CN102826617A - Spherical nickel hydroxide material and preparation method thereof - Google Patents
Spherical nickel hydroxide material and preparation method thereof Download PDFInfo
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- CN102826617A CN102826617A CN2012103571424A CN201210357142A CN102826617A CN 102826617 A CN102826617 A CN 102826617A CN 2012103571424 A CN2012103571424 A CN 2012103571424A CN 201210357142 A CN201210357142 A CN 201210357142A CN 102826617 A CN102826617 A CN 102826617A
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Abstract
The invention provides a spherical nickel hydroxide material for a super capacitor and a preparation method thereof. The preparation method comprises the following steps that: a nickel nitrate water solution is mixed with glycerol according to the volume ratio of (10:1)-(0.3:1), carbamide is added in, and mixing, reaction, impurity removal and drying are carried out to obtain the spherical nickel hydroxide electrode material formed by assembly of nano-sheets. The spherical nickel hydroxide disclosed by the invention is alpha-nickel hydroxide, and is a good reversible charging and discharging active substance, and especially the three-dimensional spherical structure formed by assembly of nano-sheets can rapidly charge and discharge during charging and discharging of a battery, has higher specific capacity and long cycle life and can improve the energy density and power density of electrodes, so that the material can be widely used in the energy storage fields of nickel-hydrogen batteries, nickel-cadmium batteries, super capacitors and the like; and the spherical nickel hydroxide material produced by using the method can be used as the electrode material of the super capacitors, and has excellent electrochemical performance.
Description
Technical field
The present invention relates to electrochemistry and field of inorganic materials, particularly, the present invention relates to a kind of ball-shape nickel hydroxide material and preparation method thereof.
Background technology
Ultracapacitor (Supercapacitors) is claimed electrochemical capacitor (Electrochemical capacitors) again, is a kind of novel energy-storing element.The ability force rate ordinary capacitor of its stored charge exceeds nearly 3 ~ 4 one magnitude; Have again simultaneously and exceed 10 ~ 100 times power density than chemical cell, but also have that charge velocities is fast, long service life, low-temperature performance is superior, storage period is long and plurality of advantages such as use temperature wide ranges.Therefore, ultracapacitor has vast market application and development prospect aspect the application of power in fields such as electronics, electromobile, communication, generating (wind power generation, solar electrical energy generation), military project, aviation, signal monitoring.
At present, electrode material for super capacitor mainly is divided three classes: carbon material, MOX and hydroxide materials thereof and conducting polymer materials.MOX and hydroxide materials thereof have higher specific storage, cyclical stability and good work-ing life, thereby caused the research interest of many researchers.The nickel hydroxide aboundresources, cheap, and have than traditional metal oxide containing precious metals RuO
2Higher specific storage is fit to large-scale develop and utilize and suitability for industrialized production.The pattern of nickel hydroxide, size, structure, pore size distribution and preparation technology etc. have very big influence to its chemical property; And ultracapacitor all has higher requirement with nickel hydroxide to purity, productive rate, raw material and the chemical property etc. of material, therefore prepares to have specific physical chemical property and the ultracapacitor that meets suitability for industrialized production become scientific effort with nickel hydroxide emphasis.
Chinese patent CN102623187A discloses the preparation method of a kind of ultracapacitor with nickel hydroxide electrode material; The speed that this method is separated out through the control precipitation agent; The thickness of dilution zone silica sand and the Heating temperature of main reaction chamber are isolated in i.e. control; Come controls reaction speed with this, finally prepared flakey nickel hydroxide with high-specific surface area.This preparation method need not dispersion agent, and the material crystal formation is single, but has defectives such as complex process, preparation condition harshness, and does not provide Electrochemical results, is difficult to its material property advantage of proof.
Chinese patent CN102544454A discloses a kind of process for preparing multi-phase nickel hydroxide with nanometer petal design; This method is raw material with the nickel salt; With urea as precipitation agent; The mixing solutions of preparation urea, nickel salt and doped metal salt carries out hydro-thermal reaction under 160 ~ 200 ℃ of temperature, obtain nanometer petal-shaped multi-phase nickel hydroxide.It is controlled that this method has pattern, low cost and other advantages, but there is a large amount of β-nickel hydroxide to exist in the product, purity is not enough, make the final chemical property of material reduce, and stability is affected.
We prepare the ball-shape nickel hydroxide that is assembled by the hierarchy nanometer sheet through a kind of simple solvent-thermal method, and this prepares material, and when charging or discharging current density was 1A/g, its specific storage can reach 1177F/g; When charging or discharging current density increased to 16A/g, its specific storage still can reach 615F/g, and this material discharges and recharges under the high current density condition continuously; Still can keep higher initial capacity, to have a processing unit simple for this method in addition, and productive rate is high; Cost is low; Pollution-free, be prone to realize characteristics such as commercial scale prodn, so this method has very big actual application prospect.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide a kind of ball-shape nickel hydroxide preparation methods.
Said ball-shape nickel hydroxide preparation methods comprises: the volume ratio with 10:1 ~ 0.3:1 is mixed nickel nitrate aqueous solution with USP Kosher, adds urea, mix, and reaction, removal of impurities, drying obtains the ball-shape nickel hydroxide material.
Preferably, said temperature of reaction is 100 ~ 210 ℃.
Preferably, the said reaction times is at least 5 hours.
Preferably, said ball-shape nickel hydroxide preparation methods may further comprise the steps:
(1) with the volume ratio of 10:1 ~ 0.3:1 nickel nitrate aqueous solution is mixed with USP Kosher;
(2) in the mixing solutions that step (1) obtains, add urea, mix;
(3) mixing solutions that step (2) is obtained placed closed reactor, 100 ~ 210 ℃ of reactions at least 5 hours;
(4) isolate the deposition that step (3) prepares, removal of impurities, drying promptly obtains the ball-shape nickel hydroxide material that is assembled by the hierarchy nanometer sheet.
Preferably; The concentration of nickelous nitrate is 0.01 ~ 0.4g/mL in the said nickel nitrate aqueous solution; For example 0.011g/mL, 0.012g/mL, 0.016g/mL, 0.019g/mL, 0.021g/mL, 0.025g/mL, 0.05g/mL, 0.09g/mL, 0.099g/mL, 0.11g/mL, 0.15g/mL, 0.19g/mL, 0.21g/mL, 0.3g/mL, 0.35g/mL, 0.38g/mL, 0.39g/mL etc.; Further be preferably 0.015 ~ 0.2g/mL, be preferably 0.02 ~ 0.1g/mL especially.
The volume ratio of said nickel nitrate aqueous solution and USP Kosher can be 9.99:1,9.9:1,9.8:1,9.5:1,9:1,8.1:1,7.9:1,7.1:1,6.9:1,6:1,4:1,2:1,1:1,0.8:1,0.61:1,0.59:1,0.51:1,0.49:1,0.4:1,0.35:1,0.32:1,0.31:1 etc.; Be preferably 8:1 ~ 0.5:1, be preferably 7:1 ~ 0.6:1 especially.
In the present invention, the volume ratio of said nickel nitrate aqueous solution and USP Kosher refers to aqueous solvent and the volume ratio of USP Kosher in the nickel nitrate aqueous solution.For example the 0.2g nickelous nitrate is dissolved in the 1ml water, and nickel nitrate aqueous solution concentration is 0.2g/mL, adds the 0.1ml USP Kosher and mixes, and then the volume ratio of nickel nitrate aqueous solution and USP Kosher is 10:1.The preferred zero(ppm) water of said aqueous solvent.
Preferably, the said of nickel nitrate aqueous solution and USP Kosher is mixed into through mixing; Preferably; Said churning time is at least 3 minutes; For example 3.1 minutes, 3.2 minutes, 3.9 minutes, 4.1 minutes, 4.9 minutes, 5.1 minutes, 8 minutes, 10 minutes, 15 minutes, 19 minutes, 21 minutes, 25 minutes, 28 minutes, 29 minutes, 31 minutes, 35 minutes, 40 minutes etc.; Further be preferably 4 ~ 30 minutes, be preferably 5 ~ 20 minutes especially.
Preferably; The add-on of urea is 0.01 ~ 0.5mol/L; For example 0.011mol/L, 0.012mol/L, 0.014mol/L, 0.02mol/L, 0.04mol/L, 0.08mol/L, 0.1mol/L, 0.15mol/L, 0.19mol/L, 0.21mol/L, 0.25mol/L, 0.29mol/L, 0.31mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.48mol/L, 0.49mol/L etc.; Further be preferably 0.013 ~ 0.3mol/L, be preferably 0.015 ~ 0.2mol/L especially.
Preferably, said being mixed at room temperature mixed through stirring behind the adding urea; Preferably; Said churning time is at least 15 minutes; For example 16 minutes, 17 minutes, 19 minutes, 21 minutes, 25 minutes, 29 minutes, 31 minutes, 35 minutes, 40 minutes, 49 minutes, 51 minutes, 55 minutes, 58 minutes, 59 minutes, 61 minutes, 65 minutes, 70 minutes, 90 minutes etc.; Further be preferably 20 ~ 60 minutes, be preferably 30 ~ 50 minutes especially.
Preferably, said closed reactor is an autoclave, is preferably the autoclave with polytetrafluoroethylliner liner especially.
Said temperature of reaction can be 101 ℃, 102 ℃, 105 ℃, 109 ℃, 111 ℃, 115 ℃, 119 ℃, 121 ℃, 130 ℃, 150 ℃, 170 ℃, 179 ℃, 181 ℃, 190 ℃, 199 ℃, 201 ℃, 205 ℃, 208 ℃, 209 ℃ etc.; Be preferably 110 ~ 200 ℃, be preferably 120 ~ 180 ℃ especially.
The said reaction times can be 5.1 hours, 5.2 hours, 5.9 hours, 6.1 hours, 7 hours, 7.9 hours, 8.1 hours, 10 hours, 15 hours, 19 hours, 21 hours, 22 hours, 23 hours, 25 hours, 30 hours etc.; Be preferably 6 ~ 24 hours, be preferably 8 ~ 20 hours especially.
Preferably, said removal of impurities is for use zero(ppm) water and absolute ethanol washing successively; Preferably, said distilled water wash number of times is 3 times at least, is preferably especially 5 times; Preferably, said absolute ethanol washing number of times is 3 times at least, is preferably especially 5 times.
Preferably, said drying is carried out in vacuum drying oven.
Preferably; Said drying temperature is 40 ~ 100 ℃; For example 41 ℃, 42 ℃, 43 ℃, 45 ℃, 49 ℃, 51 ℃, 59 ℃, 61 ℃, 70 ℃, 79 ℃, 81 ℃, 89 ℃, 91 ℃, 95 ℃, 98 ℃ or 99 ℃ etc. further are preferably 50 ~ 90 ℃, are preferably 80 ℃ especially.
Preferably; Be at least 8 hours said time of drying; For example 8.1 hours, 8.2 hours, 8.3 hours, 8.5 hours, 9 hours, 9.9 hours, 10.1 hours, 11 hours, 11.9 hours, 12.1 hours, 15 hours, 20 hours, 23 hours, 23.9 hours, 24.1 hours, 28 hours, 29.9 hours, 30.1 hours, 35 hours or 40 hours etc.; Further be preferably 10 ~ 30 hours, be preferably 12 hours especially.
Preferably, said ball-shape nickel hydroxide preparation methods may further comprise the steps:
(1) mixes with USP Kosher with the volume ratio of 10:1 ~ 0.3:1 nickel nitrate aqueous solution 0.01 ~ 0.4g/mL;
(2) in the mixing solutions that step (1) obtains, add 0.01 ~ 0.5mol/L urea, mix;
(3) mixing solutions that step (2) is obtained placed closed reactor, 100 ~ 210 ℃ of reactions at least 5 hours;
(4) isolate the deposition that step (3) prepares, removal of impurities, drying promptly obtains the ball-shape nickel hydroxide material that is assembled by the hierarchy nanometer sheet.
In the present invention, suppose that solid is dissolved into liquid after, do not change the volume of mixing solutions, promptly the volume of mixing solutions is for adding the liquid volume before the solid.
One of the object of the invention also is to provide a kind of ball-shape nickel hydroxide material by method for preparing.Said ball-shape nickel hydroxide material is an alpha-nickel hydroxide; Hierarchy nanometer sheet by two dimension assembles; The thickness of nanometer sheet is between 20-40nm; Under the current density test condition that increases successively, have satisfactory stability property, when current density was 1A/g, its high specific capacity can reach 1177F/g; When current density increased to 16A/g, its specific storage still can reach 615F/g.
One of the object of the invention also is to provide the purposes of said ball-shape nickel hydroxide material.Said ball-shape nickel hydroxide material can be used as the good large vol electrode for super capacitor material of nickel metal hydride battery, ickel-cadmium cell or chemical property, is preferably used as the electrode for super capacitor material especially.
Beneficial effect of the present invention:
(1) is reaction solvent with zero(ppm) water with the mixing solutions that USP Kosher mixes gained by certain volume ratio, pollutes lessly, and can obtain the controlled nickel hydroxide material of form;
(2) add certain amount of urea and help the growth of nickel hydroxide crystalline, help the formation of sheet structure simultaneously to spherical hierarchy;
(3) spherical nickel hydroxide is that hierarchy nanometer sheet by two dimension assembles, and the thickness of nanometer sheet is between 20-40nm;
(4) this spherical nickel hydroxide is an alpha-nickel hydroxide, compares with β-nickel hydroxide to have superior chemical property;
(5) the present invention adopts solvent-thermal method to obtain the ball-shape nickel hydroxide material, and processing unit is simple, and productive rate is high, and cost is low, and is pollution-free; This ball-shape nickel hydroxide is used for electrode material for super capacitor; Because the spherical hierarchy of its distinctive three-dimensional plate when battery charging and discharging, can discharge and recharge fast; Higher specific storage and cycle life are arranged, can improve the energy density and the power density of electrode effectively; Under the current density test condition that increases successively, have satisfactory stability property, when current density was 1A/g, its high specific capacity can reach 1177F/g; When current density increased to 16A/g, its specific storage still can reach 615F/g.
Description of drawings
Fig. 1 is the powder X-ray RD diffracting spectrum of this ball-shape nickel hydroxide electrode materials.
Fig. 2 is the awkward silence at a meeting emission scan Electronic Speculum picture of this ball-shape nickel hydroxide electrode materials.
Fig. 3 is used for electrode material for super capacitor successively at current density 1A/g for embodiment 1 gained ball-shape nickel hydroxide, 2A/g, 4A/g; Under 8A/g and the 16A/g condition; The constant current charge-discharge curve that records, wherein Time/S is the time of discharging and recharging, Voltage/V is the voltage that discharges and recharges.
Fig. 4 is used for electrode material for super capacitor successively at scanning speed 5mv/S for embodiment 1 gained ball-shape nickel hydroxide, 10mv/S, and under 20mv/S and the 50mv/S condition, the cyclic voltammetry curve that records, wherein EvsSCE/V is the sweep voltage scope, I/A is a current value.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1
Take by weighing the 1.4g nickelous nitrate, join in the zero(ppm) water of 70ml volume, dispersed with stirring 5 minutes is fully dissolved nickel salt; Measure the USP Kosher of 10ml volume again, join above-mentioned solution, dispersed with stirring 20 minutes makes two kinds of solution thorough mixing; Take by weighing 0.24g urea and be dissolved in the middle of the above-mentioned solution, the air at room temperature lower magnetic force stirred 50 minutes; The mixing solutions that obtains is put into the autoclave with polytetrafluoroethylliner liner seal, in 120 ℃ of following constant temperature 8 hours; Product respectively washs 5 times through zero(ppm) water, absolute ethyl alcohol, and 80 ℃ of dryings are 12 hours in vacuum drying oven, promptly obtain the ball-shape nickel hydroxide electrode materials that is assembled by the hierarchy nanometer sheet.
The XRD spectra of the ball-shape nickel hydroxide electrode materials that Fig. 1 obtains for present embodiment, among the figure diffraction peak all well corresponding the diffraction peak of nickel hydroxide in the JCPDS DB, collection of illustrative plates coincide, and prove that the product of inventing is monophasic nickel hydroxide.The CFSEM photo of Fig. 2; Show the globosity characteristic of serving as reasons prepared nickel hydroxide two-dimentional hierarchy nanometer sheet assembling; The diameter of ball is about 5-8 μ m, and the thickness of nanometer sheet is about 20-40nm, and hierarchy has improved the stable circulation performance of electrode materials greatly.Fig. 3 is used for electrode material for super capacitor for ball-shape nickel hydroxide; Be respectively 1A/g, 2A/g, 4A/g, 8A/g and 16A/g condition following time in current density; Its specific storage proportion by subtraction is 1177F/g, 862F/g, 738F/g, 692F/g and 615F/g; This electrode materials has higher specific storage, and stability is good.Fig. 4 is used for the cyclic voltammetry curve of electrode material for super capacitor under different scanning speed test conditions for ball-shape nickel hydroxide, and material circulating and reversible performance is good.
Embodiment 2
Take by weighing the 1.8g nickelous nitrate, join in the zero(ppm) water of 50ml volume, dispersed with stirring 15 minutes is fully dissolved nickel salt; Measure the USP Kosher of 30ml volume again, join above-mentioned solution, dispersed with stirring 10 minutes makes two kinds of solution thorough mixing; Take by weighing 0.96g urea and be dissolved in the middle of the above-mentioned solution, the air at room temperature lower magnetic force stirred 30 minutes; The mixing solutions that obtains is put into the autoclave with polytetrafluoroethylliner liner seal, in 180 ℃ of following constant temperature 15 hours; Product respectively washs 5 times through zero(ppm) water, absolute ethyl alcohol, and 80 ℃ of dryings are 12 hours in vacuum drying oven, promptly obtain the ball-shape nickel hydroxide electrode materials that is assembled by the hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 5-7 μ m, and the thickness of nanometer sheet is about 20-35nm.
Embodiment 3
Take by weighing the 2.0g nickelous nitrate, join in the zero(ppm) water of 30ml volume, dispersed with stirring 15 minutes is fully dissolved nickel salt; Measure the USP Kosher of 50ml volume again, join above-mentioned solution, dispersed with stirring 5 minutes makes two kinds of solution thorough mixing; Take by weighing 0.36g urea and be dissolved in the middle of the above-mentioned solution, the air at room temperature lower magnetic force stirred 30 minutes; The mixing solutions that obtains is put into the autoclave with polytetrafluoroethylliner liner seal, in 160 ℃ of following constant temperature 10 hours; Product respectively washs 5 times through zero(ppm) water, absolute ethyl alcohol, and 80 ℃ of dryings are 12 hours in vacuum drying oven, promptly obtain the ball-shape nickel hydroxide electrode materials that is assembled by the hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 6-7 μ m, and the thickness of nanometer sheet is about 20-30nm.
Embodiment 4
Take by weighing the 2.6g nickelous nitrate, join in the zero(ppm) water of 40ml volume, dispersed with stirring 10 minutes is fully dissolved nickel salt; Measure the USP Kosher of 40ml volume again, join above-mentioned solution, dispersed with stirring 20 minutes makes two kinds of solution thorough mixing; Take by weighing 0.84g urea and be dissolved in the middle of the above-mentioned solution, the air at room temperature lower magnetic force stirred 40 minutes; The mixing solutions that obtains is put into the autoclave with polytetrafluoroethylliner liner seal, in 140 ℃ of following constant temperature 10 hours; Product respectively washs 5 times through zero(ppm) water, absolute ethyl alcohol, and 80 ℃ of dryings are 12 hours in vacuum drying oven, promptly obtain the ball-shape nickel hydroxide electrode materials that is assembled by the hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 4-6 μ m, and the thickness of nanometer sheet is about 21-33nm.
Embodiment 5
Take by weighing the 2.8g nickelous nitrate, join in the zero(ppm) water of 60ml volume, dispersed with stirring 20 minutes is fully dissolved nickel salt; Measure the USP Kosher of 20ml volume again, join above-mentioned solution, dispersed with stirring 10 minutes makes two kinds of solution thorough mixing; Take by weighing 0.72g urea and be dissolved in the middle of the above-mentioned solution, the air at room temperature lower magnetic force stirred 50 minutes; The mixing solutions that obtains is put into the autoclave with polytetrafluoroethylliner liner seal, in 150 ℃ of following constant temperature 12 hours; Product respectively washs 5 times through zero(ppm) water, absolute ethyl alcohol, and 80 ℃ of dryings are 12 hours in vacuum drying oven, promptly obtain the ball-shape nickel hydroxide electrode materials that is assembled by the hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 6-8 μ m, and the thickness of nanometer sheet is about 25-38nm.
Embodiment 6
Take by weighing the 3.0g nickelous nitrate, join in the zero(ppm) water of 70ml volume, dispersed with stirring 15 minutes is fully dissolved nickel salt; Measure the USP Kosher of 10ml volume again, join above-mentioned solution, dispersed with stirring 15 minutes makes two kinds of solution thorough mixing; Take by weighing 0.60g urea and be dissolved in the middle of the above-mentioned solution, the air at room temperature lower magnetic force stirred 40 minutes; The mixing solutions that obtains is put into the autoclave with polytetrafluoroethylliner liner seal, in 140 ℃ of following constant temperature 15 hours; Product respectively washs 5 times through zero(ppm) water, absolute ethyl alcohol, and 80 ℃ of dryings are 12 hours in vacuum drying oven, promptly obtain the ball-shape nickel hydroxide electrode materials that is assembled by the hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 5-8 μ m, and the thickness of nanometer sheet is about 26-39nm.
Embodiment 7
Take by weighing the 0.7g nickelous nitrate, join in the zero(ppm) water of 70ml volume, dispersed with stirring 15 minutes is fully dissolved nickel salt; Measure the USP Kosher of 7ml volume again, join above-mentioned solution, dispersed with stirring 3 minutes makes two kinds of solution thorough mixing; Take by weighing 0.048g urea and be dissolved in the middle of the above-mentioned solution, the air at room temperature lower magnetic force stirred 15 minutes; The mixing solutions that obtains is put into the autoclave with polytetrafluoroethylliner liner seal, in 100 ℃ of following constant temperature 24 hours; Product respectively washs 4 times through zero(ppm) water, absolute ethyl alcohol, and 40 ℃ of dryings are 30 hours in vacuum drying oven, promptly obtain the ball-shape nickel hydroxide electrode materials that is assembled by the hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 5-6 μ m, and the thickness of nanometer sheet is about 21-35nm.
Embodiment 8
Take by weighing the 8g nickelous nitrate, join in the zero(ppm) water of 20ml volume, dispersed with stirring 20 minutes is fully dissolved nickel salt; Measure the USP Kosher of 67ml volume again, join above-mentioned solution, dispersed with stirring 30 minutes makes two kinds of solution thorough mixing; Take by weighing 2.6g urea and be dissolved in the middle of the above-mentioned solution, the air at room temperature lower magnetic force stirred 60 minutes; The mixing solutions that obtains is put into the autoclave with polytetrafluoroethylliner liner seal, in 210 ℃ of following constant temperature 5 hours; Product respectively washs 5 times through zero(ppm) water, absolute ethyl alcohol, and 100 ℃ of dryings are 8 hours in vacuum drying oven, promptly obtain the ball-shape nickel hydroxide electrode materials that is assembled by the hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 6-8 μ m, and the thickness of nanometer sheet is about 28-40nm.
Embodiment 9
Take by weighing the 12g nickelous nitrate, join in the zero(ppm) water of 60ml volume, dispersed with stirring 30 minutes is fully dissolved nickel salt; Measure the USP Kosher of 7.5ml volume again, join above-mentioned solution, dispersed with stirring 40 minutes makes two kinds of solution thorough mixing; Take by weighing 2g urea and be dissolved in the middle of the above-mentioned solution, the air at room temperature lower magnetic force stirred 70 minutes; The mixing solutions that obtains is put into the autoclave with polytetrafluoroethylliner liner seal, in 200 ℃ of following constant temperature 10 hours; Product respectively washs 5 times through zero(ppm) water, absolute ethyl alcohol, and 80 ℃ of dryings are 15 hours in vacuum drying oven, promptly obtain the ball-shape nickel hydroxide electrode materials that is assembled by the hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 7-8 μ m, and the thickness of nanometer sheet is about 29-40nm.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. ball-shape nickel hydroxide preparation methods, comprising: the volume ratio with 10:1 ~ 0.3:1 is mixed nickel nitrate aqueous solution with USP Kosher, adds urea, mix, reaction, removal of impurities, drying obtains the ball-shape nickel hydroxide material.
2. the method for claim 1 is characterized in that, said temperature of reaction is 100 ~ 210 ℃;
Preferably, the said reaction times is at least 5 hours.
3. according to claim 1 or claim 2 method is characterized in that, said method comprising the steps of:
(1) with the volume ratio of 10:1 ~ 0.3:1 nickel nitrate aqueous solution is mixed with USP Kosher;
(2) in the mixing solutions that step (1) obtains, add urea, mix;
(3) mixing solutions that step (2) is obtained placed closed reactor, 100 ~ 210 ℃ of reactions at least 5 hours;
(4) isolate the deposition that step (3) prepares, removal of impurities, drying promptly obtains the ball-shape nickel hydroxide material that is assembled by the hierarchy nanometer sheet.
4. like each described method of claim 1-3, it is characterized in that the concentration of nickelous nitrate is 0.01 ~ 0.4g/mL in the said nickel nitrate aqueous solution, further is preferably 0.015 ~ 0.2g/mL, is preferably 0.02 ~ 0.1g/mL especially;
Preferably, the volume ratio of said nickel nitrate aqueous solution and USP Kosher is 8:1 ~ 0.5:1, is preferably 7:1 ~ 0.6:1 especially.
5. like each described method of claim 1-4, it is characterized in that being mixed into of said nickel nitrate aqueous solution and USP Kosher through mixing; Preferably, said churning time is at least 3 minutes, further is preferably 4 ~ 30 minutes, is preferably 5 ~ 20 minutes especially;
Preferably, the add-on of urea is 0.01 ~ 0.5mol/L, further is preferably 0.013 ~ 0.3mol/L, is preferably 0.015 ~ 0.2mol/L especially.
6. like each described method of claim 1-5, it is characterized in that said being mixed at room temperature mixed through stirring behind the adding urea; Preferably, said churning time is at least 15 minutes, further is preferably 20 ~ 60 minutes, is preferably 30 ~ 50 minutes especially;
Preferably, said closed reactor is an autoclave, is preferably the autoclave with polytetrafluoroethylliner liner especially;
Preferably, said temperature of reaction is 110 ~ 200 ℃, is preferably 120 ~ 180 ℃ especially;
Preferably, the said reaction times is 6 ~ 24 hours, is preferably 8 ~ 20 hours especially.
7. like each described method of claim 1-6, it is characterized in that said removal of impurities is for use zero(ppm) water and absolute ethanol washing successively; Preferably, said distilled water wash number of times is 3 times at least, is preferably especially 5 times; Preferably, said absolute ethanol washing number of times is 3 times at least, is preferably especially 5 times;
Preferably, said drying is carried out in vacuum drying oven;
Preferably, said drying temperature is 40 ~ 100 ℃, further is preferably 50 ~ 90 ℃, is preferably 80 ℃ especially;
Preferably, be at least 8 hours said time of drying, further is preferably 10 ~ 30 hours, is preferably 12 hours especially.
8. according to claim 1 or claim 2 method is characterized in that, said method comprising the steps of:
(1) mixes with USP Kosher with the volume ratio of 10:1 ~ 0.3:1 nickel nitrate aqueous solution 0.01 ~ 0.4g/mL;
(2) in the mixing solutions that step (1) obtains, add 0.01 ~ 0.5mol/L urea, mix;
(3) mixing solutions that step (2) is obtained placed closed reactor, 100 ~ 210 ℃ of reactions at least 5 hours;
(4) isolate the deposition that step (3) prepares, removal of impurities, drying promptly obtains the ball-shape nickel hydroxide material that is assembled by the hierarchy nanometer sheet.
9. a ball-shape nickel hydroxide material is characterized in that said ball-shape nickel hydroxide material is by each said method preparation of claim 1-8.
10. the purposes of ball-shape nickel hydroxide material as claimed in claim 9 is characterized in that, said ball-shape nickel hydroxide material can be used as nickel metal hydride battery, ickel-cadmium cell or electrode for super capacitor material.
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| CN104891580A (en) * | 2015-05-05 | 2015-09-09 | 北京科技大学 | Preparation method of nickel hydroxide ultrathin nanosheet assemblies |
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| CN104857951A (en) * | 2015-04-23 | 2015-08-26 | 三明学院 | Preparation method of acidic oxide MoO3 / MnO / TiO2 |
| CN104857967A (en) * | 2015-04-23 | 2015-08-26 | 三明学院 | Acidic oxide MoO3 / CuO / TiO2 and preparation method and application thereof |
| CN104857967B (en) * | 2015-04-23 | 2017-10-31 | 三明学院 | A kind of acidic oxide MoO3/CuO/TiO2Preparation method |
| CN104801311B (en) * | 2015-04-23 | 2017-12-08 | 三明学院 | MoO3/NiO/TiO2Solid acid catalyst and preparation method thereof |
| CN104801311A (en) * | 2015-04-23 | 2015-07-29 | 三明学院 | MoO3/NiO/TiO2 solid acid catalyst and preparation method thereof |
| CN104891580A (en) * | 2015-05-05 | 2015-09-09 | 北京科技大学 | Preparation method of nickel hydroxide ultrathin nanosheet assemblies |
| CN106745133A (en) * | 2017-01-24 | 2017-05-31 | 武汉工程大学 | A kind of preparation method of water insoluble hydroxide |
| CN106745133B (en) * | 2017-01-24 | 2018-03-20 | 武汉工程大学 | A kind of preparation method of hydroxide not soluble in water |
| CN106865628A (en) * | 2017-03-10 | 2017-06-20 | 长春理工大学 | One kind is used for room temperature H2S gas sensing materials nickel oxide and preparation method thereof |
| CN108840313A (en) * | 2018-09-19 | 2018-11-20 | 曲阜师范大学 | A kind of preparation method of spherical two nickelous selenide of multistage |
| CN115259246A (en) * | 2022-07-08 | 2022-11-01 | 深圳市豪鹏科技股份有限公司 | Spherical alpha-nickel hydroxide, synthesis method, positive plate and battery |
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