CN102826617B - Spherical nickel hydroxide material and preparation method thereof - Google Patents
Spherical nickel hydroxide material and preparation method thereof Download PDFInfo
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- CN102826617B CN102826617B CN201210357142.4A CN201210357142A CN102826617B CN 102826617 B CN102826617 B CN 102826617B CN 201210357142 A CN201210357142 A CN 201210357142A CN 102826617 B CN102826617 B CN 102826617B
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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 Spherical nickel hydroxide material and preparation method thereof.
Background technology
Ultracapacitor (Supercapacitors), also known as electrochemical capacitor (Electrochemical capacitors), is a kind of novel energy-storing element.The energy force rate ordinary capacitor of its stored charge exceeds nearly 3 ~ 4 orders of magnitude, there is again the power density exceeding 10 ~ 100 times than chemical cell simultaneously, but also have that charge velocities is fast, long service life, low-temperature performance are superior, storage period is long and the plurality of advantages such as use temperature wide ranges.Therefore, ultracapacitor has wide market application and development prospect in the application of power in the 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 is mainly divided three classes: carbon material, metal oxide and hydroxide materials thereof and conducting polymer materials.Metal oxide and hydroxide materials thereof have higher specific storage, cyclical stability and good work-ing life, thus cause the research interest of many researchers.Nickel hydroxide aboundresources, cheap, and have than conventional precious metal oxide compound RuO
2higher specific storage, is applicable to large-scale developing and utilizing and suitability for industrialized production.The pattern of nickel hydroxide, size, structure, pore size distribution and preparation technology etc. have a great impact its chemical property, and ultracapacitor nickel hydroxide has higher requirement to the purity of material, productive rate, raw material and chemical property etc., therefore prepare the emphasis that the ultracapacitor nickel hydroxide having specific physical chemical property and meet suitability for industrialized production becomes scientific effort.
Chinese patent CN102623187A discloses a kind of preparation method of ultracapacitor nickel hydroxide electrode material, the speed that the method is separated out by controlling precipitation agent, namely the thickness of isolation dilution zone quartz sand and the Heating temperature of main reaction chamber is controlled, control speed of response with this, finally prepare the flakey nickel hydroxide with high-specific surface area.The defects such as this preparation method is without the need to dispersion agent, and material crystal formation is single, but there is complex process, and preparation condition is harsh, and do not provide Electrochemical results, be difficult to prove its material property advantage.
Chinese patent CN102544454A discloses a kind of process for preparing multi-phase nickel hydroxide with nano flower valve structure, the method take nickel salt as raw material, using urea as precipitation agent, the mixing solutions of preparation urea, nickel salt and doped metal salt, at 160 ~ 200 DEG C of temperature, carry out hydro-thermal reaction, obtain nano flower flap multi-phase nickel hydroxide.The method has morphology controllable, low cost and other advantages, but has a large amount of β-nickel hydroxide to exist in product, and purity is inadequate, and the chemical property making material final reduces, and stability is affected.
We prepare by a kind of simple solvent-thermal method the ball-shape nickel hydroxide assembled by hierarchy nanometer sheet, and this prepares material, and when charging or discharging current density is 1A/g, its specific storage can reach 1177F/g; When charging or discharging current density is increased to 16A/g, its specific storage still can reach 615F/g, and the continuous discharge and recharge under high current density condition of this material, still can keep higher initial capacity, the method has processing unit simply in addition, and productive rate is high, cost is low, pollution-free, easily realize the features such as commercial scale production, therefore the method has very large actual application prospect.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is the preparation method providing a kind of Spherical nickel hydroxide material.
The preparation method of described Spherical nickel hydroxide material comprises: mixed with glycerol by nickel nitrate aqueous solution with the volume ratio of 10:1 ~ 0.3:1, add urea, mixing, reaction, and removal of impurities is dry, obtains Spherical nickel hydroxide material.
Preferably, described temperature of reaction is 100 ~ 210 DEG C.
Preferably, the described reaction times is at least 5 hours.
Preferably, the preparation method of described Spherical nickel hydroxide material comprises the following steps:
(1) with the volume ratio of 10:1 ~ 0.3:1, nickel nitrate aqueous solution is mixed with glycerol;
(2) urea is added in the mixing solutions obtained in step (1), mixing;
(3) mixing solutions that step (2) obtains is placed in closed reactor, 100 ~ 210 DEG C of reactions at least 5 hours;
(4) precipitation prepared by step (3) is isolated, removal of impurities, dry, namely obtain the Spherical nickel hydroxide material assembled by hierarchy nanometer sheet.
Preferably, in described nickel nitrate aqueous solution, the concentration of nickelous nitrate is 0.01 ~ 0.4g/mL, such as 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., more preferably 0.015 ~ 0.2g/mL, is particularly preferably 0.02 ~ 0.1g/mL.
The volume ratio of described nickel nitrate aqueous solution and glycerol 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 particularly preferably 7:1 ~ 0.6:1.
In the present invention, the volume ratio of described nickel nitrate aqueous solution and glycerol refers to the volume ratio of aqueous solvent in nickel nitrate aqueous solution and glycerol.Such as 0.2g nickelous nitrate is dissolved in 1ml water, and nickel nitrate aqueous solution concentration is 0.2g/mL, and add the mixing of 0.1ml glycerol, then the volume ratio of nickel nitrate aqueous solution and glycerol is 10:1.The preferred distilled water of described aqueous solvent.
Preferably, be mixed into by being uniformly mixed described in nickel nitrate aqueous solution and glycerol; Preferably, described churning time is at least 3 minutes, such as 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., more preferably 4 ~ 30 minutes, be particularly preferably 5 ~ 20 minutes.
Preferably, the add-on of urea is 0.01 ~ 0.5mol/L, such as 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., more preferably 0.013 ~ 0.3mol/L, is particularly preferably 0.015 ~ 0.2mol/L.
Preferably, be mixed into described in after adding urea and at room temperature mixed by stirring; Preferably, described churning time is at least 15 minutes, such as 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., more preferably 20 ~ 60 minutes, be particularly preferably 30 ~ 50 minutes.
Preferably, described closed reactor is autoclave, is particularly preferably the autoclave with polytetrafluoroethylliner liner.
Described temperature of reaction can be 101 DEG C, 102 DEG C, 105 DEG C, 109 DEG C, 111 DEG C, 115 DEG C, 119 DEG C, 121 DEG C, 130 DEG C, 150 DEG C, 170 DEG C, 179 DEG C, 181 DEG C, 190 DEG C, 199 DEG C, 201 DEG C, 205 DEG C, 208 DEG C, 209 DEG C etc., be preferably 110 ~ 200 DEG C, be particularly preferably 120 ~ 180 DEG C.
The described 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 particularly preferably 8 ~ 20 hours.
Preferably, described removal of impurities is for use distilled water and absolute ethanol washing successively; Preferably, described distilled water wash number of times is at least 3 times, is particularly preferably 5 times; Preferably, described absolute ethanol washing number of times is at least 3 times, is particularly preferably 5 times.
Preferably, described drying is carried out in vacuum drying oven.
Preferably, described drying temperature is 40 ~ 100 DEG C, such as 41 DEG C, 42 DEG C, 43 DEG C, 45 DEG C, 49 DEG C, 51 DEG C, 59 DEG C, 61 DEG C, 70 DEG C, 79 DEG C, 81 DEG C, 89 DEG C, 91 DEG C, 95 DEG C, 98 DEG C or 99 DEG C etc., be particularly preferably 80 DEG C by more preferably 50 ~ 90 DEG C.
Preferably, described time of drying is at least 8 hours, such as 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., more preferably 10 ~ 30 hours, be particularly preferably 12 hours.
Preferably, the preparation method of described Spherical nickel hydroxide material comprises the following steps:
(1) mix with glycerol with the nickel nitrate aqueous solution of the volume ratio of 10:1 ~ 0.3:1 by 0.01 ~ 0.4g/mL;
(2) 0.01 ~ 0.5mol/L urea is added in the mixing solutions obtained in step (1), mixing;
(3) mixing solutions that step (2) obtains is placed in closed reactor, 100 ~ 210 DEG C of reactions at least 5 hours;
(4) precipitation prepared by step (3) is isolated, removal of impurities, dry, namely obtain the Spherical nickel hydroxide material assembled by hierarchy nanometer sheet.
In the present invention, after supposing that dissolution of solid enters liquid, do not change the volume of mixing solutions, namely the volume of mixing solutions is the liquid volume before adding solid.
An object of the present invention is also to provide a kind of Spherical nickel hydroxide material prepared by aforesaid method.Described Spherical nickel hydroxide material is alpha-nickel hydroxide, assembled by the hierarchy nanometer sheet of two dimension, the thickness of nanometer sheet is between 20-40nm, under the current density test condition increased successively, there is satisfactory stability, when current density is 1A/g, its high specific capacity can reach 1177F/g; When current density is increased to 16A/g, its specific storage still can reach 615F/g.
An object of the present invention is also the purposes providing described Spherical nickel hydroxide material.Described Spherical nickel hydroxide material can be used as the Large Copacity electrode for super capacitor material of nickel metal hydride battery, ickel-cadmium cell or excellent electrochemical performance, is particularly preferably used as electrode for super capacitor material.
Beneficial effect of the present invention:
(1) mix the mixing solutions of gained for reaction solvent with glycerol by certain volume ratio with distilled water, less pollution, and the controlled nickel hydroxide material of form can be obtained;
(2) add the growth that a certain amount of urea is conducive to nickel hydroxide crystal, be conducive to the formation of sheet structure to spherical hierarchy simultaneously;
(3) spherical nickel hydroxide is assembled by the hierarchy nanometer sheet of two dimension, and the thickness of nanometer sheet is between 20-40nm;
(4) this spherical nickel hydroxide is alpha-nickel hydroxide, has superior chemical property compared with β-nickel hydroxide;
(5) the present invention adopts solvent-thermal method to obtain Spherical nickel hydroxide material, and processing unit is simple, and productive rate is high, and cost is low, pollution-free; This ball-shape nickel hydroxide is used for electrode material for super capacitor, due to the spherical hierarchy of its distinctive three-dimensional plate, when battery charging and discharging, discharge and recharge can be carried out fast, there are higher specific storage and cycle life, effectively can improve energy density and the power density of electrode; Under the current density test condition increased successively, have satisfactory stability, when current density is 1A/g, its high specific capacity can reach 1177F/g; When current density is increased to 16A/g, its specific storage still can reach 615F/g.
Accompanying drawing explanation
Fig. 1 is the powder XRD pattern spectrum of this ball-shape nickel hydroxide electrode materials.
Fig. 2 is the cold field emission scanning electron microscopic picture of this ball-shape nickel hydroxide electrode materials.
Fig. 3 be embodiment 1 gained ball-shape nickel hydroxide for electrode material for super capacitor successively at current density 1A/g, 2A/g, 4A/g, under 8A/g and 16A/g condition, the constant current charge-discharge curve recorded, wherein Time/S is the discharge and recharge time, and Voltage/V is the voltage of discharge and recharge.
Fig. 4 be embodiment 1 gained ball-shape nickel hydroxide for electrode material for super capacitor successively under scanning speed 5mv/S, 10mv/S, 20mv/S and 50mv/S condition, the cyclic voltammetry curve recorded, wherein EvsSCE/V is sweep voltage scope, and I/A is current value.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
Take 1.4g nickelous nitrate, join in the distilled water of 70ml volume, dispersed with stirring 5 minutes, makes nickel salt fully dissolve; Measure the glycerol of 10ml volume again, join above-mentioned solution, dispersed with stirring 20 minutes, two kinds of solution are fully mixed; Taking 0.24g urea is dissolved in the middle of above-mentioned solution, and air at room temperature lower magnetic force stirs 50 minutes; The mixing solutions obtained is put into the autoclave with polytetrafluoroethylliner liner seal, constant temperature 8 hours at 120 DEG C; Product respectively washs 5 times through distilled water, dehydrated alcohol, and in vacuum drying oven, 80 DEG C of dryings 12 hours, namely obtain the ball-shape nickel hydroxide electrode materials assembled by hierarchy nanometer sheet.
Fig. 1 is the XRD spectra of the ball-shape nickel hydroxide electrode materials that the present embodiment obtains, and the diffraction peak of nickel hydroxide in all well corresponding JCPDS database of diffraction peak in figure, collection of illustrative plates coincide, proves that the product of invention is single-phase nickel hydroxide.The CFSEM photo of Fig. 2, show that obtained nickel hydroxide is the globosity feature assembled by two-dimentional hierarchy nanometer sheet, the diameter of ball is about 5-8 μm, and the thickness of nanometer sheet is about 20-40nm, and hierarchy substantially increases the stable circulation performance of electrode materials.Fig. 3 is that ball-shape nickel hydroxide is for electrode material for super capacitor, when current density is respectively under 1A/g, 2A/g, 4A/g, 8A/g and 16A/g condition, 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 be ball-shape nickel hydroxide for the cyclic voltammetry curve of electrode material for super capacitor under different scanning speed test conditions, material circulation reversibility is good.
Embodiment 2
Take 1.8g nickelous nitrate, join in the distilled water of 50ml volume, dispersed with stirring 15 minutes, makes nickel salt fully dissolve; Measure the glycerol of 30ml volume again, join above-mentioned solution, dispersed with stirring 10 minutes, two kinds of solution are fully mixed; Taking 0.96g urea is dissolved in the middle of above-mentioned solution, and air at room temperature lower magnetic force stirs 30 minutes; The mixing solutions obtained is put into the autoclave with polytetrafluoroethylliner liner seal, constant temperature 15 hours at 180 DEG C; Product respectively washs 5 times through distilled water, dehydrated alcohol, and in vacuum drying oven, 80 DEG C of dryings 12 hours, namely obtain the ball-shape nickel hydroxide electrode materials assembled by hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 5-7 μm, and the thickness of nanometer sheet is about 20-35nm.
Embodiment 3
Take 2.0g nickelous nitrate, join in the distilled water of 30ml volume, dispersed with stirring 15 minutes, makes nickel salt fully dissolve; Measure the glycerol of 50ml volume again, join above-mentioned solution, dispersed with stirring 5 minutes, two kinds of solution are fully mixed; Taking 0.36g urea is dissolved in the middle of above-mentioned solution, and air at room temperature lower magnetic force stirs 30 minutes; The mixing solutions obtained is put into the autoclave with polytetrafluoroethylliner liner seal, constant temperature 10 hours at 160 DEG C; Product respectively washs 5 times through distilled water, dehydrated alcohol, and in vacuum drying oven, 80 DEG C of dryings 12 hours, namely obtain the ball-shape nickel hydroxide electrode materials assembled by hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 6-7 μm, and the thickness of nanometer sheet is about 20-30nm.
Embodiment 4
Take 2.6g nickelous nitrate, join in the distilled water of 40ml volume, dispersed with stirring 10 minutes, makes nickel salt fully dissolve; Measure the glycerol of 40ml volume again, join above-mentioned solution, dispersed with stirring 20 minutes, two kinds of solution are fully mixed; Taking 0.84g urea is dissolved in the middle of above-mentioned solution, and air at room temperature lower magnetic force stirs 40 minutes; The mixing solutions obtained is put into the autoclave with polytetrafluoroethylliner liner seal, constant temperature 10 hours at 140 DEG C; Product respectively washs 5 times through distilled water, dehydrated alcohol, and in vacuum drying oven, 80 DEG C of dryings 12 hours, namely obtain the ball-shape nickel hydroxide electrode materials assembled by hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 4-6 μm, and the thickness of nanometer sheet is about 21-33nm.
Embodiment 5
Take 2.8g nickelous nitrate, join in the distilled water of 60ml volume, dispersed with stirring 20 minutes, makes nickel salt fully dissolve; Measure the glycerol of 20ml volume again, join above-mentioned solution, dispersed with stirring 10 minutes, two kinds of solution are fully mixed; Taking 0.72g urea is dissolved in the middle of above-mentioned solution, and air at room temperature lower magnetic force stirs 50 minutes; The mixing solutions obtained is put into the autoclave with polytetrafluoroethylliner liner seal, constant temperature 12 hours at 150 DEG C; Product respectively washs 5 times through distilled water, dehydrated alcohol, and in vacuum drying oven, 80 DEG C of dryings 12 hours, namely obtain the ball-shape nickel hydroxide electrode materials assembled by hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 6-8 μm, and the thickness of nanometer sheet is about 25-38nm.
Embodiment 6
Take 3.0g nickelous nitrate, join in the distilled water of 70ml volume, dispersed with stirring 15 minutes, makes nickel salt fully dissolve; Measure the glycerol of 10ml volume again, join above-mentioned solution, dispersed with stirring 15 minutes, two kinds of solution are fully mixed; Taking 0.60g urea is dissolved in the middle of above-mentioned solution, and air at room temperature lower magnetic force stirs 40 minutes; The mixing solutions obtained is put into the autoclave with polytetrafluoroethylliner liner seal, constant temperature 15 hours at 140 DEG C; Product respectively washs 5 times through distilled water, dehydrated alcohol, and in vacuum drying oven, 80 DEG C of dryings 12 hours, namely obtain the ball-shape nickel hydroxide electrode materials assembled by hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 5-8 μm, and the thickness of nanometer sheet is about 26-39nm.
Embodiment 7
Take 0.7g nickelous nitrate, join in the distilled water of 70ml volume, dispersed with stirring 15 minutes, makes nickel salt fully dissolve; Measure the glycerol of 7ml volume again, join above-mentioned solution, dispersed with stirring 3 minutes, two kinds of solution are fully mixed; Taking 0.048g urea is dissolved in the middle of above-mentioned solution, and air at room temperature lower magnetic force stirs 15 minutes; The mixing solutions obtained is put into the autoclave with polytetrafluoroethylliner liner seal, constant temperature 24 hours at 100 DEG C; Product respectively washs 4 times through distilled water, dehydrated alcohol, and in vacuum drying oven, 40 DEG C of dryings 30 hours, namely obtain the ball-shape nickel hydroxide electrode materials assembled by hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 5-6 μm, and the thickness of nanometer sheet is about 21-35nm.
Embodiment 8
Take 8g nickelous nitrate, join in the distilled water of 20ml volume, dispersed with stirring 20 minutes, makes nickel salt fully dissolve; Measure the glycerol of 67ml volume again, join above-mentioned solution, dispersed with stirring 30 minutes, two kinds of solution are fully mixed; Taking 2.6g urea is dissolved in the middle of above-mentioned solution, and air at room temperature lower magnetic force stirs 60 minutes; The mixing solutions obtained is put into the autoclave with polytetrafluoroethylliner liner seal, constant temperature 5 hours at 210 DEG C; Product respectively washs 5 times through distilled water, dehydrated alcohol, and in vacuum drying oven, 100 DEG C of dryings 8 hours, namely obtain the ball-shape nickel hydroxide electrode materials assembled by hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 6-8 μm, and the thickness of nanometer sheet is about 28-40nm.
Embodiment 9
Take 12g nickelous nitrate, join in the distilled water of 60ml volume, dispersed with stirring 30 minutes, makes nickel salt fully dissolve; Measure the glycerol of 7.5ml volume again, join above-mentioned solution, dispersed with stirring 40 minutes, two kinds of solution are fully mixed; Taking 2g urea is dissolved in the middle of above-mentioned solution, and air at room temperature lower magnetic force stirs 70 minutes; The mixing solutions obtained is put into the autoclave with polytetrafluoroethylliner liner seal, constant temperature 10 hours at 200 DEG C; Product respectively washs 5 times through distilled water, dehydrated alcohol, and in vacuum drying oven, 80 DEG C of dryings 15 hours, namely obtain the ball-shape nickel hydroxide electrode materials assembled by hierarchy nanometer sheet.This ball-shape nickel hydroxide electrode materials diameter is about 7-8 μm, and the thickness of nanometer sheet is about 29-40nm.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (21)
1. a preparation method for Spherical nickel hydroxide material, said method comprising the steps of:
(1) with the volume ratio of 10:1 ~ 0.3:1, nickel nitrate aqueous solution and glycerol are uniformly mixed at least 3min, in described nickel nitrate aqueous solution, the concentration of nickelous nitrate is 0.01 ~ 0.4g/mL;
(2) add urea in the mixing solutions obtained in step (1), at room temperature undertaken mixing at least 15min by stirring; The add-on of described urea is 0.01 ~ 0.5mol/L;
(3) mixing solutions that step (2) obtains is placed in closed reactor, 100 ~ 210 DEG C of reactions at least 5 hours;
(4) precipitation prepared by step (3) is isolated, wash 5 times respectively with distilled water and dehydrated alcohol, dry, drying temperature is 40-100 DEG C, time of drying is at least 8 hours, namely obtains the Spherical nickel hydroxide material assembled by hierarchy nanometer sheet;
Described Spherical nickel hydroxide material has satisfactory stability under the current density test condition increased successively.
2. the method for claim 1, is characterized in that, in described nickel nitrate aqueous solution, the concentration of nickelous nitrate is 0.015 ~ 0.2g/mL.
3. method as claimed in claim 2, it is characterized in that, in described nickel nitrate aqueous solution, the concentration of nickelous nitrate is 0.02 ~ 0.1g/mL.
4. the method for claim 1, is characterized in that, the volume ratio of described nickel nitrate aqueous solution and glycerol is 8:1 ~ 0.5:1.
5. method as claimed in claim 4, it is characterized in that, the volume ratio of described nickel nitrate aqueous solution and glycerol is 7:1 ~ 0.6:1.
6. the method for claim 1, is characterized in that, the time of step (1) described stirring is 4-30 minute.
7. method as claimed in claim 6, it is characterized in that, the time of step (1) described stirring is 5 ~ 20 minutes.
8. the method for claim 1, is characterized in that, the add-on of urea is 0.013 ~ 0.3mol/L.
9. method as claimed in claim 8, it is characterized in that, the add-on of urea is 0.015 ~ 0.2mol/L.
10. the method for claim 1, is characterized in that, the time of step (2) described stirring is 20 ~ 60 minutes.
11. methods as claimed in claim 10, is characterized in that, the time of step (2) described stirring is 30 ~ 50 minutes.
12. the method for claim 1, is characterized in that, described closed reactor is autoclave, and described autoclave is the autoclave with polytetrafluoroethylliner liner.
13. the method for claim 1, is characterized in that, the temperature of reaction in described closed reactor is 110 ~ 200 DEG C.
14. methods as claimed in claim 13, it is characterized in that, the temperature of reaction in described closed reactor is 120 ~ 180 DEG C.
15. the method for claim 1, is characterized in that, the reaction times in described closed reactor is 6 ~ 24 hours.
16. methods as claimed in claim 15, it is characterized in that, the reaction times in described closed reactor is 8 ~ 20 hours.
17. the method for claim 1, is characterized in that, described drying is carried out in vacuum drying oven.
18. the method for claim 1, is characterized in that, described drying temperature is 50 ~ 90 DEG C.
19. methods as claimed in claim 18, it is characterized in that, described drying temperature is 80 DEG C.
20. the method for claim 1, is characterized in that, described time of drying is 10 ~ 30 hours.
21. methods as claimed in claim 20, it is characterized in that, described time of drying is 12 hours.
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| CN108840313B (en) * | 2018-09-19 | 2022-07-08 | 曲阜师范大学 | Preparation method of multistage spherical nickel diselenide |
| 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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| CN101417823A (en) * | 2008-11-14 | 2009-04-29 | 中国科学院上海硅酸盐研究所 | Wet chemical preparation method of nickel oxide hollow microsphere without template |
| CN101618895A (en) * | 2008-07-04 | 2010-01-06 | 中国科学院福建物质结构研究所 | Multi-level structure alpha type nickel hydroxide prepared by microwave auxiliary and method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062792A (en) * | 2006-04-28 | 2007-10-31 | 长沙力元新材料股份有限公司 | Preparation method of spherical nickel hydroxid |
| CN101077794A (en) * | 2007-06-21 | 2007-11-28 | 江苏奇能电池有限公司 | Method for modifying spherical nickel hydroxide by nano carbon technique |
| CN101618895A (en) * | 2008-07-04 | 2010-01-06 | 中国科学院福建物质结构研究所 | Multi-level structure alpha type nickel hydroxide prepared by microwave auxiliary and method thereof |
| CN101417823A (en) * | 2008-11-14 | 2009-04-29 | 中国科学院上海硅酸盐研究所 | Wet chemical preparation method of nickel oxide hollow microsphere without template |
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