CN103050702A - Application of carbon material containing in-situ doped component with catalytic activity to lithium-air battery - Google Patents
Application of carbon material containing in-situ doped component with catalytic activity to lithium-air battery Download PDFInfo
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Abstract
The invention relates to an application of a carbon material containing an in-situ doped component with catalytic activity to a lithium-air battery. The carbon material containing the in-situ doped component with catalytic activity is used as an electrode material in the lithium-air battery, the component with catalytic activity is doped in the carbon material in situ, and the component with catalytic activity is 1-80wt% of the carbon material. The component with catalytic activity is doped in situ in the preparation process of the carbon material and controllable in content, and the component with the catalytic activity is uniformly dispersed in the prepared carbon material, so that the dispersibility and coverage degree of the component with catalytic activity on the surface of the carbon material are greatly improved, the utilization ratio of the component with catalytic activity is increased in the charging and discharging processes, the discharging and discharging polarization potentials are reduced, and the energy efficiency of the lithium-air battery is increased.
Description
Technical field
The present invention relates to the empty field of batteries of lithium, the particularly application of a kind of electrode material in the empty battery of lithium.
Background technology
Along with developing rapidly of electronics, communication equipment and electric motor car, people propose requirements at the higher level to battery performance.Lithium-air battery is a kind of take lithium metal as negative pole, and air electrode is anodal secondary cell.Lithium metal as negative material has minimum theoretical voltage, and its theoretical specific capacity is up to 3,862mAh/g, and can directly obtain from air as the oxygen of positive active material, 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, and the actual specific energy has application prospect also far above lithium ion battery in civilian and military domain.
At present, lithium-air battery mainly adopts various material with carbon elements as positive electrode, and by sneaking into the binding agents such as PTFE, PVDF, Nafion, employing is colded pressing, hot pressing, and the methods such as blade coating prepare air electrode.As the place that electrochemical reaction occurs, carbon material surface deposition discharging product-oxidate for lithium, its specific area, pore volume, pore-size distribution are to battery performance, and especially charge/discharge capacity has important impact.Therefore the porous carbon materials of seeking the appropriate bore structure is significant to the specific capacity that improves battery.
In addition, add catalyst in air electrode, can effectively promote to discharge and recharge the carrying out of reaction, reduce the electrode reaction overpotential, improve the energy conversion efficiency of lithium-air battery, simultaneously, the adding of catalyst also is conducive to the raising of discharge capacity of the cell.The catalyst of research comprises precious metals pt, Au, Pd etc. at present, and each type oxide take manganese oxide as representative, but the concrete mechanism of action of catalyst does not get across yet.
As shown in Figure 1, be lithium-air battery positive discharge course of reaction simulation drawing.The solid-liquid two-phase interface that exoelectrical reaction makes up between liquid electrolyte solution and carbon dust carries out, and generates the insoluble product-oxidate for lithium of solid, and in the charging process, oxidate for lithium decomposes at this interface.Sneak into catalytic active component in electrode, if active component is dispersed in the surface of material with carbon element, namely the electrode reaction place can be utilized to greatest extent.
At present, in the preparation process of electrode, the hybrid mode of material with carbon element and catalytic active component mainly contains two kinds, and a kind of is with material with carbon element and catalyst mechanical mixture, a kind of be with catalyst loading on material with carbon element.At first, the mode of mechanical mixture, the homogeneous degree that catalyst mixes with material with carbon element is limited, can not guarantee that all carbon material surfaces all have the existence of catalyst, so the utilance of catalyst is lower.Adopt catalyst loading in the form of carbon material surface, can improve to a certain extent the mixing homogeneous degree of the two, but can not guarantee that all carbon material surfaces all have the existence of catalyst, such as, be subject to the size of catalyst particle particle diameter, some duct of material with carbon element can not the deposited catalyst particle.
Summary of the invention
For the problems referred to above, the object of the present invention is to provide a kind ofly in-situ dopedly has the material with carbon element of catalytic active component to be applied in the lithium-air battery.
The described in-situ doped material with carbon element that catalytic active component arranged is as the electrode material in the lithium-air battery;
Described catalytic active component is in-situ doped in material with carbon element, and catalytic active component shared mass fraction in material with carbon element is 1-80%.
Catalytic active component is metal and/or metal oxide; Wherein metal is one or two or more kinds among Fe, Cu, Ni, Ag, Pt, Pd, Au, Ir or the Ru, and metal oxide is one or two or more kinds in the oxide of Fe, Co, Ni, Cu, Zr, Ce, Ti, Mo, Mn, Zn, W or V.
Described material with carbon element adopts hard template method, soft template method or sol-gal process to be prepared from.
Hard template method: in the order mesoporous SiO of SBA-15
2Middle dipping carbon source and catalytic activity component presoma carry out charing under 500-1700 ℃ of argon gas or nitrogen, and remove the SBA-15 template with acid or alkali, after filtration, washing, drying, namely get the material with carbon element of in-situ doped active component.
Described hard template method adopts the following steps preparation when template is nano-powder:
In required ratio carbon source, active component presoma are added the deionized water for stirring dissolving, then add nano-powder, in 50-80 ℃ of heating and mechanical agitation, treat that moisture evaporates final vacuum 60-80 ℃ drying fully;
Dried product is put into the high temperature process furnances charing, the employed inert gas of charing is nitrogen or argon gas, the carbonization temperature scope is at 500-1700 ℃, carbonization time is controlled at 1-8h, obtain nano-powder/active component/carbon complex, remove the nano-powder template with acid or alkali, after filtration, drying, namely get the complex carbon material of in-situ doped active component;
The mass percent scope of described nano-powder and carbon source is at 600%-10%;
Nano-powder comprises one or two or more kinds in the nanometer powder of magnesium carbonate, calcium carbonate, magnesium oxide, magnesium acetate, magnesium gluconate, cupric oxide, zinc oxide, ferrous oxide, di-iron trioxide, tri-iron tetroxide, tin ash, silicon dioxide, aluminium oxide, zirconia, molybdenum trioxide, vanadium trioxide or titanium oxide.
Described carbon source is sucrose, glucose, furfuryl alcohol or phenolic resins or resorcinol formaldehyde resin; The catalytic active component presoma is one or more slaines that contain Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W and V; But slaine is nitrate, carbonate, sulfate, acetate, halide, dinitroso diamine salts, the acetylacetonate of metal or encircles greatly one or two or more kinds cosolvency salt in complex compound porphyrin compound, the phthalein mountain valley with clumps of trees and bamboo compound.
Described soft template method is prepared from accordance with the following steps:
(1) surfactant is dissolved in the solvent, obtains the solution A that concentration is 8-20wt%, described surfactant is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene EO
106-PO
70-EO
106(Pluronic F127), EO
20-PO
70-EO
20(Pluronic P123) or EO
132-PO
50-EO
132In (Pluronic F108) one or two or more kinds; Described solvent is one or two or more kinds in water, ethanol, isopropyl alcohol, the methyl alcohol;
(2) add the presoma of catalytic active component in the solution A, add carbon source and silicon source after dissolving fully, through fully stirring, dry rear in 300-550 ℃ of burn off surfactant, 600-1200 ℃ of charing 2-8h under nitrogen or argon gas atmosphere is with hydrofluoric acid or sodium hydroxide solution flush away SiO
2, namely get material with carbon element after the drying; Described carbon source is phenolic resins or resorcinol formaldehyde resin, and the silicon source is tetraethoxysilane, and wherein the mass ratio in carbon source and silicon source is 20-50wt%, and surfactant and carbon source mass ratio are 50-200wt%.
Described sol-gal process is prepared from accordance with the following steps:
Resorcinol is dissolved in the solvent, the active component presoma is added in the above-mentioned clear solution, then drip formalin, mix under 30-80 ℃ until react and form gel; Gel was processed 60～100 ℃ of lower vacuumizes in aging 3-10 days, pulverized after taking out and grind, obtain pressed powder; Behind high temperature carbonization, namely get the complex carbon material of in-situ doped active component;
Described resorcinol and solvent are in the ratio of 0.1～8ml solvent/1g resorcinol, solvent is a kind of in water, ethanol, isopropyl alcohol, the ethylene glycol, the mol ratio of resorcinol and formaldehyde is 1: 1～5: 1, the mass concentration of described formalin is 30～40%, the carbonization temperature scope is at 500-1700 ℃, and carbonization time is controlled at 1-10h.
The catalytic active component presoma is one or more slaines that contain Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W and V; But slaine is nitrate, carbonate, sulfate, acetate, halide, dinitroso diamine salts, the acetylacetonate of metal or encircles greatly one or two or more kinds cosolvency salt in complex compound porphyrin compound, the phthalein mountain valley with clumps of trees and bamboo compound.
Beneficial effect of the present invention is
1. catalytic active component is mixed at material with carbon element preparation process situ, and its content is controlled, makes active component Uniform Dispersion in prepared material with carbon element, improves dispersiveness and the coverage of carbon material surface catalytic active component;
2. by doping different metal and metal oxide, make its surface uniform distribution catalytic active component, effectively catalysis discharges and recharges reaction, improves the utilance of catalyst component in charge and discharge process, reduces discharging and recharging polarization potential, improves energy content of battery efficient.
Description of drawings
Fig. 1 is lithium-air battery positive discharge course of reaction simulation drawing;
Fig. 2 is the lithium-air battery discharge performance curve chart of embodiment 5 preparations, and discharging current is 0.1mA/cm
2
Embodiment
The order mesoporous SiO of SBA-15
2Preparation, such as list of references Zhao, D., Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50to 300Angstrom Pores.Science 1998,279 (5350), 548-552.
Specifically can be prepared from accordance with the following steps: surfactant is dissolved in the solvent, obtains the solution A that concentration is 1-10wt%; In solution A, add appropriate amount of acid solution, add thereafter the silicon source, after 80-160 ℃ of crystallization 12-48h, filtration washing, drying, in 300-550 ℃ of burn off surfactant, namely get the order mesoporous SiO of SBA-15
2
Described surfactant is one or two or more kinds among F127, F108 or the P123; Described solvent is one or two or more kinds in water, ethanol, isopropyl alcohol, the methyl alcohol; Described acid solution is watery hydrochloric acid, sulfuric acid or nitric acid; Described silicon source is tetraethoxysilane.
Embodiment 1
Prepare porous carbon materials take the nano-calcium carbonate magnesium dust as template.Accurately weighing 5g sucrose, 0.29g Nickelous nitrate hexahydrate add the 15ml deionized water for stirring to dissolve complete, then add 5g magnesium carbonate, heating and mechanical agitation under 80 ℃ of water bath condition, it is dissolved each other fully, and churned mechanically power bracket is 200w, and mixing speed is 300rpm.After evaporating fully, puts into moisture 80 ℃ of vacuumize 24h.Then dried product is put into the high temperature process furnances charing, atmosphere is nitrogen, and gas flow is controlled at 30ml/min.Take out through carbonization 2h under 800 ℃ and obtain nano particle/carbon complex, add an amount of 2M watery hydrochloric acid again and remove nano-calcium carbonate magnesium, 80 ℃ of vacuumize 24h after filtering namely get the porous carbon materials of in-situ doped N iO nano particle.
Embodiment 2
Prepare porous carbon materials take nano oxidized magnesium dust as template.Accurately weighing 5g sucrose, 0.267g two nitric hydrate oxygen zirconiums add the 8ml deionized water for stirring to dissolve complete, then add 8g magnesium oxide, heating and mechanical agitation under 80 ℃ of water bath condition, it is dissolved each other fully, and churned mechanically power bracket is 200w, and mixing speed is 300rpm.After evaporating fully, puts into moisture 80 ℃ of vacuumize 24h.Then dried product is put into the high temperature process furnances charing, atmosphere is nitrogen, and gas flow is controlled at 30ml/min.Obtain nano particle/carbon complex at 900 ℃ through carbonization 2h taking-up, remove nano magnesia with an amount of 2M watery hydrochloric acid again, 80 ℃ of vacuumize 24h namely get in-situ doped ZrO after filtering
2The porous carbon materials of nano particle.
Embodiment 3
Prepare porous carbon materials take the nano-calcium carbonate barium dust as template.Accurately weighing 5g sucrose, 0.241g Gerhardite add the 8ml deionized water for stirring to dissolve complete, then add the 10g brium carbonate, heating and mechanical agitation under 80 ℃ of water bath condition, it is dissolved each other fully, and churned mechanically power bracket is 200w, and mixing speed is 300rpm.After evaporating fully, puts into moisture 80 ℃ of vacuumize 24h.Then dried product is put into the high temperature process furnances charing, atmosphere is nitrogen, and gas flow is controlled at 20ml/min.Take out through carbonization 5h at 900 ℃ and to obtain nano particle/carbon complex, again with an amount of 2M watery hydrochloric acid removal nano barium carbonate, 80 ℃ of vacuumize 24h after filtering namely get the porous carbon materials of in-situ doped copper nano-particle.
Embodiment 4
Prepare porous carbon materials take the nano-calcium carbonate calcium powder as template.Accurate weighing 5g sucrose, 0.241g Gerhardite, 0.291g cabaltous nitrate hexahydrate, add the 10ml deionized water for stirring to dissolve complete, then add 10g calcium carbonate, heating and mechanical agitation under 80 ℃ of water bath condition, it is dissolved each other fully, churned mechanically power bracket is 200w, and mixing speed is 300rpm.After evaporating fully, puts into moisture 80 ℃ of vacuumize 24h.Then dried product is put into the high temperature process furnances charing, atmosphere is nitrogen, and gas flow is controlled at 20ml/min.Take out through carbonization 2h at 700 ℃ and to obtain nano particle/carbon complex, again with an amount of 2M watery hydrochloric acid removal nano-calcium carbonate, 80 ℃ of vacuumize 24h after filtering namely get the porous carbon materials of in-situ doped copper and cobalt oxide double base component nano particle.
Embodiment 5
Prepare porous carbon materials take the nano zine oxide powder as template.Accurately weighing 5g sucrose, 0.3771g Fe(NO3)39H2O solid add the 10ml deionized water for stirring to dissolve complete, then add 15g zinc oxide, heating and mechanical agitation under 80 ℃ of water bath condition, it is dissolved each other fully, and churned mechanically power bracket is 200w, and mixing speed is 300rpm.After evaporating fully, puts into moisture 80 ℃ of vacuumize 24h.Then dried product is put into the high temperature process furnances charing, atmosphere is nitrogen, and gas flow is controlled at 30ml/min.Obtain nano particle/carbon complex at 900 ℃ through carbonization 2h taking-up, remove nano zine oxide with an amount of 2M watery hydrochloric acid again, 80 ℃ of vacuumize 24h namely get in-situ doped Fe after filtering
2O
3The porous carbon materials of nano particle.As seen from Figure 2, adopting nano-powder is that the porous carbon materials that the in-situ doped Fe2O3 of template prepares is used as the lithium-air battery positive pole, capacity doubles than commercialization carbon dust KB-600, and discharge voltage polarization reduction, greatly improves energy density and the energy efficiency of battery.Can be found out in-situ doped active component distributing very evenly on material with carbon element by Electronic Speculum figure.
Embodiment 6
Adopt sol-gal process to prepare porous carbon materials.The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution; Get 0.0107g two tungsten oxchloride solids and add in the above-mentioned clear solution, mixed dissolution evenly obtains solution; Drip 9.08g formalin in the solution in the above-mentioned stirring, further mix, in 20 ℃ of environment, continue to stir, until reaction forms gel; Gel is transferred to vacuum drying chamber at 70 ℃ of lower vacuumize burin-in process 7d, pulverizes after taking out and grind, obtain pressed powder; With pressed powder at N
2In 1700 ℃ of high temperature graphitizations process 3h, N
2Air-blowing is swept to room temperature, 1M HNO
3Solution eccysis slaine namely gets in-situ doped WO
3The porous carbon materials of nano particle.
Embodiment 7
Adopt sol-gal process to prepare porous carbon materials.The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution; Get the 0.2716g cabaltous nitrate hexahydrate and add in the above-mentioned clear solution, mixed dissolution evenly obtains solution; Drip 9.08g formalin in the solution in stir, further mix, in 25 ℃ of environment, continue to stir, until reaction forms gel; Gel is transferred to vacuum drying chamber at 70 ℃ of lower vacuumize burin-in process 6d, pulverizes after taking out and grind, obtain pressed powder; With pressed powder at N
2In 900 ℃ process 3h, N
2Air-blowing is swept to room temperature, 1M HNO
3Solution eccysis slaine namely gets the porous carbon materials of in-situ doped cobalt nanometer particle.
Embodiment 8
Adopt soft template method to prepare meso-porous carbon material.Weighing 1.6g F127 surfactant is dissolved in 8.0g ethanol, and then adding 1.0g concentration is the manganese nitrate aqueous solution of 0.2M HCl, 0.358g 50%, at 40 ℃ of lower 1h that stir, until the F127 triblock copolymer dissolves fully.Add again 2.08g TEOS (tetraethoxysilane), 5.0g 20wt% phenolic resins (PF) solution, behind the stirring 2h, transfer on the surface plate.Behind the dry 8h, change the dry 24h of 100 ℃ of vacuum drying ovens under the room temperature.Then flaxen material is scraped, put into high temperature process furnances, atmosphere is nitrogen, and gas flow is controlled at 20ml/min, and 350 ℃ keep 3h, and 700 ℃ keep 2h.Then add 30g 1M NaOH solution, agitating heating is removed SiO
2, after the centrifuge washing drying, namely get the meso-porous carbon material of in-situ doped MnO nano particle.
Embodiment 9
Adopt soft template method to prepare meso-porous carbon material.Weighing 1.6g F127 surfactant is dissolved in 8.0g ethanol, and then adding 1.0g concentration is 0.2M HCl, 0.4480g Chromium nitrate (Cr(NO3)3),nonahydrate solid, at 40 ℃ of lower 1h that stir, until the F127 triblock copolymer dissolves fully.Add again 2.08g TEOS (tetraethoxysilane), 5.0g 20wt% phenolic resins (PF) solution, behind the stirring 2h, transfer on the surface plate.Behind the dry 8h, change the dry 24h of 100 ℃ of vacuum drying ovens under the room temperature.Then flaxen material is scraped, put into high temperature process furnances, atmosphere is nitrogen, and gas flow is controlled at 20ml/min, and 350 ℃ keep 3h, and 900 ℃ keep 2h.Then add 30g 1M NaOH solution, agitating heating is removed SiO
2, after the centrifuge washing drying, namely get the meso-porous carbon material of in-situ doped chromium oxide nano particle.
Embodiment 10
Adopt hard template method to prepare meso-porous carbon material.Weighing 5g P123 surfactant, the 37%HCl of 154ml deionized water, 2ml is added in the 250ml beaker, 38 ℃ of lower magnetic forces stir until the P123 triblock copolymer dissolves fully in water-bath, add the TEOS (tetraethoxysilane) of 10.8g again, 38 ℃ of lower stirrings 24 hours.With 100 ℃ of crystallization of mentioned solution 24 hours.Take out to filter, the deionized water washing, dry (60 ℃) spend the night, and 550 ℃ of lower roastings 5 hours namely get the order mesoporous SiO of SBA-15
2The mixed aqueous solution of dipping sucrose and 0.808g Fe(NO3)39H2O in the SBA-15, dry after at N
2The lower 800 ℃ of charing 5h of atmosphere, and utilize dense hydrofluoric acid to remove template, 80 ℃ of vacuumize 24h namely get in-situ doped Fe behind the filtration washing
2O
3The meso-porous carbon material of nano particle.
Embodiment 11
Adopt hard template method to prepare meso-porous carbon material.Weighing 5g P123 surfactant, the 37%HCl of 154ml deionized water, 2ml is added in the 250ml beaker, 38 ℃ of lower magnetic forces stir until the P123 triblock copolymer dissolves fully in water-bath, add the TEOS (tetraethoxysilane) of 10.8g again, 38 ℃ of lower stirrings 24 hours.With 100 ℃ of crystallization of mentioned solution 36 hours.Take out to filter, the deionized water washing, dry (60 ℃) spend the night, and 550 ℃ of lower roastings 5 hours namely get the order mesoporous SiO of SBA-15
2The mixed aqueous solution of dipping sucrose and 0.249g four hydration cobalt acetates in the SBA-15, dry after at N
2Lower 800 ℃ of charing 5h of atmosphere, and utilize dense hydrofluoric acid to remove template, 80 ℃ of vacuumize 24h behind the filtration washing namely get the meso-porous carbon material of in-situ doped cobalt oxide nano particle.
Embodiment 12
Adopt hard template method to prepare meso-porous carbon material.Weighing 5g P123 surfactant, the 37%HCl of 154ml deionized water, 2ml is added in the 250ml beaker, 38 ℃ of lower magnetic forces stir until the P123 triblock copolymer dissolves fully in water-bath, add the TEOS (tetraethoxysilane) of 10.8g again, 38 ℃ of lower stirrings 24 hours.With 100 ℃ of crystallization of mentioned solution 48 hours.Take out to filter, the deionized water washing, dry (60 ℃) spend the night, and 550 ℃ of lower roastings 5 hours namely get the order mesoporous SiO of SBA-15
2The mixed aqueous solution of dipping sucrose and 0.1372g ammonium molybdate in the SBA-15, dry after at N
2The lower 800 ℃ of charing 5h of atmosphere, and utilize dense hydrofluoric acid to remove template, 80 ℃ of vacuumize 24h namely get in-situ doped MoO behind the filtration washing
3The meso-porous carbon material of nano particle.
Claims (10)
1. in-situ doped material with carbon element with catalytic active component is used in lithium-air battery, it is characterized in that: described in-situ doped material with carbon element with catalytic active component is used as the electrode material in the lithium-air battery;
Described catalytic active component is in-situ doped in material with carbon element, and catalytic active component shared mass fraction in material with carbon element is 1-80%.
2. application according to claim 1 is characterized in that:
Catalytic active component is metal and/or metal oxide; Wherein metal is one or two or more kinds among Fe, Cu, Ni, Ag, Pt, Pd, Au, Ir or the Ru, and metal oxide is one or two or more kinds in the oxide of Fe, Co, Ni, Cu, Zr, Ce, Ti, Mo, Mn, Zn, W or V.
3. application according to claim 1 is characterized in that:
Described material with carbon element adopts hard template method, soft template method or sol-gal process to be prepared from.
4. application according to claim 3 is characterized in that:
Hard template method: in the order mesoporous SiO of SBA-15
2Middle dipping carbon source and catalytic activity component presoma carry out charing under 500～1700 ℃ of argon gas or nitrogen, and remove the SBA-15 template with acid or alkali, after filtration, washing, drying, namely get the material with carbon element of in-situ doped active component.
5. application according to claim 3 is characterized in that:
Described hard template method adopts the following steps preparation when template is nano-powder:
In required ratio carbon source, active component presoma are added the deionized water for stirring dissolving, then add nano-powder, in 50～80 ℃ of heating and mechanical agitation, treat that moisture evaporates 60～80 ℃ of dryings of final vacuum fully;
Dried product is put into the high temperature process furnances charing, the employed inert gas of charing is nitrogen or argon gas, the carbonization temperature scope is at 500～1700 ℃, carbonization time is controlled at 1～8h, obtain nano-powder/active component/carbon complex, remove the nano-powder template with acid or alkali, after filtration, drying, namely get the complex carbon material of in-situ doped active component;
The mass percent scope of described nano-powder and carbon source is 600%～10%;
Nano-powder comprises one or two or more kinds in the nanometer powder of magnesium carbonate, calcium carbonate, magnesium oxide, magnesium acetate, magnesium gluconate, cupric oxide, zinc oxide, ferrous oxide, di-iron trioxide, tri-iron tetroxide, tin ash, silicon dioxide, aluminium oxide, zirconia, molybdenum trioxide, vanadium trioxide or titanium oxide.
6. it is characterized in that according to claim 4 or 5 described application:
Described carbon source is sucrose, glucose, furfuryl alcohol or phenolic resins or resorcinol formaldehyde resin; The catalytic active component presoma is one or more slaines that contain Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W and V; But slaine is nitrate, carbonate, sulfate, acetate, halide, dinitroso diamine salts, the acetylacetonate of metal or encircles greatly one or two or more kinds cosolvency salt in complex compound porphyrin compound, the phthalein mountain valley with clumps of trees and bamboo compound.
7. application according to claim 5 is characterized in that: churned mechanically power bracket is 70～500w, and mixing speed is 50～500rpm; The employed inert gas of carbonization is nitrogen or argon gas, and gas flow is controlled at 10～50ml/min.
8. application according to claim 3 is characterized in that: described soft template method is prepared from accordance with the following steps:
(1) surfactant is dissolved in the solvent, obtains solution A; Described surfactant is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene EO
106-PO
70-EO
106, EO
20-PO
70-EO
20Or EO
132-PO
50-EO
132In one or two or more kinds; Described solvent is one or two or more kinds in water, ethanol, isopropyl alcohol, the methyl alcohol;
(2) add the presoma of catalytic active component in the solution A, add carbon source and silicon source after dissolving fully, through fully stirring, dry rear in 300～550 ℃ of burn off surfactants, 600～1200 ℃ of charing 2～8h under nitrogen or argon gas atmosphere are with hydrofluoric acid or sodium hydroxide solution flush away SiO
2, namely get material with carbon element after the drying; Described carbon source is phenolic resins or resorcinol formaldehyde resin; Described silicon source is tetraethoxysilane.
9. application according to claim 3 is characterized in that:
Described sol-gal process is prepared from accordance with the following steps:
Resorcinol is dissolved in the solvent, the active component presoma is added in the above-mentioned clear solution, then drip formalin, mix under 30～80 ℃ until react and form gel; Gel was processed 60～100 ℃ of lower vacuumizes in aging 3～10 days, pulverized after taking out and grind, obtain pressed powder; Behind high temperature carbonization, namely get the complex carbon material of in-situ doped active component;
Described resorcinol and solvent are in the ratio of 0.1～8ml solvent/1g resorcinol, solvent is a kind of in water, ethanol, isopropyl alcohol, the ethylene glycol, the mol ratio of resorcinol and formaldehyde is 1: 1～5: 1, the mass concentration of described formalin is 30～40%, the carbonization temperature scope is at 500～1700 ℃, and carbonization time is controlled at 1～10h.
10. according to claim 8 or 9 described application, it is characterized in that: the catalytic active component presoma is one or more slaines that contain Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W and V; But slaine is nitrate, carbonate, sulfate, acetate, halide, dinitroso diamine salts, the acetylacetonate of metal or encircles greatly one or two or more kinds cosolvency salt in complex compound porphyrin compound, the phthalein mountain valley with clumps of trees and bamboo compound.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103331162A (en) * | 2013-06-17 | 2013-10-02 | 中国科学院上海硅酸盐研究所 | Mesoporous Co3O4/C composite material with high specific surface and crystallization hole wall and preparation method of material |
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| CN103331162B (en) * | 2013-06-17 | 2015-03-18 | 中国科学院上海硅酸盐研究所 | Mesoporous Co3O4/C composite material with high specific surface and crystallization hole wall and preparation method of material |
| CN103331162A (en) * | 2013-06-17 | 2013-10-02 | 中国科学院上海硅酸盐研究所 | Mesoporous Co3O4/C composite material with high specific surface and crystallization hole wall and preparation method of material |
| CN103594685A (en) * | 2013-08-20 | 2014-02-19 | 湖北文理学院 | Preparation method of lithium ion battery positive electrode material modified molybdenum trioxide |
| CN103594685B (en) * | 2013-08-20 | 2015-09-23 | 湖北文理学院 | A kind of preparation method of modification of lithium ion battery anode material molybdenum trioxide |
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| CN105810915A (en) * | 2016-05-16 | 2016-07-27 | 北京化工大学 | Preparation of graphene-coated sulfur-embedded ordered mesoporous carbon sphere composite material and application of ordered mesoporous carbon sphere composite material as lithium-sulfur battery positive electrode material |
| CN107991371B (en) * | 2017-11-10 | 2020-07-17 | 东北电力大学 | Copper oxide non-enzymatic glucose electrochemical sensor |
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| CN109971469A (en) * | 2017-12-27 | 2019-07-05 | Tcl集团股份有限公司 | The preparation method of carbon quantum dot |
| CN109971469B (en) * | 2017-12-27 | 2020-12-11 | Tcl科技集团股份有限公司 | Preparation method of carbon quantum dots |
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| CN113488666A (en) * | 2021-07-01 | 2021-10-08 | 肇庆市华师大光电产业研究院 | Preparation method of high-performance bifunctional catalyst applied to zinc-air battery |
| CN113488666B (en) * | 2021-07-01 | 2022-08-26 | 肇庆市华师大光电产业研究院 | Preparation method of high-performance bifunctional catalyst applied to zinc-air battery |
| CN113636556A (en) * | 2021-07-22 | 2021-11-12 | 武汉大学 | Ultra-small molybdenum carbide @ carbon composite material and preparation method and application thereof |
| CN113636556B (en) * | 2021-07-22 | 2022-11-18 | 武汉大学 | Ultra-small molybdenum carbide @ carbon composite material and preparation method and application thereof |
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