CN1772629A - Nanometer alpha-nickel hydroxide and its prepn - Google Patents
Nanometer alpha-nickel hydroxide and its prepn Download PDFInfo
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- CN1772629A CN1772629A CN 200510037576 CN200510037576A CN1772629A CN 1772629 A CN1772629 A CN 1772629A CN 200510037576 CN200510037576 CN 200510037576 CN 200510037576 A CN200510037576 A CN 200510037576A CN 1772629 A CN1772629 A CN 1772629A
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Abstract
The present invention provides one kind of nanometer alpha-nickel hydroxide and its preparation process. The preparation process adopts bivalent nickel slat as main material, and includes the steps of: adding doping metal salt to compound reaction solution, compounding precipitant solution with potassium hydroxide or sodium hydroxide, adding the precipitant solution to the reaction solution under stirring and ultrasonic dispersing to obtain nickel hydroxide, washing and drying to constant weight. Thus prepared nanometer alpha-nickel hydroxide has small and homogeneous particle size, great specific surface area, high heat stability, stability in alkali medium, high specific discharge capacity, and other features, and may be used as the positive pole material in secondary alkali ZnNi cell, H-Ni cell and FeNi cell.
Description
Technical field
The present invention relates to technical field of chemical power, specifically be meant a kind of nano alpha-nickel hydroxide and preparation method thereof.
Background technology
Alkaline secondary cells such as traditional Zn/Ni, Cd/Ni, M-H/Ni, Fe/Ni, its positive pole all are to be that active substance is made with β-nickel hydroxide or with the β-nickel hydroxide of the compound additive of the elements such as Co, Cd, Mn that mixed.Mainly there is the deficiency of following four aspects in this nickel electrode material:
First, the uncharged state of β-nickel hydroxide electrode can not be formed the battery that can discharge immediately with the zinc electrode electric charge coupling that is in electriferous state, charging changes into and need separately, before battery reaches optimum performance, also needs to carry out tens of inferior charge and discharge and changes into.This has caused the raising of huge energy dissipation and battery manufacturing cost with regard to the manufacturing of giving battery.
The second, by the electrode that β-nickel hydroxide constitutes, (200～235mAh/g) have only about 50% of negative pole zinc electrode capacity (about 400mAh/g) to the actual specific capacity of electrode itself usually after activation.The positive and negative electrode active substance consumption of this zinc/nickel-based battery, volume phase equal difference are bigger, bring certain degree of difficulty also for the manufacturing of battery.And, be that the nickel electrode of active substance manufacturing is that the specific discharge capacity of anodal battery is also relatively low with β-nickel hydroxide.
The 3rd, because β-nickel hydroxide is a kind of semi-conductor of conductivity extreme difference, so very poor by its conductivity as the electrode that active substance constituted, the electrode active material after the activation has influenced the discharge performance and the discharging efficiency of electrode self owing to self conductive capability difference.At present, the utilization ratio of zinc-nickel cell positive active material has only 40～60% of its total amount.
The 4th, be that the nickel electrode of active substance manufacturing is easy to cause in charge and discharge process overcharge with β-nickel hydroxide.This overcharging can make β-nickel hydroxide become the bigger gamma-hydroxy nickel oxide of volume when the electrode electrooxidation rather than become the beta-hydroxy nickel oxide close with β-nickel hydroxide volume, thereby cause electrode in the back volumetric expansion of overcharging.Simultaneously, the formation of gamma-hydroxy nickel oxide can cause that also electrode produces " memory effect ", and the expansion of electrode and " memory effect " can directly shorten the life-span that recycles of battery again.
Though people attempt to overcome above-mentioned shortcoming by the preparation alpha-nickel hydroxide recently, China 00123599.0,01129615.1,01109694.2 number application for a patent for invention discloses a kind of spherical alpha-nickel hydroxide respectively, a kind of nano alpha-nickel hydroxide and a kind of nanophase alpha-nickel hydroxide and preparation method thereof, but, above-mentioned patent is except all existing its defective separately, also there is the common weak point in they: first, in the prepared alpha-nickel hydroxide content of doped element and mix impurity level be difficult to control because its synthesis technique step, flow process is complicated and cause impurity element kind in the actual building-up process, content is uncertain; Simultaneously, impurity has not only reduced the actual capacity of active substance, and can directly reduce the electrode discharge specific storage, thereby influences the performance of battery; The second, its synthesis technique flow process is comparatively complicated, thus cause active material synthetic cost height, realize that the suitability for industrialized production difficulty is bigger; The 3rd, with prepared alpha-nickel hydroxide is that the loading capacity of positive active material manufacturing electrode is lower, and the highest specific volume value has only 59% (seeing No. 01129615.1 application for a patent for invention specification sheets embodiment one of China) of alpha-nickel hydroxide electrode Theoretical Mass specific storage (578mAh/g); The 4th, be that the production cost of battery of positive active material manufacturing is also higher with the alpha-nickel hydroxide of above-mentioned patented method preparation, performance and price is lower, lacks the market competitiveness.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, purpose of the present invention just provides a kind of nano alpha-nickel hydroxide and preparation method thereof.The chemical feedstocks that this method adopts is common, be easy to get, non-environmental-pollution or low environment pollute, stir and the condition of ultrasonic dispersing under, prepare the good nano alpha-nickel hydroxide of chemical property with easy chemical coprecipitation method.
The present invention realizes by following technical solution: the preparation method of described a kind of nano alpha-nickel hydroxide comprises the steps and processing condition:
The first step is raw material with the divalent nickel salt, adds the doped metal salt that metal ion content is equivalent to divalent nickel salt mole number 5～25%, is mixed with the reaction soln that nickel ion concentration is 0.01～10mol/L with water dissolution;
The second step amount of taking is the potassium hydroxide or the sodium hydroxide of nickel ion mole number 200～300% in the described reaction soln, is mixed with potassium hydroxide or naoh concentration is the alkaline sedimentation agent solution of 0.05～12mol/L with water dissolution;
The 3rd step is in ultrasonic dispersing, carry out under the stirring condition simultaneously, described precipitant solution is joined in the described reaction soln, control precipitation agent rate of addition, make the pH value of reaction system between 7.0～11.5, temperature of reaction is 20～60 ℃, and the reaction times is 15～120 minutes, stops to stir after reaction finishes, continue to use ultrasonic dispersing 30～300 minutes, obtain green or glaucous nickel hydroxide precipitate;
The 4th step was washed with water to described nickel hydroxide precipitate the pH value of elutant for neutral, was dried to constant weight under the condition of vacuum and room temperature.
In order to realize the present invention better, described divalent nickel salt comprises single nickel salt, nickelous nitrate or nickelous chloride; Described doped metal salt comprises one or more the mixture in trivalent aluminium salt, the trivalent iron salt; Described trivalent aluminium salt comprises aluminum nitrate, Tai-Ace S 150 or aluminum chloride; Described trivalent iron salt comprises ferric sulfate, iron(ic) chloride or iron nitrate; Described water comprises nature water, tap water, distilled water or deionized water.
Nano alpha-nickel hydroxide of the present invention forms by method for preparing.
The preparation method of nano alpha-nickel hydroxide of the present invention is a kind of chemical coprecipitation reaction method, is the brand new technical route of synthesis of nano alpha-nickel hydroxide under the condition of ultrasonic dispersing.Its reaction principle is expressed as follows with chemical equation:
(green or blue-greenish colour)
(wherein, M
N+Represent Al
3+, Fe
3+B represent insert between solid surface absorption and crystal layer, bring into and, that content limited, inherent CO that absorb by raw material itself from environment
3 2-, NO
3 -, SO
4 2-, Cl
-Deng (with CO
3 2-Be main) foreign ion; N=0.35-0.85, the total amount of expression crystalline crystal water and solid absorption water, A
+Represent the K that adsorbs between crystal layer
+, Na
+Foreign ion)
The present invention compared with prior art has following advantage and beneficial effect:
1, the nano alpha-nickel hydroxide of the present invention's preparation, because alpha-nickel hydroxide has bigger interlamellar spacing (as Fig. 1, the XRD diffractogram of nano alpha-nickel hydroxide), its interlayer can hold more CO
3 2-, NO
3 -Deng negatively charged ion, K
+, Na
+, H
3O
+Deng positively charged ion and water molecules etc., make the conductivity of nickel hydroxide strengthen greatly, particularly its proton conductivity is significantly improved, and is that the chemical property of active substance electrode is improved thereby make with the nano alpha-nickel hydroxide.
2, be the nickel electrode of electrode active material with the prepared nano alpha-nickel hydroxide of the present invention, the active substance of Charging state is a gamma-hydroxy nickel oxide, and the active substance of discharge attitude is an alpha-nickel hydroxide.And, alpha-nickel hydroxide has higher chemical stability under alkaline condition, be difficult for changing into the less β-nickel hydroxide of volume, thereby electrode is in the charge and discharge cycles process, only there is the conversion between alpha-nickel hydroxide/gamma-hydroxy nickel oxide, be so-called α/γ circulation, and do not exist other crystal habit to change or circulation, make electrode and battery have long cycle life.
3, the nano alpha-nickel hydroxide with the present invention's preparation is the nickel electrode of electrode active material preparation, in charge and discharge process, owing to only have α/γ circulation, and also the nickel of the gamma-hydroxy nickel oxide of Charging state has higher oxidation state, its average Oxidation Number is 3.55, and the highest oxidation number reaches 3.76.Therefore, adopt the nickel of the hydroxy nickel oxide making of the present invention's preparation just having higher specific discharge capacity, average specific discharge capacity surpasses 400mAh/g, the highest specific discharge capacity reaches 447mAh/g, charge-discharge performance is stable, the nickel positive pole can have specific storage matching relationship preferably with negative pole zinc, thereby has improved the utilising efficiency of battery material effectively, has reduced the comprehensive manufacturing cost of battery effectively.
4, the particle diameter of the nano alpha-nickel hydroxide of the present invention's preparation is 20～150nm, can adsorb an amount of foreign ion effectively, in addition mixed Al, Fe etc. have the doped element of better conductive capability, thereby improved the conductive capability of electrode widely, reduced the internal resistance of battery, improve the discharging efficiency and the specific discharge capacity of battery significantly, also improved the chemical stability of alpha-nickel hydroxide in alkaline medium simultaneously.
5, the alpha-nickel hydroxide with the present invention's preparation is the zinc-nickel cell of positive active material made, (than β-nickel hydroxide is the charging voltage low 30～50mV) of active substance battery to have lower charging voltage, be difficult for causing battery overcharge, effectively prolonged the work-ing life of battery; Its average open-circuit voltage is about 1.67 volts (V), and average discharge voltage is about 1.55 volts (V), has discharge platform stably, and the cycle performance of electrode is good.
6, the alpha-nickel hydroxide of the present invention preparation also has and is easy to the activatory performance characteristics, promptly the charge and discharge cycles through less number of times can reach best charge-discharge performance, do not need too many time discharge and recharge activation and promptly can form secondary cell, effectively save energy, reduction production cost of cells with the good couplings such as zinc negative pole of chemical property with good charge-discharge performance.
7, the synthesis technique flow process of alpha-nickel hydroxide of the present invention is simple, product cheap for manufacturing cost, the content of doped metallic elements, the content of alpha-nickel hydroxide and the particle diameter of product etc. all are easy to control, it is tiny that prepared alpha-nickel hydroxide has a grain diameter, particle size distribution is narrower, specific surface area is big, Heat stability is good, Stability Analysis of Structures in alkaline medium, the self-discharge rate of Charging state electrode is low, characteristics such as electrical property good stable, can be used for making alkali zinc nickel (Zn/Ni), hydrogen nickel (MH/Ni), the positive electrode material of iron nickel secondary cells such as (Fe/Ni) and the big output rating power cell of conduct just can be made production performance better high quality battery of the present invention with the production unit and the production technique of original battery under the situation that does not change original battery production technology.
Description of drawings
Fig. 1 is the XRD diffracting spectrum of typical alpha-nickel hydroxide;
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1
The first step is got 1.0 moles nickelous nitrate (Ni (NO
3)
26H
2O) and the aluminum nitrate (Al (NO of 0.05 mole (being equivalent to nickel salt mole number 5%)
3)
39H
2O) use the nature water dissolution, be mixed with the reaction soln that the 100ml nickel ion concentration is 10mol/L;
Second step, 1.2 moles potassium hydroxide, the concentration that is mixed with potassium hydroxide with 100ml nature water dissolution is the precipitant solution of 12mol/L;
The 3rd step stirred, uses under the condition of ultrasonic dispersing simultaneously at stirrer, dropwise join precipitant solution in the reaction soln, 20 ℃ of control reaction temperature, control reaction pH is about 7.0, the dropwise reaction time is about 15 minutes, stop to stir after dripping end, continued ultrasonic dispersing 300 minutes, obtain green or blue-greenish colour nickel hydroxide precipitate product;
The 4th step with suitable quantity of water washing 5 times, suction filtration, and continued nickel hydroxide precipitate to take out repeatedly and washes for several times, to the pH value of elutant be neutrality, clean nickel hydroxide precipitate is placed vacuum drying oven, be dried to constant weight at ambient temperature.
Measure the particle diameter (referring to table 1) of above-mentioned nickel hydroxide with laser particle size analyzer and projection electron microscopy, its particle diameter is 20～100nm, and median size is 35nm; Decided its crystalline structure with XRD (x-ray powder diffraction), the result show its crystalline structure be alpha-nickel hydroxide (a) referring to Fig. 1; Its chemical property adopts with the alpha-nickel hydroxide that to be that active substance is made anodal, be that negative pole, potassium hydroxide aqueous solution are that the Experimental cell of ionogen manufacturing is measured with homemade oxide powder and zinc, its highest specific discharge capacity that records its 0.1C rate charge-discharge is 389mAh/g (referring to table 1).
Embodiment 2
The first step is got 0.05 mol sulfuric acid nickel (NiSO
46H
2O), 0.0025 mole (be equivalent to nickel salt mole number 5%) iron nitrate (Fe (NO
3)
37H
2O) and 0.0025 mole of (be equivalent to nickel salt mole number 5%) aluminum chloride (AlCl
3), be mixed with the reaction soln that the 5000ml nickel ion concentration is 0.01mol/L with dissolved in distilled water;
Second step was got the potassium hydroxide of 0.15 mole (be equivalent to nickel ion mole number 300%), was mixed with the oxidizing agent solution that the 3000ml concentration of potassium hydroxide is 0.05mol/L with dissolved in distilled water;
The 3rd step stirred, uses under the condition of ultrasonic dispersing simultaneously at stirrer, dropwise join precipitant solution in the reaction soln, 30 ℃ of control reaction temperature, reaction pH is about 9.5, the dropwise reaction time is 120 minutes, stop to stir after dripping end, continued ultrasonic dispersing 180 minutes, obtain green or blue-greenish colour nickel hydroxide precipitate product;
The 4th step with suitable quantity of water washing 5 times, suction filtration, and continued nickel hydroxide precipitate to take out repeatedly and washes for several times, to the pH value of elutant be neutrality, clean nickel hydroxide precipitate is placed vacuum drying oven, be dried to constant weight at ambient temperature.
Measure the particle diameter (referring to table 1) of above-mentioned nickel hydroxide with laser particle size analyzer and projection electron microscopy, its particle diameter is 20～120nm, and median size is 60nm; Decided its crystalline structure with XRD (x-ray powder diffraction), the result shows that its crystalline structure is an alpha-nickel hydroxide; Its chemical property adopts with the alpha-nickel hydroxide that to be that active substance is made anodal, be that negative pole, potassium hydroxide aqueous solution are that the Experimental cell of ionogen manufacturing is measured with homemade oxide powder and zinc, its highest specific discharge capacity that records its 0.1C rate charge-discharge is 423mAh/g (referring to table 1).
Embodiment 3
The first step is got 0.5 mole nickelous nitrate (Ni (NO
3)
26H
2Aluminum nitrate (Al (the NO of O), 0.065 mole (being equivalent to nickel salt mole number 13%)
3)
39H
2O), be mixed with the reaction soln that the 2000ml nickel ion concentration is 0.25mol/L with dissolved in distilled water;
Second step was got 1.1 moles of (be equivalent to nickel ion mole number 220%) potassium hydroxide, was mixed with the oxidizing agent solution 275ml that concentration of potassium hydroxide is about 4mol/L with distilled water;
The 3rd step stirred, uses under the condition of ultrasonic dispersing simultaneously at stirrer, dropwise join precipitant solution in the reaction soln, 35 ℃ of control reaction temperature, control reaction pH is about 8.0, the dropwise reaction time is 30 minutes, stop to stir after dripping end, continued ultrasonic dispersing 60 minutes, obtain green or blue-greenish colour nickel hydroxide precipitate product;
The 4th step with suitable quantity of water washing 5 times, suction filtration, and continued nickel hydroxide precipitate to take out repeatedly and washes for several times, to the pH value of elutant be neutrality, clean nickel hydroxide precipitate is placed vacuum drying oven, be dried to constant weight at ambient temperature.
Measure the particle diameter (referring to table 1) of above-mentioned nickel hydroxide with laser particle size analyzer and projection electron microscopy, its particle diameter is 60～150nm, and median size is 100nm; Decided its crystalline structure with XRD (x-ray powder diffraction), the result shows that its crystalline structure is alpha-nickel hydroxide (referring to Fig. 1 b); Its chemical property adopts with the alpha-nickel hydroxide that to be that active substance is made anodal, be that negative pole, potassium hydroxide aqueous solution are that the Experimental cell of ionogen manufacturing is measured with homemade oxide powder and zinc, its highest specific discharge capacity that records its 0.1C rate charge-discharge is 447mAh/g (referring to table 1).
Embodiment 4
The first step is got 0.1 mole of nickelous chloride (NiCl
26H
2Aluminum chloride (the AlCl of O), 0.01 mole (be equivalent to nickel salt mole number 10%)
3), the iron(ic) chloride (FeCl of 0.005 mole (be equivalent to nickel salt mole number 5%)
3), be mixed with the reaction soln that the 500ml nickel ion concentration is 0.2mol/L with deionized water dissolving;
Second step was got the sodium hydroxide of 0.25 mole (be equivalent to nickel ion mole number 250%), was mixed with the oxidizing agent solution that the 500ml concentration of potassium hydroxide is 0.5mol/L with deionized water dissolving;
The 3rd step stirred, uses under the condition of ultrasonic dispersing simultaneously at stirrer, dropwise join precipitant solution in the reaction soln, 45 ℃ of control reaction temperature, control reaction pH is about 9.5, the dropwise reaction time is 90 minutes, stop to stir after dripping end, continued ultrasonic dispersing 120 minutes, obtain green or blue-greenish colour nickel hydroxide precipitate product;
The 4th step with suitable quantity of water washing 5 times, suction filtration, and continued nickel hydroxide precipitate to take out repeatedly and washes for several times, to the pH value of elutant be neutrality, clean nickel hydroxide precipitate is placed vacuum drying oven, be dried to constant weight at ambient temperature.
Measure the particle diameter (referring to table 1) of above-mentioned nickel hydroxide with laser particle size analyzer and projection electron microscopy, its particle diameter is 50～150nm, and median size is 85nm; Decided its crystalline structure with XRD (x-ray powder diffraction), the result shows that its crystalline structure is an alpha-nickel hydroxide; Its chemical property adopts with the alpha-nickel hydroxide that to be that active substance is made anodal, be that negative pole, potassium hydroxide aqueous solution are that the Experimental cell of ionogen manufacturing is measured with homemade oxide powder and zinc, its highest specific discharge capacity that records its 0.1C rate charge-discharge is 386mAh/g (referring to table 1).
Embodiment 5
The first step is got 0.1 mole nickelous nitrate (Ni (NO
3)
26H
2Tai-Ace S 150 (the Al of O), 0.01 mole (being equivalent to nickel salt mole number 10%)
2(SO
4)
318H
2O), be mixed with the reaction soln that the 100ml nickel ion concentration is 0.2mol/L with dissolved in distilled water;
Second step was got 0.25 mole of (be equivalent to nickel ion mole number 250%) potassium hydroxide, was made into 50ml (concentration of potassium hydroxide is 5mol/L's) oxidizing agent solution with distilled water;
The 3rd step stirred, uses under the condition of ultrasonic dispersing simultaneously at stirrer, dropwise join precipitant solution in the reaction soln, 60 ℃ of control reaction temperature, control reaction pH is about 9.0, the dropwise reaction time is 30 minutes, stop to stir after dripping end, continued ultrasonic dispersing 100 minutes, obtain green or blue-greenish colour nickel hydroxide precipitate product;
The 4th step with suitable quantity of water washing 5 times, suction filtration, and continued nickel hydroxide precipitate to take out repeatedly and washes for several times, to the pH value of elutant be neutrality, clean nickel hydroxide precipitate is placed vacuum drying oven, be dried to constant weight at ambient temperature.
Measure the particle diameter (referring to table 1) of above-mentioned nickel hydroxide with laser particle size analyzer and projection electron microscopy, its particle diameter is 35～85nm, and median size is 60nm; Decided its crystalline structure with XRD (x-ray powder diffraction), the result shows that its crystalline structure is an alpha-nickel hydroxide; Its chemical property adopts with the alpha-nickel hydroxide that to be that active substance is made anodal, be that negative pole, potassium hydroxide aqueous solution are that the Experimental cell of ionogen manufacturing is measured with homemade oxide powder and zinc, its highest specific discharge capacity that records its 0.1C rate charge-discharge is 431mAh/g (referring to table 1).
Embodiment 6
The first step is got 0.5 mole single nickel salt (NiSO
46H
2O), 0.125 mole (iron ion is equivalent to nickel salt mole number 25%) ferric sulfate (Fe
2(SO
4)
318H
2O), be mixed with the reaction soln that the 100ml nickel ion concentration is 5mol/L with dissolved in distilled water;
Second step was got 1.2 moles of (be equivalent to nickel ion mole number 240%) potassium hydroxide, was mixed with the oxidizing agent solution that the 100ml concentration of potassium hydroxide is 12mol/L with dissolved in distilled water;
The 3rd step stirred, uses under the condition of ultrasonic dispersing simultaneously at stirrer, dropwise join precipitant solution in the reaction soln, 35 ℃ of control reaction temperature, control reaction pH is about 7.5, the dropwise reaction time is 90 minutes, stop to stir after dripping end, continued ultrasonic dispersing 210 minutes, obtain green or blue-greenish colour nickel hydroxide precipitate product;
The 4th step with suitable quantity of water washing 5 times, suction filtration, and continued nickel hydroxide precipitate to take out repeatedly and washes for several times, to the pH value of elutant be neutrality, clean nickel hydroxide precipitate is placed vacuum drying oven, be dried to constant weight at ambient temperature.
Measure the particle diameter (referring to table 1) of above-mentioned nickel hydroxide with laser particle size analyzer and projection electron microscopy, its particle diameter is 30～120nm, and median size is 50nm; Decided its crystalline structure with XRD (x-ray powder diffraction), the result shows that its crystalline structure is an alpha-nickel hydroxide; Its chemical property adopts with the alpha-nickel hydroxide that to be that active substance is made anodal, be that negative pole, potassium hydroxide aqueous solution are that the Experimental cell of ionogen manufacturing is measured with homemade oxide powder and zinc, its highest specific discharge capacity that records its 0.1C rate charge-discharge is 404mAh/g (referring to table 1).
Embodiment 7
The first step is got 2.0 moles nickelous nitrate (Ni (NO
3)
26H
2Aluminum nitrate (Al (the NO of O), 0.16 mole (being equivalent to nickel salt mole number 8%)
3)
39H
2Iron nitrate (Fe (the NO of O), 0.1 mole (being equivalent to nickel salt mole number 5%)
3)
39H
2O), be mixed with the reaction soln that the 2000ml nickel ion concentration is 1.0mol/L with dissolved in distilled water;
Second step was got 6.0 moles of (be equivalent to nickel ion mole number 300%) potassium hydroxide, was mixed with the oxidizing agent solution 1000ml that concentration of potassium hydroxide is about 6mol/L with distilled water;
The 3rd step stirred, uses under the condition of ultrasonic dispersing simultaneously at stirrer, dropwise join precipitant solution in the reaction soln, 55 ℃ of control reaction temperature, it is 60 minutes that control reaction pH was about for 8.0 dropwise reaction times, stop to stir after dripping end, continue ultrasonic dispersing 90 minutes, and obtained green or blue-greenish colour nickel hydroxide precipitate product;
The 4th step with suitable quantity of water washing 5 times, suction filtration, and continued nickel hydroxide precipitate to take out repeatedly and washes for several times, to the pH value of elutant be neutrality, clean nickel hydroxide precipitate is placed vacuum drying oven, be dried to constant weight at ambient temperature.
Measure the particle diameter (referring to table 1) of above-mentioned nickel hydroxide with laser particle size analyzer and projection electron microscopy, its particle diameter is 30～80nm, and median size is 40nm; Decided its crystalline structure with XRD (x-ray powder diffraction), the result shows that its crystalline structure is an alpha-nickel hydroxide; Its chemical property adopts with the alpha-nickel hydroxide that to be that active substance is made anodal, be that negative pole, potassium hydroxide aqueous solution are that the Experimental cell of ionogen manufacturing is measured with homemade oxide powder and zinc, its highest specific discharge capacity that records its 0.1C rate charge-discharge is 436mAh/g (referring to table 1).
Embodiment 8
The first step is got 1.0 moles nickelous nitrate (Ni (NO
3)
26H
2Aluminum nitrate (Al (the NO of O), 0.2 mole (being equivalent to nickel salt mole number 20%)
3)
39H
2O), be mixed with the reaction soln that the 300ml nickel ion concentration is 3.0mol/L with dissolved in distilled water;
Second step was got 2.5 moles of (be equivalent to nickel ion mole number 210%) potassium hydroxide, was mixed with the oxidizing agent solution 1000ml that concentration of potassium hydroxide is about 2.5mol/L with distilled water;
The 3rd step stirred, uses under the condition of ultrasonic dispersing simultaneously at stirrer, dropwise join precipitant solution in the reaction soln, 35 ℃ of control reaction temperature, control reaction pH is about 9.0, the dropwise reaction time is about 30 minutes, stop to stir after dripping end, continued ultrasonic dispersing 45 minutes, obtain green or blue-greenish colour nickel hydroxide precipitate product;
The 4th step with suitable quantity of water washing 5 times, suction filtration, and continued nickel hydroxide precipitate to take out repeatedly and washes for several times, to the pH value of elutant be neutrality, clean nickel hydroxide precipitate is placed vacuum drying oven, be dried to constant weight at ambient temperature.
Measure the particle diameter (referring to table 1) of above-mentioned nickel hydroxide with laser particle size analyzer and projection electron microscopy, its particle diameter is 30～100nm, and median size is 60nm; Decided its crystalline structure with XRD (x-ray powder diffraction), the result shows that its crystalline structure is an alpha-nickel hydroxide; Its chemical property adopts with the alpha-nickel hydroxide that to be that active substance is made anodal, be that negative pole, potassium hydroxide aqueous solution are that the Experimental cell of ionogen manufacturing is measured with homemade oxide powder and zinc, its highest specific discharge capacity that records its 0.1C rate charge-discharge is 400mAh/g (referring to table 1).
Embodiment 9
The first step is got 0.8 mole nickelous nitrate (Ni (NO
3)
26H
2Iron nitrate (Fe (the NO of O), 0.08 mole (being equivalent to nickel salt mole number 10%)
3)
39H
2O), be mixed with the reaction soln that the 100ml nickel ion concentration is 8mol/L with the tap water dissolving;
Second step was got 2.0 moles of (be equivalent to nickel ion mole number 250%) sodium hydroxide, was mixed with the precipitant solution 275ml that naoh concentration is about 4mol/L with tap water;
The 3rd step stirred, uses under the condition of ultrasonic dispersing simultaneously at stirrer, dropwise join precipitant solution in the reaction soln, 60 ℃ of control reaction temperature, control reaction pH is about 11.5, the dropwise reaction time is 30 minutes, stop to stir after dripping end, continued ultrasonic dispersing 30 minutes, obtain green or blue-greenish colour nickel hydroxide precipitate product;
The 4th step with suitable quantity of water washing 5 times, suction filtration, and continued nickel hydroxide precipitate to take out repeatedly and washes for several times, to the pH value of elutant be neutrality, clean nickel hydroxide precipitate is placed vacuum drying oven, be dried to constant weight at ambient temperature.
Measure the particle diameter (referring to table 1) of above-mentioned nickel hydroxide with laser particle size analyzer and projection electron microscopy, its particle diameter is 20～80nm, and median size is 45nm; Decided its crystalline structure with XRD (x-ray powder diffraction), the result shows that its crystalline structure is alpha-nickel hydroxide (referring to Fig. 1 c); Its chemical property adopts with the alpha-nickel hydroxide that to be that active substance is made anodal, be that negative pole, potassium hydroxide aqueous solution are that the Experimental cell of ionogen manufacturing is measured with homemade oxide powder and zinc, its highest specific discharge capacity that records its 0.1C rate charge-discharge is 413mAh/g (referring to table 1).
Typical nano alpha-nickel hydroxide of table 1 and zinc-nickel cell part test parameter
| Embodiment | Temperature of reaction (℃)/and the pH value | Ultrasonic wave action time (minute) | NiOOH particle diameter (nm) | Doped element and proportioning content (wt%) | Charge and discharge circulation life (inferior) | The highest specific discharge capacity (mAh/g) |
| 1 | 20/7.0 | 315 | 20～100 | Al/5 | 209 | 398 |
| 2 | 30/9.5 | 300 | 20～120 | Al/5，Fe/5 | 215 | 423 |
| 3 | 35/8.0 | 90 | 60～150 | Al/13 | 245 | 447 |
| 4 | 45/9.5 | 210 | 40～100 | Al/5，Fe/10 | 203 | 386 |
| 5 | 60/9.0 | 130 | 35～85 | Al/10 | 230 | 431 |
| 6 | 35/7.5 | 300 | 30～120 | Fe/25 | 200 | 397 |
| 7 | 55/8.0 | 150 | 40～120 | Al/8，Fe/5 | 220 | 436 |
| 8 | 35/9.0 | 75 | 30～100 | Al/20 | 211 | 400 |
| 9 | 60/11.5 | 90 | 30-80 | Fe/10 | 205 | 413 |
As mentioned above, can realize the present invention preferably.
Claims (7)
1, a kind of preparation method of nano alpha-nickel hydroxide comprises the steps and processing condition:
The first step is raw material with the divalent nickel salt, adds the doped metal salt that metal ion content is equivalent to divalent nickel salt mole number 5～25%, is mixed with the reaction soln that nickel ion concentration is 0.01～10mol/L with water dissolution;
The second step amount of taking is the potassium hydroxide or the sodium hydroxide of nickel ion mole number 200～300% in the described reaction soln, is mixed with potassium hydroxide or naoh concentration is the alkaline sedimentation agent solution of 0.05～12mol/L with water dissolution;
The 3rd step is in ultrasonic dispersing, carry out under the stirring condition simultaneously, described precipitant solution is joined in the described reaction soln, control precipitation agent rate of addition, make the pH value of reaction system between 7.0～11.5, temperature of reaction is 20～60 ℃, and the reaction times is 15～120 minutes, stops to stir after reaction finishes, continue to use ultrasonic dispersing 30～300 minutes, obtain green or glaucous nickel hydroxide precipitate;
The 4th step was washed with water to described nickel hydroxide precipitate the pH value of elutant for neutral, was dried to constant weight under the condition of vacuum and room temperature.
2, the preparation method of a kind of nano alpha-nickel hydroxide according to claim 1 is characterized in that, described divalent nickel salt comprises single nickel salt, nickelous nitrate or nickelous chloride.
3, the preparation method of a kind of nano alpha-nickel hydroxide according to claim 1 is characterized in that, described doped metal salt comprises one or more the mixture in trivalent aluminium salt, the trivalent iron salt.
4, the preparation method of a kind of nano alpha-nickel hydroxide according to claim 3 is characterized in that, described trivalent aluminium salt comprises aluminum nitrate, Tai-Ace S 150 or aluminum chloride.
5, the preparation method of a kind of nano alpha-nickel hydroxide according to claim 3 is characterized in that, described trivalent iron salt comprises ferric sulfate, iron(ic) chloride or iron nitrate.
6, the preparation method of a kind of nano alpha-nickel hydroxide according to claim 1 is characterized in that, described water comprises nature water, tap water, distilled water or deionized water.
7, a kind of nano alpha-nickel hydroxide for preparing according to each described preparation method of claim 1～6.
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