CN103131211B - 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
- Publication number
- CN103131211B CN103131211B CN201310024732.XA CN201310024732A CN103131211B CN 103131211 B CN103131211 B CN 103131211B CN 201310024732 A CN201310024732 A CN 201310024732A CN 103131211 B CN103131211 B CN 103131211B
- Authority
- CN
- China
- Prior art keywords
- nickel oxide
- lithium
- titanium doped
- doped nickel
- carbon nanotube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
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
The 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 preparing at present high dielectric constant material is made matrix material for the filler such as conductor or dielectric ceramic is added in polymeric matrix.But conductor/polymer composites and Dielectric-ceramic/Polymer Composite Material differ from one another, the former is mainly in the time that the addition of conductor reaches percolation threshold, and material can obtain very high specific inductivity, but also has very high dielectric loss simultaneously.And Dielectric-ceramic/Polymer Composite Material will obtain the dielectric ceramic that high-k generally should add high-content, be unfavorable for processing, and may reduce flexibility and the mechanical property of material.
Therefore, people start 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, between two kinds of fillers, lacks interaction force, can not realize synergistic effect, causes the material properties obtaining all can not reach perfect condition.Before the present invention makes, Chinese invention patent (CN1432598A) discloses 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 ceramic increased content, the effect of conductor is just 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) is 75%, although the dielectric loss under matrix material 100Hz is 0.18, specific inductivity is 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, preparation is a kind of to be made up of conductor and dielectric ceramic, and by the filler of chemical bonds, uses it for the preparation of matrix material, 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.
The technical scheme that realizes 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, the titanium doped nickel oxide of lithium that 10 parts of particle diameters is less than to 106 microns is distributed in the superoxol that 50～60 parts of massfractions are 35%～40%, is to react 5～6h under the condition of 90～100 ℃ in temperature; 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 and mixed, obtain suspension; In ethanolic soln, adding massfraction is 1.0%～2.0% γ-aminopropyl triethoxysilane, and 20～30 parts are added in described suspension, is to react 5～6h under the condition of 60～65 ℃ in temperature, after filtration, washing, is dried, and obtains the titanium doped nickel oxide of lithium of silanization;
3, by mass, 1 part of carbon nanotube dispersed with carboxyl, in 300～400 parts of DMFs, is added to the titanium doped nickel oxide of lithium of 0.05～5 part of silanization, at 60～70 ℃ of reaction 12～24h; After filtration, washing, after being dried, 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 titanium doped nickel oxide of described lithium is Li
0.3ti
0.02ni
0.68o; 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 to 8～10h under the temperature condition of 150～160 ℃, reheat solution to 350～400 ℃ insulation 2～3h, obtain grey powder; Grind grey powder to particle diameter and be less than 106 microns, then at the temperature lower calcination 1～2h of 800～850 ℃, obtain the titanium doped nickel oxide of lithium of black.
The preparation method of the described carbon nanotube with carboxyl comprises the steps: by mass, and 1 part of carbon nanotube is placed in to the nitric acid that 9～10 parts of massfractions are 50%～60%, obtains mixed solution; In mixed solution, add deionized water, at 60～70 ℃, stir 5～6h; Filter, washed product is to neutral, dry, obtains the carbon nanotube with carboxyl.
Technical solution of the present invention also comprises the titanium doped nickel oxide mixture of carbon nanotube-lithium obtaining 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 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 carbon nanotube to be in contact with one another the leakage current causing simultaneously, 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 aspect high-k and low-dielectric loss material and has outstanding advantage in research and development.
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 titanium doped nickel oxide quantity of lithium that the performance of the titanium doped nickel oxide mixture of carbon nanotube-lithium can graft on carbon nano tube surface by adjusting controls, thereby can meet the requirement in different application field.
4, the titanium doped nickel oxide mixture of carbon nanotube-lithium is as novel filler, add resin matrix to make after matrix material, can in the situation that addition is very little, obtain higher specific inductivity and lower dielectric loss, for the low cost fabrication of high performance composite provides possibility.
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, starting material source is abundant, suitability is wide.
Accompanying drawing explanation
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, the infrared spectrum contrast of carbon nanotube with carboxyl;
Fig. 2 is the X-ray diffraction spectrogram contrast of 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 the carbon nanotube with carboxyl;
Fig. 3 is the Raman spectrogram contrast of 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 the carbon nanotube with 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 example band carboxyl that provides of the embodiment of the present invention 1 and carbon nanotube-lithium is with the curve of frequency change;
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 example band carboxyl that provides of the embodiment of the present invention 11 and carbon nanotube-lithium is with the curve of frequency change;
Fig. 8 is 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 with carboxyl and embodiment 2～6 in the embodiment of the present invention 2;
Fig. 9 is the specific conductivity graphic representation of the titanium doped nickel oxide mixture of carbon nanotube-lithium in the carbon nanotube with carboxyl and embodiment 2～6 in the embodiment of the present invention 2;
Figure 10 is the X-ray diffraction spectrogram of the titanium doped nickel oxide mixture of carbon nanotube-lithium in the carbon nanotube with 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
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, under the temperature condition of 150 ℃, be incubated 8h, reheat solution to 350 ℃ insulation 2h, obtain grey powder; Grind grey powder, make it by 140 mesh sieves; Under the temperature condition of 800 ℃, calcine 1h, obtain the titanium doped nickel oxide of lithium of black, its infrared spectrum, Raman spectrogram, X-ray diffraction spectrogram are as shown in Figure 1,2 and 3.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
After 10g is ground, can be scattered in 50mL massfraction by the titanium doped nickel oxide of the lithium of 140 mesh sieves is in 35% superoxol, is to react 5h under the condition of 90 ℃ in temperature; After reaction finishes, with deionized water wash, suction filtration, and vacuum-drying 18 hours at 60 ℃, obtain the titanium doped nickel oxide of hydroxylated lithium.Its infrared spectrum, Raman spectrogram, X-ray diffraction spectrogram are as shown in Figure 1,2 and 3.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into 100mL dehydrated alcohol, mix, in the suspension obtaining, adding 20mL massfraction is the ethanolic soln of 1.0% γ-aminopropyl triethoxysilane, at 60 ℃, stirs 5h.With absolute ethanol washing, suction filtration, and vacuum-drying 12 hours at 70 ℃, obtain the titanium doped nickel oxide of lithium of silanization.Its infrared spectrum, Raman spectrogram, X-ray diffraction spectrogram are as shown in Figure 1,2 and 3.
3, the preparation of the carbon nanotube with carboxyl
It is 50% nitric acid that 1g multi-walled carbon nano-tubes is placed in to 9g massfraction, adds 90mL deionized water in the mixed solution obtaining, and under the temperature condition of 60 ℃, stirs 5h; Filter, by deionized water washed product, to neutral, suction filtration, and vacuum-drying 16 hours at 65 ℃, 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
Carbon nanotube dispersed by 300mg with carboxyl, in 90mL DMF, adds the titanium doped nickel oxide of lithium of 1500mg silanization, under the temperature condition of 60 ℃, reacts 12h.With absolute ethanol washing, suction filtration, and vacuum-drying 16 hours at 65 ℃, 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, the preparation of the carbon nano tube/epoxy resin composite material with carboxyl: carbon nanotube and the 100g epoxy resin (trade mark E-51) of the 0.5g that the present embodiment is provided with carboxyl joins in reactor, at 60 ℃ stir and ultrasonic 1h after, vacuum defoamation 30min; 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, 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 shown in respectively accompanying drawing 6 and 7.
Comparative example 2, the preparation of the titanium doped nickel oxide mixture/epoxy resin composite material of the lithium of carbon nanotube-silanization: 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, at 60 ℃ stir and ultrasonic 1h after, vacuum defoamation 30min, add 4g 2-ethyl-4-methylimidazole, continue to stir 10min, obtain uniform mixture; Mixture is poured in mould, and vacuum defoamation 20min, carries out thermofixation, 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 shown in 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, the infrared spectrum of carbon nanotube with 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 retained 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 place, corresponding to the stretching vibration of C-N in DMF; 1090cm
-1there is a stronger absorption peak at 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 the total characteristic peak of carbon nanotube with carboxyl, at 3408 cm
-1in place, strong peak can be regarded the N-H stretching vibration in amido linkage as, illustrates between nickel oxide pottery that lithium is titanium doped and carbon nanotube and is 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
-1place is D peak (the asymmetric vibration of the defect in graphite and amorphous C) and G peak (stretching vibration of C-C plane) of corresponding carbon nanotube respectively.The Raman spectrogram of the titanium doped nickel oxide mixture of carbon nanotube-lithium 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 grow, the red shift of G peak and peak shape broaden and exist and interact between nickel oxide that these two phenomenons show that lithium is titanium doped jointly and carbon nanotube, and be not simple physical blending, 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, the X-ray diffraction spectrogram of carbon nanotube with 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 titanium doped nickel oxide of lithium, position and the relative intensity at five peaks 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 completely.In the titanium doped nickel oxide mixture of carbon nanotube-lithium, remove five peaks that the nickel oxide titanium doped with lithium is identical, locate 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 is the coated titanium doped nickel oxide of a fairly large number of lithium of equably.
Based on above analysis, the present embodiment has successfully been prepared the nickel oxide mixture titanium doped by 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 titanium doped nickel oxide surfaces of lithium reacts and has realized silanization with silane coupling agent, make the carboxyl reaction of the titanium doped nickel oxide of lithium and carbon nano tube surface, generated the nickel oxide mixture titanium doped with the connected carbon nanotube-lithium of amido linkage.
Referring to accompanying drawing 6, it is that the specific inductivity of matrix material of comparative example 1 and 2 preparation is with the change curve of frequency.As seen from the figure, the band carboxyl carbon nano tube/epoxy resin composite material that the titanium doped nickel oxide mixture/epoxy resin composite material of carbon nanotube-lithium prepared by comparative example 2 is prepared higher than comparative example 1 at the specific inductivity of low frequency range, shows that this mixture has significant application prospect preparing aspect high dielectric constant material.
Referring to accompanying drawing 7, it is that the dielectric loss of matrix material of comparative example 1 and 2 preparation is with the change curve of frequency.Dielectric loss with carboxyl carbon nano tube/epoxy resin composite material prepared by comparative example 1 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 carbon nanotube-lithium prepared by comparative example 2 weakens greatly to the dependency of frequency, simultaneously the dielectric loss under low frequency obviously reduces (dielectric loss of the matrix material under 1Hz is low to moderate 5.08), shows that this mixture has outstanding advantage preparing aspect low-dielectric loss matrix material.Comprehensive accompanying drawing 6,7 is 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 aspect high-k, low-dielectric loss matrix material and has significant advantage in preparation.
1, the titanium doped nickel oxide of lithium is synthetic
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 grey powder; Grind grey powder, make it by 140 mesh sieves; At 850 ℃ of calcining 2h, obtain the titanium doped nickel oxide of lithium of black.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
After 10g is ground, can be that particle diameter is less than the titanium doped nickel oxide of lithium of 106 microns to be scattered in 60mL massfraction be in 40% superoxol by 140 mesh sieves, be to react 5.5h under the condition of 100 ℃ in temperature; After reaction finishes, with deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain the titanium doped nickel oxide of hydroxylated lithium.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into 110mL dehydrated alcohol and mix, in the suspension obtaining, adding 30mL massfraction is the ethanolic soln of 2.0% γ-aminopropyl triethoxysilane, is to react 6h under the condition of 65 ℃ in temperature.With absolute ethanol washing, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain the titanium doped nickel oxide of lithium of silanization.
3, the preparation of the carbon nanotube with carboxyl
It is 60% nitric acid that 1g multi-walled carbon nano-tubes is placed in to 10g massfraction, adds 100mL deionized water in the mixed solution obtaining, and under the temperature condition of 70 ℃, stirs 6h; By deionized water washed product, to neutral, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain the carbon nanotube with carboxyl.Its amplify 30,000 times scanning electron microscope diagram, conductivity map, X-ray diffraction spectrogram as shown in Figure 8,9, 10.
4, the preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
Carbon nanotube dispersed by 300mg with carboxyl, in 120mL DMF, adds the titanium doped nickel oxide of lithium of 600mg silanization, under the temperature condition of 70 ℃, reacts 24h.With absolute ethanol washing, suction filtration, and vacuum-drying 24 hours at 50 ℃, 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.Scanning electron microscope diagram, conductivity map and X-ray diffraction spectrogram that its amplification is 30,000 times are respectively as shown in Figure 8,9, 10.
Embodiment 3
The preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
Carbon nanotube dispersed with carboxyl prepared by 300mg embodiment 2, in 120mL DMF, adds the titanium doped nickel oxide of lithium of silanization prepared by 300mg embodiment 2, under the temperature condition of 70 ℃, reacts 24h.With absolute ethanol washing, suction filtration, and vacuum-drying 24 hours at 50 ℃, 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.Its amplify 30,000 times scanning electron microscope diagram, conductivity map, X-ray diffraction spectrogram as shown in Figure 8,9, 10.
Embodiment 4
The preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
Carbon nanotube dispersed with carboxyl prepared by 300mg embodiment 2, in 120mL DMF, adds the titanium doped nickel oxide of lithium of silanization prepared by 60mg embodiment 2, under the temperature condition of 70 ℃, reacts 24h.With absolute ethanol washing, suction filtration, and vacuum-drying 24 hours at 50 ℃, 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.Its amplify 30,000 times scanning electron microscope diagram, conductivity map, X-ray diffraction spectrogram as shown in Figure 8,9, 10.
Embodiment 5
The preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
Carbon nanotube dispersed with carboxyl prepared by 300mg embodiment 2, in 120mL DMF, adds the titanium doped nickel oxide of lithium of silanization prepared by 30mg embodiment 2, under the temperature condition of 70 ℃, reacts 24h.With absolute ethanol washing, suction filtration, and vacuum-drying 24 hours at 50 ℃, 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.Its amplify 30,000 times scanning electron microscope diagram, conductivity map, X-ray diffraction spectrogram as shown in Figure 8,9, 10.
The preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
Carbon nanotube dispersed with carboxyl prepared by 300mg embodiment 2, in 120mL DMF, adds the titanium doped nickel oxide of lithium of silanization prepared by 15mg embodiment 2, under the temperature condition of 70 ℃, reacts 24h.With absolute ethanol washing, suction filtration, and vacuum-drying 24 hours at 50 ℃, 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.Its amplify 30,000 times scanning electron microscope diagram, conductivity map, X-ray diffraction spectrogram as shown in Figure 8,9, 10.
Referring to accompanying drawing 8, it is the scanning electron microscope diagram of the titanium doped nickel oxide mixture of the carbon nanotube-lithium of the carbon nanotube with 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, successively decrease from embodiment 2～6, its dispersiveness also presents the trend of successively decreasing.This phenomenon absolutely proves that the grafting of the titanium doped nickel oxide of lithium is for the important impact of being dispersed with of carbon nanotube, and change grafting amount number can directly control its dispersiveness.
Referring to accompanying drawing 9, it is that the specific conductivity of the titanium doped nickel oxide mixture of the carbon nanotube-lithium of the carbon nanotube with carboxyl and embodiment 2～6 preparations in embodiment 2 is with the change curve of frequency.Can find out, along with the minimizing of the titanium doped nickel oxide add-on of lithium, successively decrease from embodiment 2 to 6, the specific conductivity of the titanium doped nickel oxide mixture of carbon nanotube-lithium 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 the contact between carbon nanotube by space geometry effect, makes its dispersed increasing, and is not easy each other to form path, and therefore 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, and therefore 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 on the one hand illustrates that the quantity of the titanium doped nickel oxide grafting of lithium can control, simultaneously side reflected the titanium doped nickel oxide grafting quantity of lithium number can directly affect the dispersiveness of carbon nanotube.
Referring to accompanying drawing 10, it is the X ray diffracting spectrum of the titanium doped nickel oxide mixture of the carbon nanotube-lithium of the carbon nanotube with 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, successively decrease from embodiment 2 to 6, the characteristic peak of the titanium doped nickel oxide of lithium is faint gradually, and the characteristic peak of carbon nanotube becomes more and more obvious.The titanium doped nickel oxide of lithium that can grafting different mass on this phenomenon explanation carbon nanotube, and grafting amount is controlled.
Can find out according to above performance data, the titanium doped nickel oxide mixture of carbon nanotube-lithium prepared by the present invention is keeping on the basis of good dispersion, also there is dispersed controlled feature, 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
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 to 10h under the temperature condition of 150 ℃, reheat solution to 350 ℃ insulation 3h, obtain grey powder; Grind grey powder, make it by 140 mesh sieves; At 800 ℃ of calcining 2h, obtain the titanium doped nickel oxide of lithium of black.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
After 10g is ground, can be that particle diameter is less than the titanium doped nickel oxide of lithium of 106 microns to be scattered in 55mL massfraction be in 35% superoxol by 140 mesh sieves, be to react 6h under the condition of 95 ℃ in temperature; After reaction finishes, with deionized water wash, suction filtration, and vacuum-drying 24 hours at 50 ℃, obtain the titanium doped nickel oxide of hydroxylated lithium.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into 120mL dehydrated alcohol and mix, in the suspension obtaining, adding 27mL massfraction is the ethanolic soln of 1.0% γ-aminopropyl triethoxysilane, under the temperature condition of 60 ℃, stirs 6h.With absolute ethanol washing, suction filtration, and vacuum-drying 24 hours at 70 ℃, obtain the titanium doped nickel oxide of lithium of silanization.
3, the preparation of the carbon nanotube with carboxyl
It is 50% nitric acid that 1g Single Walled Carbon Nanotube is placed in to 10g massfraction, adds 95mL deionized water in the mixed solution obtaining, and at 60 ℃, stirs 6h; By deionized water washed product, to neutral, suction filtration, and vacuum-drying 16 hours at 55 ℃, obtain the carbon nanotube with carboxyl.
4, the preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
Carbon nanotube dispersed by 300mg with carboxyl, in 90mL DMF, adds the titanium doped nickel oxide of lithium of 300mg silanization, under the temperature condition of 70 ℃, reacts 24h.With absolute ethanol washing, suction filtration, and vacuum-drying 24 hours at 60 ℃, the titanium doped nickel oxide mixture of carbon nanotube-lithium obtained.
1, the titanium doped nickel oxide of lithium is synthetic
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 to 8h under the temperature condition of 160 ℃, reheat solution to 400 ℃ insulation 2h, obtain grey powder; Grind grey powder, make it by 140 mesh sieves; Under the temperature condition of 800 ℃, calcine 2h, obtain the titanium doped nickel oxide of lithium of black.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
After 10g is ground, can be that particle diameter is less than the titanium doped nickel oxide of lithium of 106 microns to be scattered in 55mL massfraction be in 35% superoxol by 140 mesh sieves, be to react 5.5h under the condition of 100 ℃ in temperature; After reaction finishes, with deionized water wash, suction filtration, and vacuum-drying 24 hours at 70 ℃, obtain the titanium doped nickel oxide of hydroxylated lithium.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into 120mL dehydrated alcohol and mix, in the suspension obtaining, adding 28mL massfraction is the ethanolic soln of 2.0% γ-aminopropyl triethoxysilane, under the temperature condition of 60 ℃, reacts 6h.With absolute ethanol washing, suction filtration, and vacuum-drying 18 hours at 55 ℃, obtain the titanium doped nickel oxide of lithium of silanization.
3, the preparation of the carbon nanotube with carboxyl
It is 60% nitric acid that the mixture of 1g multi-walled carbon nano-tubes and Single Walled Carbon Nanotube is placed in to 9g massfraction, adds 100mL deionized water in mixed solution, under the temperature condition of 60 ℃, stirs 6h; By deionized water washed product, to neutral, suction filtration, and vacuum-drying 24 hours at 60 ℃, obtain the carbon nanotube with carboxyl.
4, the preparation of the titanium doped nickel oxide mixture of the lithium of carbon nanotube-silanization
Carbon nanotube dispersed by 300mg with carboxyl, in 120mL DMF, adds the titanium doped nickel oxide of lithium of 60mg silanization, under the temperature condition of 70 ℃, reacts 12h.With absolute ethanol washing, suction filtration, and vacuum-drying 10 hours at 70 ℃, 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
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 to 9h under the temperature condition of 150 ℃, reheat solution to 350 ℃ insulation 3h, obtain grey powder; Grind grey powder, make it by 140 mesh sieves; At the temperature lower calcination 1h of 800 ℃, obtain the titanium doped nickel oxide of lithium of black.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
After 10g is ground, can be that particle diameter is less than the titanium doped nickel oxide of lithium of 106 microns to be scattered in 60mL massfraction be in 40% superoxol by 140 mesh sieves, be to react 5h under the condition of 100 ℃ in temperature; After reaction finishes, with deionized water wash, suction filtration, and vacuum-drying 18 hours at 60 ℃, obtain the titanium doped nickel oxide of hydroxylated lithium.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into 110mL dehydrated alcohol and mix, in the suspension obtaining, adding 30mL massfraction is the ethanolic soln of 2.0% γ-aminopropyl triethoxysilane, is to stir 6h under the condition of 65 ℃ in temperature.With absolute ethanol washing, suction filtration, and vacuum-drying 12 hours at 70 ℃, obtain the titanium doped nickel oxide of lithium of silanization.
3, the preparation of the carbon nanotube with carboxyl
It is 60% nitric acid that 1g multi-walled carbon nano-tubes is placed in to 10g massfraction, adds 95mL deionized water in the mixed solution obtaining, and at 60 ℃, stirs 6h; By deionized water washed product, to neutral, suction filtration, and vacuum-drying 12 hours at 50 ℃, obtain the carbon nanotube with carboxyl.
4, the preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
Carbon nanotube dispersed by 300mg with carboxyl, in 90mL DMF, adds the titanium doped nickel oxide of lithium of 30mg silanization, under the temperature condition of 65 ℃, reacts 20h.With absolute ethanol washing, suction filtration, and vacuum-drying 24 hours at 65 ℃, the titanium doped nickel oxide mixture of carbon nanotube-lithium obtained.
1, the titanium doped nickel oxide of lithium is synthetic
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 to 10h under the temperature condition of 160 ℃, reheat solution to 350 ℃ insulation 2h, obtain grey powder; Grind grey powder, make it by 140 mesh sieves; At the temperature lower calcination 2h of 800 ℃, obtain the titanium doped nickel oxide of lithium of black.
2, the preparation of the titanium doped nickel oxide of the lithium of silanization
After 10g is ground, can be that particle diameter is less than the titanium doped nickel oxide of lithium of 106 microns to be scattered in 60mL massfraction be in 37% superoxol by 140 mesh sieves, be to react 6h under the condition of 90 ℃ in temperature; After reaction finishes, with deionized water wash, suction filtration, and vacuum-drying 24 hours at 60 ℃, obtain the titanium doped nickel oxide of hydroxylated lithium.
Get the titanium doped nickel oxide of the hydroxylated lithium of 10g and put into 100mL dehydrated alcohol and mix, in the suspension obtaining, adding 30mL massfraction is the ethanolic soln of 1.0% γ-aminopropyl triethoxysilane, is to stir 6h under the condition of 60 ℃ in temperature.With absolute ethanol washing, suction filtration, and vacuum-drying 18 hours at 50 ℃, obtain the titanium doped nickel oxide of lithium of silanization.
3, the preparation of the carbon nanotube with carboxyl
It is 60% nitric acid that 1g multi-walled carbon nano-tubes is placed in to 9g massfraction, adds 90mL deionized water in the mixed solution obtaining, and under the temperature condition of 60 ℃, stirs 6h; By deionized water washed product, to neutral, suction filtration, and vacuum-drying 16 hours at 70 ℃, obtain the carbon nanotube with carboxyl.
4, the preparation of the titanium doped nickel oxide mixture of carbon nanotube-lithium
Carbon nanotube dispersed by 300mg with carboxyl, in 120mL DMF, adds the titanium doped nickel oxide of lithium of 15mg silanization, under the temperature condition of 65 ℃, reacts 18h.With absolute ethanol washing, suction filtration, and vacuum-drying 12 hours at 60 ℃, the titanium doped nickel oxide mixture of carbon nanotube-lithium obtained.
Claims (5)
1. a preparation method for the titanium doped nickel oxide mixture of carbon nanotube-lithium, is characterized in that comprising the steps:
(1) by mass, the titanium doped nickel oxide of lithium that 10 parts of particle diameters is less than to 106 microns is distributed in the superoxol that 50～60 parts of massfractions are 35%～40%, is to react 5～6h under the condition of 90～100 ℃ in temperature; 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 and mixed, obtain suspension; In ethanolic soln, adding massfraction is 1.0%～2.0% γ-aminopropyl triethoxysilane, and 20～30 parts are added in described suspension, is to react 5～6h under the condition of 60～65 ℃ in temperature, after filtration, washing, is dried, and obtains the titanium doped nickel oxide of lithium of silanization;
(3) by mass, 1 part of carbon nanotube dispersed with carboxyl, in 300～400 parts of DMFs, is added to the titanium doped nickel oxide of lithium of 0.05～5 part of silanization, at 60～70 ℃ of reaction 12～24h; After filtration, washing, after being dried, 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, 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, is characterized in that: the chemical formula of the titanium doped nickel oxide of described lithium is Li
0.3ti
0.02ni
0.68o; 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 to 8～10h under the temperature condition of 150～160 ℃, reheat solution to 350～400 ℃ insulation 2～3h, obtain grey powder; Grind grey powder to particle diameter and be less than 106 microns, then at the temperature lower calcination 1～2h of 800～850 ℃, 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 the described carbon nanotube with carboxyl comprises the steps: by mass, 1 part of carbon nanotube is placed in to the nitric acid that 9～10 parts of massfractions are 50%～60%, obtains mixed solution; In mixed solution, add deionized water, at 60～70 ℃, stir 5～6h; Filter, washed product is to neutral, dry, obtains the carbon nanotube with carboxyl.
5. the nickel oxide mixture that the carbon nanotube-lithium obtaining by preparation method claimed in claim 1 is titanium doped.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310024732.XA CN103131211B (en) | 2013-01-23 | 2013-01-23 | Carbon nano tube-lithium titanium doped nickel oxide compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310024732.XA CN103131211B (en) | 2013-01-23 | 2013-01-23 | Carbon nano tube-lithium titanium doped nickel oxide compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103131211A CN103131211A (en) | 2013-06-05 |
| CN103131211B true CN103131211B (en) | 2014-05-14 |
Family
ID=48491687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310024732.XA Expired - Fee Related CN103131211B (en) | 2013-01-23 | 2013-01-23 | Carbon nano tube-lithium titanium doped nickel oxide compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103131211B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114093955B (en) * | 2021-10-15 | 2024-03-08 | 华南理工大学 | Gallium arsenide solar cell with carbon nanofiber doped with nickel oxide hole transport layer and preparation method of gallium arsenide solar cell |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1432598A (en) * | 2003-02-28 | 2003-07-30 | 清华大学 | High-dielectric composite material containing carbon nanotube and its prepn process |
| CN102081990A (en) * | 2010-12-27 | 2011-06-01 | 河南城建学院 | High-dielectric composite material containing carbon nanotube fluids (CNTFs) |
| CN102174236A (en) * | 2011-03-16 | 2011-09-07 | 哈尔滨师范大学 | Preparation method of polyvinylidene fluoride-based composite with high dielectric constant |
| CN102246246A (en) * | 2008-09-30 | 2011-11-16 | 肖克科技有限公司 | Voltage switchable dielectric material containing conductive core shelled particles |
| CN102249596A (en) * | 2011-03-25 | 2011-11-23 | 四川大学 | Niobate-series leadless piezoelectric ceramic-polymer three-phase composite material with high dielectric constant |
| CN102569782A (en) * | 2010-12-30 | 2012-07-11 | 河南科隆集团有限公司 | Cobalt-aluminum-doped nickel oxyhydroxide and preparation method thereof |
-
2013
- 2013-01-23 CN CN201310024732.XA patent/CN103131211B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1432598A (en) * | 2003-02-28 | 2003-07-30 | 清华大学 | High-dielectric composite material containing carbon nanotube and its prepn process |
| CN102246246A (en) * | 2008-09-30 | 2011-11-16 | 肖克科技有限公司 | Voltage switchable dielectric material containing conductive core shelled particles |
| CN102081990A (en) * | 2010-12-27 | 2011-06-01 | 河南城建学院 | High-dielectric composite material containing carbon nanotube fluids (CNTFs) |
| CN102569782A (en) * | 2010-12-30 | 2012-07-11 | 河南科隆集团有限公司 | Cobalt-aluminum-doped nickel oxyhydroxide and preparation method thereof |
| CN102174236A (en) * | 2011-03-16 | 2011-09-07 | 哈尔滨师范大学 | Preparation method of polyvinylidene fluoride-based composite with high dielectric constant |
| CN102249596A (en) * | 2011-03-25 | 2011-11-23 | 四川大学 | Niobate-series leadless piezoelectric ceramic-polymer three-phase composite material with high dielectric constant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103131211A (en) | 2013-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Young et al. | High energy density supercapacitors composed of nickel cobalt oxide nanosheets on nanoporous carbon nanoarchitectures | |
| Shinde et al. | Facile chemical synthesis and potential supercapattery energy storage application of hydrangea-type Bi2MoO6 | |
| CN103094540B (en) | The complex method of Graphene and metal oxide/metallic compound and composite material thereof | |
| CN105295303B (en) | Resin, the composite block material of ferrite and MXenes, preparation method and application | |
| CN105923623A (en) | Preparation method of graphene powder with three-dimensional hierarchical porous structure | |
| CN101475161B (en) | Method for preparing BaTiO3 / multi-wall carbon nano-tube (MWCNTs) nano composite material | |
| CN102745675A (en) | Preparation method of spinel-type magnetic MFe2O4/graphene composite material | |
| CN106898435B (en) | A kind of preparation method of high-bulk-density flexible electrode material | |
| CN103073847B (en) | Modified carbon nano tube/thermosetting resin composite material and preparation method thereof | |
| CN110416548A (en) | A kind of preparation method and applications of the two-dimensional structure of N doping porous carbon | |
| CN107293730A (en) | A kind of Ni@N C composite positive poles, preparation method and the application in lithium-air battery | |
| CN109243845A (en) | A kind of cubic crystal Co3O4The preparation and application of doped graphene porous carbon composite | |
| CN105140044B (en) | A kind of method for preparing graphene-based nickel oxide nano composite | |
| CN110364712A (en) | A kind of preparation method and applications of porous carbon@N doping porous carbon core-shell structure | |
| CN109749105A (en) | A kind of highly conductive electromagnetic shielding composite material and preparation method thereof | |
| Yang et al. | Flower-like Bi 2 O 3 with enhanced rate capability and cycling stability for supercapacitors | |
| CN114284515B (en) | Ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Preparation method and application of composite material | |
| CN113351177B (en) | Humidity capturing gel, preparation method and application | |
| Liu et al. | Multifunctional Nd2O3/CNFs composite for microwave absorption and anti-corrosion applications | |
| Liu et al. | Ni/C-carbon nanotube multidimensional heterospheres for highly efficient microwave absorbers | |
| CN103131211B (en) | Carbon nano tube-lithium titanium doped nickel oxide compound and preparation method thereof | |
| CN110527323A (en) | A kind of nano hybridization filler and preparation method thereof using the preparation of electrostatic self-assembled method | |
| CN113130918B (en) | High-catalytic-performance M-N-C catalyst and preparation method and application thereof | |
| CN110931271B (en) | Preparation and application of hydrophobic Schiff base cobalt @ beta cyclodextrin-graphene porous carbon composite material | |
| CN107958793A (en) | A kind of three-dimensional grapheme and preparation method and application of CoO doping |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140514 Termination date: 20210123 |