CN102945969A - 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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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, because its anodal O that participates in chemical reaction
2Do not derive from external environment at inside battery, so lithium-air battery can provide the energy density (5000 Wh/kg) of superelevation, be more than ten times of equal in quality lithium ion battery.The 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 using comparatively widely future in the fields such as electric automobile.Because cell reaction product and electrolyte decomposition product such as Li
2O, Li
2O
2, Li
2CO
3Partly deposit Deng at positive pole, catabolite is attached to the cell catalyst surface, the oxygen transmission passage is produced stop up, and the catalyst utilization ratio is reduced greatly, causes common lithium-air battery that enough energy densities can't be provided.
Classification meso-porous nano material is because architectural features such as its large specific area, better permeability, more Adsorptions, can reduce lithium-air battery product and electrolyte decomposition product to the obstruction of oxygen transmission passage, improve the catalyst utilization ratio, improve the lithium-air battery energy density, it is possessed in many-sided widely application prospects such as catalysis, electrochemistry.Because the fault of construction of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen material can provide good oxygen channel, has important application in the electro-catalysis field.
In addition, adopt the method for simple multi step mini-emulsion self assembly, process in conjunction with the later stage slow annealing, only need to control reaction time and reaction temperature, can realize the 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, have 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 the technical scheme that adopts: 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 the bulk deposition hole, and described nanometer stub diameter is 30 ~ 50 nm, and there is the aperture that causes owing to fault of construction in a large number in its surface, and it is the product of following method preparation:
1) press isooctane: n-butanol=15 ~ 18 ml:3 ml prepare isooctane/n-butanol mixed liquor, add 3.0 g CTAB, and magnetic agitation repeats above-mentioned steps until without bulky grain, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml slowly is added dropwise in the mixture of a copy of it isooctane-n-butanol that step 1) obtains-CTAB, 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 is pressed La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and slowly is added dropwise in the mixture of another part isooctane/n-butanol that step 1) obtains/CTAB, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2Microemulsion;
4) with 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 then rapid stirring 1 hour slowly stirred 4 ~ 6 hours, obtained product;
5) ethanol and deionized water repeatedly centrifuge washing, drying are used in the product centrifugation that step 4) is obtained, and obtain Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
Press such scheme, wash the product that obtains lower dry 12 ~ 24 hours at 80 ℃.
Press such scheme, also include annealing in process, be about to desciccate programming rate with 1 ℃/min under argon gas and be warmed up to 750 ~ 850 ℃.
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 prepare isooctane/n-butanol mixed liquor, add 3.0 g CTAB, and magnetic agitation repeats above-mentioned steps until without bulky grain, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml slowly is added dropwise in the mixture of a copy of it isooctane-n-butanol that step 1) obtains-CTAB, 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 is pressed La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and slowly is added dropwise in the mixture of another part isooctane/n-butanol that step 1) obtains/CTAB, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2Microemulsion;
4) with 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 then rapid stirring 1 hour slowly stirred 4 ~ 6 hours, obtained product;
5) ethanol and deionized water repeatedly centrifuge washing, drying and annealing in process are used in the product centrifugation that step 4) is obtained, and obtain Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
Press such scheme, wash the product that obtains lower dry 12 ~ 24 hours at 80 ℃.
Press such scheme, also include annealing in process, be about to desciccate programming rate with 1 ℃/min under argon gas and be warmed up to 750 ~ 850 ℃.
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 the multi step mini-emulsion self-assembly method, process in conjunction with post annealed, obtained 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, good electrocatalysis characteristic is arranged, have high specific capacitance; The present invention has the characteristics of raw material cheapness, the simple environmental protection of technique, material electrochemical performance excellence; The present invention has larger application potential at 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
1The second, even in the situation that the electrolyte decomposition product is deposited on catalyst and electrode surface, discrete pore passage structure that the LSCO nanometer stub that mutually overlaps provides still can be passing to of oxygen provides continuous passage; The 3rd, the loose structure on the structure that has defective of Ca-Ti ore type itself and LSCO nanometer stub surface can increase at lower yardstick the flowability of oxygen, improves the ORR catalytic efficiency in dynamics; The 4th, this hierarchy can effectively reduce material from the generation of reuniting, and guarantees in catalytic process and fully the contacting of oxygen, and gives full play to the advantage of nano material.This shows that the 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 at lithium-air battery, fuel cell or other electrochemical devices.
Description of 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 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 invention 1 gained
2The adsorption/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 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 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 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 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 invention 1 gained;
Fig. 8 be the embodiment of the invention 1 gained the ORR polarization current curve of glass-carbon electrode under different rotating speeds of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line+active carbon (AC);
Fig. 9 is ORR, the OER polarization curve of glass-carbon electrode under the rotating speed of 1600 rpm of the embodiment of the invention 1 gained;
Figure 10 is based on the discharge curve of lithium-air battery in the normal pressure pure oxygen of the Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line+active carbon (AC) of the embodiment of the invention 1 gained.
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 not only is 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 prepare isooctane/n-butanol mixed liquor, add 3.0 g CTAB, and magnetic agitation repeats above-mentioned steps until without bulky grain, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml slowly is added dropwise in the mixture of a copy of it isooctane-n-butanol that step 1) obtains-CTAB, 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 is pressed La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and slowly is added dropwise in the mixture of another part isooctane/n-butanol that step 1) obtains/CTAB, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2Microemulsion;
4) with 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 then rapid stirring 1 hour slowly stirred 6 hours, obtained product;
5) repeatedly centrifuge washing of ethanol and deionized water is used in the product centrifugation that step 4) is obtained; The product that washs is lower dry 24 hours at 80 ℃; Desciccate programming rate with 1 ℃/min under argon gas is warmed up to 800 ℃ of annealing in process, obtains Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line is determined by x-ray diffractometer among the present invention.As shown in Figure 1, X-ray diffracting spectrum shows, the lanthanum-strontium-cobalt-oxygen classification meso-porous nano line that obtains 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 because 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 the bulk deposition hole.Further information can obtain from TEM and HRTEM figure, shown in 4-5, the length of classification meso-porous nano line is 1-2 μ m, nanometer stub diameter 40 nm of LSCO, and still there is the pore structure that causes owing to fault of construction in a large number in discovery on LSCO nanometer stub surface.Nanometer stub link node place in the 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 when forming LSCO classification meso-porous nano line on atomic scale.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 at 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 nuclear size in the microemulsion, self assembly will occur in LSCO nanometer stub, simultaneously, LSCO nanometer stub with 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 is considerably beyond the nano wire of similar size.
The catalytic activity of the oxygen reduction reaction of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen (LSCO) classification meso-porous nano line and oxygen evolution reaction adopts the test of rotating disk electrode (r.d.e) method among the present invention, get 0.75 mg LSCO classification meso-porous nano line and mix 4.25 mg active carbon AC(XC-72), be dispersed in and contain the 1 ml water that 122 μ l mass fractions are 5 wt% Nafion: the isopropyl alcohol volume ratio is in the liquid of 3:1, ultrasonic processing obtains homogeneous prepared Chinese ink shape liquid.Get the material of the preparation of same quality, at first drip and be attached to glass-carbon electrode surface (diameter is 5mm), about 20 μ g after the oven dry.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 when rotating speed is 1600 rpm is at ~ 0.77V, comparing AC, LSCO nano particle+AC has significantly and shuffles, and illustrates that the catalyst activity is significantly improved through constructing classification meso-porous nano line.The limit of LSCO classification meso-porous nano line+AC expands the calculation electric current can reach-13 mA cm
-2, far surpass 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.
Ca-Ti ore type lanthanum-strontium-cobalt-oxygen (LSCO) classification meso-porous nano line assembling lithium-air battery is tested in purity oxygen among the present invention, 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 about 2.7 V, 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 prepare isooctane/n-butanol mixed liquor, add 3.0 g CTAB, and magnetic agitation repeats above-mentioned steps until without bulky grain, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml slowly is added dropwise in the mixture of a copy of it isooctane-n-butanol that step 1) obtains-CTAB, 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 is pressed La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and slowly is added dropwise in the mixture of another part isooctane/n-butanol that step 1) obtains/CTAB, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2Microemulsion;
4) with 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 then rapid stirring 1 hour slowly stirred 6 hours, obtained product;
5) step 4) is obtained the product centrifugation, use repeatedly centrifuge washing of ethanol and deionized water; The product that washs is lower dry 24 hours at 80 ℃; Desciccate programming rate with 1 ℃/min under argon gas is warmed up to 750 ℃ of annealing in process, 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 prepare isooctane/n-butanol mixed liquor, add 3.0 g CTAB, and magnetic agitation repeats above-mentioned steps until without bulky grain, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml slowly is added dropwise in the mixture of a copy of it isooctane-n-butanol that step 1) obtains-CTAB, 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 is pressed La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and slowly is added dropwise in the mixture of another part isooctane/n-butanol that step 1) obtains/CTAB, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2Microemulsion;
4) with 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 then rapid stirring 1 hour slowly stirred 5 hours, obtained product;
5) step 4) is obtained the product centrifugation, use repeatedly centrifuge washing of ethanol and deionized water; The product that washs is lower dry 24 hours at 80 ℃; Desciccate programming rate with 1 ℃/min under argon gas is warmed up to 800 ℃ of annealing in process, 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 prepare isooctane/n-butanol mixed liquor, add 3.0 g CTAB, and magnetic agitation repeats above-mentioned steps until without bulky grain, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml slowly is added dropwise in the mixture of a copy of it isooctane-n-butanol that step 1) obtains-CTAB, 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 is pressed La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and slowly is added dropwise in the mixture of another part isooctane/n-butanol that step 1) obtains/CTAB, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2Microemulsion;
4) with 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 then rapid stirring 1 hour slowly stirred 4 hours, obtained product;
5) step 4) is obtained the product centrifugation, use repeatedly centrifuge washing of ethanol and deionized water; The product that washs is lower dry 12 hours at 80 ℃; Desciccate programming rate with 1 ℃/min under argon gas is warmed up to 850 ℃ of annealing in process, 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 prepares isooctane/n-butanol mixed liquor, adds 3.0 g CTAB, and magnetic agitation repeats above-mentioned steps until without bulky grain, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml slowly is added dropwise in the mixture of a copy of it isooctane-n-butanol that step 1) obtains-CTAB, 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 is pressed La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and slowly is added dropwise in the mixture of another part isooctane/n-butanol that step 1) obtains/CTAB, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2Microemulsion;
4) with 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 then rapid stirring 1 hour slowly stirred 4 hours, obtained product;
5) step 4) is obtained the product centrifugation, use repeatedly centrifuge washing of ethanol and deionized water; The product that washs is lower dry 12 hours at 80 ℃; Obtain Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
Claims (7)
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 the bulk deposition hole, and described nanometer stub diameter is 30 ~ 50 nm, and there is the aperture that causes owing to fault of construction in a large number in its surface, and it is the product of following method preparation:
1) press isooctane: n-butanol=15 ~ 18 ml:3 ml prepare isooctane/n-butanol mixed liquor, add 3.0 g CTAB, and magnetic agitation repeats above-mentioned steps until without bulky grain, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml slowly is added dropwise in the mixture of a copy of it isooctane-n-butanol that step 1) obtains-CTAB, 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 is pressed La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and slowly is added dropwise in the mixture of another part isooctane/n-butanol that step 1) obtains/CTAB, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2Microemulsion;
4) with 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 then rapid stirring 1 hour slowly stirred 4 ~ 6 hours, obtained product;
5) ethanol and deionized water repeatedly centrifuge washing, drying are used in the product centrifugation that step 4) is obtained, and obtain Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
2. press Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line claimed in claim 1, it is characterized in that washing the product that obtains lower dry 12 ~ 24 hours at 80 ℃.
3. by claim 1 or 2 described Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano lines, characterized by further comprising annealing in process, be about to desciccate programming rate with 1 ℃/min under argon gas and be warmed up to 750 ~ 850 ℃.
4. 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 prepare isooctane/n-butanol mixed liquor, add 3.0 g CTAB, and magnetic agitation repeats above-mentioned steps until without bulky grain, obtains the mixture of two parts of isooctane-n-butanol-CTAB;
2) the 1 M KOH aqueous solution of 2.75 ml slowly is added dropwise in the mixture of a copy of it isooctane-n-butanol that step 1) obtains-CTAB, 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 is pressed La (NO
3)
3: Sr (NO
3)
2: Co (NO
3)
2=0.5ml:0.5ml:1ml evenly mixes, and slowly is added dropwise in the mixture of another part isooctane/n-butanol that step 1) obtains/CTAB, and magnetic agitation is to forming the stable La (NO of clarification
3)
3-Sr (NO
3)
2-Co (NO
3)
2Microemulsion;
4) with 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 then rapid stirring 1 hour slowly stirred 4 ~ 6 hours, obtained product;
5) ethanol and deionized water repeatedly centrifuge washing, drying and annealing in process are used in the product centrifugation that step 4) is obtained, and obtain Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line.
5. press the preparation method of Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano line claimed in claim 4, it is characterized in that washing the product that obtains lower dry 12 ~ 24 hours at 80 ℃.
6. by the preparation method of claim 4 or 5 described Ca-Ti ore type lanthanum-strontium-cobalt-oxygen classification meso-porous nano lines, characterized by further comprising annealing in process, be about to desciccate programming rate with 1 ℃/min under argon gas and be warmed up to 750 ~ 850 ℃.
7. 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9472833B1 (en) | 2016-06-28 | 2016-10-18 | Abigail Thurmond | Methods and apparatuses relating to zinc-air batteries |
| CN111018003A (en) * | 2019-11-29 | 2020-04-17 | 南京理工大学 | Method for preparing nano zinc cobaltate particles by reverse microemulsion method |
| CN113140786A (en) * | 2021-03-15 | 2021-07-20 | 佛山仙湖实验室 | Solid electrolyte and preparation method and application thereof |
| CN113332990A (en) * | 2021-06-30 | 2021-09-03 | 华南农业大学 | Perovskite catalytic material and green synthesis method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974887A (en) * | 2006-11-10 | 2007-06-06 | 北京工业大学 | Prepn process of nanometer wire and nanometer rod of monocrystalline perovskite type compound oxide La0.6Sr0.4CoO3 |
| US20070138459A1 (en) * | 2005-10-13 | 2007-06-21 | Wong Stanislaus S | Ternary oxide nanostructures and methods of making same |
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2012
- 2012-10-29 CN CN201210420109.1A patent/CN102945969B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070138459A1 (en) * | 2005-10-13 | 2007-06-21 | Wong Stanislaus S | Ternary oxide nanostructures and methods of making same |
| CN1974887A (en) * | 2006-11-10 | 2007-06-06 | 北京工业大学 | Prepn process of nanometer wire and nanometer rod of monocrystalline perovskite type compound oxide La0.6Sr0.4CoO3 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9472833B1 (en) | 2016-06-28 | 2016-10-18 | Abigail Thurmond | Methods and apparatuses relating to zinc-air batteries |
| CN111018003A (en) * | 2019-11-29 | 2020-04-17 | 南京理工大学 | Method for preparing nano zinc cobaltate particles by reverse microemulsion method |
| CN113140786A (en) * | 2021-03-15 | 2021-07-20 | 佛山仙湖实验室 | Solid electrolyte and preparation method and application thereof |
| CN113332990A (en) * | 2021-06-30 | 2021-09-03 | 华南农业大学 | Perovskite catalytic material and green synthesis method and application thereof |
| CN113332990B (en) * | 2021-06-30 | 2023-01-10 | 华南农业大学 | Perovskite catalytic material and green synthesis method and application thereof |
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