CN103318978A - Preparation method of mesoporous nickel cobaltate fiber and application thereof - Google Patents
Preparation method of mesoporous nickel cobaltate fiber and application thereof Download PDFInfo
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Abstract
The invention brings forward a preparation method of mesoporous nickel cobaltate fiber. According to the preparation method, an organic solvent is added during the preparation process of a precursor; a mixed phase of a water phase and an organic phase is used as a solvent, soluble nickel salt and cobalt salt are used as raw materials, and oxalate is used as a precipitating agent; in a system of Ni<2+>-Co<2+>-NH3-NH4<+>-SG<n->-C2O4<2->-H20-C2H5OH, a fibrous precursor is prepared; and the fibrous precursor is subjected to thermal decomposition in the air atmosphere at 250-400 DEG C so as to obtain the mesoporous NiCo2O4 fiber. According to the invention, coprecipitation based on the Ni-Co ratio set in the raw materials is effectively realized. The prepared NiCo2O4 powder is a cubic phase, has high purity and large specific surface area, is fibrous and porous, and is applicable to be used as a catalyst or an alkaline solution oxygen-evolution/hydrogen-evolution electrode material or direct alcohol fuel cell anode catalyst. The method provided by the invention is simple to operate and easy to control, has advantages of mild condition and low cost, and is suitable for commercialized production.
Description
Technical field
The invention belongs to one dimension transition metal oxide field, be specifically related to a kind of preparation method and application thereof of cobalt acid nickel.
Background technology
In recent years, direct alcohol fuel cell obtains extensive concern because of its nontoxicity, theoretical energy density advantages of higher.Currently used anode catalyst mostly is precious metal and binary or the multicomponent materials such as platinum, ruthenium, cost is high, easily CO poisons in cell reaction, therefore seek the base metal anode catalyst as an alternative with good catalytic and low cost, become the direct alcohol fuel cell development in the urgent need to.Cobalt acid nickel (NiCo
2O
4) be a kind of composite oxides with inverse spinel structure, have good chemical property, its electroconductibility and electrochemical activity are higher than single metallic nickel, cobalt/cobalt oxide, have Co
3+/ Co
2+And Ni
3+/ Ni
2+Redox couple is widely applied in catalytic field, electrochemical industry, field of environment protection.For example: in the catalyzer application facet, owing to having the NiCo of spinel structure
2O
4Active high, good stability, the active ingredient as administering the Organic Waste Gas Pollution catalyst system therefor can replace the precious metals such as expensive platinum, rhodium, palladium; Aspect electrode materials, NiCo
2O
4A kind of desirable anode of electrolytic water material, separating out and reducing and all have preferably catalytic performance oxygen; As electrode material for super capacitor, cobalt acid nickel has higher ratio electric capacity, alternative RuO
2In addition, because its good electrocatalysis characteristic, cobalt acid nickel can also be as anode material of lithium-ion battery, high multiplying power lithium ion anode material etc.Although the purposes of cobalt acid nickel is so extensive, up to the present, people to cobalt acid nickel in the applied research aspect the direct alcohol fuel cell also seldom.In addition, how much patterns of the performance of material and material have direct relation, and the one dimension porous nanometer material is owing to having good contact, and short electronics and ion transport path and high specific conductivity can its electrocatalysis characteristics of Effective Raise, become people's study hotspot.
The main synthetic method of cobalt acid nickel has: high temperature solid-state method, mechanochemical synthesis, sol-gel method, liquid phase chemical co-precipitation, spraying thermolysis, hydrothermal method etc.But because its heat-labile character, can decomposed between 400～600 ℃ become a simple oxide and another to be rich in the Spinel of cobalt, some active as catalytic activity is reduced, therefore, conventional high temperature solid-state method is to the sour nickel of cobalt and be not suitable for.Introduce a large amount of strains and defective, product bad dispersibility in the mechanochemistry building-up process; The powder diameter of spray heating decomposition preparation is larger, and solute segregation easily occurs; Sol-gel method is by adding tensio-active agent, and the grain diameter of product is little, distributed components, but cost is higher, easily introduces impurity.Hydrothermal method needs higher temperature and pressure, and reaction conditions and equipment material are had relatively high expectations, and is difficult to the industrialization expanding production.By contrast, the co-precipitation thermal decomposition method has that powder morphology is controlled, stoichiometry accurately, be easy to the advantage such as suitability for industrialized production, be the method for present most study.But because the solubleness of different metal compound is different with precipitation kinetics, traditional coprecipitation method is easy to occur segregation, cause coprecipitation process to be actually the fractional precipitation of each component, namely coprecipitated product belongs to mechanical mixture at microcosmic, has affected NiCo
2O
4The physicals of powder and chemical property.Therefore, research and develop and a kind ofly can effectively realize the metal ion co-precipitation, pattern is controlled, cost is lower, and the product physicochemical property is good, is to realize suitability for industrialized production high-performance NiCo
2O
4The effective way of powder.People (the Hao Jiang et al.Hierarchical porous NiCo such as Jiang Hao
2O
4Nanowires for high-rate supercapacitors.Chem.Comm., 2012,48,4465-4467) adopting oxalic acid is precipitation agent, Ni (NO
3) 6H
2O and Co (NO
3) 6H
2O is raw material, P123 is soft template, ethanol and PEG are solvent, adopt the co-precipitation thermal decomposition method to synthesize and have classifying porous cobalt acid nickel fiber, and studied its application as high magnification electrical condenser aspect, the method is take P123 as soft template, processing condition are restive in the production process, in addition, because in a large number with an organic solvent, cause cost compare high.Chinese patent (CN201110195864.X, 2011) provides a kind of coprecipitation method of nickel cobaltate nano particles, respectively with precipitation agent sodium hydroxide and nickel cobalt metal nitrate Ni (NO
3) 6H
2O and Co (NO
3) 6H
2O is dissolved in ethylene glycol or the dimethyl formyl ammonium organic solvent, metal salt solution is joined in the precipitant solution, under 0-80 ℃ of conditions, stirred 0.5-48 hours, can obtain presoma, then presoma has been obtained the nano nickel cobalt oxide material 300-400 ℃ of thermolysis, made capacitor electrode material with this material, it can reach 671Fg than electric capacity
-1The method is simple to operate, mild condition, but used organic reagent is ethylene glycol or dimethylformamide, and with the ratio of deionized water be 1～10:1, cost compare is high, in addition, owing to adding sodium hydroxide, specific filtration resistance is difficulty, the industrialization operational difficulty.Patent (CN03159576,2003) has been invented a kind of preparation method who prepares the fibrous nickel cobalt composite oxide powder, at Ni
2+-Co
2+-NH
3-NH
4+-SG
N--C
2O
4 2--H
2In the O reaction system, adopt to cooperate the co-precipitation thermal decomposition method, under 600 ℃ of-900 ℃ of conditions, prepared the fibrous nickel cobalt composite oxide powder.The method is in the precursor synthesis process, its pH is controlled in the weakly alkaline environment of 7.0-9.0, the nickel cobalt ion is difficult to enter in the co-precipitation common property thing with the nickel cobalt proportioning of setting in the raw material, and experimentation needs accurately control, realizes poor reproducibility, industrial application is difficult, heat decomposition temperature is high, energy consumption is large, and product purity is low, is generally the mixture of nickel oxide, cobalt oxide, nickel/cobalt composite oxide, specific surface area is little, and catalytic activity is low.The applicant once Ph D dissertation (profound cyanines. the research of fibrous porous superfine special nickel cobalt (alloy) and composite oxide power novel preparation method, the doctorate paper, Central South University, 2006) a kind of preparation method who prepares fibrous nickel cobalt-base alloy and composite oxides powder of cobalt nicker end is disclosed, at Ni
2+-Co
2+-NH
3-NH
4+-Cl
--C
2O
4 2--H
2In O-A reaction system, adopt to cooperate the co-precipitation thermal decomposition method, in oxygen atmosphere, prepared fibrous porous composite oxides powder of cobalt nicker end.The method is in oxygen atmosphere, and presoma need to just can obtain fibrous porous cobalt acid nickel about 500 ℃ of heat decomposition temperatures, and according to the character of cobalt acid nickel itself as can be known, the sour nickel powder purity of this kind cobalt is low, and specific surface area is little, and catalytic activity is low, and energy consumption is high.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, propose a kind of preparation method of mesoporous cobalt acid nickel fiber.Described mesoporous NiCo
2O
4The preparation method of fiber is that oxalate is precipitation agent take soluble nickel salt and cobalt salt as raw material, and ammonia is pH value conditioning agent, and ethanol and deionized water are solvent, at Ni
2+-Co
2+-NH
3-NH
4 +-SG
N--C
2O
4 2--H
2O-C
2H
5OH (SG
N-Represent acid group Cl
-, SO
4 2-, NO
3-Perhaps CH
3COO
-) obtaining precursor solution in the system, presoma obtains mesoporous cobalt acid nickel fiber through washing, drying and thermolysis.
Another object of the present invention is to propose the mesoporous cobalt acid nickel fiber that this preparation method obtains.
The 3rd purpose of the present invention is to propose mesoporous cobalt acid nickel fiber as the application of alcohol fuel battery electrode materials.
The technical scheme that realizes above-mentioned purpose of the present invention is:
A kind of preparation method of mesoporous cobalt acid nickel fiber comprises step:
1) soluble nickel salt and solubility cobaltates are dissolved in the deionized water, are configured to contain Ni
2+/ Co
2+Mol ratio is the mixed salt solution A of 1:2;
2) will be dissolved in the mixed solvent of organic reagent and deionized water by stoichiometric oxalate, be configured to oxalate solution B;
3) the mixed salt solution A with step 1) configuration joins step 2) among the oxalate solution B of configuration, controlling simultaneously temperature of reaction is 50～75 ℃, with ammoniacal liquor regulator solution pH to 7.5～8.6, dropwise and continue to stir 0-2 hour, obtain precursor solution;
4) with step 3) precursor solution that obtains filters, and is with deionized water and absolute ethanol washing, that the presoma after the washing is dry;
5) with step 4) the dried presoma that makes places under 250～400 ℃ of the temperature, carries out thermolysis 0.5～5 hour under air atmosphere, obtains mesoporous NiCo after the cooling
2O
4Fiber.
In the step 3), need when solution A joins among the oxalate solution B fully to disperse, but stir while dripping.
Available deionized water wash is 3-5 time in the step 4), then uses absolute ethanol washing 2-3 time.Described drying can adopt and be placed in vacuum drying oven or the air dry oven, descends dry 10-48 hour in 70-150 ℃; Also can adopt the additive method of this area routine, for example seasoning is except anhydrating and dehydrated alcohol.
Wherein, described soluble nickel salt is selected from a kind of in six water nickelous chlorides, seven water single nickel salts, six water nickelous nitrates, nickelous chloride, single nickel salt, the nickelous nitrate; Described solubility cobalt salt is selected from a kind of in cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, CoCL2 6H2O, heptahydrate, the cobalt nitrate hexahydrate.
Wherein, among the described mixed salt solution A, Ni
2+And Co
2+Total concn be 0.3mol/L～1.2mol/L.
Wherein, described organic reagent is purity greater than 99.0% ethanol; Described step 3) in the precursor solution in, the volume ratio of organic reagent and deionized water is 1:1-20.
Preferably, in the described precursor solution, the volume ratio of organic reagent and deionized water is 1:1-9.
Wherein, described oxalate is oxalic acid or ammonium oxalate, and the concentration of oxalate is 0.3mol/L～1.8mol/L.
Wherein, the Ni among described step 3) Oxalate and the described mixed salt solution A
2+And Co
2+The ratio of total amount of substance be 1:1.0～1.5.
The mesoporous cobalt acid nickel fiber that method of the present invention prepares.
The application of mesoporous cobalt acid nickel fiber of the present invention in preparation direct alcohol fuel cell electrode materials.Described application is with the fiber-modified glass-carbon electrode of mesoporous cobalt acid nickel.
Preferably, described direct alcohol fuel cell is preferably Direct Ethanol Fuel Cell, and described electrode materials is anode electrode material.The concrete method of using is: mesoporous cobalt acid nickel is scattered in the water, is coated in the glass-carbon electrode surface, and then applies Nafion solution, and drying makes anode electrode material.Active substance charge capacity 0.1-1mg/cm on the glass-carbon electrode that mesoporous cobalt acid nickel is modified
2
Beneficial effect of the present invention is:
1. the present invention adopts the co-precipitation thermal decomposition method, at normal temperatures and pressures at Ni
2+-Co
2+-NH
3-NH
4 +-SG
N--C
2O
4 2--H
2O-C
2H
5OH (SG
N-Represent acid group Cl
-, SO
4 2-, NO
3 -Perhaps CH
3COO
-) effectively realized in the system setting in the raw material co-precipitation of nickel cobalt proportioning having formed fibrous presoma, in 250-400 ℃ of air atmosphere, can obtain mesoporous cobalt acid nickel fiber; Whole preparation process is simple to operate, environmental friendliness, and the experiment circulation ratio is very good, and cost is low, be easy to suitability for industrialized production.
2. the mesoporous NiCo of the method preparation that proposes of the present invention
2O
4Fiber, purity is high, and specific surface area is large, is applicable to electrochemical catalysis.The result of electro-chemical test shows, the fiber-modified glass-carbon electrode of mesoporous cobalt acid nickel has good catalytic performance, and has long-term cyclical stability.
The mesoporous cobalt of gained acid nickel fiber be spinel type Emission in Cubic, purity high, have higher specific surface area, can be used as the Direct Ethanol Fuel Cell anode catalyst, but catalysis concentration is also analysed oxygen, hydrogen evolution electrode material, electrode material for super capacitor in the applicable basic solution greater than the ethanol of 5mmol/L.
Description of drawings
Fig. 1 is the mesoporous NiCo of embodiment 1 preparation
2O
4The SEM figure of Precursors of Fibers
Fig. 3 is the SEM figure of the mesoporous cobalt acid nickel fiber of embodiment 1 preparation
Fig. 2 is the mesoporous cobalt acid nickel Co of embodiment 1 preparation
2O
4The XRD figure spectrum of fiber;
Fig. 4 is the nitrogen adsorption-desorption isothermal curve of mesoporous cobalt acid nickel fiber.
Fig. 5 is the pore size distribution curve of the mesoporous cobalt acid nickel fiber that makes.
Fig. 6 is the cyclic voltammetry curve of platinum carbon dioxide process carbon electrode under different ethanol concentration that fibrous cobalt acid nickel is modified.
Fig. 7 is glass-carbon electrode and the CV figure of blank glass-carbon electrode in having or not ethanolic soln that porous cobalt acid nickel is modified.
Fig. 8 is the cycle life figure (electrolyte solution is 1MNaOH solution) of fibrous cobalt acid nickel
Embodiment
Now with following most preferred embodiment the present invention is described, but is not used for limiting the scope of the invention.
Embodiment 1:
1) weighing 0.02mol purity is 98.0% NiCl respectively
26H
2O and 0.04mol purity are 99.0%CoCl
26H
2O, NiCl
26H
2O and CoCl
26H
2The ratio of O amount is 1:2.With NiCl
26H
2O and CoC
L26H
2O is dissolved in the 100ml deionized water jointly, is mixed with to contain Ni
2+And Co
2+Mixed salt solution A100ml, among this mixed salt solution A, Ni
2+And Co
2+Total concn is 0.6mol/L.
2) be that 99% oxalic acid is dissolved in the mixed solvent of 50ml organic reagent ethanol and 50ml deionized water with 0.072mol purity, described organic reagent is that purity is 99.7% ethanol, is configured to oxalic acid solution B.
3) the 100ml mixed salt solution A with step 1 configuration is added drop-wise among the oxalic acid solution B of 100ml step 2 configuration, stirs while dripping, and controlling simultaneously temperature of reaction is 60 ℃, regulate the pH value with ammoniacal liquor, keeping the pH value is 8.2, dropwises to continue to stir 0.5 hour, obtains precursor solution;
4) with step 3) precursor solution that obtains filters, and with deionized water wash four times, with absolute ethanol washing twice, makes presoma, and this presoma is placed on vacuum drying oven, and under 100 ℃ of conditions of temperature dry 24 hours; Dried presoma SEM photo such as Fig. 1.
5) with step 4) electric furnace that the dried presoma that makes places PID to regulate, the control temperature is 300 ℃, carries out thermolysis 1 hour under air atmosphere, cooling obtains mesoporous NiCo
2O
4Fiber.Its SEM photo such as Fig. 2.
6) with step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes position and the Spinel NiCo of XRD figure spectrum (Fig. 3) corresponding X ray diffracting data and diffraction peak
2O
4Standard card (JCPDS No.20-0781) consistent, other impurity phases do not appear, show the synthetic cobalt acid nickel that is, purity is high.By the nitrogen adsorption of Fig. 4-desorption isothermal curve result as can be known, synthetic mesoporous cobalt acid nickel fiber has higher specific surface area (54.5m
2g
-1), the pore size distribution curve of Fig. 5 shows that the hole of cobalt acid nickel powder is mesoporous (mean pore size is 13.4nm), the larger (76.8m of desorption pore specific surface area
2g
-1).
Embodiment 2: electrode materials and the electrochemical Characterization thereof of the preparation of mesoporous cobalt acid nickel
Use the glass-carbon electrode of modifying as working electrode.At first the aluminum oxide polishing powder with 50nm grinds glass-carbon electrode on polishing cloth, to smooth surface; Afterwards supersound washing three times in distilled water is dried rear stand-by.Get the mesoporous cobalt acid nickel by powder 0.05g of step embodiment 1 preparation, be dissolved in the 2mL distilled water, ultra-sonic dispersion is even; Draw 0.4 μ L sample with microsyringe, be coated in the glass-carbon electrode surface.After drying at normal temperatures, the Nafion solution (0.5wt%) of getting 0.2 μ L is coated in sample surfaces.After the drying, namely obtain the glass-carbon electrode that mesoporous cobalt acid nickel is modified under the normal temperature, charge capacity is 0.5mg/cm
2
The glass-carbon electrode that mesoporous cobalt acid nickel is modified places and contains ethanol and NaOH solution, (1cm * 1cm) is as to electrode with platinized platinum, 232 type saturated calomel electrode (SCE) are as reference electrode, the platinum carbon dioxide process carbon electrode that cobalt acid nickel is modified carries out electro-chemical test (Fig. 6, cyclic voltammetry curve, sweep velocity 50mV/s).Among Fig. 6, the alcohol concn that each sequence number represents is respectively 1:0.5M, 2:0.2M, 3:0.1M, 4:0.05M, 5:0.02M, 6:0.005M, 7:0M.During to alcohol catalysis, the ethanol Cmin only has 0.005mol/L, has embodied the good electrical catalytic performance.
Not have glass-carbon electrode that mesoporous cobalt acid nickel modifies as working electrode, do equally electro-chemical test (cyclic voltammetric), the result of the glass-carbon electrode of modifying with mesoporous cobalt acid nickel relatively sees Fig. 7.Each sequence number represents 1 among Fig. 7: cobalt acid nickel modified glassy carbon electrode is at ethanolic soln (the concentration 0.5M of ethanol, electrolyte solution is 1MNaOH solution) in the CV curve, 2: cobalt acid nickel modified glassy carbon electrode is without the CV curve in the ethanolic soln, 3: blank glass-carbon electrode is the CV curve in ethanolic soln, and 4: blank glass-carbon electrode is without the CV curve in the ethanolic soln.As shown in Figure 7, mesoporous cobalt acid nickel has good catalytic performance.
Such as Fig. 8.Mesoporous cobalt acid nickel modified glassy carbon electrode carries out 500 circulations in 0.5M ethanolic soln (electrolyte solution is 1MNaOH solution), the curve (2-500th cycle) that compares the 1st circulation (1-1st cycle) and the 500th circulation, the result shows through 500 redox circulations, peak current has only descended 25%, has good cyclical stability.
Embodiment 3:
1) weighing 0.02mol purity is 98.0% NiCl respectively
26H
2O and 0.04mol purity are 99.0%CoCl
26H
2O, described NiCl
26H
2O and CoCl
26H
2The ratio of O amount is 1:2.With described NiCl
26H
2O and CoCl
26H
2O is dissolved in the 100ml deionized water jointly, is mixed with to contain Ni
2+And Co
2+Mixed salt solution A100ml, among the described mixed salt solution A, Ni
2+And Co
2+Total concn is 0.6mol/L.
2) be that 99.0% ammonium oxalate is dissolved in the mixed solvent of 20ml ethanol and 80ml deionized water with 0.072mol purity, this ethanol is that purity is 99.7% ethanol, is configured to oxalate solution B.
3) the 100ml mixed salt solution A with step 1 configuration is added drop-wise to 100ml step 2) among the oxalic acid solution B of configuration, the stirring while dripping, controlling simultaneously temperature of reaction is 60 ℃, regulate the pH value with ammoniacal liquor, keeping the pH value is 8.0, dropwises to continue to stir 0.5 hour, obtains precursor solution;
4) with step 3) the described precursor solution that obtains filters, and with deionized water wash 5 times, with absolute ethanol washing 2 times, makes presoma, and this presoma was placed on the vacuum drying oven inner drying 24 hours;
5) with step 4) electric furnace that the presoma of the drying that makes places PID to regulate, the control temperature is 280 ℃, carries out thermolysis 2 hours under air atmosphere, obtains mesoporous NiCo
2O
4Fiber.
With step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes, the XRD figure stave bright synthetic be the sour nickel of cobalt, purity is high, does not have impurity.Tested as can be known by nitrogen adsorption-desorption isothermal curve, synthetic mesoporous cobalt acid nickel fiber has 53.9m
2g
-1Specific surface area.
Embodiment 4:
1) weighing 0.02mol purity is 98.0% NiCl respectively
26H
2O and 0.04mol purity are 99.0%CoCl
26H
2O, NiCl
26H
2O and CoCl
26H
2The ratio of O amount is 1:2.With NiCl
26H
2O and CoCl
26H
2O is dissolved in the 100ml deionized water jointly, is mixed with to contain Ni
2+And Co
2+Mixed salt solution A100ml, among this mixed salt solution A, Ni
2+And Co
2+Total concn is 0.6mol/L.
2) be that 99.0% oxalic acid is dissolved in the mixed solvent of 90ml organic reagent ethanol (purity is 99.7%) and 10ml deionized water with 0.072mol purity, be configured to oxalic acid solution B.
3) the 100ml mixed salt solution A with step 1 configuration is added drop-wise among the oxalic acid solution B of 100ml step 2 configuration, stirs while dripping, and controlling simultaneously temperature of reaction is 60 ℃, regulate the pH value with ammoniacal liquor, keeping the pH value is 8.6, dropwises to continue to stir 0.5 hour, obtains precursor solution;
4) with step 3) precursor solution that obtains filters, and with deionized water wash 4 times, with absolute ethanol washing 3 times, makes presoma, and this presoma was placed on vacuum drying oven dry 24 hours;
5) with step 4) electric furnace that the presoma of the drying that makes places PID to regulate, the control temperature is 400 ℃, carries out thermolysis 1 hour under air atmosphere, obtains mesoporous NiCo
2O
4Fiber.
With step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes, the XRD figure stave bright synthetic be the sour nickel of cobalt, purity is high, does not have impurity.Tested as can be known by nitrogen adsorption-desorption isothermal curve, synthetic mesoporous cobalt acid nickel fiber has 55.2m
2g
-1Specific surface area.
Embodiment 5:
1) weighing 0.01mol purity is 98.0% Ni(NO respectively
3)
26H
2O and 0.02mol purity are 99.0%Co(NO
3)
26H
2O, Ni(NO
3)
26H
2O and Co(NO
3)
26H
2The ratio of O amount is 1:2.With Ni(NO
3)
26H
2O and Co(NO
3)
26H
2O is dissolved in the 100ml deionized water jointly, is mixed with to contain Ni
2+And Co
2+Mixed salt solution A100ml, among the described mixed salt solution A, Ni
2+And Co
2+Total concn is 0.3mol/L.
2) be that 99.0% ammonium oxalate is dissolved in the mixed solvent of 50ml organic reagent ethanol and 50ml deionized water with 0.045mol purity, described organic reagent is that purity is 99.7% ethanol, is configured to oxalic acid solution B.
3) the 100ml mixed salt solution A with step 1 configuration is added drop-wise among the oxalic acid solution B of 100ml step 2 configuration, stirs while dripping, and controlling simultaneously temperature of reaction is 60 ℃, with ammoniacal liquor condition pH value, keeping the pH value is 8.2, dropwises to continue to stir 0.5 hour, obtains precursor solution;
4) with step 3) the described precursor solution that obtains filters, and with deionized water wash four times, with absolute ethanol washing twice, makes presoma, and this presoma was placed on vacuum drying oven dry 24 hours;
5) with step 4) electric furnace that the described presoma of the drying that makes places PID to regulate, the control temperature is 280 ℃, carries out thermolysis 1 hour under air atmosphere, obtains mesoporous NiCo
2O
4Fiber.
With step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes, the XRD figure stave bright synthetic be the sour nickel of cobalt, purity is high, does not have impurity.Tested as can be known by nitrogen adsorption-desorption isothermal curve, synthetic mesoporous cobalt acid nickel fiber has 55.8m
2g
-1Specific surface area.
Embodiment 6:
1) weighing 0.04mol purity is 98.0% NiSO respectively
47H
2O and 0.08mol purity are 99.0%CoSO
47H
2O, NiSO
47H
2O and CoSO
47H
2The ratio of O amount is 1:2.With NiSO
47H
2O and CoSO
47H
2O is dissolved in the 100ml deionized water jointly, is mixed with to contain Ni
2+And Co
2+Mixed salt solution A100ml, among the described mixed salt solution A, Ni
2+And Co
2+Total concn is 1.2mol/L.
2) be that 99.0% ammonium oxalate is dissolved in the mixed solvent of 50ml organic reagent ethanol and 10ml deionized water with 0.18mol purity, described organic reagent is that purity is 99.7% ethanol, is configured to oxalate solution B.
3) the 100ml mixed salt solution A with step 1 configuration is added drop-wise to 100ml step 2) among the oxalate solution B of configuration, the stirring while dripping, controlling simultaneously temperature of reaction is 65 ℃, regulate the pH value with ammoniacal liquor, keeping the pH value is 8.2, dropwises to continue to stir 0.5 hour, obtains precursor solution;
4) with step 3) the described precursor solution that obtains filters, and with deionized water wash four times, with absolute ethanol washing twice, makes presoma, and this presoma was placed on vacuum drying oven dry 24 hours;
5) with step 4) electric furnace that the described presoma of the drying that makes places PID to regulate, the control temperature is 350 ℃, carries out thermolysis 1 hour under air atmosphere, obtains mesoporous NiCo
2O
4Fiber.
With step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes, the XRD figure stave bright synthetic be the sour nickel of cobalt, purity is high, does not have impurity.Tested as can be known by nitrogen adsorption-desorption isothermal curve, synthetic mesoporous cobalt acid nickel fiber has 54.9m
2g
-1Specific surface area.
Embodiment 7:
1) weighing 0.04mol purity is 98.0% NiCl respectively
26H
2O and 0.08mol purity are 99.0%CoCl
26H
2O, described NiCl
26H
2O and CoCl
26H
2The ratio of O amount is 1:2.With described NiCl
26H
2O and CoCl
26H
2O is dissolved in the 100ml deionized water jointly, is mixed with to contain Ni
2+And Co
2+Mixed salt solution A100ml, among the described mixed salt solution A, Ni
2+And Co
2+Total concn is 1.2mol/L.
2) be that 99.0% ammonium oxalate is dissolved in the mixed solvent of 50ml organic reagent ethanol and 50ml deionized water with 0.18mol purity, described organic reagent is that purity is 99.7% ethanol, is configured to oxalate solution B.
3) the 100ml mixed salt solution A with step 1 configuration is added drop-wise among the oxalate solution B of 100ml step 2 configuration, stirs while dripping, and controlling simultaneously temperature of reaction is 65 ℃, with ammoniacal liquor condition pH value, keeping the pH value is 8.2, dropwises to continue to stir 0.5 hour, obtains precursor solution;
4) with step 3) the described precursor solution that obtains filters, and with deionized water wash four times, with absolute ethanol washing twice, makes presoma, and this presoma was placed on vacuum drying oven dry 24 hours;
5) with step 4) electric furnace that the presoma of the drying that makes places PID to regulate, the control temperature is 350 ℃, carries out thermolysis 1 hour under air atmosphere, obtains mesoporous NiCo
2O
4Fiber.
With step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes, the XRD figure stave bright synthetic be the sour nickel of cobalt, purity is high, does not have impurity.Tested as can be known by nitrogen adsorption-desorption isothermal curve, synthetic mesoporous cobalt acid nickel fiber has 55.8g
-1Specific surface area.
Other physicochemical property of embodiment 1,2-7 product is as follows: minor axis≤250nm, fiber major diameter 〉=10 μ m, carbon≤0.01wt%, sulphur≤0.001wt%, iron≤0.01wt%.
Above embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various modification and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (10)
1. the preparation method of a mesoporous cobalt acid nickel fiber is characterized in that, comprises step:
1) soluble nickel salt and solubility cobaltates are dissolved in the deionized water, are configured to contain Ni
2+/ Co
2+Mol ratio is the mixed salt solution A of 1:2;
2) will be dissolved in the mixed solvent of organic reagent and deionized water by stoichiometric oxalate, be configured to oxalate solution B;
3) the mixed salt solution A with step 1) configuration joins step 2) among the oxalate solution B of configuration, controlling simultaneously temperature of reaction is 50～75 ℃, regulating the pH value with ammoniacal liquor is 7.5～8.6, dropwises to continue to stir 0～2 hour, obtains precursor solution;
4) with step 3) precursor solution that obtains filters, and is with deionized water and absolute ethanol washing, that the presoma after the washing is dry;
5) with step 4) the dried presoma that makes places under 250～400 ℃ of temperature, carries out thermolysis 0.5～5 hour under air atmosphere.
2. preparation method according to claim 1 is characterized in that, described soluble nickel salt is selected from a kind of in six water nickelous chlorides, seven water single nickel salts, six water nickelous nitrates, nickelous chloride, single nickel salt, the nickelous nitrate; Described solubility cobalt salt is selected from a kind of in cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, CoCL2 6H2O, heptahydrate, the cobalt nitrate hexahydrate.
3. preparation method according to claim 1 is characterized in that, among the described mixed salt solution A, and Ni
2+And Co
2+Total concn be 0.3mol/L～1.2mol/L.
4. preparation method according to claim 1 is characterized in that, described organic reagent is purity greater than 99.0% ethanol.
5. arbitrary described preparation method is characterized in that according to claim 1～4, described step 3) in precursor solution in, the volume ratio of organic reagent and deionized water is 1:1～20; Preferably, in the described precursor solution, the volume ratio of organic reagent and deionized water is 1:1～9.
6. preparation method according to claim 1 is characterized in that, among the described oxalate solution B, described oxalate is oxalic acid or ammonium oxalate, and the concentration of oxalate is 0.3mol/L～1.8mol/L.
7. preparation method according to claim 1 is characterized in that, the Ni among described step 3) Oxalate and the described mixed salt solution A
2+And Co
2+The ratio of total amount of substance be 1:1.0～1.5.
8. the mesoporous cobalt acid nickel fiber for preparing of the arbitrary described method of claim 1～7.
9. mesoporous cobalt acid nickel fiber claimed in claim 8 can be used as the direct alcohol fuel cell electrode materials.
10. application according to claim 9 is characterized in that, is to use the fiber-modified glass-carbon electrode of mesoporous cobalt acid nickel.
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