CN105161311A - Method for preparing titanium nitride/carbon composite materials - Google Patents
Method for preparing titanium nitride/carbon composite materials Download PDFInfo
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- CN105161311A CN105161311A CN201510489658.8A CN201510489658A CN105161311A CN 105161311 A CN105161311 A CN 105161311A CN 201510489658 A CN201510489658 A CN 201510489658A CN 105161311 A CN105161311 A CN 105161311A
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Abstract
The invention provides a method for preparing titanium nitride/carbon composite materials. A surfactant is dissolved in a solvent, an organic titanium source and inorganic salt are added, uniform mixing is performed, then a phenolic resin ethanol solution is added, and finally an organic silicon source is added. Complete stirring is performed in a water bath of 35-45 DEG C to form a homogeneous solution, then the homogeneous solution is poured into a reaction container, and the reaction container is placed in a drying box for crosslinking, so that a transparent membrane object is obtained. The transparent membrane object is scraped off, roasted under the protection of nitrogen in a tubular furnace, and then naturally cooled to the room temperature, so that a TiN/SiO2/C compound is obtained. The TiN/SiO2/C compound is added in a sodium hydroxide solution for water-bath stirring and then centrifugal washing until an effluent liquid is neutral, and the effluent liquid is naturally dried, so that a TiN/C composite nanometer material is obtained. The invention is simple in process and low in synthesis temperature.
Description
Technical field
The invention belongs to the field of inorganic material synthesis, relate to a kind of electrode material of ultracapacitor, specifically a kind of preparation method of titanium nitride/carbon composite nano-material.
Background technology
Along with the fast development in portable electron device and hybrid vehicle market, greatly developing environmentally friendly high-performance energy storage device becomes one of important topic of current world economy sustainable development.Traditional energy storage device common is in the market battery (comprising the secondary cell such as the primary cells such as alkali manganese, silver-colored zinc and plumbic acid, NI-G, ni-mh, lithium ion, polymer) and traditional capacitor, although but during the relatively large energy storage of battery energy density, the charging interval is longer, power density is relatively low, be difficult to meet the specific application scenarios such as such as some high energy pulses, although and traditional capacitor can fast charging and discharging, power density is high but its energy density is lower, scope of its application constantly reduces.
The appearance of ultracapacitor and electrochemical capacitor makes above-mentioned problem be resolved.Ultracapacitor has the advantages such as power density is large, long service life, charge/discharge rates are fast.In addition ultracapacitor can be matched to hybrid energy-storing device with the energy storage device of other high-energy-density, as assembling lithium ion battery or fuel cell coupling, is applied in the hybrid-electric car of low-emission.The chemical property wherein affecting electrochemical capacitor is its electrode material, therefore finds the emphasis that high performance electrode material is research.The material be applied in now on electrochemical capacitor comprises carbon-based material, metal oxide materials, conducting polymer materials and composite material.Because carbon-based material has good conductivity and higher mechanical strength, but the mainly electric double layer capacitance that carbon-based material provides, its capacitance is preferential, and metal oxide and its capacitance of conducting polymer are more a lot of than the height of carbon-based material, therefore two kinds of different materials are combined composition composite material and make it have better capacitive property.(Xie little Ying, Zhang Chen, Yang Quanhong. electrode material for super capacitor progress [J]. chemical industry and engineering .2014,01,013,63-71; Li Ying. the electrochemical capacitance performance [D] of manganese dioxide and manganese dioxide/graphene oxide combination electrode. Tianjin: University Of Tianjin, 2012; Qian Luming. the electrode of super capacitor preparation [D] of novel hybride material with carbon element. Nanjing: Institutes Of Technology Of Nanjing, 2013).
Transition metal nitride TiN has high-melting-point, high rigidity, excellent chemical stability and corrosion resistance, therefore becomes the preferred material of cutting tools, wear parts, and the enhancing be simultaneously often used as in composite material is equal.Zhu Fuxing etc. adopt electrolysis to prepare titanium nitride, concrete grammar prepares in the process of Titanium in titanium soluble anode point solution, and pass into nitrogen at negative electrode, the titanium that nitrogen and negative electrode produce reacts and generates titanium nitride, separate electrolyte and titanium nitride afterwards, namely obtains titanium nitride product.The temperature of its mid point solution is 650 ~ 850 DEG C, needs the step using distillation, washing and pickling etc. in the process of separate electrolyte.The temperature of distillation is 950 ~ 1000 DEG C.Although he can take a step to prepare titanium nitride, synthesis step cumbersome, and distillation needed for temperature also higher, general device can not meet the demands, and therefore this method still exists very large defect (Zhu Fuxing, Mu Tianzhu, Deng Bin, what Anxi, Cheng Xiaozhe, Ma Shangrun, mass troops, Zheng Quan, Zhang Yao. prepare the method for titanium nitride, China, CN104498982A.2015-04-08.).
Etc. RomuloR.M. cathode cage plasma technique is utilized to prepare TiN, utilize the conventional plasma reactor with two concentric cathode cages exactly, be 1500V at maximum voltage, when electric current is 2A, place at cathode cage two titanium sheet that two thickness are 2.0mm, in the process of preparation, pass into N afterwards
2/ H
2(80%N
2) gaseous mixture, treatment temperature remains on 400 DEG C, prepares titanium nitride.Although obtain titanium nitride by this method, but will when high voltage, not too safe, therefore (RomuloR.M.deSousa to be further improved in addition, PatriciaS.Sato, BartolomeuC.Viana, ClodomiroAlvesJr, AkioNishimoto, PedroA.P.Nascente.CathodiccageplasmadepositionofTiNandTi O2thinfilmsonsiliconsubstrates.J.Vac.Sci.Technol.A33 (4), Jul/Aug2015).
Lu Yuan etc. for raw material, adopt carbothermic method to prepare porous titanium nitride with titanium dioxide and carbon dust.Concrete steps are that the ratio taking mol ratio as 1:2 titanium dioxide and carbon black prepares, then the powder prepared and abrading-ball are put into mixing tank, take absolute ethyl alcohol as medium planetary ball mill wet mixing 24h, post-drying, sieve with 200 object screen clothes, put afterwards and be pressed into rectangle in a mold, sinter under being then placed on the nitrogen pressure of 0.5MPa, the temperature of sintering is 1600 ~ 1750 DEG C, obtains the titanium nitride of high porosity.But sintering temperature is higher in experiment, can not meet daily prepare needs (Lu Yuan, Gong Nan, Jing Qiangzheng, Li Jingjing, soot Ke. carbothermic method prepares porous titanium nitride pottery [J]. ceramic journal, 2009,32(2), 177-182).
In sum, prepared TiN powder in the past, have plenty of through mechanical lapping, and then to obtain through high-temperature roasting, also have and realize object through methods such as solutions, but generally speaking the temperature to need of high-temperature roasting is all more than 1000 DEG C, general tube furnace can not meet the requirement of experiment, and higher through the equipment requirement of physical grinding process need, not easy to operate, and the requirement all very high of the equipment of electrolytic process needs.Therefore need to find one easy and simple to handle, roasting can just obtain TiN nano particle at low temperatures.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of preparation method of titanium nitride/carbon composite nano-material, the preparation method of described this titanium nitride/carbon composite nano-material solves and of the prior artly prepares titanium nitride/carbon composite nano-material complex process, the technical problem high to the requirement of equipment.
The preparation method of a kind of titanium nitride/carbon composite of the present invention, comprises the following steps:
(1), surfactant is dissolved in solvent, then organic titanium source and inorganic salts are added, be uniformly mixed, add the phenolic resins ethanolic solution that mass percent concentration is 15 ~ 25% afterwards, finally add organosilicon source, fully stir under 35 ~ 45 DEG C of water-baths and form homogeneous phase solution, pour in a reaction vessel subsequently, be placed on 35 ~ 45 DEG C of air dry oven 15 ~ 30h, be then put in 80 ~ 110 DEG C of air dry ovens and be cross-linked, thus obtain transparent membranoid substance;
The mass ratio of above-mentioned surfactant used, solvent, organic titanium source, inorganic salts, silicon source, phenol resin solution is 1.0:10 ~ 30:1.5 ~ 5:1 ~ 4:0.3 ~ 4:0.8 ~ 3;
Described surfactant is EO
20pO
70eO
20, EO
106pO
70eO
106, or EO
132pO
60eO
132in one or more mixture;
Described solvent is two or more mixture in ethanol, water, formic acid, ethylene glycol or methyl ether;
Described organic titanium source is Titanium Citrate;
Described inorganic salts are one or both and above mixture in Nickelous nitrate hexahydrate, Fe(NO3)39H2O or cabaltous nitrate hexahydrate;
Described organosilicon source is the mixture of one or more compositions in tetraethyl orthosilicate, positive quanmethyl silicate, positive silicic acid orthocarbonate or positive silicic acid four butyl ester;
(2), by the transparent membranoid substance obtained in step (1) scrape, in tube furnace, be warming up to 700 ~ 900 DEG C under nitrogen protection carry out roasting 1 ~ 3 hour, then naturally cool to room temperature, namely obtain TiN/SiO
2the compound of/C;
(3), by TiN/SiO that step (2) obtains
2/ C compound joins in the sodium hydroxide solution of 0.2 ~ 2mol/L, wherein TiN/SiO
2/ C and concentration are the consumption of the sodium hydroxide solution of 0.2 ~ 2mol/L, by TiN/SiO
2/ C: the ratio of concentration to be the sodium hydroxide solution of 0.2 ~ 2mol/L be 1g:10 ~ 30ml calculates, and 35 ~ 45 DEG C of stirring in water bath 10 ~ 40min, then centrifugal washing, wash efflux for neutral, then natural drying, obtains TiN/C composite nano materials.
Further, the preparation process of described Titanium Citrate is as follows;
100mmol butyl titanate is dissolved in 50ml alcohol solvent and prepares solution A, 100mmol citric acid is dissolved in 100ml alcohol solvent and prepares B solution, B solution instills in solution A under fast stirring lentamente afterwards, and under 40 DEG C of water-baths, stir 2h, then 40 DEG C of reduction vaporization 1h, the colloidal sol obtained again is dissolved in distilled water and is made into the 1M Titanium Citrate aqueous solution, and density is about 1g/ml.
Further, the intensification described in step (2), is first raised to 300 DEG C by speed 1 DEG C/min from room temperature, and then is that 5 DEG C/min rises to 700 ~ 900 DEG C by speed.
Further, the mass ratio of surfactant used in step (1), solvent, organic titanium source, inorganic salts, silicon source, phenol resin solution is 1:10:1.5:1:0.3:0.8; Described surfactant is EO
20pO
70eO
20; Described organosilicon source is tetraethyl orthosilicate; Described organic titanium source is Titanium Citrate; Described inorganic salts are Nickelous nitrate hexahydrate; Described solvent is ethylene glycol and water.
Further, the mass ratio of surfactant used in step (1), solvent, organic titanium source, inorganic salts, silicon source, phenol resin solution is 1:20:3:2.5:2.2:1.9; Described surfactant is EO
106pO
70eO
106; Described organosilicon source is positive quanmethyl silicate; Described organic titanium source is Titanium Citrate; Described inorganic salts are Fe(NO3)39H2O; Described solvent is second alcohol and water.
Further, the mass ratio of surfactant used in step (1), solvent, organic titanium source, inorganic salts, silicon source, phenol resin solution is 1:30:5:4:4:3; Described surfactant is EO
132pO
60eO
132; Described organosilicon source is positive silicic acid orthocarbonate; Described organic titanium source is Titanium Citrate; Described inorganic salts are cabaltous nitrate hexahydrate; Described solvent is first alcohol and water.
Present invention also offers the purposes of titanium nitride/carbon composite nano-material in the electrode material making ultracapacitor obtained by above-mentioned preparation method.
Surfactant, organic titanium source, inorganic salts, silicon source and carbon source are dissolved in a solvent according to certain ratio by the present invention, at a certain temperature, acted synergistically by organic and inorganic, and carbonization under high temperature nitrogen atmosphere further, obtain the compound of titanium nitride/silicon/carbon dioxide, remove silicon dioxide with aqueous slkali.Owing to adding the silicon source as hard mould agent in preparation process, subsiding of duct in high-temperature calcination process can be stoped, thus prepare the titanium nitride/carbon nanomaterial with high-specific surface area.The specific area of the titanium nitride/carbon composite nano-material finally obtained is 383 ~ 514m2/g, pore volume is 2.3 ~ 3.2nm, and the specific capacity be applied on electrochemical capacitor is 79 ~ 145F/g.
The present invention compares with prior art, and its technological progress is significant.The invention solves preparation method of the prior art to need higher temperature roasting, operate the shortcomings such as complicated, thus inhibit the technical problem of the large-scale production of TiN.The present invention utilizes organic titanium and phenolic resins respectively as titanium source and carbon source, wherein adds inorganic salts as catalyst, utilizes the method for evaporation-induced self-assembly to obtain TiN/C composite nano materials at a lower temperature.The present invention has that technique is simple, raw material mixes, generated time is short, synthesis temperature is low, and general tube furnace can meet the requirement of roasting, is applicable to the features such as large-scale production.
Accompanying drawing explanation
Fig. 1 is the high-crystallinity of embodiment 1 gained, the little angle XRD of the titanium nitride/composite nano materials of bigger serface schemes;
Fig. 2 is the titanium nitride/composite nano materials big angle XRD collection of illustrative plates of high-crystallinity in embodiment 1, bigger serface;
Fig. 3 is the nitrogen adsorption-desorption figure of the high-crystallinity of gained in embodiment 1, the titanium nitride/composite nano materials of bigger serface;
Fig. 4 is the cyclic voltammogram of the high-crystallinity of gained in embodiment 1, the titanium nitride/composite nano materials of bigger serface.
Embodiment
Also come by reference to the accompanying drawings to conduct further description the present invention below by way of specific embodiment, but protection scope of the present invention is not limited thereto.
Described method if no special instructions.Be conventional method.Described material if no special instructions, all can buy from open commercial sources.
Model and manufacturer's information of the instrument that various embodiments of the present invention are used or equipment are as follows:
Electronic balance JA203 Shanghai Haikang Electronic Instruments Plant
Muffle furnace DC-B8/11 Beijing original creation Science and Technology Ltd.
Electrochemical workstation CH660D Shanghai Chen Hua instrument company
The permanent scientific instrument in electric heating constant-temperature blowing drying box DHG-9070A Shanghai one
Tube furnace, model SL1700 II type, manufacturer: Shanghai Sheng Li tester Co., Ltd;
X-ray diffractometer (XRD), PANalytical company of XPERTPRO Holland;
Full-automatic physical Sorption Analyzer, Merck & Co., Inc of the ASAP2020 U.S.;
Embodiment 1
A preparation method for TiN/C composite nano materials at a lower temperature, is characterized in that comprising the following steps:
(1), at 40 DEG C, 0.3g surfactant is dissolved in the solution mixed in 4g solvent, then 0.5ml organic titanium source and 0.3g inorganic salts are added, be uniformly mixed, add the phenolic resins ethanolic solution that 0.4g mass percent concentration is 20% afterwards, finally add 0.24g organosilicon source, fully stir under 40 DEG C of water-baths and form homogeneous phase solution, pour into subsequently in surface plate, be placed on 40 DEG C of air dry oven 24h, be then put in 100 DEG C of air dry ovens and be cross-linked.Thus obtain transparent membranoid substance.
Above-mentioned surfactant used, solvent, organic titanium source, inorganic salts, silicon source, mass percent concentration are the amount of the phenol resin solution of 20%, calculate in mass ratio, surfactant: solvent: organic titanium source: inorganic salts: silicon source: mass percent concentration be 20% phenol resin solution be 1.0:13:1.7:1:1.3:0.8;
Described surfactant is EO
20pO
70eO
20;
Described solvent is the mixture of second alcohol and water;
Described organic titanium source is Titanium Citrate;
Described inorganic salts are Nickelous nitrate hexahydrate;
Described organosilicon source is tetraethyl orthosilicate;
(2), the transparent membranoid substance obtained in step 1 is scraped; in tube furnace, be first raised to 300 DEG C by speed 1 DEG C/min from room temperature under nitrogen protection, roasting two hours, then be that 5 DEG C/min rises to 700 DEG C and carries out roasting 2h by speed; then naturally cool to room temperature, namely obtain TiN/SiO
2the compound of/C.
(3), by TiN/SiO that step (2) obtains
2/ C compound joins in the sodium hydroxide solution of 0.2mol/L, 40 DEG C of stirring in water bath 10min, then centrifugal washing, and wash efflux for neutral, then natural drying, obtains TiN/C composite nano materials.
X-ray powder diffraction instrument (PANalyticalX ' Pertdiffractometer) is adopted to measure the final high-crystallinity of gained of above-mentioned steps (3), the titanium nitride/carbon nano-composite material of bigger serface, the little angle XRD collection of illustrative plates of gained as shown in Figure 1, as can be seen from Figure 1, the high-crystallinity of gained, the iron oxide/carbon nano-composite material of bigger serface have an obvious diffraction maximum in about 1 °, 2 this tower, indicate iron oxide/carbon nano-composite material thus and have good order.
X-ray powder diffraction instrument (PANalyticalX ' Pertdiffractometer) is adopted to measure the final high-crystallinity of gained of above-mentioned steps (3), the titanium nitride/carbon nano-composite material of bigger serface, the big angle XRD collection of illustrative plates of gained as shown in Figure 2, the diffraction maximum representing TiN is as can be seen from Figure 2 very sharp-pointed, the TiN demonstrating formation has high cleanliness factor, and nickel exists with the form of simple substance, do not participate in reaction and form compound, be the effect of catalyst.
Adopt specific area and lacunarity analysis instrument, measure according to the titanium nitride/carbon nano-composite material of nitrogen adsorption-desorption method to above-mentioned steps (3) gained, nitrogen adsorption-desorption the result of gained as shown in Figure 3, as can be seen from Figure 3 curve has and obviously returns stagnant ring, indicating the ferrous oxide/carbon nano-composite material prepared thus is mesoporous material, and to have its specific area of large specific area be 456m
2/ g, pore volume is 0.339cm
3/ g, aperture is 2.9nm.
By the mesoporous titanium nitride/carbon composite nano-material grind into powder of above-mentioned gained, with conductive agent acetylene black, polytetrafluoroethylene in mass ratio for the ratio of 8:1:1 mixes, be coated in uniformly in the nickel foam of precise, in vacuum drying chamber, control temperature processes 12h at 120 DEG C, at 10MPa tableting under pressure, is made into work electrode, with reference electrode Ag/AgCl, to electrode platinum electrode, and the KOH aqueous solution of 1mol/L is that electrolyte forms three-electrode system, is used for testing chemical property.
The electrode material that the ultracapacitor of above-mentioned gained is used adopts cyclic voltammetry to measure by Shanghai occasion China CHI660C electrochemical workstation, as shown in Figure 4, the capacitance of capacitance under 10mV/s, 20mV/s, 50mV/s, 100mV/s, 200mV/s sweep speed that result obtains electrode is respectively 97F/g, 87F/g, 81F/g, 75F/g, 68F/g to result.
Embodiment 2
A preparation method for TiN/C composite nano materials at a lower temperature, is characterized in that comprising the following steps:
(1), at 40 DEG C, 0.6g surfactant is dissolved in the solution mixed in 12g solvent, then 1.8ml organic titanium source and 1.5g inorganic salts are added, be uniformly mixed, add the phenolic resins ethanolic solution that 1.2g mass percent concentration is 20% afterwards, finally add 0.6g organosilicon source, fully stir under 40 DEG C of water-baths and form homogeneous phase solution, pour into subsequently in surface plate, be placed on 40 DEG C of air dry oven 24h, be then put in 100 DEG C of air dry ovens and be cross-linked.Thus obtain transparent membranoid substance.
Above-mentioned surfactant used, solvent, organic titanium source, inorganic salts, silicon source, mass percent concentration are the amount of the phenol resin solution of 20%, calculate in mass ratio, surfactant: solvent: organic titanium source: inorganic salts: silicon source: mass percent concentration be 20% phenol resin solution be 1.0:20:3:2.5:2:1;
Described surfactant is EO
132pO
60eO
132;
Described solvent is the mixture of first alcohol and water;
Described organic titanium source is Titanium Citrate;
Described inorganic salts are Fe(NO3)39H2O;
Described organosilicon source is positive quanmethyl silicate;
(2), the transparent membranoid substance obtained in step 1 is scraped; in tube furnace, be first raised to 300 DEG C by speed 1 DEG C/min from room temperature under nitrogen protection, roasting two hours, then be that 5 DEG C/min rises to 800 DEG C and carries out roasting 2h by speed; then naturally cool to room temperature, namely obtain TiN/SiO
2the compound of/C.
(3), by TiN/SiO that step (2) obtains
2/ C compound joins in the sodium hydroxide solution of 0.5mol/L, 40 DEG C of stirring in water bath 30min, then centrifugal washing, and wash efflux for neutral, then natural drying, obtains TiN/C composite nano materials.
Adopt specific area and lacunarity analysis instrument, measure according to the mesoporous titanium nitride/carbon nano-composite material of nitrogen adsorption-desorption method to above-mentioned steps (3) gained, the specific area of the material of nitrogen adsorption-desorption result survey of gained is 385m
2/ g, pore volume is 0.278cm
3/ g, aperture is 2.3nm.
By the mesoporous titanium nitride/carbon composite nano-material grind into powder of above-mentioned gained, with conductive agent acetylene black, polytetrafluoroethylene in mass ratio for the ratio of 8:1:1 mixes, be coated in uniformly in the nickel foam of precise, in vacuum drying chamber, control temperature processes 12h at 120 DEG C, at 10MPa tableting under pressure, is made into work electrode, with reference electrode Ag/AgCl, to electrode platinum electrode, and the KOH aqueous solution of 1mol/L is that electrolyte forms three-electrode system, is used for testing chemical property.
The electrode material that the ultracapacitor of above-mentioned gained is used adopts cyclic voltammetry to measure by Shanghai occasion China CHI660C electrochemical workstation, result as shown in Figure 4, is 82F/g under the current density of the capacitance that result obtains electrode under 10mV/s sweep speed.
Embodiment 3
A preparation method for TiN/C composite nano materials at a lower temperature, is characterized in that comprising the following steps:
(1), at 40 DEG C, 1g surfactant is dissolved in the solution mixed in 30g solvent, then 5ml organic titanium source and 4g inorganic salts are added, be uniformly mixed, add the phenolic resins ethanolic solution that 4g mass percent concentration is 20% afterwards, finally add 3g organosilicon source, fully stir under 40 DEG C of water-baths and form homogeneous phase solution, pour into subsequently in surface plate, be placed on 40 DEG C of air dry oven 24h, be then put in 100 DEG C of air dry ovens and be cross-linked.Thus obtain transparent membranoid substance.
Above-mentioned surfactant used, solvent, organic titanium source, inorganic salts, silicon source, mass percent concentration are the amount of the phenol resin solution of 20%, calculate in mass ratio, surfactant: solvent: organic titanium source: inorganic salts: silicon source: mass percent concentration be 20% phenol resin solution be 1.0:30:5:4:4:3;
Described surfactant is EO
106pO
70eO
106;
Described solvent is the mixture of ethylene glycol and water;
Described organic titanium source is Titanium Citrate;
Described inorganic salts are cabaltous nitrate hexahydrate;
Described organosilicon source is positive silicic acid orthocarbonate;
(2), the transparent membranoid substance obtained in step 1 is scraped; in tube furnace, be first raised to 300 DEG C by speed 1 DEG C/min from room temperature under nitrogen protection, roasting two hours, then be that 5 DEG C/min rises to 900 DEG C and carries out roasting 2h by speed; then naturally cool to room temperature, namely obtain TiN/SiO
2the compound of/C.
(3), by TiN/SiO that step (2) obtains
2/ C compound joins in the sodium hydroxide solution of 2mol/L, 40 DEG C of stirring in water bath 30min, then centrifugal washing, and wash efflux for neutral, then natural drying, obtains TiN/C composite nano materials.
Adopt specific area and lacunarity analysis instrument, measure according to the mesoporous titanium nitride/carbon nano-composite material of nitrogen adsorption-desorption method to above-mentioned steps (3) gained, the specific area of the material of nitrogen adsorption-desorption result survey of gained is 512m
2/ g, pore volume is 0.423cm
3/ g, aperture is 3.1nm.
By the mesoporous titanium nitride/carbon composite nano-material grind into powder of above-mentioned gained, with conductive agent acetylene black, polytetrafluoroethylene in mass ratio for the ratio of 8:1:1 mixes, be coated in uniformly in the nickel foam of precise, in vacuum drying chamber, control temperature processes 12h at 120 DEG C, at 10MPa tableting under pressure, is made into work electrode, with reference electrode Ag/AgCl, to electrode platinum electrode, and the KOH aqueous solution of 1mol/L is that electrolyte forms three-electrode system, is used for testing chemical property.
The electrode material that the ultracapacitor of above-mentioned gained is used adopts cyclic voltammetry to measure by Shanghai occasion China CHI660C electrochemical workstation, result as shown in Figure 4, is 145F/g under the current density of the capacitance that result obtains electrode under 10mV/s sweep speed.
Claims (7)
1. a preparation method for titanium nitride/carbon composite, is characterized in that: comprise the following steps:
(1), surfactant is dissolved in solvent, then organic titanium source and inorganic salts are added, be uniformly mixed, add the phenolic resins ethanolic solution that mass percent concentration is 15 ~ 25% afterwards, finally add organosilicon source, fully stir under 35 ~ 45 DEG C of water-baths and form homogeneous phase solution, pour in a reaction vessel subsequently, be placed on 35 ~ 45 DEG C of air dry oven 15 ~ 30h, be then put in 80 ~ 110 DEG C of air dry ovens and be cross-linked, thus obtain transparent membranoid substance;
The mass ratio of above-mentioned surfactant used, solvent, organic titanium source, inorganic salts, silicon source, phenol resin solution is 1.0:10 ~ 30:1.5 ~ 5:1 ~ 4:0.3 ~ 4:0.8 ~ 3;
Described surfactant is EO
20pO
70eO
20, EO
106pO
70eO
106, or EO
132pO
60eO
132in one or more mixture;
Described solvent is two or more mixture in ethanol, water, formic acid, ethylene glycol or methyl ether;
Described organic titanium source is Titanium Citrate;
Described inorganic salts are one or both and above mixture in Nickelous nitrate hexahydrate, Fe(NO3)39H2O or cabaltous nitrate hexahydrate;
Described organosilicon source is the mixture of one or more compositions in tetraethyl orthosilicate, positive quanmethyl silicate, positive silicic acid orthocarbonate or positive silicic acid four butyl ester;
(2), by the transparent membranoid substance obtained in step (1) scrape, in tube furnace, be warming up to 700 ~ 900 DEG C under nitrogen protection carry out roasting 1 ~ 3 hour, then naturally cool to room temperature, namely obtain TiN/SiO
2the compound of/C;
(3), by TiN/SiO that step (2) obtains
2/ C compound joins in the sodium hydroxide solution of 0.2 ~ 2mol/L, wherein TiN/SiO
2/ C and concentration are the consumption of the sodium hydroxide solution of 0.2 ~ 2mol/L, by TiN/SiO
2/ C: the ratio of concentration to be the sodium hydroxide solution of 0.2 ~ 2mol/L be 1g:10 ~ 30ml calculates, and 35 ~ 45 DEG C of stirring in water bath 10 ~ 40min, then centrifugal washing, wash efflux for neutral, then natural drying, obtains TiN/C composite nano materials.
2. the preparation method of a kind of titanium nitride/carbon composite as claimed in claim 1, is characterized in that: the preparation process of described Titanium Citrate is as follows;
100mmol butyl titanate is dissolved in 50ml alcohol solvent and prepares solution A, 100mmol citric acid is dissolved in 100ml alcohol solvent and prepares B solution, B solution instills in solution A under fast stirring lentamente afterwards, and under 40 DEG C of water-baths, stir 2h, then 40 DEG C of reduction vaporization 1h, the colloidal sol obtained again is dissolved in distilled water and is made into the 1M Titanium Citrate aqueous solution, and density is about 1g/ml.
3. the preparation method of a kind of titanium nitride/carbon composite as claimed in claim 1, is characterized in that: the intensification described in step (2), is first raised to 300 DEG C by speed 1 DEG C/min from room temperature, and then is that 5 DEG C/min rises to 700 ~ 900 DEG C by speed.
4. the preparation method of a kind of titanium nitride/carbon composite as claimed in claim 1, is characterized in that: the mass ratio of surfactant used in step (1), solvent, organic titanium source, inorganic salts, silicon source, phenol resin solution is 1:10:1.5:1:0.3:0.8; Described surfactant is EO
20pO
70eO
20; Described organosilicon source is tetraethyl orthosilicate; Described organic titanium source is Titanium Citrate; Described inorganic salts are Nickelous nitrate hexahydrate; Described solvent is ethylene glycol and water.
5. the preparation method of a kind of titanium nitride/carbon composite as claimed in claim 1, is characterized in that: the mass ratio of surfactant used in step (1), solvent, organic titanium source, inorganic salts, silicon source, phenol resin solution is 1:20:3:2.5:2.2:1.9; Described surfactant is EO
106pO
70eO
106; Described organosilicon source is positive quanmethyl silicate; Described organic titanium source is Titanium Citrate; Described inorganic salts are Fe(NO3)39H2O; Described solvent is second alcohol and water.
6. the preparation method of a kind of titanium nitride/carbon composite as claimed in claim 1, is characterized in that: the mass ratio of surfactant used in step (1), solvent, organic titanium source, inorganic salts, silicon source, phenol resin solution is 1:30:5:4:4:3; Described surfactant is EO
132pO
60eO
132; Described organosilicon source is positive silicic acid orthocarbonate; Described organic titanium source is Titanium Citrate; Described inorganic salts are cabaltous nitrate hexahydrate; Described solvent is first alcohol and water.
7. the purposes of the titanium nitride/carbon composite nano-material obtained by preparation method according to claim 1 in the electrode material making ultracapacitor.
Priority Applications (1)
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