The Graphene skeleton face of described carbon compound relative to the axis of a cylinder direction of columnar structures with the angular slope of more than 10 degree less than 60 degree.
3. material with carbon element as claimed in claim 1, is characterized in that,
Described columnar structures has the hollow structure of end with depression.
4. material with carbon element as claimed in claim 1, is characterized in that,
The Graphene skeleton face of described carbon compound is less than more than 5% 90% in described carbon compound relative to the axis of a cylinder direction of columnar structures with the compound of the angular slope of more than 5 degree less than 80 degree.
5. material with carbon element as claimed in claim 1, is characterized in that,
The diameter of columnar structures is 30nm to 500nm.
6. material with carbon element as claimed in claim 1, is characterized in that,
A part of carbon atom of described Graphene skeleton is bonded with oxygen atom.
7. the material with carbon element according to any one of claim 1 ~ 6, is characterized in that, also contains:
More than one metallic in chosen from Fe, cobalt and manganese,
More than one metal ion in chosen from Fe, cobalt and manganese,
Be selected from monophosphate, few phosphoric acid and polyphosphoric acid more than one phosphorus compound or
In platinum particles at least any one.
8. the manufacture method of material with carbon element, is characterized in that, has:
The carbon fiber with the overlapping structure in Graphene face contains metallic, makes the operation that described metallic dissolves; And
A part for carbon atom is replaced into the operation of nitrogen-atoms after described operation.
9. the manufacture method of material with carbon element, is characterized in that, has:
The carbon fiber with the overlapping structure in Graphene face contains metallic, makes the operation that described metallic dissolves;
By the operation of the above-mentioned carbon fiber of solution-treated containing potassium permanganate; And
After the process of above-mentioned carbon fiber, above-mentioned use contains thing hydrazine or the ammonia solution process of the solution-treated of potassium permanganate, the operation of less than 900 heat treated more than 700 DEG C.
10. the manufacture method of material with carbon element as claimed in claim 8 or 9, is characterized in that,
The described operation a part of carbon atom being replaced into nitrogen-atoms comprises: process described carbon fiber in the acid solution comprising potassium permanganate,
After the treatment, carry out processing and heating with hydrazine or ammonia solution.
11. electrochemical cells, is characterized in that, possess:
Positive pole,
Negative pole and
By the electrolyte that described positive pole and described negative pole clamp,
Described positive pole or described negative pole comprise material with carbon element, described material with carbon element is the columnar structures that carbon compound that replaced by nitrogen-atoms by a part for contained carbon atom, that have Graphene skeleton is laminated, the Graphene skeleton face of described carbon compound relative to the axis of a cylinder direction of column structure with the angular slope of more than 5 degree less than 80 degree.
12. electrochemical cells as claimed in claim 11, is characterized in that,
Described electrochemical cell is used for cell of fuel cell, subtracts oxygen unit, Dehumidifying element or water electrolysis unit.
13. electrochemical cells as claimed in claim 11, is characterized in that,
Described negative pole bag silicon-containing particle, described electrochemical cell is used for lithium secondary battery.
14. subtract oxygen device, it is characterized in that possessing:
Positive pole,
Negative pole and
By the electrolyte that described positive pole and described negative pole clamp,
Also have and subtract oxygen container, this subtracts oxygen container and is separated by the electrochemical cell comprising material with carbon element in described negative or positive electrode, described material with carbon element is the columnar structures that carbon compound that replaced by nitrogen-atoms by a part for contained carbon atom, that have black alkene skeleton is laminated, the Graphene skeleton face of described carbon compound relative to the axis of a cylinder direction of column structure with the angular slope of more than 5 degree less than 80 degree.
15. refrigerators, is characterized in that, have and subtract oxygen device, described in subtract oxygen device and possess:
Positive pole,
Negative pole and
By the electrolyte that described positive pole and described negative pole clamp,
Also have and subtract oxygen container, the described oxygen container that subtracts is separated by the electrochemical cell comprising material with carbon element in described negative or positive electrode, described material with carbon element is the columnar structures that carbon compound that replaced by nitrogen-atoms by a part for contained carbon atom, that have Graphene skeleton is laminated, the Graphene skeleton face of described carbon compound relative to the axis of a cylinder direction of column structure with the angular slope of more than 5 degree less than 80 degree.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-232600 | 2013-11-08 | ||
| JP2013232600A JP2014114205A (en) | 2012-11-14 | 2013-11-08 | Carbon material, method for producing the same, and electrochemical cell, oxygen reduction device and refrigerator using the same |
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| US20090075077A1 (en) * | 2002-10-17 | 2009-03-19 | Nexen Nano Tech Co., Ltd. | Ultra-fine fibrous carbon and preparation method thereof |
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