CN103021662A - Nanometer multilayer mesoporous metal nitride/graphene composite materials for super capacitor and preparation method thereof - Google Patents
Nanometer multilayer mesoporous metal nitride/graphene composite materials for super capacitor and preparation method thereof Download PDFInfo
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Abstract
The invention relates to multilayer metal nitride/graphene electrochemical super capacitor composite electrode materials and a preparation method thereof. The preparation method of the multilayer metal nitride/graphene electrochemical super capacitor composite electrode materials comprises (1) preparing graphene oxide; (2) self-assembling silicon source on the surface of the oxidized graphene to obtain layered graphene oxide-mesoporous silica composite materials GO-SiO2 under an alkaline condition with a cationic surface active agent as a template agent; (3) roasting carbon tetrachloride and ethylenediamine in inert gas after polymerization with the GO-SiO2 as a template and then removing the SiO2 in the template agent to obtain layered graphene-mesoporous carbon nitride composite materials G-C3N4 and (4) cross-linking a metal precursor on the template agent G-C3N4 and then roasting in inert atmosphere to obtain the multilayer metal nitride/graphene electrochemical super capacitor composite electrode materials. The electrode materials prepared from the method have the advantages of being up to 876 farads per gram in specific capacitance, being capable of remaining over 95% in specific capacitance after charge-discharge cycles for 2000 times, being long in service life and being good in cycling stability.
Description
Technical field
The present invention relates to a kind of electrode material for super capacitor with nanometer multilayer metal nitride/graphene composite material and preparation method thereof, belong to electrochemistry and field of material synthesis technology.
Background technology
The energy and environmental problem are the two large problems that the present mankind need solution badly.Fossil energy day by day exhausted, environmental pollution is day by day serious, today of global warming, seeks to substitute the renewable green energy resource of traditional fossil energy, the harmony of seeking human and environment seems particularly urgent.Novel regenerative resource, such as the utilization of wind energy and solar energy etc.; The progressively marketization of electric automobile, hybrid-power electric vehicle, the fast development of various portable power devices all needs energy accumulating system efficient, practical, " green ".For novel " green " energy storage device, in its " green " deeply concerned, high power density, high-energy-density then are its important indicators that whether can really substitute conventional energy accumulating system.Ultracapacitor is present important " green " energy storage device.And wherein the core is the electrode material of excellent performance.
Graphene, as a kind of novel material with carbon element, super large and perfectly the sp2 hybrid systems make it have impayable interior charge transport properties (103-104S/m), the thickness of monolayer makes again its theoretical surface with superelevation amass (2630m
2/ g).Especially have flexible Graphene superthin section and can be piled into by the form of self assembly the 3 D stereo conductive network, the electric charge that this special construction not only is conducive between electroactive material and the collector shifts, also be conducive to migration and the infiltration of charged component in the electrolyte, greatly shorten its diffusion stroke, thereby impel carrying out fast of electrochemical reaction, estimate its electrode material as ultracapacitor is had broad application prospects.
Transition metal nitride is that elemental nitrogen is inserted between a metalloid that generates in the transition metal lattice and fills the type compound, and it is with the character of covalent compound, ionic crystals and 3 kinds of materials of transition metal.Because the insertion of elemental nitrogen causes the metal lattice expansion, it is large that intermetallic distance and lattice constant become, interaction force between metallic atom weakens, produce the redistribution of corresponding d band contraction modification and near the density of states of Fermi energy level, valence electron number increases, and structure also changes thereupon.This modulation makes this compounds of transition metal nitride have unique physics and chemistry performance, such as having the performance in noble metal catalysts such as Pt and Rh in no way inferior, is described as " accurate platinum catalyst ".And as the electrode material aspect of ultracapacitor, the ratio electric capacity of metal nitride even surpassed ruthenium-oxide, the material of this class low cost, high molar density, excellent chemical impedance will be the first-selection of cheap, efficient electrode material for super capacitor of future generation.But metal nitride has two very fatal shortcomings, the one, poorly conductive as super capacitor material; Be that nano material is assembled easily in addition, this has caused tremendous influence to its application.Graphene has excellent conductivity, and huge surface area is the dispersing nanometer particle effectively, has just in time solved the above-mentioned shortcoming of metal nitride as electrode material for super capacitor.
Summary of the invention
The object of the invention is to overcome metal nitride as the defective that super capacitor material exists, and prepares high power capacity, the super capacitor material of environmental protection.The invention provides a kind of nanometer laminated structure metal nitride/graphene composite material and preparation method thereof that has, the metal nitride that is characterized as the about 2nm in aperture, the about 20nm of thickness that it is concrete loads on the single-layer graphene, consists of stratiform mesoporous metal nitride/graphene composite material.Graphene as the matrix skeleton has excellent conductivity, and the laminated metal nitride is close to the Graphene matrix and is realized satisfactory electrical conductivity, has improved the apparent conductivity of composite material.
Ultracapacitor of the present invention makes by following step: (1) preparation graphene oxide with nanometer multilayer mesoporous metal nitride/graphene composite material; (2) take cationic surfactant as template, under the alkali condition, the silicon source obtains layered graphite oxide alkene-meso-porous titanium dioxide silicon composite at the graphene oxide surface self-organization; (3) take layered graphite oxide alkene-meso-porous titanium dioxide silicon composite as template, after carbon tetrachloride and the ethylenediamine polymerization, then roasting in inert gas removes the SiO in the template
2, obtain lamellar graphite alkene-mesoporous carbonitride composite material; (4) so that lamellar graphite alkene-mesoporous carbonitride composite material is as template, metal precursor is crosslinked on template, and then roasting in inert atmosphere obtains lamellar graphite alkene-mesoporous metal nitride.
Concrete operations are:
(1) preparation graphene oxide dispersion liquid (GO): prepare the graphene oxide dispersion liquid from graphite powder.Can be according to the Hummer method.
(2) the graphene oxide-loaded multi-layer mesoporous SiO of preparation
2Material (GO-SiO
2): graphene oxide aqueous dispersions 10 ~ 100mL of 0.25 ~ 2.5mg/L that step (1) is prepared and 0.1 ~ 5g CTAB or CTAC cationic surfactant, 0.01 ~ 0.2g NaOH mix, ultrasonic 30min, fully dissolving, be warming up to 40 ℃, drip silicon precursor 0.1 ~ 3g, at last behind 40 ℃ of insulation reaction 8h, centrifugal, washing, drying obtains GO-SiO
2
(3) preparation stratiform Graphene-mesoporous carbonitride composite material (G-C
3N
4): the graphene oxide-loaded multi-layer mesoporous SiO that step (2) is obtained
2Composite material 1 ~ 5g joins in the reaction bulb, then adds ethylenediamine 2 ~ 15g, and carbon tetrachloride 5 ~ 50mL is centrifugal behind the back flow reaction 8h, washing, and drying, roasting 6h in nitrogen or argon atmospher, product is removed SiO with hydrofluoric acid
2Template, washing, drying obtains G-C
3N
4
(4) preparation stratiform Graphene-mesoporous metal nitride ceramic composites (G-M
xN
y): with the G-C that arrives of step (3)
3N
4Composite material 1-5g join in the reaction bulb, then add metal precursor 1-5g, alcohol solvent 10 ~ 50mL stirs, and exposes 72h and form spawn in air, then dry, solid is roasting 6h in nitrogen or argon atmospher, obtains G-M
xN
yThe ultracapacitor combination electrode material, wherein, M is V, Mo, Ti, Cr or Ni.
The described cationic surfactant of above-mentioned steps (2) refers to softex kw or hexadecyltrimethylammonium chloride.
The described silicon precursor of above-mentioned steps (2) refers to tetraethoxysilane or sodium metasilicate.
The sintering temperature of above-mentioned steps (3) is 400-800 ℃.
The described metal precursor of above-mentioned steps (4) refers to alcoxylates or the acetate of titanium, vanadium, molybdenum, chromium, nickel.Described sintering temperature is 500-750 ℃.
Above-mentioned steps (3) and the described inert gas of step (4) refer to nitrogen and argon gas.
Embodiment
Embodiment (one)
The concentrated sulfuric acid, 2.4g potassium peroxydisulfate, the 2.5g phosphorus pentoxide that add successively 25g in the 500mL container stir, and slowly are warming up to 80 ℃ under water-bath, add 5.0g graphite, stir 10 hours, naturally cool to normal temperature, and behind the suction filtration, drying obtains pre-oxidation graphite.In flask, add 2.5g pre-oxidation graphite, 1.3g natrium nitrosum, the 105g concentrated sulfuric acid, stir under the ice bath, slowly add 7.5g potassium permanganate, the control temperature was 0-5 ℃ of reaction 1 hour, then use 35 ℃ of heating water baths instead, insulation reaction 8 hours, remove water-bath and drip distilled water (T＜98 ℃) with dropper, heating water bath is warming up to 96 ℃, and insulation reaction 30 minutes adds 7.4g 5% hydrochloric acid and 5mL30% hydrogen peroxide in bottle when temperature is reduced to 50-60 ℃, be washed with distilled water to neutrality, ultrasonicly peel off, dialyse, drying obtains graphene oxide.
Take by weighing the 10mg graphite oxide in 20mL water, then add CTAB 0.1g, NaOH 0.01g, ultrasonic dispersion 30min is warming up to 40 ℃, then slowly drips tetraethoxysilane 0.1g, and is centrifugal behind the reaction 12h, the ethanol washing, drying obtains GO-SiO
2Composite material.
Take by weighing 1.0g GO-SiO
2In reaction bulb, then add 2g ethylenediamine and 5mL carbon tetrachloride, 90 ℃ of back flow reaction 12h, the dry 12h of dark-brown solution is ground into fine powder, in blanket of nitrogen, 600 ℃ of roasting 5h, product 5% hydrofluoric acid dissolution filters, the ethanol washing, 100 ℃ of dryings obtain G-C
3N
4Composite material.
Take by weighing 1.0g G-C
3N
4In reaction bulb, add 10mL ethanol and disperse, then add the 1g tetraethyl titanate, stir, in air, expose 72h, form gel, drying, then in blanket of nitrogen, 500 ℃ of roasting 6h obtain the G-TiN composite material.
Through transmission electron microscope observation (TEM), atomic force microscope (AFM), N
2Adsorption-desorption instrument etc. characterize finds that the size of G-TiN is about 1 μ m, and thickness is about 20nm, and the aperture is 2nm, and specific area is 350m
2/ g, the Graphene of above-mentioned preparation-nanometer multilayer TiN is prepared into work electrode, take nickel foam as negative pole, mercury/mercury oxide is as the worn coin electrode, and electrolyte is 1M KOH, charging/discharging voltage is-0.1 ~ 0.6V, under the room temperature, the test of 400mA/g constant current charge-discharge, recording than electric capacity is 636F/g, through 2000 cycle charge-discharges, than capacitance fade less than 5%.
Embodiment (two)
The same embodiment of the preparation of graphene oxide (one).
Take by weighing the 50mg graphite oxide in 40mL water, then add CTAC 5g, NaOH 0.2g, ultrasonic dispersion 30min is warming up to 40 ℃, then slowly drips tetraethoxysilane 3g, and is centrifugal behind the reaction 8h, the ethanol washing, drying obtains GO-SiO
2Composite material.
Take by weighing 5g GO-SiO
2In reaction bulb, then add 15g ethylenediamine and 50mL carbon tetrachloride, 90 ℃ of back flow reaction 24h, the dry 12h of dark-brown solution, be ground into fine powder, in blanket of nitrogen, 800 ℃ of roasting 6h, product 5% hydrofluoric acid dissolution, filter, the ethanol washing, 100 ℃ of dryings obtain G-C
3N
4Composite material.
Take by weighing 1.0g G-C
3N
4In reaction bulb, add 15mL ethanol and disperse, then add 5g triethoxy molybdenum, stir, in air, expose 48h, form gel, drying, then in blanket of nitrogen, 750 ℃ of roasting 6h obtain G-Mo
3N
2Composite material.
Through transmission electron microscope observation (TEM), atomic force microscope (AFM), N
2Adsorption-desorption instrument etc. characterize finds G-Mo
3N
2Size be about 1 μ m, thickness is about 18nm, the aperture is 2.5nm, specific area is 435m
2/ g is with the Graphene of above-mentioned preparation-nanometer multilayer G-Mo
3N
2Be prepared into work electrode, carry out constant current charge-discharge test according to the method for embodiment (), recording than electric capacity is 745F/g, through 2000 cycle charge-discharges, than capacitance fade less than 5%.
Embodiment (three)
The same embodiment of the preparation of graphene oxide (one).
Take by weighing the 20mg graphite oxide in 20mL water, then add CTAB 0.5g, NaOH 0.02g, ultrasonic dispersion 30min is warming up to 40 ℃, then slowly drips tetraethoxysilane 0.75g, and is centrifugal behind the reaction 8h, the ethanol washing, drying obtains GO-SiO
2Composite material.
Take by weighing 0.5g GO-SiO
2In reaction bulb, then add 2.5g ethylenediamine and 7.5mL carbon tetrachloride, 90 ℃ of back flow reaction 24h, the dry 12h of dark-brown solution, be ground into fine powder, in argon atmospher, 600 ℃ of roasting 5h, product 5% hydrofluoric acid dissolution, filter, the ethanol washing, 100 ℃ of dryings obtain G-C
3N
4Composite material.
Take by weighing 1.0g G-C
3N
4In reaction bulb, add 15mL ethanol and disperse, then add 2.2g triethoxy vanadium, stir, in air, expose 72h, form gel, drying, then in argon atmospher, 650 ℃ of roasting 6h obtain the G-VN composite material.
Through transmission electron microscope observation (TEM), atomic force microscope (AFM), N
2Adsorption-desorption instrument etc. characterize finds that the size of G-VN is about 1 μ m, and thickness is about 22nm, and the aperture is 2.2nm, and specific area is 415m
2/ g, the Graphene of above-mentioned preparation-nanometer multilayer G-VN is prepared into work electrode, carries out constant current charge-discharge test according to the method for embodiment (), recording than electric capacity is 798F/g, through 2000 cycle charge-discharges, than capacitance fade less than 5%.
Embodiment (four)
The same embodiment of the preparation of graphene oxide (one).
Take by weighing the 20mg graphite oxide in 40mL water, then add CTAB 1.0g, NaOH 0.03g, ultrasonic dispersion 30min is warming up to 40 ℃, then slowly drips tetraethoxysilane 0.55g, and is centrifugal behind the reaction 8h, the ethanol washing, drying obtains GO-SiO
2Composite material.
Take by weighing 0.5g GO-SiO
2In reaction bulb, then add 2.2g ethylenediamine and 5.0mL carbon tetrachloride, 90 ℃ of back flow reaction 12h, the dry 12h of dark-brown solution, be ground into fine powder, in blanket of nitrogen, 600 ℃ of roasting 6h, product 5% hydrofluoric acid dissolution, filter, the ethanol washing, 100 ℃ of dryings obtain G-C
3N
4Composite material.
Take by weighing 1.0g G-C
3N
4In reaction bulb, add 15mL ethanol and disperse, then add 2.2g triethoxy chromium, stir, in air, expose 72h, form gel, drying, then in blanket of nitrogen, 700 ℃ of roasting 5h obtain the G-CrN composite material.
Through transmission electron microscope observation (TEM), atomic force microscope (AFM), N
2Adsorption-desorption instrument etc. characterize finds that the size of G-CrN is about 1 μ m, and thickness is about 20nm, and the aperture is 2.5nm, and specific area is 398m
2/ g, the Graphene of above-mentioned preparation-nanometer multilayer G-CrN is prepared into work electrode, carries out constant current charge-discharge test according to the method for embodiment (), recording than electric capacity is 532F/g, through 2000 cycle charge-discharges, than capacitance fade less than 5%.
Embodiment (five)
The same embodiment of the preparation of graphene oxide (one).
Take by weighing the 20mg graphite oxide in 40mL water, then add CTAB 1.5g, NaOH 0.03g, ultrasonic dispersion 30min is warming up to 40 ℃, then slowly drips tetraethoxysilane 0.55g, and is centrifugal behind the reaction 8h, the ethanol washing, drying obtains GO-SiO
2Composite material.
Take by weighing 0.5g GO-SiO
2In reaction bulb, then add 2.5g ethylenediamine and 5.0mL carbon tetrachloride, 90 ℃ of back flow reaction 12h, the dry 12h of dark-brown solution, be ground into fine powder, in blanket of nitrogen, 700 ℃ of roasting 6h, product 5% hydrofluoric acid dissolution, filter, the ethanol washing, 100 ℃ of dryings obtain G-C
3N
4Composite material.
Take by weighing 1.0g G-C
3N
4In reaction bulb, add 15mL ethanol and disperse, then add 1.9g triethoxy vanadium and 0.5g nickel acetate, stir, in air, expose 72h, form gel, drying, then in blanket of nitrogen, 800 ℃ of roasting 5h obtain G-Ni
xV
yN
zComposite material.
Through transmission electron microscope observation (TEM), atomic force microscope (AFM), N
2Adsorption-desorption instrument etc. characterize finds G-Ni
xV
yN
zSize be about 1 μ m, thickness is about 24nm, the aperture is 2.1nm, specific area is 432m
2/ g, the Graphene of above-mentioned preparation-nanometer multilayer G-Ni
xV
yN
zBe prepared into work electrode, carry out constant current charge-discharge test according to the method for embodiment (), recording than electric capacity is 876F/g, through 2000 cycle charge-discharges, than capacitance fade less than 5%.
Claims (10)
1. a ultracapacitor is characterized in that may further comprise the steps with nanometer multilayer mesoporous metal nitride/graphene composite material preparation method:
(1) preparation graphene oxide;
(2) take cationic surfactant as template, under the alkali condition, the silicon source obtains layered graphite oxide alkene-meso-porous titanium dioxide silicon composite at the graphene oxide surface self-organization;
(3) take layered graphite oxide alkene-meso-porous titanium dioxide silicon composite as template, after carbon tetrachloride and the ethylenediamine polymerization, then roasting in inert gas removes the SiO in the template
2, obtain lamellar graphite alkene-mesoporous carbonitride composite material;
(4) so that lamellar graphite alkene-mesoporous carbonitride composite material is as template, metal precursor is crosslinked on template, and then roasting in inert atmosphere obtains lamellar graphite alkene-mesoporous metal nitride.
2. ultracapacitor according to claim 1 is characterized in that concrete steps are as follows with nanometer multilayer mesoporous metal nitride/graphene composite material preparation method:
(1) preparation graphene oxide: prepare the graphene oxide aqueous dispersions with graphite powder;
(2) preparation stratiform graphene oxide-meso-porous titanium dioxide silicon composite: take graphene oxide, cationic surfactant, NaOH, silicon precursor as raw material, water is solvent, quality 10 ~ 50mg in graphene oxide: quality 0.01 ~ 0.2g of the quality 0.1 ~ 5g:NaOH of cationic surfactant: the ratio of the volume 10 ~ 50mL of water is mixed in container, then in the quality 0.1 ~ 5g of cationic surfactant: the ratio of the quality 0.1 ~ 3g of silicon precursor drips silicon precursor, at last behind 40 ℃ of insulation reaction 8h, centrifugal, washing, drying;
(3) preparation stratiform Graphene-mesoporous carbonitride composite material: in the quality 1 ~ 5g of graphene oxide-mesoporous silicon oxide: the quality 2 ~ 15g of ethylenediamine: the ratio of the volume 5 ~ 50mL of carbon tetrachloride, in container, behind the back flow reaction 8h, centrifugal, washing, drying, roasting 6h in the inert gas atmosphere obtains solid and removes SiO with hydrofluoric acid
2Rear washing, drying;
(4) preparation stratiform Graphene-mesoporous metal nitride ceramic composites: by the quality 1-5g of Graphene-mesoporous carbonitride: the ratio of the quality 1-5g of metal precursor is mixed, and stirring exposes 72h, drying, roasting 6h in the inert gas atmosphere in air.
3. a kind of ultracapacitor according to claim 2 is with the preparation method of nanometer multilayer mesoporous metal nitride/graphene composite material, it is characterized in that the described cationic surfactant of step (2) refers to softex kw or hexadecyltrimethylammonium chloride.
4. a kind of ultracapacitor according to claim 2 is characterized in that with the preparation method of nanometer multilayer mesoporous metal nitride/graphene composite material the described silicon precursor of step (2) refers to tetraethoxysilane or sodium metasilicate.
5. a kind of ultracapacitor according to claim 1 is characterized in that with the preparation method of nanometer multilayer mesoporous metal nitride/graphene composite material the sintering temperature of step (3) is 400-800 ℃.
6. a kind of ultracapacitor according to claim 1 is with the preparation method of nanometer multilayer mesoporous metal nitride/graphene composite material, it is characterized in that the described metal precursor of step (4) refers to alcoxylates or its acetate of titanium, vanadium, molybdenum, chromium, nickel.
7. a kind of ultracapacitor according to claim 1 is characterized in that with the preparation method of nanometer multilayer mesoporous metal nitride/graphene composite material the described sintering temperature of step (4) is 500-750 ℃.
8. a kind of ultracapacitor according to claim 1 is characterized in that with the preparation method of nanometer multilayer mesoporous metal nitride/graphene composite material step (3) and the described inert gas of step (4) refer to nitrogen and argon gas.
9. a ultracapacitor is characterized in that making by following method: (1) preparation graphene oxide with nanometer multilayer mesoporous metal nitride/graphene composite material; (2) take cationic surfactant as template, under the alkali condition, the silicon source obtains layered graphite oxide alkene-meso-porous titanium dioxide silicon composite at the graphene oxide surface self-organization; (3) take layered graphite oxide alkene-meso-porous titanium dioxide silicon composite as template, after carbon tetrachloride and the ethylenediamine polymerization, then roasting in inert gas removes the SiO in the template
2, obtain lamellar graphite alkene-mesoporous carbonitride composite material; (4) so that lamellar graphite alkene-mesoporous carbonitride composite material is as template, metal precursor is crosslinked on template, and then roasting in inert atmosphere obtains lamellar graphite alkene-mesoporous metal nitride.
10. a kind of ultracapacitor according to claim 9 is characterized in that making by following concrete steps with nanometer multilayer mesoporous metal nitride/graphene composite material:
(1) preparation graphene oxide: prepare the graphene oxide aqueous dispersions with graphite powder;
(2) preparation stratiform graphene oxide-meso-porous titanium dioxide silicon composite: take graphene oxide, cationic surfactant, NaOH, silicon precursor as raw material, water is solvent, quality 10 ~ 50mg in graphene oxide: quality 0.01 ~ 0.2g of the quality 0.1 ~ 5g:NaOH of cationic surfactant: the ratio of the volume 10 ~ 50mL of water is mixed in container, then in the quality 0.1 ~ 5g of cationic surfactant: the ratio of the quality 0.1 ~ 3g of silicon precursor drips silicon precursor, at last behind 40 ℃ of insulation reaction 8h, centrifugal, washing, drying;
(3) preparation stratiform Graphene-mesoporous carbonitride composite material: in the quality 1 ~ 5g of graphene oxide-mesoporous silicon oxide: the quality 2 ~ 15g of ethylenediamine: the ratio of the volume 5 ~ 50mL of carbon tetrachloride, in container, behind the back flow reaction 8h, centrifugal, washing, drying, roasting 2-8h in the inert gas atmosphere obtains solid and removes SiO with hydrofluoric acid
2Rear washing, drying;
(4) preparation stratiform Graphene-mesoporous metal nitride ceramic composites: by the quality 1-5g of Graphene-mesoporous carbonitride: the ratio of the quality 1-5g of metal precursor is mixed, and stirring exposes 72h, drying, roasting 6h in the inert gas atmosphere in air.
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