CN103855365A - Nitrogen-doped porous carbon material for lithium-air battery positive electrode - Google Patents
Nitrogen-doped porous carbon material for lithium-air battery positive electrode Download PDFInfo
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- CN103855365A CN103855365A CN201210496062.7A CN201210496062A CN103855365A CN 103855365 A CN103855365 A CN 103855365A CN 201210496062 A CN201210496062 A CN 201210496062A CN 103855365 A CN103855365 A CN 103855365A
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/861—Porous electrodes with a gradient in the porosity
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
Abstract
The present invention relates to a nitrogen-doped porous carbon material for a lithium-air battery positive electrode. The nitrogen-doped porous carbon material is characterized in that the nitrogen-doped porous carbon material has an interconnected graded pore structure, N is uniformly doped in the C skeleton, N accounts for 0.2-15% of the carbon material atomic ratio, the graded pores comprise mass transfer pores and deposition holes, the deposition holes account for 40-95% of the total pore volume, and the mass transfer pores account for 4-55% of the total pore volume. According to the present invention, with application of the carbon material as the lithium-air battery electrode material, the space utilization rate of the carbon material during the charge-discharge process can be increased at a maximum, and the energy density and the power density of the lithium-air battery can be effectively increased; and the preparation process is simple, the material source is wide, the pore structure of the graded pore carbon material can be regulated, the regulation manner is diverse, and the nitrogen doping manner is easily achieved.
Description
Technical field
The invention belongs to energy-storage battery field, be specifically related to a kind of material with carbon element, its material with carbon element doping nitrogen, and there is grading-hole distribution, and be applied to lithium-air battery positive pole, there is high energy density and power density.
Background technology
The develop rapidly of electric motor car and mobile electronic device is in the urgent need to developing the more battery of high-energy-density.Though the laboratory specific energy of lithium ion battery has reached 250Wh/kg at present, but the restriction that further improved by positive electrode specific capacity, its specific energy is difficult to improve a lot again, and will aggravate safety problem by improving charging voltage with the approach that increases specific energy, thereby it is imperative to develop new electrochemical energy storage system.In new energy storage system, lithium-air battery is a kind of taking lithium metal as negative pole, and air electrode is anodal secondary cell.Have minimum theoretical voltage as the lithium metal of negative material, its theoretical specific capacity is up to 3,862mAh/g, and can directly from air, obtain as the oxygen of positive active material, and therefore, lithium-air battery has high specific capacity and specific energy.Taking lithium as standard, its theoretical specific energy density can reach 11,140Wh/Kg, has application prospect in civilian and military domain.
At present, lithium-air battery mainly adopts various material with carbon elements as positive electrode, by sneaking into PTFE, and PVDF, the binding agents such as Nafion are prepared air electrode.As shown in Figure 1, be lithium-air battery positive discharge course of reaction simulation drawing.Exoelectrical reaction is carried out on the solid-liquid two-phase interface building between liquid electrolyte solution and material with carbon element, and carbon material surface generates the insoluble product-oxidate for lithium of solid, and along with reaction is carried out, solid product accumulation is stopped up inner duct and then caused discharge off.
As electrochemical reaction occur place, material with carbon element pore structure physical parameter as: specific area, pore volume, pore-size distribution are to battery performance, and especially charge/discharge capacity has important impact.The capacity that the researchs such as Tran show electrode is determined by the amount that can not affect oxidate for lithium in the large scale duct of mass transfer.Material with carbon element micropore canals and part mesopore duct can be discharged the oxidate for lithium obstruction that initial period forms, and the surface in this part hole cannot, again by air and electrolyte, therefore no longer participate in electrochemical reaction, cause discharge off.But the material with carbon element being made up of large hole dimension is completely in discharge process, due to oxidate for lithium poorly conductive, the ulking thickness of discharging product on hole wall is limited, and the core of macropore is not used, and can not give full play to the space that utilizes in hole.Therefore how constructing the material with carbon element of appropriate bore structure, make it be beneficial to electrolyte and the transmission of air in loose structure, thereby accelerate electrode reaction speed and increase effective utilization in hole, is a current difficult problem urgently to be resolved hurrily.
In addition, the material with carbon element of nitrogen doping has shown excellent hydrogen reduction activity in fuel cell, can partly substitute precious metals pt/C catalyst.Studies show that doping nitrogen-atoms has changed microstructure and the surface electronic state of nano-carbon material, by N-O or C-O " two locations (dual site) absorption ", can weaken the O-O key in oxygen molecule, be beneficial to generation reduction reaction.
The carbon nano-tube of at present relevant nitrogen doping, the application of the grapheme material of nitrogen doping in lithium-air battery have a small amount of report, result shows that nitrogen doping can cause carbon edge defect, effectively increasing this part active sites exposes, to promote oxygen reduction reaction, effectively improve discharge capacity and the discharge voltage of lithium-air battery.But above-mentioned material is due to its preparation method complexity, and cost is higher, and requirement for experiment condition is higher, is unfavorable for large-scale commercial Application and preparation, still can not meet the requirement of lithium-air battery to material.
Summary of the invention
The object of the present invention is to provide a kind of lithium-air battery electrode material with carbon element and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is as follows,
The porous carbon materials of nitrogen doping for lithium-air battery positive pole, the porous carbon materials of described nitrogen doping has the hierarchical porous structure of mutual perforation, N is doped in C skeleton equably, wherein N accounts for material with carbon element atomic ratio 0.2-15%, grading-hole comprises mass transfer hole and deposition hole, 40 ~ 95% of deposition Zhan Zong hole, hole pore volume, 4 ~ 55% of Zhan Zong hole, mass transfer hole pore volume, all the other are less than the hole of 5nm for aperture, deposition aperture, hole is 5 ~ 90nm, aperture, mass transfer hole is 0.1 ~ 6um, between mass transfer hole, mutual spacing is 0.1 ~ 8um, mass transfer hole is interconnected by deposition hole, the total pore volume of material with carbon element is 0.5 ~ 5cm
3/ g.
Described material with carbon element adopts sol-gal process to be prepared from conjunction with foaming in conjunction with activation method or sol-gal process.
Preferred sols gel method is in conjunction with activation method.
Concrete preparation method is as follows:
A sol-gal process is in conjunction with activation method
Described sol-gal process is included in catalytic activation in carbonisation in conjunction with activation method, or the material with carbon element that sol-gal process is made carries out rear activation, and a kind of in the two or two kinds are combined with.
NH in preferred sols gel method carbonisation in catalytic activation and rear activation
3heat treatment activation method.
Described sol-gal process catalytic activation in carbonisation is prepared from according to the following procedure, resorcinol is scattered in solvent, then add slaine or metal hydroxides and continue to dissolve and disperse, then drip formalin, be uniformly mixed until react formation gel at 30 ~ 80 DEG C; Vacuumize at 60～100 DEG C of gels is processed for aging 3 ~ 10 days, after taking out, pulverized and grind, obtain pressed powder; Through high temperature NH
3under atmosphere, after carbonization, remove slaine or metal hydroxides with acid or alkali, after filtration, dry, obtain porous carbon materials, wherein NH
3charge flow rate is controlled at 2 ~ 100ml/min.
Described slaine or metal hydroxides are one or two or more kinds slaine or the metal hydroxides containing Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Nb, Y, Rh, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W, Sn, La and V; Slaine be nitrate, carbonate, sulfate, acetate, halide, dinitroso diamine salts, the acetylacetonate of metal or encircle greatly complex compound and porphyrin compound, phthalein mountain valley with clumps of trees and bamboo compound in one or two or more kinds.Preferably Fe, Co, Ni, Cu, Mo, Mn, the nitrate of Mo, acetate.
The material with carbon element that described sol-gal process makes carries out rear activation, comprises that following one or more methods are in conjunction with being prepared from:
(1) physical activation method: resorcinol is scattered in solvent, then drips formalin, be uniformly mixed at 30 ~ 80 DEG C until react and form gel; Vacuumize at 60～100 DEG C of gels is processed for aging 3 ~ 10 days, after taking out, pulverized and grind, obtain pressed powder; Through high temperature NH
3under atmosphere, after carbonization, pass into steam, CO
2, and can produce in the compound of one of above-mentioned two kinds of gases one or more activate; Activation temperature is controlled at 400 ~ 1300 DEG C, and soak time is controlled at 10min ~ 5h, NH
3, steam or CO
2charge flow rate is controlled at 2 ~ 100ml/min;
(2) NH
3heat treatment activation method: resorcinol is scattered in solvent, then drips formalin, be uniformly mixed at 30 ~ 80 DEG C until react and form gel; Vacuumize at 60～100 DEG C of gels is processed for aging 3 ~ 10 days, after taking out, pulverized and grind, obtain pressed powder; Through high temperature N
2or after Ar carbonization, the material with carbon element obtaining is at NH
3under atmosphere, heat-treat activation.Heat treatment temperature is controlled at 400 ~ 1300 DEG C, and the time is controlled at 10min ~ 6h, N
2or Ar, NH
3charge flow rate is controlled at 2 ~ 100ml/min;
(3) chemical activation method: resorcinol is scattered in solvent, then drips formalin, be uniformly mixed at 30 ~ 80 DEG C until react and form gel; Vacuumize at 60～100 DEG C of gels is processed for aging 3 ~ 10 days, after taking out, pulverized and grind, obtain pressed powder; Through high temperature NH
3under atmosphere after carbonization, material with carbon element ground and mixed prepared by activating reagent and sol-gal process is even, and activating reagent is 10 ~ 300% of material with carbon element quality, and activation temperature is controlled at 300 ~ 900 DEG C, and soak time is controlled at 10min ~ 5h; After activation, material with carbon element washs and is dried with deionized water; Wherein NH
3charge flow rate is controlled at 2 ~ 100ml/min; Described activating reagent comprises bases activating reagent KOH, acids activating reagent H
3pO
4, salt activating reagent is ZnCl
2, K
2cO
3or Na
2cO
3.
B sol-gal process is in conjunction with foaming
Described material with carbon element adopts sol-gal process to be prepared from according to the following procedure in conjunction with foaming: resorcinol and blowing agent are scattered in solvent, then drip formalin, be uniformly mixed until react formation gel at 30 ~ 80 DEG C; Vacuumize at 60～100 DEG C of gels is processed for aging 3 ~ 10 days, after taking out, pulverized and grind, obtain pressed powder; Through high temperature NH
3under atmosphere after carbonization, remove blowing agent with acid or alkali, after filtration, dry, obtain porous carbon materials; Wherein NH
3charge flow rate is controlled at 2 ~ 100ml/min.
Described blowing agent is one or more blowing agents of citric acid, calcium carbonate, magnesium carbonate, sodium acid carbonate, sodium carbonate, ammonium carbonate, Ammonium bicarbonate food grade, ammonium nilrite, lauryl sodium sulfate, softex kw, sodium sulfate of polyethenoxy ether of fatty alcohol, pentane, n-hexane, normal heptane, benzinum, animal/vegetable protein class blowing agent.Optimization citric acid, ammonium carbonate, carbonic hydroammonium, sodium acid carbonate, calcium carbonate.
Beneficial effect of the present invention:
1. the hierarchical porous structure of i.e. structure doping nitrogen in material with carbon element preparation process, be respectively used to the mass transfer of the deposition of discharging product and oxygen, electrolyte, this material with carbon element is used as to lithium-air battery electrode, can improve to greatest extent the utilance in material with carbon element hole, in addition, the introducing of nitrogen makes carbon edge cause defect, introduces the more active sites of polyoxy reduction reaction.Consider, this new carbon, improves the space availability ratio of electrode greatly, Each performs its own functions to make the hole of each aperture size, the nitrogen that simultaneously adulterates has catalytic activity, effectively improves specific discharge capacity, voltage platform and the multiplying power discharging ability of battery, improves energy density and the power density of battery.
2. the grading-hole material with carbon element preparation method of nitrogen doping is simple, raw material wide material sources and cheap, the gentleer environmental protection of preparation process, without strong acid and strong base, and be easy to amplify the preparation in enormous quantities that realizes product, meet the requirement of lithium-air battery to positive electrode, advance the commercial applications of lithium-air battery.
The grading-hole material with carbon element pore structure of nitrogen doping can regulate and control and control methods various; Mix N mode various and be easy to realize.Importing or produce containing N structure using method on carbon carrier surface has: in-situ doped N, is included in NH
3carbonization under atmosphere; And after mix N, as after porous carbon materials carbonization at NH
3middle heat treatment.
4. the grading-hole material with carbon element pore structure of nitrogen doping can regulate and control, from micron to nanometer range and modification scope is wide and mode is various;
5. sol-gal process in conjunction with the advantage of activation method is: the three-dimensional net structure that utilizes sol-gal process to form, can form electric conductivity excellence and there is micropore and less mesoporous material with carbon element, and by the mode of activation, can be to the further reaming in the hole of network configuration, form the hole of larger aperture, final form the mesoporous hierarchical porous structure to macropore scope containing N material with carbon element, meet battery discharge procedure needs.Wherein in catalytic activation method preparation process, can be easy to realize the doping of metal/metal oxide simultaneously, be applied to lithium-air battery and can play catalytic action to charge and discharge process, reduce and discharge and recharge polarization, improve energy content of battery efficiency.
6. sol-gal process in conjunction with the advantage of foaming is: the three-dimensional net structure that utilizes sol-gal process to form, can form electric conductivity excellence and there is micropore and less mesoporous material with carbon element, and by adding blowing agent mode, can foam and form the hole of larger aperture, and the blowing agent adding decomposes in carbonisation, do not need pickling or alkali cleaning processing.Final form the mesoporous hierarchical porous structure to macropore scope containing N material with carbon element, meet battery discharge procedure needs.
Brief description of the drawings
Fig. 1 is electrode process simulation drawing;
Fig. 2 is that embodiment 1 adopts the contrast in conjunction with the standby classifying porous material with carbon element of catalytic activation legal system and commercialization carbon powder material surface topography with sol-gal process, and A is the classifying porous material with carbon element (HPC-N) of doping N, and B is commercialization KB600 carbon dust.
Embodiment
Embodiment 1
The hierarchical porous structure porous carbon materials that adopts sol-gal process to adulterate for nitrogen in conjunction with catalytic activation legal system.6.16g resorcinol is dissolved in to 10mL deionized water, forms clear solution; Get 0.29g Nickelous nitrate hexahydrate and add in above-mentioned clear solution, mixed dissolution evenly obtains solution; In the solution in above-mentioned stirring, drip 9.08g formalin, be further uniformly mixed, in 20 DEG C of environment, continue to stir, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 7d at 70 DEG C, after taking out, pulverizes and grind, obtain pressed powder; By pressed powder at NH
3in 900 DEG C of carbonization treatment 3h, with appropriate 1M HCl eccysis nickel oxide, filtration drying, obtains described material with carbon element.
The prepared positive electrode structure of embodiment 1 has 10 ~ 40 a large amount of nano aperture deposition holes, has the grading-hole in 0.1 ~ 0.5 micron order mass transfer hole, and between mass transfer hole, mutual spacing is 1um left and right, and mass transfer hole runs through deposition hole; Material with carbon element is honeycomb-like network pore structure (ESEM result Fig. 2 demonstration).BET result shows in addition, and prepared material with carbon element has concentrated pore size distribution in 20nm left and right, and total pore volume of material with carbon element is 0.9cm
3/ g, 85% of deposition Zhan Zong hole, hole pore volume.Wherein in HPC-N through X-ray photoelectron spectroscopic analysis, it is 1.8% that nitrogen accounts for material with carbon element atomic ratio.
The classifying porous material with carbon element of the prepared doping N of embodiment 1 is as lithium-air battery positive pole, and its electrode load amount is 3mg/cm
2 carbon, under the electrolyte of lithium trifluoromethanesulp,onylimide electrolytic salt and tetraethylene glycol dimethyl ether solvent formation, room temperature is with 0.1mA/cm
2under current density, the O of 99.99% purity under 1atm
2under condition, test, first circle discharge capacity reaches 6500mAh/g.
Comparative example:
Adopt commercialization KB-600 carbon dust as lithium-air battery positive pole, under the same terms, its first circle discharge capacity is only 3000mAh/g, and the graded porous carbon material capacity of the prepared doping N of embodiment 1 has improved 116% compared with commercialization carbon dust KB-600, and discharge voltage plateau improves.
Embodiment 2
Adopt sol-gal process to prepare the hierarchical porous structure porous carbon materials of nitrogen doping in conjunction with activation method.6.16g resorcinol is dissolved in to 10mL deionized water, forms clear solution; Get 0.808g ferric nitrate and add in above-mentioned clear solution, mixed dissolution evenly obtains solution; In the solution in above-mentioned stirring, drip 9.08g formalin, be further uniformly mixed, in 20 DEG C of environment, continue to stir, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 3d at 70 DEG C, after taking out, pulverizes and grind, obtain pressed powder; By pressed powder at NH
3in 1000 DEG C of carbonization treatment 5h, with appropriate 1M HCl eccysis iron oxide, filtration drying, obtains described material with carbon element.
Embodiment 3
Adopt sol-gal process to prepare the hierarchical porous structure porous carbon materials of nitrogen doping in conjunction with activation method.6.16g resorcinol is dissolved in to 10mL deionized water, forms clear solution; Get 0.2716g cabaltous nitrate hexahydrate and add in above-mentioned clear solution, mixed dissolution evenly obtains solution; In the solution in above-mentioned stirring, drip 9.08g formalin, be further uniformly mixed, in 20 DEG C of environment, continue to stir, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 7d at 70 DEG C, after taking out, pulverizes and grind, obtain pressed powder; By pressed powder at NH
3in 900 DEG C of carbonization treatment 3h, with appropriate 1M HCl eccysis cobalt oxide, filtration drying, obtains described material with carbon element.
Embodiment 4
Adopt sol-gal process to prepare the hierarchical porous structure porous carbon materials of nitrogen doping in conjunction with foaming.6.16g resorcinol is dissolved in to 10mL deionized water, forms clear solution; In the solution in above-mentioned stirring, add 9.08g formalin and 1g carbonic hydroammonium, be further uniformly mixed, in 20 DEG C of environment, continue to stir, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 7d at 70 DEG C, after taking out, pulverizes and grind, obtain pressed powder; By pressed powder at NH
3in 850 DEG C process 2h, obtain described material with carbon element.
Embodiment 5
Adopt sol-gal process to prepare the hierarchical porous structure porous carbon materials of nitrogen doping in conjunction with foaming.6.16g resorcinol is dissolved in to 10mL deionized water, forms clear solution; In the solution in above-mentioned stirring, add 9.08g formalin and 1g citric acid, be further uniformly mixed, in 20 DEG C of environment, continue to stir, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 7d at 70 DEG C, after taking out, pulverizes and grind, obtain pressed powder; By pressed powder at NH
3in 850 DEG C process 2h, obtain described material with carbon element.
Embodiment 6
Adopt sol-gal process to prepare the hierarchical porous structure porous carbon materials of nitrogen doping in conjunction with foaming.6.16g resorcinol is dissolved in to 10mL deionized water, forms clear solution; In the solution in above-mentioned stirring, add 9.08g formalin and 1g softex kw, be further uniformly mixed, in 20 DEG C of environment, continue to stir, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 3d at 70 DEG C, after taking out, pulverizes and grind, obtain pressed powder; By pressed powder at NH
3in 1050 DEG C process 2h, obtain described material with carbon element.
Claims (10)
1. the anodal porous carbon materials that uses nitrogen doping of lithium-air battery, it is characterized in that: the porous carbon materials of described nitrogen doping has the hierarchical porous structure of mutual perforation, N is doped in C skeleton equably, wherein N accounts for material with carbon element atomic ratio 0.2-15%, grading-hole comprises mass transfer hole and deposition hole, 40 ~ 95% of deposition Zhan Zong hole, hole pore volume, 4 ~ 55% of Zhan Zong hole, mass transfer hole pore volume, all the other are less than the hole of 5nm for aperture, deposition aperture, hole is 5 ~ 90nm, aperture, mass transfer hole is 0.1 ~ 6um, between mass transfer hole, mutual spacing is 0.1 ~ 8um, mass transfer hole is interconnected by deposition hole, the total pore volume of material with carbon element is 0.5 ~ 5cm
3/ g.
2. the porous carbon materials of nitrogen doping according to claim 1, is characterized in that: described material with carbon element adopts sol-gal process to be prepared from conjunction with foaming in conjunction with activation method or sol-gal process.
3. the porous carbon materials of nitrogen doping according to claim 2, is characterized in that:
Described sol-gal process is included in catalytic activation in carbonisation in conjunction with activation method, or the material with carbon element that sol-gal process is made carries out rear activation, and a kind of in the two or two kinds are combined with.
4. the porous carbon materials of nitrogen doping according to claim 3, is characterized in that:
Described sol-gal process catalytic activation in carbonisation is prepared from according to the following procedure, resorcinol is scattered in solvent, then add slaine or metal hydroxides and continue to dissolve and disperse, then drip formalin, be uniformly mixed until react formation gel at 30 ~ 80 DEG C; Vacuumize at 60～100 DEG C of gels is processed for aging 3 ~ 10 days, after taking out, pulverized and grind, obtain pressed powder; Through high temperature NH
3under atmosphere, after carbonization, remove slaine or metal hydroxides with acid or alkali, after filtration, dry, obtain porous carbon materials, wherein NH
3charge flow rate is controlled at 2 ~ 100ml/min.
5. the porous carbon materials of nitrogen doping according to claim 4, is characterized in that:
Described slaine or metal hydroxides are one or two or more kinds slaine or the metal hydroxides containing Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Nb, Y, Rh, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W, Sn, La and V; Slaine be nitrate, carbonate, sulfate, acetate, halide, dinitroso diamine salts, the acetylacetonate of metal or encircle greatly complex compound and porphyrin compound, phthalein mountain valley with clumps of trees and bamboo compound in one or two or more kinds, wherein the mass percent scope of slaine or metal hydroxides and resorcinol is 1 ~ 15%.
6. the porous carbon materials of nitrogen doping according to claim 3, is characterized in that:
The material with carbon element that described sol-gal process makes carries out rear activation, comprises that following one or more methods are in conjunction with being prepared from:
(1) physical activation method: resorcinol is scattered in solvent, then drips formalin, be uniformly mixed at 30 ~ 80 DEG C until react and form gel; Vacuumize at 60～100 DEG C of gels is processed for aging 3 ~ 10 days, after taking out, pulverized and grind, obtain pressed powder; Through high temperature NH
3under atmosphere, after carbonization, pass into steam, CO
2, and can produce in the compound of one of above-mentioned two kinds of gases one or more activate; Activation temperature is controlled at 400 ~ 1300 DEG C, and soak time is controlled at 10min ~ 5h, NH
3, steam or CO
2charge flow rate is controlled at 2 ~ 100ml/min;
(2) NH
3heat treatment activation method: resorcinol is scattered in solvent, then drips formalin, be uniformly mixed at 30 ~ 80 DEG C until react and form gel; Vacuumize at 60～100 DEG C of gels is processed for aging 3 ~ 10 days, after taking out, pulverized and grind, obtain pressed powder; Through high temperature N
2or after Ar carbonization, the material with carbon element obtaining is at NH
3under atmosphere, heat-treat activation.Heat treatment temperature is controlled at 400 ~ 1300 DEG C, and the time is controlled at 10min ~ 6h, N
2or Ar, NH
3charge flow rate is controlled at 2 ~ 100ml/min;
(3) chemical activation method: resorcinol is scattered in solvent, then drips formalin, be uniformly mixed at 30 ~ 80 DEG C until react and form gel; Vacuumize at 60～100 DEG C of gels is processed for aging 3 ~ 10 days, after taking out, pulverized and grind, obtain pressed powder; Through high temperature NH
3under atmosphere after carbonization, material with carbon element ground and mixed prepared by activating reagent and sol-gal process is even, and activating reagent is 10 ~ 300% of material with carbon element quality, and activation temperature is controlled at 300 ~ 900 DEG C, and soak time is controlled at 10min ~ 5h; After activation, material with carbon element washs and is dried with deionized water; Wherein NH
3charge flow rate is controlled at 2 ~ 100ml/min; Described activating reagent comprises bases activating reagent KOH, acids activating reagent H
3pO
4, salt activating reagent is ZnCl
2, K
2cO
3or Na
2cO
3.
7. according to the porous carbon materials of the nitrogen doping described in claim 4 or 6, it is characterized in that:
Described resorcinol and solvent are in the ratio of 0.1～8ml solvent/1g resorcinol; Solvent is water, ethanol, isopropyl alcohol or ethylene glycol, and the mol ratio of resorcinol and formaldehyde is 1:1～5:1, and the mass concentration of described formalin is 30～40%, and carburizing temperature scope is at 500 ~ 1700 DEG C, and carbonization time is controlled at 1 ~ 10h.
8. porous carbon materials according to claim 2, is characterized in that:
Described material with carbon element adopts sol-gal process to be prepared from according to the following procedure in conjunction with foaming: resorcinol and blowing agent are scattered in solvent, then drip formalin, be uniformly mixed until react formation gel at 30 ~ 80 DEG C; Vacuumize at 60～100 DEG C of gels is processed for aging 3 ~ 10 days, after taking out, pulverized and grind, obtain pressed powder; Through high temperature NH
3under atmosphere, after carbonization, remove blowing agent with acid or alkali, through washing, filtration, dry, obtain porous carbon materials.
9. porous carbon materials according to claim 8, is characterized in that:
Described resorcinol and solvent are in the ratio of 0.1～8ml solvent/1g resorcinol; Solvent is water, ethanol, isopropyl alcohol or ethylene glycol, and the mol ratio of resorcinol and formaldehyde is 1:1～5:1, and the mass concentration of described formalin is 30～40%, wherein NH
3charge flow rate is controlled at 2 ~ 100ml/min, and carburizing temperature scope is at 500 ~ 1700 DEG C, and carbonization time is controlled at 1 ~ 10h, and wherein the mass percent scope of blowing agent and resorcinol is 3 ~ 100%.
10. porous carbon materials according to claim 8, is characterized in that:
Described blowing agent is one or more blowing agents of citric acid, calcium carbonate, magnesium carbonate, sodium acid carbonate, sodium carbonate, ammonium carbonate, Ammonium bicarbonate food grade, ammonium nilrite, lauryl sodium sulfate, softex kw, sodium sulfate of polyethenoxy ether of fatty alcohol, pentane, n-hexane, normal heptane, benzinum, animal/vegetable protein class blowing agent; The acid solution of removing blowing agent use is 0.5 ~ 3M hydrochloric acid, sulfuric acid or nitric acid, and aqueous slkali is 0.5 ~ 3M sodium hydroxide solution.
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| CN105514397A (en) * | 2016-03-02 | 2016-04-20 | 桂林理工大学 | Method for preparing nitrogen-doped carbon nanotube |
| CN105645408A (en) * | 2016-03-09 | 2016-06-08 | 湘潭大学 | Process using date pits to prepare nitrogen-doped porous carbon material and preparation method of super-capacitor electrode |
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| CN107265433A (en) * | 2017-05-12 | 2017-10-20 | 中国科学院上海硅酸盐研究所 | Three-dimensional porous nitrating carbon material and its preparation method and application |
| CN108172792A (en) * | 2017-12-26 | 2018-06-15 | 刘春丽 | A kind of composite cathode material for lithium ion cell and preparation method thereof |
| CN108622877A (en) * | 2018-04-09 | 2018-10-09 | 中国矿业大学 | A kind of nitrogen-doped porous carbon material and the preparation method and application thereof with multi-stage porous construction |
| CN110690423A (en) * | 2019-09-27 | 2020-01-14 | 中国电子科技集团公司第十八研究所 | Heteroatom doped carbon material and preparation method and application thereof |
| CN112038604A (en) * | 2020-09-03 | 2020-12-04 | 青海凯金新能源材料有限公司 | Battery negative electrode material with good conductivity and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284223A (en) * | 2007-04-13 | 2008-10-15 | 中国科学院金属研究所 | Magnetic porous carbon adsorbent and preparation method thereof |
| CN101454243A (en) * | 2006-05-31 | 2009-06-10 | 促进科学E.V.麦克斯-普朗克公司 | Porous carbon electrode with conductive polymer coating |
| CN102104157A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Preparation method for carbon dry gel |
| CN102294255A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Carbon gel catalyst and application thereof |
| CN102299347A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Application of catalyst in alkaline fuel cell |
| WO2012111169A1 (en) * | 2011-02-16 | 2012-08-23 | Toyota Jidosha Kabushiki Kaisha | Method for producing cathode material for rechargeable lithium-air batteries, cathode material for rechargeable lithium-air batteries and rechargeable lithium-air battery |
-
2012
- 2012-11-28 CN CN201210496062.7A patent/CN103855365B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101454243A (en) * | 2006-05-31 | 2009-06-10 | 促进科学E.V.麦克斯-普朗克公司 | Porous carbon electrode with conductive polymer coating |
| CN101284223A (en) * | 2007-04-13 | 2008-10-15 | 中国科学院金属研究所 | Magnetic porous carbon adsorbent and preparation method thereof |
| CN102104157A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Preparation method for carbon dry gel |
| CN102294255A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Carbon gel catalyst and application thereof |
| CN102299347A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Application of catalyst in alkaline fuel cell |
| WO2012111169A1 (en) * | 2011-02-16 | 2012-08-23 | Toyota Jidosha Kabushiki Kaisha | Method for producing cathode material for rechargeable lithium-air batteries, cathode material for rechargeable lithium-air batteries and rechargeable lithium-air battery |
Non-Patent Citations (1)
| Title |
|---|
| CHRIS TRAN ET AL.: ""Ivestigation of the gas-diffusion-electrode used as lithium/air cathode in non-aqueous electrolyte and the importance of carbon material porosity"", 《JOURNAL OF POWER SOURCES》, vol. 195, no. 7, 13 October 2009 (2009-10-13), pages 2057 - 2063, XP026796111 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106467323B (en) * | 2015-08-18 | 2019-06-11 | 同济大学 | A kind of copper-iron-carbon silica aerogel electrode preparation method |
| CN106467323A (en) * | 2015-08-18 | 2017-03-01 | 同济大学 | A kind of preparation method of copper-ferrum-carbon silica aerogel electrode |
| CN107026272A (en) * | 2016-02-01 | 2017-08-08 | 台湾奈米碳素股份有限公司 | Method for manufacturing nitrogen-containing carbon electrode and flow battery thereof |
| CN105514397A (en) * | 2016-03-02 | 2016-04-20 | 桂林理工大学 | Method for preparing nitrogen-doped carbon nanotube |
| CN105645408A (en) * | 2016-03-09 | 2016-06-08 | 湘潭大学 | Process using date pits to prepare nitrogen-doped porous carbon material and preparation method of super-capacitor electrode |
| CN106654208A (en) * | 2016-12-21 | 2017-05-10 | 深圳市沃特玛电池有限公司 | Preparation method for negative electrode material of lithium iron phosphate battery |
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| CN108172792A (en) * | 2017-12-26 | 2018-06-15 | 刘春丽 | A kind of composite cathode material for lithium ion cell and preparation method thereof |
| CN108622877A (en) * | 2018-04-09 | 2018-10-09 | 中国矿业大学 | A kind of nitrogen-doped porous carbon material and the preparation method and application thereof with multi-stage porous construction |
| CN108622877B (en) * | 2018-04-09 | 2022-01-28 | 中国矿业大学 | Nitrogen-doped porous carbon material with hierarchical pore structure and preparation method and application thereof |
| CN110690423A (en) * | 2019-09-27 | 2020-01-14 | 中国电子科技集团公司第十八研究所 | Heteroatom doped carbon material and preparation method and application thereof |
| CN110690423B (en) * | 2019-09-27 | 2021-06-29 | 中国电子科技集团公司第十八研究所 | Heteroatom doped carbon material and preparation method and application thereof |
| CN112038604A (en) * | 2020-09-03 | 2020-12-04 | 青海凯金新能源材料有限公司 | Battery negative electrode material with good conductivity and preparation method thereof |
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