CN103131211A - Carbon nano tube-lithium titanium doped nickel oxide compound and preparation method thereof - Google Patents
Carbon nano tube-lithium titanium doped nickel oxide compound and preparation method thereof Download PDFInfo
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- CN103131211A CN103131211A CN201310024732XA CN201310024732A CN103131211A CN 103131211 A CN103131211 A CN 103131211A CN 201310024732X A CN201310024732X A CN 201310024732XA CN 201310024732 A CN201310024732 A CN 201310024732A CN 103131211 A CN103131211 A CN 103131211A
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Abstract
The invention discloses a carbon nano tube-lithium titanium doped nickel oxide compound and a preparation method of the nickel oxide compound. Carbon nano tubes with carboxyl are dispersed in N, N-dimethyl formamide, silanization lithium titanium doped nickel oxide is added, and carbon nano tube surface grafting lithium titanium doped nickel oxide compound is obtained by reagents after the reagents are filtered, washed and dried. Active groups such as silicon oxygen bonds, amino and hydroxyl are arranged on the surface of the compound and can be applied to composite resin material preparation and development of other novel materials. The performance of the compound can be controlled by adjusting the amount of grafting materials, provides possibility to preparation of function materials such as conducting materials and dielectric materials and regulation and control to performance of the function materials and particularly has outstanding advantages in an aspect of preparation of both high dielectric constant and low dielectric lossy materials. The carbon nano tube-lithium titanium doped nickel oxide compound further has the advantages of being wide in preparation method applicability and simple in operation technology.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, particularly titanium doped nickel oxide mixture of a kind of carbon nanotube-lithium and preparation method thereof.
Background technology
Novel dielectric materials with high-k has important application prospect in fields such as information technology, microelectronics, power engineering, science and techniques of defence, therefore causes people's extensive concern.
The main method of preparation high dielectric constant material is made matrix material for the fillers such as conductor or dielectric ceramic are added in polymeric matrix at present.But conductor/polymer composites and Dielectric-ceramic/Polymer Composite Material differ from one another, and the former is mainly when the addition of conductor reaches percolation threshold, and material can obtain very high specific inductivity, but also have very high dielectric loss simultaneously.And Dielectric-ceramic/Polymer Composite Material will obtain high-k and generally should add the dielectric ceramic of high-content, is unfavorable for processing, and may reduce flexibility and the mechanical property of material.
Therefore, people begin to develop conductor/dielectric ceramic/polymer ternary matrix material, to the advantage of integrated two class binary matrix materials.But the method for simple physical blend is mainly taked in the preparation of trielement composite material at present, lacks interaction force between two kinds of fillers, can not realize synergistic effect, and the material properties that causes obtaining all can not reach perfect condition.Before the present invention made, Chinese invention patent (CN1432598A) disclosed a kind of carbon nanotube/barium titanate/polyvinylidene difluoride (PVDF) system, and its preparation method is that two kinds of filler blend are in polymkeric substance.This two classes filler lacks active group and interaction, need to add a large amount of potteries to avoid being in contact with one another of carbon nanotube (conductor), thereby reduces dielectric loss.But when the increased content of pottery, the effect of conductor just is difficult for performance, causes the specific inductivity of matrix material not high.For example.In the document, calculate with volume ratio, when the add-on of carbon nanotube is 5%, barium titanate is 20%, and when polyvinylidene difluoride (PVDF) was 75%, although the dielectric loss under matrix material 100Hz is 0.18, specific inductivity was only also 50.The consequence that blending method directly causes is that the consumption of filler increases, and so high loading level is unfavorable for the low cost fabrication of high performance composite.
There are some researches show in a large number, the structure of filler and performance are the key factors that determines its matrix material dielectric properties.Therefore, prepare and a kind ofly formed by conductor and dielectric ceramic, and the filler by chemical bonds, use it for composite manufacture, will overcome the deficiency of existing conductor/dielectric ceramic/polymer ternary matrix material.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, titanium doped nickel oxide mixture of a kind of carbon nanotube-lithium and preparation method thereof is provided.
Realize that the technical scheme of the object of the invention is to provide the preparation method of the titanium doped nickel oxide mixture of a kind of carbon nanotube-lithium, comprises the steps:
1, by mass, it is in 35%～40% superoxol that 10 parts of particle diameters are distributed to 50～60 parts of massfractions less than the titanium doped nickel oxide of the lithium of 106 microns, in temperature is to react 5～6h under the condition of 90～100 ℃; After reaction finishes, through washing, suction filtration, obtain the titanium doped nickel oxide of hydroxylated lithium;
2, by mass, 10 parts of titanium doped nickel oxide of hydroxylated lithium are joined in 100～120 parts of dehydrated alcohols mix, obtain suspension; Adding massfraction in ethanolic soln is 1.0%～2.0% γ-aminopropyl triethoxysilane, and 20～30 parts are added in described suspension, in temperature is to react 5～6h under the condition of 60～65 ℃, after filtration, washing, drying obtains the titanium doped nickel oxide of lithium of silanization;
3, by mass, the carbon nanotube dispersed with 1 part with carboxyl adds the titanium doped nickel oxide of lithium of 0.05～5 part of silanization in 300～400 parts of DMFs, at 60～70 ℃ of reaction 12～24h; After filtration, washing after drying, obtains the titanium doped nickel oxide mixture of carbon nanotube-lithium.
Carbon nanotube of the present invention is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes or its combination.
The chemical formula of the nickel oxide that described lithium is titanium doped is Li
0.3Ti
0.02Ni
0.68O； The preparation method comprises the steps: by mol, 1 part of citric acid is dissolved in 1～2.5 part of ethylene glycol, under the temperature condition of 100～120 ℃, add successively 0.3 part of lithium nitrate, 0.68 part of nickelous nitrate and 0.02 part of butyl (tetra) titanate, solution is incubated 8～10h under the temperature condition of 150～160 ℃, reheat solution to 350～400 ℃ insulation 2～3h, obtain the grey powder; Grind the grey powder to particle diameter less than 106 microns, then at the temperature lower calcination 1～2h of 800～850 ℃, namely obtain the titanium doped nickel oxide of lithium of black.
The preparation method of described carbon nanotube with carboxyl comprises the steps: by mass, and it is 50%～60% nitric acid that 1 part of carbon nanotube is placed in 9～10 parts of massfractions, obtains mixed solution; Add deionized water in mixed solution, stir 5～6h under 60～70 ℃; Filter, washed product is to neutral, and drying obtains the carbon nanotube with carboxyl.
Technical solution of the present invention also comprises the titanium doped nickel oxide mixture of carbon nanotube-lithium that obtains by the above preparation method.
Compared with prior art, the obtained beneficial effect of the present invention is:
1, the present invention because the titanium doped nickel oxide of the lithium that grafts on carbon nano tube surface has been isolated the contact of carbon nanotube, has overcome the problem of the easy reunion of carbon nanotube, is conducive to matrix material and obtains high-k; Avoid simultaneously carbon nanotube to be in contact with one another the leakage current that causes, thereby greatly reduced the dielectric loss of matrix material.The titanium doped nickel oxide mixture of carbon nanotube-lithium provided by the invention has concurrently in research and development has outstanding advantage aspect high-k and low-dielectric loss material.
2, the titanium doped nickel oxide composite surface of carbon nanotube-lithium contains siloxane bond, amino, hydroxyl isoreactivity group, for the exploitations compound, other type materials of itself and resin are laid a good foundation.
3, the performance of the titanium doped nickel oxide mixture of carbon nanotube-lithium can be controlled by the titanium doped nickel oxide quantity of lithium that adjusting grafts on carbon nano tube surface, thereby can satisfy the requirement in different application field.
4, the titanium doped nickel oxide mixture of carbon nanotube-lithium is as novel filler, after adding resin matrix to make matrix material, can be in the situation that very little higher specific inductivity and the lower dielectric loss of obtaining of addition, for the low cost fabrication of high performance composite provides may.
5, the preparation method of the titanium doped nickel oxide mixture of carbon nanotube-lithium provided by the invention has the advantages that operating procedure is simple, the starting material source is abundant, suitability is wide.
Description of drawings
Fig. 1 is the titanium doped nickel oxide of the titanium doped nickel oxide mixture of carbon nanotube-lithium of providing of the embodiment of the present invention 1 and lithium titanium doped nickel oxide, hydroxylated lithium, with the infrared spectrum contrast of the carbon nanotube of carboxyl;
Fig. 2 is the titanium doped nickel oxide of the lithium of the titanium doped nickel oxide of the titanium doped nickel oxide mixture of carbon nanotube-lithium of providing of the embodiment of the present invention 1 and lithium titanium doped nickel oxide, hydroxylated lithium, silanization and with the X-ray diffraction spectrogram contrast of the carbon nanotube of carboxyl;
Fig. 3 is the titanium doped nickel oxide of the lithium of the titanium doped nickel oxide of the titanium doped nickel oxide mixture of carbon nanotube-lithium of providing of the embodiment of the present invention 1 and lithium titanium doped nickel oxide, hydroxylated lithium, silanization and with the Raman spectrogram contrast of the carbon nanotube of carboxyl;
Fig. 4 is the scanning electron microscope diagram of 50,000 times of the amplifications of the titanium doped nickel oxide mixture of carbon nanotube-lithium of providing of the embodiment of the present invention 1;
Fig. 5 is the structural representation of the titanium doped nickel oxide mixture of carbon nanotube-lithium of providing of the embodiment of the present invention 1;
Fig. 6 is that the specific inductivity of the titanium doped nickel oxide mixture/epoxy resin composite material of the carbon nano tube/epoxy resin composite material of the Comparative Examples band carboxyl that provides of the embodiment of the present invention 1 and carbon nanotube-lithium is with the curve of change of frequency;
Fig. 7 is that the dielectric loss of the titanium doped nickel oxide mixture/epoxy resin composite material of the carbon nano tube/epoxy resin composite material of the Comparative Examples band carboxyl that provides of the embodiment of the present invention 11 and carbon nanotube-lithium is with the curve of change of frequency;
Fig. 8 is with the scanning electron microscope diagram of 30,000 times of the amplifications of the titanium doped nickel oxide mixture of carbon nanotube-lithium in the carbon nanotube of carboxyl and embodiment 2～6 in the embodiment of the present invention 2;
Fig. 9 is with the specific conductivity graphic representation of the titanium doped nickel oxide mixture of carbon nanotube-lithium in the carbon nanotube of carboxyl and embodiment 2～6 in the embodiment of the present invention 2;
Figure 10 is with the X-ray diffraction spectrogram of the titanium doped nickel oxide mixture of carbon nanotube-lithium in the carbon nanotube of carboxyl and embodiment 2～6 in the embodiment of the present invention 2.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention will be further described.
Embodiment 1
1, the titanium doped nickel oxide of lithium is synthetic
The 50g citric acid is dissolved in 80 mL ethylene glycol, under the temperature condition of 100 ℃, add successively 5.12g lithium nitrate, 49.5g nickelous nitrate and 1.7g butyl (tetra) titanate, be incubated 8h under the temperature condition of 150 ℃, reheat solution to 350 ℃ insulation 2h, obtain the grey powder; Grind the grey powder, make it by 140 mesh sieves; Calcine 1h under the temperature condition of 800 ℃, namely obtain the titanium doped nickel oxide of lithium of black, its infrared spectrum, Raman spectrogram, X-ray diffraction spectrogram are as shown in Fig. 1,2 and 3.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
Can be scattered in the 50mL massfraction by the titanium doped nickel oxide of the lithium of 140 mesh sieves after 10g is ground is in 35% superoxol, in temperature is to react 5h under the condition of 90 ℃; Reaction is used deionized water wash after finishing, suction filtration, and 60 ℃ of lower vacuum-dryings 18 hours, obtain the titanium doped nickel oxide of hydroxylated lithium.Its infrared spectrum, Raman spectrogram, X-ray diffraction spectrogram are as shown in Fig. 1,2 and 3.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into the 100mL dehydrated alcohol, mix, adding the 20mL massfraction in the suspension that obtains is the ethanolic soln of 1.0% γ-aminopropyl triethoxysilane, stirs 5h under 60 ℃.Use absolute ethanol washing, suction filtration, and 70 ℃ of lower vacuum-dryings 12 hours, obtain the titanium doped nickel oxide of lithium of silanization.Its infrared spectrum, Raman spectrogram, X-ray diffraction spectrogram are as shown in Fig. 1,2 and 3.
3, with the preparation of the carbon nanotube of carboxyl
It is 50% nitric acid that the 1g multi-walled carbon nano-tubes is placed in the 9g massfraction, adds the 90mL deionized water in the mixed solution that obtains, and stirs 5h under the temperature condition of 60 ℃; Filter, extremely neutral with the deionized water washed product, suction filtration, and 65 ℃ of lower vacuum-dryings 16 hours, obtain the carbon nanotube with carboxyl.Its infrared spectrum, Raman spectrogram, X-ray diffraction spectrogram are as shown in Figure 1, 2, 3.
4, the preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
With 300mg with the carbon nanotube dispersed of carboxyl in the 90mL DMF, add the titanium doped nickel oxide of lithium of 1500mg silanization, react 12h under the temperature condition of 60 ℃.Use absolute ethanol washing, suction filtration, and 65 ℃ of lower vacuum-dryings 16 hours, obtain the titanium doped nickel oxide mixture of carbon nanotube-lithium, wherein the titanium doped nickel oxide grafting amount of lithium is 5 times of carbon nanotube quality.Its infrared spectrum, Raman spectrogram, X-ray diffraction spectrogram, amplify the scanning electron microscope diagram of 50,000 times and structural representation as shown in Fig. 1,2,3,4,5.
Comparative example 1, preparation with the carbon nano tube/epoxy resin composite material of carboxyl: the 0.5g that the present embodiment is provided joins in reactor with carbon nanotube and the 100g epoxy resin (trade mark E-51) of carboxyl, after stirring and ultrasonic 1h under 60 ℃, vacuum defoamation 30min; The 4g 2-ethyl-4-methylimidazole is added in reactor, continue to stir 10min, obtain uniform mixture; Mixture is poured in mould, and vacuum defoamation 20min carries out thermofixation, namely obtains the carbon nano tube/epoxy resin composite material with carboxyl according to 80 ℃/2h+100 ℃/2h+120 ℃/2h+140 ℃/4h technique.Its specific inductivity-frequency variation curve, dielectric loss-frequency variation curve are seen respectively accompanying drawing 6 and 7.
Comparative example 2, the preparation of nickel oxide mixture/epoxy resin composite material that the lithium of carbon nanotube-silanization is titanium doped: titanium doped nickel oxide mixture and the 100g epoxy resin (trade mark E-51) of 3.0g carbon nanotube-lithium that the present embodiment is provided joins in flask, after stirring and ultrasonic 1h under 60 ℃, vacuum defoamation 30min, add the 4g 2-ethyl-4-methylimidazole, continue to stir 10min, obtain uniform mixture; Mixture is poured in mould, and vacuum defoamation 20min carries out thermofixation, namely obtains the titanium doped nickel oxide mixture/epoxy resin composite material of carbon nanotube-lithium according to 80 ℃/2h+100 ℃/2h+120 ℃/2h+140 ℃/4h technique.Its specific inductivity-frequency variation curve, dielectric loss-frequency variation curve are seen respectively accompanying drawing 6 and 7.
Referring to accompanying drawing 1, it is the titanium doped nickel oxide of the lithium of the titanium doped nickel oxide of lithium, silanization in the present embodiment, with the infrared spectrum of the carbon nanotube of carboxyl and the titanium doped nickel oxide mixture of carbon nanotube-lithium.Can find out following some: the titanium doped nickel oxide of lithium of (1) silanization has kept the skeleton structure of the titanium doped nickel oxide of lithium, at 2900cm
-1Place's absorption peak strengthens, this be because on the titanium doped nickel oxide of the lithium of silanization-CH
3,-CH
2Content is higher; 1420 cm
-1There is strong peak at the place, corresponding to the stretching vibration of C-N in DMF; 1090cm
-1There is a stronger absorption peak at the place, shows the existence of Si-O.(2) the titanium doped nickel oxide mixture of carbon nanotube-lithium has been contained the titanium doped nickel oxide of the lithium of silanization and with the total characteristic peak of the carbon nanotube of carboxyl, at 3408 cm
-1In the place, strong peak can be regarded the N-H stretching vibration in amido linkage as, illustrates between the titanium doped nickel oxide pottery of lithium and carbon nanotube to be connected by silane coupling agent.
Referring to accompanying drawing 2, it is the titanium doped nickel oxide mixture of the lithium of the titanium doped nickel oxide of titanium doped nickel oxide, the hydroxylated lithium of lithium, silanization in the present embodiment titanium doped nickel oxide, carbon nanotube-lithium and the Raman spectrogram of carbon nanotube.In carbon nanotube, wave number is 1325cm
-1And 1590cm
-1The place is D peak (the asymmetric vibration of the defective in graphite and amorphous C) and the G peak (C-C plane stretching vibration) of corresponding carbon nanotube respectively.The Raman spectrogram of the nickel oxide mixture that carbon nanotube-lithium is titanium doped can be regarded the titanium doped nickel oxide of the lithium of silanization and the stack spectrogram of carbon nanotube spectrogram as.The red shift of D peak and grow, G peak red shift and peak shape broaden to exist between nickel oxide that these two phenomenons show that jointly lithium is titanium doped and carbon nanotube and interact, and be not simple physical blending, namely the titanium doped nickel oxide of lithium is grafted on carbon nanotube by silane coupling agent.
Referring to accompanying drawing 3, it is the titanium doped nickel oxide of the lithium of the titanium doped nickel oxide of titanium doped nickel oxide, the hydroxylated lithium of lithium, silanization in the present embodiment, with the X-ray diffraction spectrogram of the carbon nanotube of carboxyl and the titanium doped nickel oxide mixture of carbon nanotube-lithium.As seen from the figure, in the X ray diffracting spectrum of the nickel oxide that lithium is titanium doped, the position at five peaks and relative intensity have all illustrated the nickel oxide that has cubic crystal structure in the titanium doped nickel oxide of lithium, meet X-ray powder diffraction standard card number 04-0835 fully.In the titanium doped nickel oxide mixture of carbon nanotube-lithium, remove five peaks identical with the titanium doped nickel oxide of lithium, located Yi Longfeng at 25.8 °, peak shape is mild and wide, corresponding to the peak of 26 ° of protuberances in carbon nanotube, the titanium doped nickel oxide of lithium that shown on carbon nanotube successfully grafting.
Referring to accompanying drawing 4, it is that the titanium doped nickel oxide mixture of carbon nanotube-lithium that the present embodiment provides amplifies the scanning electron microscope (SEM) photograph of 50,000 times.Can find out, carbon nano tube surface has coated the titanium doped nickel oxide of a fairly large number of lithium equably.
Based on above analysis, the present embodiment has successfully been prepared by the titanium doped nickel oxide mixture of the carbon nanotube-lithium of chemical bonds, and its structural representation as shown in Figure 5.As seen from the figure, the hydroxyl of the nickel oxide surfaces that lithium is titanium doped and silane coupling agent reaction have realized silanization, make the carboxyl reaction of the titanium doped nickel oxide of lithium and carbon nano tube surface, generated the titanium doped nickel oxide mixture of carbon nanotube-lithium that is connected with amido linkage.
Referring to accompanying drawing 6, it is that the specific inductivity of comparative example 1 and 2 matrix materials that prepare is with the change curve of frequency.As seen from the figure, the titanium doped nickel oxide mixture/epoxy resin composite material of the carbon nanotube-lithium of comparative example 2 preparation shows that at the specific inductivity of the low frequency range band carboxyl carbon nano tube/epoxy resin composite material higher than comparative example 1 preparation this mixture has significant application prospect aspect the preparation high dielectric constant material.
Referring to accompanying drawing 7, it is that the dielectric loss of comparative example 1 and 2 matrix materials that prepare is with the change curve of frequency.The dielectric loss with the carboxyl carbon nano tube/epoxy resin composite material of comparative example 1 preparation depends on frequency strongly, has very high dielectric loss (for example the dielectric loss of the matrix material under 1Hz is up to 1440) under low frequency.And the dielectric loss of the titanium doped nickel oxide mixture/epoxy resin composite material of the carbon nanotube-lithium of comparative example 2 preparation weakens greatly to the dependency of frequency, dielectric loss under low frequency obviously reduces (dielectric loss of the matrix material under 1Hz is low to moderate 5.08) simultaneously, shows that this mixture has outstanding advantage aspect preparation low-dielectric loss matrix material.Comprehensive accompanying drawing 6,7 as can be known, the specific inductivity that adds a small amount of titanium doped nickel oxide mixture of carbon nanotube-lithium that this enforcements provides can improve matrix material also reduces dielectric loss greatly, has concurrently in preparation to have significant advantage aspect high-k, low-dielectric loss matrix material.
1, the titanium doped nickel oxide of lithium is synthetic
The 100g citric acid is dissolved in 80mL ethylene glycol, under the temperature condition of 120 ℃, add successively 10.35g lithium nitrate, 99g nickelous nitrate and 3.4g butyl (tetra) titanate, solution is incubated 10h under the temperature condition of 155 ℃, reheat solution to 400 ℃ insulation 3h, obtain the grey powder; Grind the grey powder, make it by 140 mesh sieves; At 850 ℃ of calcining 2h, namely obtain the titanium doped nickel oxide of lithium of black.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
Can to be particle diameter be scattered in the 60mL massfraction less than the titanium doped nickel oxide of the lithium of 106 microns is in 40% superoxol by 140 mesh sieves after 10g is ground, be to react 5.5h under the condition of 100 ℃ in temperature; Reaction is used deionized water wash after finishing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide of hydroxylated lithium.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into the 110mL dehydrated alcohol and mix, adding the 30mL massfraction in the suspension that obtains is the ethanolic soln of 2.0% γ-aminopropyl triethoxysilane, in temperature is to react 6h under the condition of 65 ℃.Use absolute ethanol washing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide of lithium of silanization.
3, with the preparation of the carbon nanotube of carboxyl
It is 60% nitric acid that the 1g multi-walled carbon nano-tubes is placed in the 10g massfraction, adds the 100mL deionized water in the mixed solution that obtains, and stirs 6h under the temperature condition of 70 ℃; Extremely neutral with the deionized water washed product, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the carbon nanotube with carboxyl.The scanning electron microscope diagram that its amplification is 30,000 times, conductivity map, X-ray diffraction spectrogram are as shown in Fig. 8,9,10.
4, the preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
With 300mg with the carbon nanotube dispersed of carboxyl in the 120mL DMF, add the titanium doped nickel oxide of lithium of 600mg silanization, react 24h under the temperature condition of 70 ℃.Use absolute ethanol washing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide mixture of carbon nanotube-lithium, wherein the titanium doped nickel oxide grafting amount of lithium is 2 times of carbon nanotube quality.Its scanning electron microscope diagram, conductivity map and X-ray diffraction spectrogram that amplifies 30,000 times is respectively as shown in Fig. 8,9,10.
Embodiment 3
The preparation of the nickel oxide mixture that carbon nanotube-lithium is titanium doped
With 300mg embodiment 2 preparation with the carbon nanotube dispersed of carboxyl in the 120mL DMF, add the titanium doped nickel oxide of lithium of the silanization of 300mg embodiment 2 preparations, react 24h under the temperature condition of 70 ℃.Use absolute ethanol washing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide mixture of carbon nanotube-lithium, wherein the titanium doped nickel oxide grafting amount of lithium is 1 times of carbon nanotube quality.The scanning electron microscope diagram that its amplification is 30,000 times, conductivity map, X-ray diffraction spectrogram are as shown in Fig. 8,9,10.
Embodiment 4
The preparation of the nickel oxide mixture that carbon nanotube-lithium is titanium doped
With 300mg embodiment 2 preparation with the carbon nanotube dispersed of carboxyl in the 120mL DMF, add the titanium doped nickel oxide of lithium of the silanization of 60mg embodiment 2 preparations, react 24h under the temperature condition of 70 ℃.Use absolute ethanol washing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide mixture of carbon nanotube-lithium, wherein the titanium doped nickel oxide grafting amount of lithium is 0.2 times of carbon nanotube quality.The scanning electron microscope diagram that its amplification is 30,000 times, conductivity map, X-ray diffraction spectrogram are as shown in Fig. 8,9,10.
Embodiment 5
The preparation of the nickel oxide mixture that carbon nanotube-lithium is titanium doped
With 300mg embodiment 2 preparation with the carbon nanotube dispersed of carboxyl in the 120mL DMF, add the titanium doped nickel oxide of lithium of the silanization of 30mg embodiment 2 preparations, react 24h under the temperature condition of 70 ℃.Use absolute ethanol washing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide mixture of carbon nanotube-lithium, wherein the titanium doped nickel oxide grafting amount of lithium is 0.1 times of carbon nanotube quality.The scanning electron microscope diagram that its amplification is 30,000 times, conductivity map, X-ray diffraction spectrogram are as shown in Fig. 8,9,10.
The preparation of the nickel oxide mixture that carbon nanotube-lithium is titanium doped
With 300mg embodiment 2 preparation with the carbon nanotube dispersed of carboxyl in the 120mL DMF, add the titanium doped nickel oxide of lithium of the silanization of 15mg embodiment 2 preparations, react 24h under the temperature condition of 70 ℃.Use absolute ethanol washing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide mixture of carbon nanotube-lithium, wherein the titanium doped nickel oxide grafting amount of lithium is 0.05 times of carbon nanotube quality.The scanning electron microscope diagram that its amplification is 30,000 times, conductivity map, X-ray diffraction spectrogram are as shown in Fig. 8,9,10.
Referring to accompanying drawing 8, it is with the scanning electron microscope diagram of the titanium doped nickel oxide mixture of the carbon nanotube-lithium of the carbon nanotube of carboxyl and embodiment 2～6 preparations in embodiment 2.As seen from the figure, the carbon nanotube of the titanium doped nickel oxide of grafting lithium does not present serious aggregating state, and in grafting after the titanium doped nickel oxide of lithium, the dispersiveness of carbon nanotube improves significantly, and along with reducing of grafting amount, namely successively decrease from embodiment 2～6, its dispersiveness also presents the trend of successively decreasing.This phenomenon proves absolutely the grafting of the nickel oxide that lithium is titanium doped for the important impact of being dispersed with of carbon nanotube, and change the grafting amount what can directly control its dispersiveness.
Referring to accompanying drawing 9, it is with the specific conductivity of the titanium doped nickel oxide mixture of the carbon nanotube-lithium of the carbon nanotube of carboxyl and embodiment 2～6 preparations change curve with frequency in embodiment 2.Can find out, along with the minimizing of the titanium doped nickel oxide add-on of lithium, namely successively decrease from embodiment 2 to 6, the specific conductivity of the nickel oxide mixture that carbon nanotube-lithium is titanium doped raises gradually, but all lower than the carbon nanotube with carboxyl.This is because the titanium doped NiO nanoparticle of lithium of insulation grafts on carbon nano tube surface, has completely cut off contact between carbon nanotube by the space geometry effect, makes its dispersed increasing, and be not easy each other to form path, so specific conductivity reduces.Along with increasing of the titanium doped nickel oxide add-on of lithium, the isolated effect in this space is more obvious, so the specific conductivity of the titanium doped nickel oxide mixture of carbon nanotube-lithium progressively reduces by the order of the increase of the titanium doped nickel oxide grafting quantity of lithium.This quantity that nickel oxide grafting that lithium is titanium doped is described on the one hand can control, and the dispersiveness that how much can directly affect carbon nanotube of the nickel oxide grafting quantity that lithium is titanium doped has been reflected in the side simultaneously.
Referring to accompanying drawing 10, it is with the X ray diffracting spectrum of the titanium doped nickel oxide mixture of the carbon nanotube-lithium of the carbon nanotube of carboxyl and embodiment 2～6 preparations in the embodiment of the present invention 2.As can be seen from the figure, along with the minimizing of the titanium doped nickel oxide add-on of lithium, namely successively decrease from embodiment 2 to 6, the characteristic peak of the nickel oxide that lithium is titanium doped is faint gradually, and the characteristic peak of carbon nanotube becomes more and more obvious.The titanium doped nickel oxide of lithium that can the grafting different mass on this phenomenon explanation carbon nanotube, and the grafting amount is controlled.
Can find out according to above performance data, the titanium doped nickel oxide mixture of the carbon nanotube-lithium of the present invention preparation is on the basis that keeps good dispersion, also have dispersed controlled characteristics, can be used for preparing stable electro-conductive material, high dielectric constant material etc., have a extensive future.
Embodiment 7
1, the titanium doped nickel oxide of lithium is synthetic
The 100g citric acid is dissolved in 85mL ethylene glycol, under the temperature condition of 110 ℃, add successively 10.35g lithium nitrate, 99g nickelous nitrate and 3.4g butyl (tetra) titanate, solution is incubated 10h under the temperature condition of 150 ℃, reheat solution to 350 ℃ insulation 3h, obtain the grey powder; Grind the grey powder, make it by 140 mesh sieves; At 800 ℃ of calcining 2h, namely obtain the titanium doped nickel oxide of lithium of black.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
Can to be particle diameter be scattered in the 55mL massfraction less than the titanium doped nickel oxide of the lithium of 106 microns is in 35% superoxol by 140 mesh sieves after 10g is ground, be to react 6h under the condition of 95 ℃ in temperature; Reaction is used deionized water wash after finishing, suction filtration, and 50 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide of hydroxylated lithium.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into the 120mL dehydrated alcohol and mix, adding the 27mL massfraction in the suspension that obtains is the ethanolic soln of 1.0% γ-aminopropyl triethoxysilane, stirs 6h under the temperature condition of 60 ℃.Use absolute ethanol washing, suction filtration, and 70 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide of lithium of silanization.
3, with the preparation of the carbon nanotube of carboxyl
It is 50% nitric acid that the 1g Single Walled Carbon Nanotube is placed in the 10g massfraction, adds the 95mL deionized water in the mixed solution that obtains, and stirs 6h under 60 ℃; Extremely neutral with the deionized water washed product, suction filtration, and 55 ℃ of lower vacuum-dryings 16 hours, obtain the carbon nanotube with carboxyl.
4, the preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
With 300mg with the carbon nanotube dispersed of carboxyl in the 90mL DMF, add the titanium doped nickel oxide of lithium of 300mg silanization, react 24h under the temperature condition of 70 ℃.Use absolute ethanol washing, suction filtration, and 60 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide mixture of carbon nanotube-lithium.
Embodiment 8
1, the titanium doped nickel oxide of lithium is synthetic
The 100g citric acid is dissolved in 70mL ethylene glycol, under the temperature condition of 100 ℃, add successively 10.35g lithium nitrate, 99g nickelous nitrate and 3.4g butyl (tetra) titanate, solution is incubated 8h under the temperature condition of 160 ℃, reheat solution to 400 ℃ insulation 2h, obtain the grey powder; Grind the grey powder, make it by 140 mesh sieves; Calcine 2h under the temperature condition of 800 ℃, namely obtain the titanium doped nickel oxide of lithium of black.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
Can to be particle diameter be scattered in the 55mL massfraction less than the titanium doped nickel oxide of the lithium of 106 microns is in 35% superoxol by 140 mesh sieves after 10g is ground, be to react 5.5h under the condition of 100 ℃ in temperature; Reaction is used deionized water wash after finishing, suction filtration, and 70 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide of hydroxylated lithium.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into the 120mL dehydrated alcohol and mix, adding the 28mL massfraction in the suspension that obtains is the ethanolic soln of 2.0% γ-aminopropyl triethoxysilane, reacts 6h under the temperature condition of 60 ℃.Use absolute ethanol washing, suction filtration, and 55 ℃ of lower vacuum-dryings 18 hours, obtain the titanium doped nickel oxide of lithium of silanization.
3, with the preparation of the carbon nanotube of carboxyl
It is 60% nitric acid that the mixture of 1g multi-walled carbon nano-tubes and Single Walled Carbon Nanotube is placed in the 9g massfraction, adds the 100mL deionized water in mixed solution, stirs 6h under the temperature condition of 60 ℃; Extremely neutral with the deionized water washed product, suction filtration, and 60 ℃ of lower vacuum-dryings 24 hours, obtain the carbon nanotube with carboxyl.
4, the preparation of the titanium doped nickel oxide mixture of the lithium of carbon nanotube-silanization
With 300mg with the carbon nanotube dispersed of carboxyl in the 120mL DMF, add the titanium doped nickel oxide of lithium of 60mg silanization, react 12h under the temperature condition of 70 ℃.Use absolute ethanol washing, suction filtration, and 70 ℃ of lower vacuum-dryings 10 hours, obtain the titanium doped nickel oxide mixture of lithium of carbon nanotube-silanization.
Embodiment 9
1, the titanium doped nickel oxide of lithium is synthetic
The 50g citric acid is dissolved in 90mL ethylene glycol, under the temperature condition of 120 ℃, add successively 5.12g lithium nitrate, 49.5g nickelous nitrate and 1.7g butyl (tetra) titanate, solution is incubated 9h under the temperature condition of 150 ℃, reheat solution to 350 ℃ insulation 3h, obtain the grey powder; Grind the grey powder, make it by 140 mesh sieves; At the temperature lower calcination 1h of 800 ℃, namely obtain the titanium doped nickel oxide of lithium of black.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
Can to be particle diameter be scattered in the 60mL massfraction less than the titanium doped nickel oxide of the lithium of 106 microns is in 40% superoxol by 140 mesh sieves after 10g is ground, be to react 5h under the condition of 100 ℃ in temperature; Reaction is used deionized water wash after finishing, suction filtration, and 60 ℃ of lower vacuum-dryings 18 hours, obtain the titanium doped nickel oxide of hydroxylated lithium.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into the 110mL dehydrated alcohol and mix, adding the 30mL massfraction in the suspension that obtains is the ethanolic soln of 2.0% γ-aminopropyl triethoxysilane, in temperature is to stir 6h under the condition of 65 ℃.Use absolute ethanol washing, suction filtration, and 70 ℃ of lower vacuum-dryings 12 hours, obtain the titanium doped nickel oxide of lithium of silanization.
3, with the preparation of the carbon nanotube of carboxyl
It is 60% nitric acid that the 1g multi-walled carbon nano-tubes is placed in the 10g massfraction, adds the 95mL deionized water in the mixed solution that obtains, and stirs 6h under 60 ℃; Extremely neutral with the deionized water washed product, suction filtration, and 50 ℃ of lower vacuum-dryings 12 hours, obtain the carbon nanotube with carboxyl.
4, the preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
With 300mg with the carbon nanotube dispersed of carboxyl in the 90mL DMF, add the titanium doped nickel oxide of lithium of 30mg silanization, react 20h under the temperature condition of 65 ℃.Use absolute ethanol washing, suction filtration, and 65 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide mixture of carbon nanotube-lithium.
1, the titanium doped nickel oxide of lithium is synthetic
The 100g citric acid is dissolved in 120mL ethylene glycol, under the temperature condition of 120 ℃, add successively 10.35g lithium nitrate, 99g nickelous nitrate and 3.4g butyl (tetra) titanate, solution is incubated 10h under the temperature condition of 160 ℃, reheat solution to 350 ℃ insulation 2h, obtain the grey powder; Grind the grey powder, make it by 140 mesh sieves; At the temperature lower calcination 2h of 800 ℃, namely obtain the titanium doped nickel oxide of lithium of black.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
Can to be particle diameter be scattered in the 60mL massfraction less than the titanium doped nickel oxide of the lithium of 106 microns is in 37% superoxol by 140 mesh sieves after 10g is ground, be to react 6h under the condition of 90 ℃ in temperature; Reaction is used deionized water wash after finishing, suction filtration, and 60 ℃ of lower vacuum-dryings 24 hours, obtain the titanium doped nickel oxide of hydroxylated lithium.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into the 100mL dehydrated alcohol and mix, adding the 30mL massfraction in the suspension that obtains is the ethanolic soln of 1.0% γ-aminopropyl triethoxysilane, in temperature is to stir 6h under the condition of 60 ℃.Use absolute ethanol washing, suction filtration, and 50 ℃ of lower vacuum-dryings 18 hours, obtain the titanium doped nickel oxide of lithium of silanization.
3, with the preparation of the carbon nanotube of carboxyl
It is 60% nitric acid that the 1g multi-walled carbon nano-tubes is placed in the 9g massfraction, adds the 90mL deionized water in the mixed solution that obtains, and stirs 6h under the temperature condition of 60 ℃; Extremely neutral with the deionized water washed product, suction filtration, and 70 ℃ of lower vacuum-dryings 16 hours, obtain the carbon nanotube with carboxyl.
4, the preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
With 300mg with the carbon nanotube dispersed of carboxyl in the 120mL DMF, add the titanium doped nickel oxide of lithium of 15mg silanization, react 18h under the temperature condition of 65 ℃.Use absolute ethanol washing, suction filtration, and 60 ℃ of lower vacuum-dryings 12 hours, obtain the titanium doped nickel oxide mixture of carbon nanotube-lithium.
Claims (5)
1. the preparation method of the titanium doped nickel oxide mixture of a carbon nanotube-lithium, is characterized in that comprising the steps:
(1) by mass, it is in 35%～40% superoxol that 10 parts of particle diameters are distributed to 50～60 parts of massfractions less than the titanium doped nickel oxide of the lithium of 106 microns, in temperature is to react 5～6h under the condition of 90～100 ℃; After reaction finishes, through washing, suction filtration, obtain the titanium doped nickel oxide of hydroxylated lithium;
(2) by mass, 10 parts of titanium doped nickel oxide of hydroxylated lithium are joined in 100～120 parts of dehydrated alcohols mix, obtain suspension; Adding massfraction in ethanolic soln is 1.0%～2.0% γ-aminopropyl triethoxysilane, and 20～30 parts are added in described suspension, in temperature is to react 5～6h under the condition of 60～65 ℃, after filtration, washing, drying obtains the titanium doped nickel oxide of lithium of silanization;
(3) by mass, the carbon nanotube dispersed with 1 part with carboxyl adds the titanium doped nickel oxide of lithium of 0.05～5 part of silanization in 300～400 parts of DMFs, at 60～70 ℃ of reaction 12～24h; After filtration, washing after drying, obtains the titanium doped nickel oxide mixture of carbon nanotube-lithium.
2. the preparation method of the titanium doped nickel oxide mixture of a kind of carbon nanotube-lithium according to claim 1, it is characterized in that: described carbon nanotube is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes or its combination.
3. the preparation method of the titanium doped nickel oxide mixture of a kind of carbon nanotube-lithium according to claim 1, it is characterized in that: the chemical formula of the nickel oxide that described lithium is titanium doped is Li
0.3Ti
0.02Ni
0.68O； The preparation method comprises the steps: by mol, 1 part of citric acid is dissolved in 1～2.5 part of ethylene glycol, under the temperature condition of 100～120 ℃, add successively 0.3 part of lithium nitrate, 0.68 part of nickelous nitrate and 0.02 part of butyl (tetra) titanate, solution is incubated 8～10h under the temperature condition of 150～160 ℃, reheat solution to 350～400 ℃ insulation 2～3h, obtain the grey powder; Grind the grey powder to particle diameter less than 106 microns, then at the temperature lower calcination 1～2h of 800～850 ℃, namely obtain the titanium doped nickel oxide of lithium of black.
4. the preparation method of the titanium doped nickel oxide mixture of a kind of carbon nanotube-lithium according to claim 1, it is characterized in that: the preparation method of described carbon nanotube with carboxyl comprises the steps: by mass, it is 50%～60% nitric acid that 1 part of carbon nanotube is placed in 9～10 parts of massfractions, obtains mixed solution; Add deionized water in mixed solution, stir 5～6h under 60～70 ℃; Filter, washed product is to neutral, and drying obtains the carbon nanotube with carboxyl.
5. titanium doped nickel oxide mixture of carbon nanotube-lithium that obtains by preparation method claimed in claim 1.
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