CN102945969B - Perovskite type lanthanum-strontium-cobalt-oxygen hierarchy mesoporous nanowires, preparation method and applications thereof - Google Patents
Perovskite type lanthanum-strontium-cobalt-oxygen hierarchy mesoporous nanowires, preparation method and applications thereof Download PDFInfo
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- CN102945969B CN102945969B CN201210420109.1A CN201210420109A CN102945969B CN 102945969 B CN102945969 B CN 102945969B CN 201210420109 A CN201210420109 A CN 201210420109A CN 102945969 B CN102945969 B CN 102945969B
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Abstract
The present invention relates to perovskite type lanthanum-strontium-cobalt-oxygen hierarchy mesoporous nanowires and a preparation method thereof, wherein the lanthanum-strontium-cobalt-oxygen hierarchy mesoporous nanowires can be adopted as a catalyst material of lithium air batteries, fuel cells or other electrochemical devices, have characteristic of a diameter of 100-150 nm, a length of 1-2 mum and a specific surface area of up to 96.8 m<2>/g, and are prepared through overlapping of a plurality of mutually connected nanometer short rods, the overlapping part forms a large amount of accumulation holes, a diameter of the nanometer short rod is 30-50 nm, and a large of small holes caused by structural defects exist on the surface of the nanometer short rod. According to the present invention, a multi-step micro-emulsion self-assembly method is adopted, and a post-annealing treatment is combined to obtain the perovskite type lanthanum-strontium-cobalt-oxygen hierarchy mesoporous nanowires, wherein the perovskite type lanthanum-strontium-cobalt-oxygen hierarchy mesoporous nanowires can be adopted as a catalyst material of lithium air batteries, fuel cells, other electrochemical devices and the like, and have characteristics of good electrocatalytic property and extreme high specific capacitance. In addition, characteristics of cheap raw materials, simple process, environmental protection, and excellent electrochemical performance of materials are provided.
Description
Technical field
The invention belongs to nano material and electrochemical device technical field, be specifically related to a kind of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen (LSCO) classification meso-hole structure nano wire and preparation method thereof, this material can be used as the catalyst material at lithium-air battery, fuel cell or other electrochemical devices.
Background technology
Lithium-air battery with the specific capacity of its superelevation and energy density by energy storage field scholars' extensive concern, due to its anodal O that participates in chemical reaction
2do not derive from external environment at inside battery, therefore lithium-air battery can provide the energy density (5000 Wh/kg) of superelevation, is the more than ten times of equal in quality lithium ion battery.Simultaneous reactions process can not produce environmentally harmful material, provides selection for studying high power capacity green energy-storing device of new generation, and may obtain applying comparatively widely future in the fields such as electric automobile.Because cell reaction product and electrolyte decomposition product are as Li
2o, Li
2o
2, Li
2cO
3deposit Deng in positive pole part, catabolite is attached to cell catalyst surface, and oxygen transmission passage is produced and stopped up, and catalyst utilization ratio is reduced greatly, causes common lithium-air battery that enough energy densities cannot be provided.
Classification meso-porous nano material is due to architectural features such as its large specific area, better permeability, more Adsorptions, can reduce lithium-air battery product and the obstruction of electrolyte decomposition product to oxygen transmission passage, improve catalyst utilization ratio, improve lithium-air battery energy density, it is possessed in many-sided application prospect widely such as catalysis, electrochemistry.Due to the fault of construction of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen material, good oxygen channel can be provided, there is important application in electro-catalysis field.
In addition, adopt the method for simple multi step mini-emulsion self assembly, in conjunction with later stage slow annealing processing, only need to control reaction time and reaction temperature, can realize product controlledly synthesis, method is simple, is beneficial to the marketization and promotes.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, there is Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line of good electric catalytic performance and preparation method thereof.
The present invention also provides the application of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line as the catalyst material of lithium-air battery, fuel cell or other electrochemical devices.
The present invention solves the problems of the technologies described above adopted technical scheme: Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line, and its diameter is 100 ~ 150 nm, and length is 1-2 μ m, and its specific area is up to 96.8 m
2/ g, it is formed by a large amount of interconnective nanometer stub overlap joints, and overlap forms bulk deposition hole, and described nanometer stub diameter is 30 ~ 50 nm, and there is the aperture causing due to fault of construction in a large number, the product that it is prepared for following method in its surface:
1) press isooctane: n-butanol=15 ~ 18 ml:3 ml preparation isooctane/n-butanol mixed liquor, add 3.0 g CTAB, magnetic agitation until without bulky grain, repeat above-mentioned steps, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml is slowly added dropwise in the mixture of a copy of it isooctane-n-butanol-CTAB that step 1) obtains, magnetic agitation is to forming the stable KOH microemulsion of clarification again;
3) La (NO of preparation 0.5 mol/L
3)
3, Sr (NO
3)
2and Co (NO
3)
2the aqueous solution, by La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and is slowly added dropwise in the mixture of another part of isooctane/n-butanol/CTAB that step 1) obtains, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion;
4) by step 2) the KOH microemulsion of gained and the La (NO of step 3) gained
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion mixes, and rapid stirring 1 hour, then slowly stirs 4 ~ 6 hours, obtains product;
5) product centrifugation step 4) being obtained, with ethanol and deionized water centrifuge washing, dry repeatedly, obtains Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
Press such scheme, the product that washing obtains is dried 12 ~ 24 hours at 80 DEG C.
Press such scheme, also include annealing in process, under argon gas, be warmed up to 750 ~ 850 DEG C with the programming rate of 1 DEG C/min by desciccate.
The preparation method of described Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line, is characterized in that including following steps:
1) press isooctane: n-butanol=15 ~ 18 ml:3 ml preparation isooctane/n-butanol mixed liquor, add 3.0 g CTAB, magnetic agitation until without bulky grain, repeat above-mentioned steps, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml is slowly added dropwise in the mixture of a copy of it isooctane-n-butanol-CTAB that step 1) obtains, magnetic agitation is to forming the stable KOH microemulsion of clarification again;
3) La (NO of preparation 0.5 mol/L
3)
3, Sr (NO
3)
2and Co (NO
3)
2the aqueous solution, by La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and is slowly added dropwise in the mixture of another part of isooctane/n-butanol/CTAB that step 1) obtains, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion;
4) by step 2) the KOH microemulsion of gained and the La (NO of step 3) gained
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion mixes, and rapid stirring 1 hour, then slowly stirs 4 ~ 6 hours, obtains product;
5) product centrifugation step 4) being obtained, by ethanol and deionized water centrifuge washing, dry and annealing in process repeatedly, obtains Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
Press such scheme, the product that washing obtains is dried 12 ~ 24 hours at 80 DEG C.
Press such scheme, also include annealing in process, under argon gas, be warmed up to 750 ~ 850 DEG C with the programming rate of 1 DEG C/min by desciccate.
Described Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line is as the application of the catalyst material of lithium-air battery, fuel cell or other electrochemical devices.
The invention has the beneficial effects as follows: the present invention utilizes multi step mini-emulsion self-assembly method, in conjunction with post annealed processing, obtain Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line, this material is as catalyst materials such as lithium-air battery, fuel cell or other electrochemical devices, there is good electrocatalysis characteristic, there is high specific capacitance; The present invention has the feature of raw material cheapness, the simple environmental protection of technique, material electrochemical performance excellence; The present invention has larger application potential on lithium-air battery, fuel cell or other electrochemical devices.
The classification meso-hole structure of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line of the present invention and the raising of its performance are closely related, and the first, electrocatalysis characteristic and specific area have close relation, and the specific area of LSCO classification meso-porous nano line is up to 96.8 m
2g
– 1, apparently higher than LSCO material and LSCO nano particle 11.87 m of bibliographical information
2g
1; The second, even in the situation that electrolyte decomposition product is deposited on catalyst and electrode surface, discrete pore passage structure that the LSCO nanometer stub of overlap joint provides mutually still can be passing to of oxygen provides continuous passage; The 3rd, the loose structure on the structure that has defect of Ca-Ti ore type itself and LSCO nanometer stub surface can increase the mobility of oxygen on lower yardstick, improves ORR catalytic efficiency in dynamics; The 4th, this hierarchy can effectively reduce material from the generation of reuniting, and in catalytic process, ensures and fully the contacting of oxygen, and gives full play to the advantage of nano material.This shows that classification meso-hole structure can improve chemical property effectively, and Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line has larger application potential on lithium-air battery, fuel cell or other electrochemical devices.
Brief description of the drawings
Fig. 1 is the XRD figure of the Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line of the embodiment of the present invention 1 gained, and embedding figure is Ca-Ti ore type lanthanum-strontium-cobalt-oxygen atomic structure model figure;
Fig. 2 is the Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line N of the embodiment of the present invention 1 gained
2adsorption/desorption curve, embedding figure is the BJH pore size distribution curve of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line;
Fig. 3 is the SEM figure of the Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line of the embodiment of the present invention 1 gained;
Fig. 4 is the TEM figure of the Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line of the embodiment of the present invention 1 gained;
Fig. 5 is the HRTEM figure of the Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line of the embodiment of the present invention 1 gained;
Fig. 6 is HRTEM figure and the selected areas FFT style of the Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line Nodes of the embodiment of the present invention 1 gained;
Fig. 7 is the synthesis mechanism figure of the Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line of the embodiment of the present invention 1 gained;
Fig. 8 be the embodiment of the present invention 1 gained ORR polarization current curve under different rotating speeds of the glass-carbon electrode of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line+active carbon (AC);
Fig. 9 is the glass-carbon electrode of the embodiment of the present invention 1 gained ORR, the OER polarization curve under the rotating speed of 1600 rpm;
Figure 10 is the lithium-air battery of the Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line+active carbon (AC) based on the embodiment of the present invention 1 gained discharge curve in normal pressure pure oxygen.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
embodiment 1:
The preparation method of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line, comprises the steps:
1) press isooctane: n-butanol=15 ml:3 ml preparation isooctane/n-butanol mixed liquor, add 3.0 g CTAB, magnetic agitation until without bulky grain, repeat above-mentioned steps, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml is slowly added dropwise in the mixture of a copy of it isooctane-n-butanol-CTAB that step 1) obtains, magnetic agitation is to forming the stable KOH microemulsion of clarification again;
3) La (NO of preparation 0.5 mol/L
3)
3, Sr (NO
3)
2and Co (NO
3)
2the aqueous solution, by La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and is slowly added dropwise in the mixture of another part of isooctane/n-butanol/CTAB that step 1) obtains, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion;
4) by step 2) the KOH microemulsion of gained and the La (NO of step 3) gained
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion mixes, and rapid stirring 1 hour, then slowly stirs 6 hours, obtains product;
5) product centrifugation step 4) being obtained, with ethanol and deionized water centrifuge washing repeatedly; The product of washing is dried 24 hours at 80 DEG C; Desciccate is warmed up to 800 DEG C of annealing in process with the programming rate of 1 DEG C/min under argon gas, obtains Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
In the present invention, Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line is determined by x-ray diffractometer.As shown in Figure 1, X-ray diffracting spectrum shows, the lanthanum-strontium-cobalt-oxygen classification meso-porous nano line obtaining after annealing is pure phase La
0.5sr
0.5coO
2.91, JCPDS card No. 00-048-0122:a=5.4300, b=5.4300, c=13.2516.By atomic structure model, determine that LSCO is typical perovskite structure, and due to the existence of oxygen vacancy, may further increase the conduction of ion or oxygen.As shown in Figure 3, scanning electron microscope test shows, product Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano linear diameter is about 150 nm, formed by a large amount of interconnective nanometer stubs overlap joints, and overlap forms bulk deposition hole.Further information can obtain from TEM and HRTEM figure, as shown in 4-5, the length of classification meso-porous nano line is 1-2 μ m, and nanometer stub diameter 40 nm of LSCO find still to exist on LSCO nanometer stub surface the pore structure causing due to fault of construction in a large number.Nanometer stub link node place in close-ups LSCO classification meso-porous nano line, finds that LSCO nanometer stub is not simply to overlap, but has the connection of orientation.Observe the HRTEM figure at node place, find that LSCO nanometer stub closely links together on atomic scale in the time forming LSCO classification meso-porous nano line.As shown in Figure 6, by the lattice fringe of HRTEM with at the FFT of position, constituency diffraction pattern, find the bond sites between LSCO nanometer stub, exist the different directions of growth, therefore, this shows that it is not synchronous that the crystallization of LSCO nanometer stub and classification meso-porous nano line forms.As shown in Figure 7, LSCO nanometer stub is first at La (NO
3)
3, Sr (NO
3)
2, Co (NO
3)
2with crystallization growth under the high-speed stirred effect of the microemulsion of KOH, along with the reduction of mixing speed and control the increase of water core size in microemulsion, will there is self assembly in LSCO nanometer stub, simultaneously, LSCO nanometer stub is using self as template, the further oriented growth of guiding nanometer stub, finally forms LSCO classification meso-porous nano line.As shown in Figure 2, N
2adsorption/desorption curve and BJH pore size distribution curve show the hole that LSCO classification meso-porous nano line existence nanorod surfaces duct own and nanometer rods accumulation form, and average pore size is 10.17nm, is typical meso-porous nano line.The specific area of classification meso-porous nano line is 96.8 m
2/ g, considerably beyond the nano wire of similar size.
In the present invention, the oxygen reduction reaction of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen (LSCO) classification meso-porous nano line and the catalytic activity of oxygen evolution reaction adopt the test of rotating disk electrode (r.d.e) method, get 0.75 mg LSCO classification meso-porous nano line and mix 4.25 mg active carbon AC(XC-72), being dispersed in containing 122 μ l mass fractions is the 1 ml water of 5 wt% Nafion: in the liquid that isopropyl alcohol volume ratio is 3:1, ultrasonic processing, obtains homogeneous prepared Chinese ink shape liquid.Get the material of the preparation of same quality, first drip and be attached to glass-carbon electrode surface (diameter is 5mm), approximately 20 μ g after drying.At the logical oxygen of 0.1M KOH, sweep speed 5mVs
-1, test is at room temperature carried out.As shown in Figure 8, the half wave potential of LSCO classification meso-porous nano line+AC in the time that rotating speed is 1600 rpm is at ~ 0.77V, comparing AC, LSCO nano particle+AC has significantly and shuffles, and illustrates that catalyst activity is significantly improved through constructing classification meso-porous nano line.The limit of LSCO classification meso-porous nano line+AC expands calculation electric current can reach-13 mA cm
-2, far exceed active carbon or other lithium-air battery catalyst of equivalent.
As can be seen from Figure 9, Ca-Ti ore type lanthanum-strontium-cobalt-oxygen (LSCO) classification meso-porous nano line has good ORR, OER catalytic activity.
In the present invention, Ca-Ti ore type lanthanum-strontium-cobalt-oxygen (LSCO) classification meso-porous nano line assembling lithium-air battery is tested in purity oxygen, the lithium-air battery of LSCO classification meso-porous nano line+AC has the specific capacity of superelevation, as shown in figure 10, can reach 11059 mAh/g, discharge platform is in 2.7 V left and right, and corresponding specific energy is up to 27647 Wh/kg.Its specific capacity is far above AC (1444 mAh/g), LSCO nano particle+AC (5302 mA/g) lithium-air battery.
embodiment 2:
The preparation method of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen (LSCO) classification meso-porous nano line, comprises the steps:
1) press isooctane: n-butanol=15 ml:3 ml preparation isooctane/n-butanol mixed liquor, add 3.0 g CTAB, magnetic agitation until without bulky grain, repeat above-mentioned steps, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml is slowly added dropwise in the mixture of a copy of it isooctane-n-butanol-CTAB that step 1) obtains, magnetic agitation is to forming the stable KOH microemulsion of clarification again;
3) La (NO of preparation 0.5 mol/L
3)
3, Sr (NO
3)
2and Co (NO
3)
2the aqueous solution, by La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and is slowly added dropwise in the mixture of another part of isooctane/n-butanol/CTAB that step 1) obtains, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion;
4) by step 2) the KOH microemulsion of gained and the La (NO of step 3) gained
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion mixes, and rapid stirring 1 hour, then slowly stirs 6 hours, obtains product;
5) step 4) is obtained to product centrifugation, with ethanol and deionized water centrifuge washing repeatedly; The product of washing is dried 24 hours at 80 DEG C; Desciccate is warmed up to 750 DEG C of annealing in process with the programming rate of 1 DEG C/min under argon gas, obtains Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
embodiment 3:
The preparation method of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen (LSCO) classification meso-porous nano line, comprises the steps:
1) press isooctane: n-butanol=18 ml:3 ml preparation isooctane/n-butanol mixed liquor, add 3.0 g CTAB, magnetic agitation until without bulky grain, repeat above-mentioned steps, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml is slowly added dropwise in the mixture of a copy of it isooctane-n-butanol-CTAB that step 1) obtains, magnetic agitation is to forming the stable KOH microemulsion of clarification again;
3) La (NO of preparation 0.5 mol/L
3)
3, Sr (NO
3)
2and Co (NO
3)
2the aqueous solution, by La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and is slowly added dropwise in the mixture of another part of isooctane/n-butanol/CTAB that step 1) obtains, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion;
4) by step 2) the KOH microemulsion of gained and the La (NO of step 3) gained
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion mixes, and rapid stirring 1 hour, then slowly stirs 5 hours, obtains product;
5) step 4) is obtained to product centrifugation, with ethanol and deionized water centrifuge washing repeatedly; The product of washing is dried 24 hours at 80 DEG C; Desciccate is warmed up to 800 DEG C of annealing in process with the programming rate of 1 DEG C/min under argon gas, obtains Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
embodiment 4:
The preparation method of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen (LSCO) classification meso-porous nano line, comprises the steps:
1) press isooctane: n-butanol=15 ml:3 ml preparation isooctane/n-butanol mixed liquor, add 3.0 g CTAB, magnetic agitation until without bulky grain, repeat above-mentioned steps, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml is slowly added dropwise in the mixture of a copy of it isooctane-n-butanol-CTAB that step 1) obtains, magnetic agitation is to forming the stable KOH microemulsion of clarification again;
3) La (NO of preparation 0.5 mol/L
3)
3, Sr (NO
3)
2and Co (NO
3)
2the aqueous solution, by La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and is slowly added dropwise in the mixture of another part of isooctane/n-butanol/CTAB that step 1) obtains, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion;
4) by step 2) the KOH microemulsion of gained and the La (NO of step 3) gained
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion mixes, and rapid stirring 1 hour, then slowly stirs 4 hours, obtains product;
5) step 4) is obtained to product centrifugation, with ethanol and deionized water centrifuge washing repeatedly; The product of washing is dried 12 hours at 80 DEG C; Desciccate is warmed up to 850 DEG C of annealing in process with the programming rate of 1 DEG C/min under argon gas, obtains Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
embodiment 5:
The preparation method of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen (LSCO) classification meso-porous nano line, comprises the steps:
1) press isooctane: n-butanol=15ml:3 ml preparation isooctane/n-butanol mixed liquor, add 3.0 g CTAB, magnetic agitation until without bulky grain, repeat above-mentioned steps, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml is slowly added dropwise in the mixture of a copy of it isooctane-n-butanol-CTAB that step 1) obtains, magnetic agitation is to forming the stable KOH microemulsion of clarification again;
3) La (NO of preparation 0.5 mol/L
3)
3, Sr (NO
3)
2and Co (NO
3)
2the aqueous solution, by La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and is slowly added dropwise in the mixture of another part of isooctane/n-butanol/CTAB that step 1) obtains, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion;
4) by step 2) the KOH microemulsion of gained and the La (NO of step 3) gained
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion mixes, and rapid stirring 1 hour, then slowly stirs 4 hours, obtains product;
5) step 4) is obtained to product centrifugation, with ethanol and deionized water centrifuge washing repeatedly; The product of washing is dried 12 hours at 80 DEG C; Obtain Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
Claims (5)
1. Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line, its diameter is 100 ~ 150 nm, and length is 1-2 μ m, and its specific area is up to 96.8 m
2/ g, it is formed by a large amount of interconnective nanometer stub overlap joints, and overlap forms bulk deposition hole, and described nanometer stub diameter is 30 ~ 50 nm, and there is the aperture causing due to fault of construction in a large number, the product that it is prepared for following method in its surface:
1) press isooctane: n-butanol=15 ~ 18 ml:3 ml preparation isooctane/n-butanol mixed liquor, add 3.0 g CTAB, magnetic agitation until without bulky grain, repeat above-mentioned steps, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml is slowly added dropwise in the mixture of a copy of it isooctane-n-butanol-CTAB that step 1) obtains, magnetic agitation is to forming the stable KOH microemulsion of clarification again;
3) La (NO of preparation 0.5 mol/L
3)
3, Sr (NO
3)
2and Co (NO
3)
2the aqueous solution, by La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and is slowly added dropwise in the mixture of another part of isooctane/n-butanol/CTAB that step 1) obtains, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion;
4) by step 2) the KOH microemulsion of gained and the La (NO of step 3) gained
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion mixes, and rapid stirring 1 hour, then slowly stirs 4 ~ 6 hours, obtains product;
5) product centrifugation step 4) being obtained, by ethanol and deionized water centrifuge washing, dry and annealing in process repeatedly, described annealing in process, for desciccate is warmed up to 750 ~ 850 DEG C with the programming rate of 1 DEG C/min under argon gas, obtains Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
2. by Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line claimed in claim 1, it is characterized in that the product that washing obtains is dried 12 ~ 24 hours at 80 DEG C.
3. the preparation method of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line claimed in claim 1, is characterized in that including following steps:
1) press isooctane: n-butanol=15 ~ 18 ml:3 ml preparation isooctane/n-butanol mixed liquor, add 3.0 g CTAB, magnetic agitation until without bulky grain, repeat above-mentioned steps, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml is slowly added dropwise in the mixture of a copy of it isooctane-n-butanol-CTAB that step 1) obtains, magnetic agitation is to forming the stable KOH microemulsion of clarification again;
3) La (NO of preparation 0.5 mol/L
3)
3, Sr (NO
3)
2and Co (NO
3)
2the aqueous solution, by La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and is slowly added dropwise in the mixture of another part of isooctane/n-butanol/CTAB that step 1) obtains, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion;
4) by step 2) the KOH microemulsion of gained and the La (NO of step 3) gained
3)
3-Sr (NO
3)
2-Co (NO
3)
2microemulsion mixes, and rapid stirring 1 hour, then slowly stirs 4 ~ 6 hours, obtains product;
5) product centrifugation step 4) being obtained, by ethanol and deionized water centrifuge washing, dry and annealing in process repeatedly, described annealing in process, for desciccate is warmed up to 750 ~ 850 DEG C with the programming rate of 1 DEG C/min under argon gas, obtains Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
4. by the preparation method of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line claimed in claim 3, it is characterized in that the product that washing obtains is dried 12 ~ 24 hours at 80 DEG C.
5. Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line claimed in claim 1 is as the application of the catalyst material of lithium-air battery, fuel cell or other electrochemical devices.
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