CN103855365B - Lithium-air battery positive pole uses the porous carbon materials of N doping - Google Patents
Lithium-air battery positive pole uses the porous carbon materials of N doping Download PDFInfo
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- CN103855365B CN103855365B CN201210496062.7A CN201210496062A CN103855365B CN 103855365 B CN103855365 B CN 103855365B CN 201210496062 A CN201210496062 A CN 201210496062A CN 103855365 B CN103855365 B CN 103855365B
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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
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- 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
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Abstract
The present invention relates to the porous carbon materials of lithium-air battery positive pole N doping, it is characterized in that: the porous carbon materials of described N doping has mutually through hierarchical porous structure, N is doped in C framework 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; This material with carbon element is used as lithium-air battery electrode material, the space availability ratio of material with carbon element in charge and discharge process can be improved to greatest extent, effectively improve energy density and the power density of lithium-air battery.Advantage of the present invention is: preparation technology is simple, and material source is extensive, grading-hole material with carbon element pore structure controllable and control methods are various, and nitrating mode is easy to realize.
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, 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 battery of more high-energy-density.Though the laboratory specific energy of current lithium ion battery reaches 250Wh/kg, but by the restriction that positive electrode specific capacity improves further, its specific energy is difficult to improve a lot again, and will safety problem be aggravated by improving charging voltage with the approach increasing specific energy, thus develop new electrochemical energy storage system imperative.In new energy storage system, lithium-air battery is a kind of is negative pole with lithium metal, and air electrode is the secondary cell of positive pole.Lithium metal as negative material has minimum theoretical voltage, and its theoretical specific capacity up to 3,862mAh/g, and can directly obtain as the oxygen of positive active material from air, and therefore, lithium-air battery has high specific capacity and specific energy.Take 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 element as positive electrode, and by being mixed into PTFE, air electrode prepared by the binding agents such as PVDF, Nafion.As shown in Figure 1, be lithium-air battery positive discharge Reaction process Simulation figure.The solid-liquid two-phase interface that exoelectrical reaction builds between liquid electrolyte solution and material with carbon element carries out, and carbon material surface generates the insoluble product-oxidate for lithium of solid, and along with reaction is carried out, solid product accumulation makes internal gutter block and then causes 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 research such as Tran shows that the capacity of electrode determined by the amount of oxidate for lithium in the large scale duct that can not affect mass transfer.Material with carbon element micropore canals and part mesopore duct can be discharged the oxidate for lithium that initial period formed and block, and the surface in this part hole again by air and electrolyte, therefore no longer cannot participate in electrochemical reaction, cause discharge off.But the material with carbon element be made up of macropore size is completely in discharge process, and 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 what can not give full play to hole utilizes space.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, thus accelerate electrode reaction speed and increase effective utilization in hole, is a difficult problem urgently to be resolved hurrily at present.
In addition, the material with carbon element of N doping has shown excellent oxygen reduction activity in a fuel cell, can Some substitute precious metals pt/C catalyst.Research display doping nitrogen-atoms changes microstructure and the surface electronic state of nano-carbon material, by N-O or C-O " two location (dualsite) adsorbs ", can weaken the O-O key in oxygen molecule, be beneficial to generation reduction reaction.
At present about the carbon nano-tube of N doping, the application of grapheme material in lithium-air battery of N doping have a small amount of report, result display N doping can cause carbon edge defect, effectively increase this part active sites to expose, 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 lithium-air battery positive pole N doping, the porous carbon materials of described N doping has mutually through hierarchical porous structure, N is doped in C framework 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 obtained to sol-gal process carries out rear activation, and the one in the two or two kinds are combined.
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 continuation dissolving dispersion, then drip formalin, be uniformly mixed until react formation gel at 30 ~ 80 DEG C; By the process in aging 3 ~ 10 days of vacuumize at gel 60 ~ 100 DEG C, pulverize grinding after taking-up, obtain pressed powder; Through high temperature NH
3under atmosphere after carbonization with acid or alkali removing slaine or metal hydroxides, after filtration, dry, obtain porous carbon materials, wherein NH
3charge flow rate controls at 2 ~ 100ml/min.
Described slaine or metal hydroxides are one or two or more kinds slaine or the metal hydroxides that contain 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 is one or two or more kinds in the nitrate of metal, carbonate, sulfate, acetate, halide, dinitroso diamine salts, acetylacetonate or large ring complex compound and porphyrin compound, phthalein mountain valley with clumps of trees and bamboo compound.The nitrate of preferred Fe, Co, Ni, Cu, Mo, Mn, Mo, acetate.
The material with carbon element that described sol-gal process obtains carries out rear activation, comprises one or more methods combining following and is prepared from:
(1) physical activation method: be scattered in by resorcinol in solvent, then drip formalin, is uniformly mixed until react formation gel at 30 ~ 80 DEG C; By the process in aging 3 ~ 10 days of vacuumize at gel 60 ~ 100 DEG C, pulverize grinding after taking-up, obtain pressed powder; Through high temperature NH
3under atmosphere after carbonization, pass into steam, CO
2, and one or more that can produce in the compound of one of above-mentioned two kinds of gases activate; Activation temperature controls at 400 ~ 1300 DEG C, and soak time controls at 10min ~ 5h, NH
3, steam or CO
2charge flow rate controls at 2 ~ 100ml/min;
(2) NH
3heat treatment activation method: be scattered in by resorcinol in solvent, then drip formalin, is uniformly mixed until react formation gel at 30 ~ 80 DEG C; By the process in aging 3 ~ 10 days of vacuumize at gel 60 ~ 100 DEG C, pulverize grinding after taking-up, obtain pressed powder; Through high temperature N
2or after Ar carbonization, the material with carbon element obtained is at NH
3activation is heat-treated under atmosphere.Heat treatment temperature controls at 400 ~ 1300 DEG C, and time controling is at 10min ~ 6h, N
2or Ar, NH
3charge flow rate controls at 2 ~ 100ml/min;
(3) chemical activation method: be scattered in by resorcinol in solvent, then drip formalin, is uniformly mixed until react formation gel at 30 ~ 80 DEG C; By the process in aging 3 ~ 10 days of vacuumize at gel 60 ~ 100 DEG C, pulverize grinding after taking-up, obtain pressed powder; Through high temperature NH
3under atmosphere after carbonization, material with carbon element ground and mixed activating reagent and sol-gal process prepared is even, and activating reagent is 10 ~ 300% of material with carbon element quality, and activation temperature controls at 300 ~ 900 DEG C, and soak time controls at 10min ~ 5h; After activation, material with carbon element spends deionized water and drying; Wherein NH
3charge flow rate controls 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: be scattered in solvent by resorcinol and blowing agent, then drip formalin, is uniformly mixed until react formation gel at 30 ~ 80 DEG C; By the process in aging 3 ~ 10 days of vacuumize at gel 60 ~ 100 DEG C, pulverize grinding after taking-up, obtain pressed powder; Through high temperature NH
3under atmosphere after carbonization, with acid or alkali removing blowing agent, after filtration, dry, porous carbon materials is obtained; Wherein NH
3charge flow rate controls 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. in material with carbon element preparation process, namely construct the hierarchical porous structure of doping nitrogen, be respectively used to the mass transfer of the deposition of discharging product and oxygen, electrolyte, this material with carbon element is used as lithium-air battery electrode, the utilance in material with carbon element hole can be improved to greatest extent, in addition, the introducing of nitrogen makes carbon edge cause defect, introduces the active sites of more polyoxy reduction reaction.Consider, this new carbon, greatly improve the space availability ratio of electrode, Each performs its own functions to make the hole of each aperture size, the nitrogen that simultaneously adulterates has catalytic activity, effectively improves the specific discharge capacity of battery, voltage platform and multiplying power discharging ability, improves energy density and the power density of battery.
2. the grading-hole material with carbon element preparation method of N doping is simple, raw material sources is extensive 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 realizing product, meet the requirement of lithium-air battery to positive electrode, advance the commercial applications of lithium-air battery.
3. N doping grading-hole material with carbon element pore structure controllable and control methods are various; Mix N mode various and be easy to realize.Importing at carbon support or produce has containing N structure using method: 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 controllable of N doping, 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: utilize the three-dimensional net structure that sol-gal process is formed, electric conductivity excellence can be formed and there is micropore and less mesoporous material with carbon element, and the mode by activating, can to the further reaming in the hole of network configuration, form the hole of larger aperture, the mesoporous hierarchical porous structure to macropore scope of final formation containing N material with carbon element, meet battery discharge procedure needs.Wherein can be easy to the doping simultaneously realizing metal/metal oxide in catalytic activation method preparation process, be applied to lithium-air battery and can play catalytic action to charge and discharge process, reduce discharge and recharge polarization, improve energy content of battery efficiency.
6. sol-gal process in conjunction with the advantage of foaming is: utilize the three-dimensional net structure that sol-gal process is formed, electric conductivity excellence can be formed 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 added decomposes in carbonisation, do not need pickling or alkali cleaning process.The mesoporous hierarchical porous structure to macropore scope of final formation containing N material with carbon element, meet battery discharge procedure needs.
Accompanying drawing explanation
Fig. 1 is electrode process simulation drawing;
Fig. 2 is that embodiment 1 adopts with the contrast of sol-gal process in conjunction with the standby classifying porous material with carbon element of catalytic activation legal system and commercialization carbon powder material surface topography, 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
Adopt sol-gal process in conjunction with the hierarchical porous structure porous carbon materials of catalytic activation legal system for N doping.6.16g resorcinol is dissolved in 10mL deionized water, forms clear solution; Get 0.29g Nickelous nitrate hexahydrate to add in above-mentioned clear solution, mixed dissolution evenly obtains solution; In the solution in above-mentioned stirring, drip 9.08g formalin, be uniformly mixed further, Keep agitation in 20 DEG C of environment, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 7d at 70 DEG C, pulverizes grinding after taking-up, obtain pressed powder; By pressed powder at NH
3in 900 DEG C of carbonization treatment 3h, with appropriate 1MHCl eccysis nickel oxide, filtration drying, obtains described material with carbon element.
Cathode material structure prepared by embodiment 1 has 10 ~ 40 a large amount of nano aperture deposition holes, and have the grading-hole in 0.1 ~ 0.5 micron order mass transfer hole, between mass transfer hole, mutual spacing is about 1um, and mass transfer hole runs through deposition hole; Material with carbon element is honeycomb-like network pore structure (ESEM result Fig. 2 shows).BET result shows in addition, and prepared material with carbon element has concentrated pore size distribution at about 20nm, 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 doping N prepared by embodiment 1 is used as lithium air battery positive electrode, and its electrode load amount is 3mg/cm
2 carbon, under the electrolyte that lithium trifluoromethanesulp,onylimide electrolytic salt and tetraethylene glycol dimethyl ether solvent are formed, room temperature is with 0.1mA/cm
2under current density, the O of 99.99% purity under 1atm
2test under condition, first circle discharge capacity reaches 6500mAh/g.
Comparative example:
Adopt commercialization KB-600 carbon dust as lithium air battery positive electrode, under the same terms, its first circle discharge capacity is only 3000mAh/g, and the graded porous carbon material capacity of the doping N prepared by embodiment 1 comparatively commercialization carbon dust KB-600 improves 116%, and discharge voltage plateau improves.
Embodiment 2
Sol-gal process is adopted to prepare the hierarchical porous structure porous carbon materials of N doping in conjunction with activation method.6.16g resorcinol is dissolved in 10mL deionized water, forms clear solution; Get 0.808g ferric nitrate to add in above-mentioned clear solution, mixed dissolution evenly obtains solution; In the solution in above-mentioned stirring, drip 9.08g formalin, be uniformly mixed further, Keep agitation in 20 DEG C of environment, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 3d at 70 DEG C, pulverizes grinding after taking-up, obtain pressed powder; By pressed powder at NH
3in 1000 DEG C of carbonization treatment 5h, with appropriate 1MHCl eccysis iron oxide, filtration drying, obtains described material with carbon element.
Embodiment 3
Sol-gal process is adopted to prepare the hierarchical porous structure porous carbon materials of N doping in conjunction with activation method.6.16g resorcinol is dissolved in 10mL deionized water, forms clear solution; Get 0.2716g cabaltous nitrate hexahydrate to add in above-mentioned clear solution, mixed dissolution evenly obtains solution; In the solution in above-mentioned stirring, drip 9.08g formalin, be uniformly mixed further, Keep agitation in 20 DEG C of environment, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 7d at 70 DEG C, pulverizes grinding after taking-up, obtain pressed powder; By pressed powder at NH
3in 900 DEG C of carbonization treatment 3h, with appropriate 1MHCl eccysis cobalt oxide, filtration drying, obtains described material with carbon element.
Embodiment 4
Sol-gal process is adopted to prepare the hierarchical porous structure porous carbon materials of N doping in conjunction with foaming.6.16g resorcinol is dissolved in 10mL deionized water, forms clear solution; In the solution in above-mentioned stirring, add 9.08g formalin and 1g carbonic hydroammonium, be uniformly mixed further, Keep agitation in 20 DEG C of environment, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 7d at 70 DEG C, pulverizes grinding after taking-up, obtain pressed powder; By pressed powder at NH
3in 850 DEG C process 2h, obtain described material with carbon element.
Embodiment 5
Sol-gal process is adopted to prepare the hierarchical porous structure porous carbon materials of N doping in conjunction with foaming.6.16g resorcinol is dissolved in 10mL deionized water, forms clear solution; In the solution in above-mentioned stirring, add 9.08g formalin and 1g citric acid, be uniformly mixed further, Keep agitation in 20 DEG C of environment, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 7d at 70 DEG C, pulverizes grinding after taking-up, obtain pressed powder; By pressed powder at NH
3in 850 DEG C process 2h, obtain described material with carbon element.
Embodiment 6
Sol-gal process is adopted to prepare the hierarchical porous structure porous carbon materials of N doping in conjunction with foaming.6.16g resorcinol is dissolved in 10mL deionized water, forms clear solution; In the solution in above-mentioned stirring, add 9.08g formalin and 1g softex kw, be uniformly mixed further, Keep agitation in 20 DEG C of environment, until reaction forms gel; Gel is transferred to vacuum drying chamber vacuumize burin-in process 3d at 70 DEG C, pulverizes grinding after taking-up, obtain pressed powder; By pressed powder at NH
3in 1050 DEG C process 2h, obtain described material with carbon element.
Claims (10)
1. lithium-air battery positive pole uses the porous carbon materials of N doping, it is characterized in that: the porous carbon materials of described N doping has mutually through hierarchical porous structure, N is doped in C framework equably, wherein N accounts for the 0.2-15% of C atom in material with carbon element, 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 ~ 6 μm, between mass transfer hole, mutual spacing is 0.1 ~ 8 μm, mass transfer hole is interconnected by deposition hole, the total pore volume of material with carbon element is 0.9 ~ 5cm
3/ g.
2. the porous carbon materials of N doping according to claim 1, is characterized in that: the porous carbon materials of described N doping 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 N doping according to claim 2, it 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 obtained to sol-gal process carries out rear activation, the one in the two or two kinds are combined.
4. the porous carbon materials of N doping according to claim 3, it 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 slaine or metal hydroxides continuation dissolving dispersion is added, then drip formalin, be uniformly mixed until react formation gel at 30 ~ 80 DEG C; By the process in aging 3 ~ 10 days of vacuumize at gel 60 ~ 100 DEG C, pulverize grinding after taking-up, obtain pressed powder; Through high temperature NH
3under atmosphere after carbonization with acid or alkali removing slaine or metal hydroxides, after filtration, dry, obtain the porous carbon materials of N doping, wherein NH
3charge flow rate controls at 2 ~ 100mL/min.
5. the porous carbon materials of N 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 that contain 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 is one or two or more kinds in the nitrate of metal, carbonate, sulfate, acetate, halide, dinitroso diamine salts, acetylacetonate or large ring complex compound and porphyrin compound, phthalein mountain valley with clumps of trees and bamboo compound, and wherein slaine or metal hydroxides account for the mass percent scope of resorcinol is 1 ~ 15%.
6. the porous carbon materials of N doping according to claim 3, is characterized in that: the material with carbon element that described sol-gal process obtains carries out rear activation, comprises one or more methods combining following and is prepared from:
(1) physical activation method: be scattered in by resorcinol in solvent, then drip formalin, is uniformly mixed until react formation gel at 30 ~ 80 DEG C; By the process in aging 3 ~ 10 days of vacuumize at gel 60 ~ 100 DEG C, pulverize grinding after taking-up, obtain pressed powder; Through high temperature NH
3under atmosphere after carbonization, pass into steam, CO
2, and one or more that can produce in the compound of one of above-mentioned two kinds of gases activate; Activation temperature controls at 400 ~ 1300 DEG C, and soak time controls at 10min ~ 5h, NH
3, steam or CO
2charge flow rate controls at 2 ~ 100mL/min;
(2) NH
3heat treatment activation method: be scattered in by resorcinol in solvent, then drip formalin, is uniformly mixed until react formation gel at 30 ~ 80 DEG C; By the process in aging 3 ~ 10 days of vacuumize at gel 60 ~ 100 DEG C, pulverize grinding after taking-up, obtain pressed powder; Through high temperature N
2or after Ar carbonization, the material with carbon element obtained is at NH
3heat-treat activation under atmosphere, heat treatment temperature controls at 400 ~ 1300 DEG C, and time controling is at 10min ~ 6h, N
2or Ar, NH
3charge flow rate controls at 2 ~ 100mL/min;
(
3) chemical activation method: resorcinol is scattered in solvent, then drips formalin, be uniformly mixed until react formation gel at 30 ~ 80 DEG C; By the process in aging 3 ~ 10 days of vacuumize at gel 60 ~ 100 DEG C, pulverize grinding after taking-up, obtain pressed powder; Through high temperature NH
3under atmosphere after carbonization, material with carbon element ground and mixed activating reagent and sol-gal process prepared is even, and activating reagent is 10 ~ 300% of material with carbon element quality, and activation temperature controls at 300 ~ 900 DEG C, and soak time controls at 10min ~ 5h; After activation, material with carbon element spends deionized water and drying; Wherein NH
3charge flow rate controls 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. the porous carbon materials of the N doping according to claim 4 or 6, 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 controls at 1 ~ 10h.
8. porous carbon materials according to claim 2, it is characterized in that: the porous carbon materials of described N doping adopts sol-gal process to be prepared from according to the following procedure in conjunction with foaming: be scattered in solvent by resorcinol and blowing agent, then drip formalin, be uniformly mixed until react formation gel at 30 ~ 80 DEG C; By the process in aging 3 ~ 10 days of vacuumize at gel 60 ~ 100 DEG C, pulverize grinding after taking-up, obtain pressed powder; Through high temperature NH
3under atmosphere after carbonization, with acid or alkali removing blowing agent, through washing, filtration, drying, obtain the porous carbon materials of N doping.
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 controls at 2 ~ 100mL/min, and carburizing temperature scope is at 500 ~ 1700 DEG C, and carbonization time controls at 1 ~ 10h, and wherein blowing agent accounts for the mass percent scope of resorcinol 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, carbonic hydroammonium, 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 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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| TWI552424B (en) * | 2016-02-01 | 2016-10-01 | 台灣奈米碳素股份有限公司 | Method for manufacturing a nitrogen contained carbon electrode and a flow battery using it |
| CN105514397A (en) * | 2016-03-02 | 2016-04-20 | 桂林理工大学 | Method for preparing nitrogen-doped carbon nanotube |
| CN105645408B (en) * | 2016-03-09 | 2017-10-13 | 湘潭大学 | A kind of utilization jujube core prepares the technique of nitrogen-doped porous carbon material and the preparation method of electrode of super capacitor |
| CN106654208B (en) * | 2016-12-21 | 2018-07-24 | 深圳市沃特玛电池有限公司 | A kind of preparation method of lithium iron phosphate battery negative electrode material |
| 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 |
| 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 |
| 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 |
| CN116031383A (en) * | 2023-01-09 | 2023-04-28 | 南京航空航天大学 | Carbon composite material, preparation method and application thereof, and lithium ion thermal battery |
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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
|---|
| "Ivestigation of the gas-diffusion-electrode used as lithium/air cathode in non-aqueous electrolyte and the importance of carbon material porosity";Chris Tran et al.;《Journal of Power Sources》;20091013;第195卷(第7期);第2057-2063页 * |
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