CN102259936B - Preparation method of nano nickel cobalt oxide - Google Patents
Preparation method of nano nickel cobalt oxide Download PDFInfo
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- CN102259936B CN102259936B CN201110195864.XA CN201110195864A CN102259936B CN 102259936 B CN102259936 B CN 102259936B CN 201110195864 A CN201110195864 A CN 201110195864A CN 102259936 B CN102259936 B CN 102259936B
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Abstract
The invention provides a preparation method of nano nickel cobalt oxide. In the preparation method, an organic solvent is added during a precursor preparation process, an aqueous and organic mixed phase is used as a solvent, and nano nickel cobalt oxide with high purity, uniform particle size and good crystallinity is acquired by a co-precipitation method. By using the nano nickel cobalt oxide prepared by the preparation method as an electrode material for a supercapacitor, a higher specific capacitance (up to 348-617 F.g<-1>) can be acquired. The preparation method provided by the invention has the advantages that operation is simple, conditions are mild and easy to control and cost is low, is suitable for large-scale preparation, and is suitable for commercial production.
Description
Technical field
The present invention relates to a kind of electrode material for super capacitor: nano nickel cobalt oxide (NiCo
2o
4) preparation method.
Background technology
The oxide compound (oxyhydroxide) of transition metal Co, Ni, as Co
3o
4, α-CO(OH)
2, NiO and (Co+Ni) (OH)
2nH
2o is the material of current electrode material for super capacitor most study, and with the bimetallic oxide nano nickel cobalt oxide NiCo of spinel structure
2o
4do electrode material for super capacitor, the people of concern is also few.
Spinel NiCo
2o
4material has Stability Analysis of Structures, is better than electroconductibility and the reactive behavior of single metallic nickel, cobalt/cobalt oxide, is the first-selected research material in catalyticing research field, and other physicalies such as its magnetic properties are also one of focuses of research, still, and for spinel NiCo
2o
4the research of good electrochemical electrode material find, but only in 2002 by Hispanic study group report [R.Alc á ntara et al., Chem.Mater.2002,14,2847-2848], they find the NiCo of spinel structure
2o
4on anode material of lithium-ion battery, apply, there is good chemical property, and just be it is found that [Te-Yu Wei et al. for its late to 2009 of character year of excellent ultracapacitor, Adv.Mater.2009,21,1-5], the NiCo of spinel structure cheaply that the people such as the Hu of Taiwan National Tsing Hua University prepare by the method for epoxide extension
2o
4aerogel, there is 1400F g
-1ratio electric capacity, become alternative RuO
2one of most potential material.Spinel NiCo like this
2o
4the ultracapacitor character of material just starts to attract much attention.
For nano nickel cobalt oxide NiCo
2o
4the research of synthetic method also a lot, as thermolysis, co-precipitation, spraying thermolysis, co-precipitation, sol-gel etc.For high performance spinel structure NiCo
2o
4aerogel, it is a kind of super light material, there is very low mass density, continuous pore structure, high specific surface area and high electroconductibility, being the potential material of richness of battery and ultracapacitor, preparing the active electrode material of aerogel state, should be also the very effective means that improve electrode materials electric property.But prepare aerogel technique more complicated, laboratory or industrial operation are more difficult, therefore find more easy method and prepare high performance NiCo
2o
4it is one of problem that should solve at present.Afterwards, the people such as Vinay Gupta has found spinel structure NiCo prepared by electro-deposition method
2o
4, can obtain 580F g
-1ratio electric capacity [Vinay Gupta et al., J.Power Sources, 2010,195,3757-3760], although the method operation is relatively simple, greatly, production cost is higher in power consumption, and the NiCo for preparing of the method
2o
4, more relatively low than electric capacity as electrode material for super capacitor, be unfavorable for large-scale industrialization production.CN101549890B adopts organic solvent propyl carbinol or n-propyl alcohol and the water mixed solvent dispersion agent as nickel acetate and nickel acetate, the method of employing solvent thermal is prepared particle size and is less than 12nm, uniform nano nickel cobalt oxide material, owing to having used in reaction, autoclave, safety, in the handiness of operational condition regulation and control, all bring certain difficulty, make suitability for industrialized production bring certain difficulty.
Summary of the invention
The object of the invention is to overcome the defect of existing synthetic technology, a kind of cobalt acid nickel (NiCo is provided
2o
4) the coprecipitation method of nano particle, product purity of the present invention is high, and particle is thin, distribution of sizes homogeneous, and crystallinity is good.The prepared NiCo of the inventive method
2o
4for spinel structure, be of a size of 10nm left and right.Product nano nickel cobalt oxide material of the present invention is for electrode material for super capacitor, and the ratio electric capacity of product can reach 348～617Fg
-1.
Coprecipitation method can obtain that specific surface area is larger, particle diameter is less, more high conductivity, single-phase spinel NiCo
2o
4material, and simple to operate, easily obtains, and the present invention is by adding organic complexing agent/tensio-active agent to play a positive role at the particle size uniformity of product, the restriction aspects such as growth of reuniting, thereby obtains more preferably electrode material for super capacitor.
The present invention adopts the coprecipitation method under water and organic phase mixed phase, in the process of preparing presoma, adds organic solvent.
Sequence of process steps of the present invention is as follows:
1, weigh the Ni (NO that purity is 98.0%
3)
26H
2o and purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of organic reagent and deionized water jointly, and in described mixed solvent, organic reagent is any ratio with deionized water, is mixed with containing Ni
2+and Co
2+mixed salt solution A, in described mixed salt solution A, Ni
2+concentration be 0.01～1molL
-1, Co
2+concentration be 0.02～2molL
-1.Described organic reagent is that purity is the dimethyl formamide that 96.0% ethylene glycol or purity are 99.5%;
2, be that 96.0% sodium hydroxide is dissolved in organic reagent by purity, preparation amount of substance concentration is 0.05～5molL
-1the solution B of NaOH, metal-salt Ni (NO in mixed salt solution A described in NaOH amount of substance and step 1 in described solution B
3)
2and Co (NO
3)
2the ratio of total amount of substance is greater than 2, and described organic reagent is that purity is the dimethyl formamide that 96.0% ethylene glycol or purity are 99.5%;
3, the described mixed salt solution A at 0～80 ℃, step 1 being prepared all transfers in the solution B that step 2 prepares by dripping, stir on dropping limit, limit, dropwise, continue to stir 0.5～48h at 0～80 ℃, obtain precursor solution, in described precursor solution, the volume ratio of organic reagent ethylene glycol or dimethyl formamide and deionized water is 1～10:1;
4, described precursor solution whizzer step 3 being obtained separates with the rotating speed of 8000 revs/min, uses deionized water wash three times, makes presoma;
5, described presoma step 4 being made is dried 2～48h at 20～100 ℃ in air dry oven;
6, dry presoma step 5 being made is at 300～400 ℃, and in retort furnace, under atmosphere, sintering 2～24h obtains nano nickel cobalt oxide.
The inventive method is simple to operate, and mild condition and easily control, be suitable for preparation in enormous quantities, and cost is low, is suitable for commercially producing.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the cobalt acid nickel nano material prepared of embodiment 1 and embodiment 2;
Fig. 2 is HRTEM (high-resolution-ration transmission electric-lens) collection of illustrative plates of the cobalt acid nickel nano material prepared of embodiment 1;
Fig. 3 is the discharge and recharge collection of illustrative plates of the cobalt acid nickel nano material prepared of embodiment 1 as electrode materials.
Embodiment
Below knot and drawings and Examples are described in further detail the present invention.
Embodiment 1
1, weighing respectively 0.004mol purity is 98.0% Ni (NO
3)
26H
2o and 0.008mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 20ml organic reagent ethylene glycol and 80ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, in described mixed salt solution A, Ni
2+and Co
2+concentration is respectively 0.04molL
-1and 0.08molL
-1.Described organic reagent is that purity is 96.0% ethylene glycol;
2, the sodium hydroxide that is 96.0% by 0.026mol purity is dissolved in 270ml organic reagent ethylene glycol, and preparation amount of substance concentration is 0.096molL
-1the solution B 270ml of NaOH, described organic reagent is the ethylene glycol of purity 96.0%;
3, the 100ml mixed salt solution A at room temperature step 1 being prepared is added drop-wise in the solution B that 270ml step 2 prepares, stir on dropping limit, limit, dropwise, continue at room temperature to stir 18h, the precursor solution that the volume ratio that obtains ethylene glycol and deionized water is 3.625:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 48h at 80 ℃ in air dry oven;
6, by through the dry presoma of step 5 at 375 ℃, sintering 8h under atmosphere in retort furnace, obtains nano nickel cobalt oxide.The XRD figure of products therefrom is composed as shown in Figure 1, from collection of illustrative plates, can find out the generation of the nano nickel cobalt oxide of the spinel structure of single-phase, HRTEM collection of illustrative plates as shown in Figure 2, can be found out from collection of illustrative plates, the nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.Resulting materials is made electrode material for super capacitor and is done charge-discharge test, can reach 671Fg than electric capacity
-1.
Embodiment 2
1, weighing respectively 0.004mol purity is 98.0% Ni (NO
3)
26H
2o and 0.008mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 20ml organic reagent ethylene glycol and 80ml deionized water jointly, is mixed with Ni
2+and Co
2+mixed salt solution A100ml, in mixed salt solution A, Ni
2+and Co
2+concentration is respectively 0.04molL
-1and 0.08molL
-1..Described organic reagent is that purity is 96.0% ethylene glycol;
2, the sodium hydroxide that is 96.0% by 0.026mol purity is dissolved in 270ml organic reagent ethylene glycol, and preparation amount of substance concentration is 0.096molL
-1the solution B 270ml of NaOH, described organic reagent is that purity is 96.0% ethylene glycol;
3, the 100ml mixed salt solution A at room temperature step 1 being prepared is added drop-wise in the 270ml solution B that step 2 prepares, stir on dropping limit, limit, dropwise, continue to stir 18h under room temperature the precursor solution that the volume ratio that obtains ethylene glycol and deionized water is 3.625:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 48h at 80 ℃ in air dry oven;
6, by through the dry presoma of step 5 at 375 ℃, sintering 2h under atmosphere in retort furnace, obtains nano nickel cobalt oxide.The XRD figure of products therefrom is composed as shown in Figure 1, can find out the generation of the nano nickel cobalt oxide of the spinel structure of single-phase from collection of illustrative plates, and the nano nickel cobalt oxide material crystallinity of generation is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.Resulting materials is made electrode material for super capacitor and is done charge-discharge test, can reach 348Fg than electric capacity
-1.
Embodiment 3
1, weighing respectively 0.004mol purity is 98.0% Ni (NO
3)
26H
2o and 0.008mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 10ml organic reagent ethylene glycol and 40ml deionized water jointly, is mixed with Ni
2+and Co
2+mixed salt solution A50ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 0.08molL
-1and 0.16molL
-1.Described organic reagent is that purity is 96.0% ethylene glycol;
2, be that 96.0% sodium hydroxide is dissolved in 60ml organic reagent ethylene glycol by 0.03mol purity, preparation amount of substance concentration is 0.5molL
-1the solution B 60ml of NaOH, described organic reagent is that purity is 96.0% ethylene glycol;
3, the mixed salt solution A50ml at 0 ℃, step 1 being prepared is added drop-wise in the solution B 60ml that step 2 prepares, stir on dropping limit, limit, dropwise, continue to stir 48h at 0 ℃ the precursor solution that the volume ratio that obtains ethylene glycol and deionized water is 1.75:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 48h at 80 ℃ in air dry oven;
6, by 350 ℃ of the dry presomas of step 5, in retort furnace, under atmosphere, sintering 2h obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 4
1, weighing respectively 0.04mol purity is 98.0% Ni (NO
3)
26H
2o and 0.08mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 20ml organic reagent dimethyl formamide and 80ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 0.4molL
-1and 0.8molL
-1.Described organic reagent is that purity is 99.5% dimethyl formamide;
2, the sodium hydroxide that is 96.0% by 0.27mol purity is dissolved in 270ml organic reagent ethylene glycol, and preparation amount of substance concentration is 1molL
-1the solution B 270ml of NaOH, described organic reagent is that purity is 99.5% dimethyl formamide;
3, the mixed salt solution A100ml at room temperature step 1 being prepared is added drop-wise in the solution B 270ml that step 2 prepares, stir on dropping limit, limit, dropwise, continue at room temperature to stir 18h, the precursor solution that the volume ratio that obtains dimethyl formamide and deionized water is 3.625:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 24h at 60 ℃ in air dry oven;
6,, by 375 ℃ of the dry presomas of step 5, sintering 8h under atmosphere in retort furnace, obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.Resulting materials is made electrode material for super capacitor and is done charge-discharge test, can reach 374Fg than electric capacity
-1.
Embodiment 5
1, weighing respectively 0.001mol purity is 98.0% Ni (NO
3)
26H
2o and 0.002mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 25ml organic reagent dimethyl formamide and 25ml deionized water jointly, is mixed with Ni
2+and Co
2+mixed salt solution A50ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 0.02molL
-1and 0.04molL
-1.Described organic reagent is that purity is 99.5% dimethyl formamide;
2, the sodium hydroxide that is 96.0% by 0.12mol purity is dissolved in 200ml organic reagent dimethyl formamide, and preparation amount of substance concentration is 0.6molL
-1the solution B 200ml of NaOH, described organic reagent is that purity is 99.5% dimethyl formamide;
3, the mixed salt solution A50ml at 40 ℃, step 1 being prepared is added drop-wise in the solution B 200ml that step 2 prepares, stir on dropping limit, limit, dropwise, continue to stir 24h at 40 ℃ the precursor solution that the volume ratio that obtains dimethyl formamide and deionized water is 9:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 24h at 50 ℃ in air dry oven;
6,, by 350 ℃ of the dry presomas of step 5, sintering 12h under atmosphere in retort furnace, obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 6
1, weighing respectively 0.004mol purity is 98.0% Ni (NO
3)
26H
2o and 0.008mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 50ml organic reagent ethylene glycol and 50ml deionized water jointly, is mixed with Ni
2+and Co
2+mixed salt solution A100ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 0.04molL
-1and 0.08molL
-1.Described organic reagent is that purity is 96.0% ethylene glycol;
2, be that 96.0% sodium hydroxide is dissolved in 100ml organic reagent ethylene glycol by 0.025mol purity, preparation amount of substance concentration is 0.25molL
-1the solution B 100ml of NaOH, described organic reagent is that purity is 96.0% ethylene glycol;
3, the mixed salt solution A100ml at 35 ℃, step 1 being prepared is added drop-wise in the solution B 100ml that step 2 prepares, stir on dropping limit, limit, dropwise, continue to stir 20h at 35 ℃ the precursor solution that the volume ratio that obtains ethylene glycol and deionized water is 3:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 32h at 90 ℃ in air dry oven;
6, by 350 ℃ of the dry presomas of step 5, in retort furnace, under atmosphere, sintering 10h obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 7
1, weighing respectively 0.004mol purity is 98.0% Ni (NO
3)
26H
2o and 0.008mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 50ml organic reagent ethylene glycol and 50ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 0.04molL
-1and 0.08molL
-1.Described organic reagent is that purity is 96.0% ethylene glycol;
2, be that 96.0% sodium hydroxide is dissolved in 250ml organic reagent ethylene glycol by 0.025mol purity, preparation amount of substance concentration is 0.1molL
-1the solution B 250ml of NaOH, described organic reagent is that purity is 96.0% ethylene glycol;
3, the mixed salt solution A100ml at 35 ℃, step 1 being prepared is added drop-wise in the solution B 250ml that step 2 prepares, stir on dropping limit, limit, dropwise, stir 20h at continuing 35 ℃, the precursor solution that the volume ratio that obtains ethylene glycol and deionized water is 6:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 32h at 90 ℃ in air dry oven;
6, by 350 ℃ of the dry presomas of step 5, in retort furnace, under atmosphere, sintering 10h obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 8
1, weighing respectively 0.001mol purity is 98.0% Ni (NO
3)
26H
2o and 0.002mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 40ml organic reagent ethylene glycol and 40ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A80ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 0.0125molL
-1and 0.025molL
-1.Described organic reagent is that purity is 96.0% ethylene glycol;
2, be that 96.0% sodium hydroxide is dissolved in 200ml organic reagent ethylene glycol by 0.0135mol purity, preparation amount of substance concentration is 0.0675molL-
1the solution B 200ml of NaOH, described organic reagent is that purity is 96.0% ethylene glycol;
3, the mixed salt solution A80ml at room temperature step 1 being prepared is added drop-wise in the solution B 200ml that step 2 prepares, stir on dropping limit, limit, dropwise, continue at room temperature to stir 48h, the precursor solution that the volume ratio that obtains ethylene glycol and deionized water is 6:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 48h at 20 ℃ in air dry oven;
6, by 300 ℃ of the dry presomas of step 5, in retort furnace, under atmosphere, sintering 24h obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 9
1, weighing respectively 0.001mol purity is 98.0% Ni (NO
3)
26H
2o and 0.002mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 20ml organic reagent dimethyl formamide and 80ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 1molL
-1and 2molL
-1.Described organic reagent is that purity is 99.5% dimethyl formamide;
2, the sodium hydroxide that is 96.0% by 0.12mol purity is dissolved in 120ml organic reagent dimethyl formamide, and preparation amount of substance concentration is 1molL
-1the solution B 120ml of NaOH, described organic reagent is that purity is 99.5% dimethyl formamide;
3, the mixed salt solution A100ml at 80 ℃, step 1 being prepared is all added drop-wise in the solution B 120ml that step 2 prepares, stir on dropping limit, limit, dropwise, continue to stir 0.5h at 80 ℃ the precursor solution that the volume ratio that obtains dimethyl formamide and deionized water is 10:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 24h at 60 ℃ in air dry oven;
6,, by 360 ℃ of the dry presomas of step 5, sintering 2h under atmosphere in retort furnace, obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 10
1, weighing respectively 0.003mol purity is 98.0% Ni (NO
3)
26H
2o and 0.006mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 60ml organic reagent ethylene glycol and 60ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A120ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 0.025molL
-1and 0.05molL
-1.Described organic reagent is that purity is 96.0% ethylene glycol;
2, be that 96.0% sodium hydroxide is dissolved in 250ml organic reagent ethylene glycol by 0.025mol purity, preparation amount of substance concentration is 0.1molL
-1the solution B 250ml of NaOH, described organic reagent is that purity is 96.0% ethylene glycol;
3, the mixed salt solution A120ml at 35 ℃, step 1 being prepared is all added drop-wise in the solution B 250ml that step 2 prepares, stir on dropping limit, limit, dropwise, continue to stir 20h at 35 ℃ the precursor solution that the volume ratio that obtains ethylene glycol and deionized water is 5.167:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 32h at 90 ℃ in air dry oven;
6, by 350 ℃ of the dry presomas of step 5, in retort furnace, under atmosphere, sintering 10h obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 11
1, weighing respectively 0.001mol purity is 98.0% Ni (NO
3)
26H
2o and 0.002mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 50ml organic reagent dimethyl formamide and 50ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 0.01molL
-1and 0.02molL
-1.Described organic reagent is that purity is 99.5% dimethyl formamide;
2, the sodium hydroxide that is 96.0% by 0.12mol purity is dissolved in 200ml organic reagent dimethyl formamide, and preparation amount of substance concentration is 0.6molL
-1the solution B 200ml of NaOH, described organic reagent is that purity is 99.5% dimethyl formamide;
3, the mixed salt solution A100ml at 40 ℃, step 1 being prepared all transfers in the solution B 200ml that step 2 prepares by dripping, stir on dropping limit, limit, dropwise, continue to stir 24h at 40 ℃ the precursor solution that the volume ratio that obtains dimethyl formamide and deionized water is 5:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 24h at 50 ℃ in air dry oven;
6,, by 350 ℃ of the dry presomas of step 5, sintering 12h under atmosphere in retort furnace, obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 12
1, weighing respectively 0.1mol purity is 98.0% Ni (NO
3)
26H
2o and 0.2mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 40ml organic reagent ethylene glycol and 160ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A200ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 0.05molL
-1and 1molL
-1.Described organic reagent is that purity is 96.0% ethylene glycol;
2, be that 96.0% sodium hydroxide is dissolved in 135ml organic reagent ethylene glycol by 1.35mol purity, preparation amount of substance concentration is 10molL
-1the solution B 135ml of NaOH, described organic reagent is that purity is 96.0% ethylene glycol;
3, the mixed salt solution A200ml at room temperature step 1 being prepared all transfers in the solution B 135ml that step 2 prepares by dripping, stir on dropping limit, limit, dropwise, continue at room temperature to stir 2h, the precursor solution that the volume ratio that obtains ethylene glycol and deionized water is 1.094:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 2h at 100 ℃ in air dry oven;
6, by 400 ℃ of the dry presomas of step 5, in retort furnace, under atmosphere, sintering 2h obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 13
1, weighing respectively 0.007mol purity is 98.0% Ni (NO
3)
26H
2o and 0.014mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 30ml organic reagent dimethyl formamide and 40ml deionized water jointly, is mixed with Ni
2+and Co
2+mixed salt solution A70ml, Ni in A
2+and Co
2+concentration be respectively 1molL
-1and 2molL
-1.Described organic reagent is that purity is 99.5% dimethyl formamide;
2, the sodium hydroxide that is 96.0% by 0.12mol purity is dissolved in 200ml organic reagent dimethyl formamide, and preparation amount of substance concentration is 0.6molL
-1the solution B 200ml of NaOH, described organic reagent is that purity is 99.5% dimethyl formamide;
3, the mixed salt solution A70ml at 50 ℃, step 1 being prepared is added drop-wise in the solution B 200ml that step 2 prepares, stir on dropping limit, limit, dropwise, continue to stir 24h at 50 ℃ the precursor solution that the volume ratio that obtains dimethyl formamide and deionized water is 5.75:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 24h at 60 ℃ in air dry oven;
6,, by 350 ℃ of the dry presomas of step 5, sintering 4h under atmosphere in retort furnace, obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 14
1, weighing respectively 0.001mol purity is 98.0% Ni (NO
3)
26H
2o and 0.002mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 50ml organic reagent dimethyl formamide and 50ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 0.01molL
-1and 0.02molL
-1.Described organic reagent is that purity is 99.5% dimethyl formamide;
2, the sodium hydroxide that is 96.0% by 0.12mol purity is dissolved in 200ml organic reagent dimethyl formamide, and preparation amount of substance concentration is 0.6molL
-1the solution B 200ml of NaOH, described organic reagent is that purity is 99.5% dimethyl formamide;
3, the mixed salt solution A100ml at 50 ℃, step 1 being prepared is all added drop-wise in the solution B 200ml that step 2 prepares, stir on dropping limit, limit, dropwise, continue to stir 24h at 50 ℃ the precursor solution that the volume ratio that obtains dimethyl formamide and deionized water is 5:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 24h at 60 ℃ in air dry oven;
6,, by 350 ℃ of the dry presomas of step 5, sintering 4h under atmosphere in retort furnace, obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 15
1, weighing respectively 0.1mol purity is 98.0% Ni (NO
3)
26H
2o and 0.2mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 20ml organic reagent ethylene glycol and 80ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 1molL
-1and 2molL
-1.Described organic reagent is that purity is 96.0% ethylene glycol;
2, be that 96.0% sodium hydroxide is dissolved in 270ml organic reagent ethylene glycol by 1.35mol purity, preparation amount of substance concentration is 5molL
-1the solution B 270ml of NaOH, described organic reagent is that purity is 96.0% ethylene glycol;
3, the mixed salt solution A100ml at room temperature step 1 being prepared all transfers in the solution B 270ml that step 2 prepares by dripping, stir on dropping limit, limit, dropwise, continue at room temperature to stir 2h, the precursor solution that the volume ratio that obtains ethylene glycol and deionized water is 3.625:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 2h at 100 ℃ in air dry oven;
6, by 400 ℃ of the dry presomas of step 5, in retort furnace, under atmosphere, sintering 2h obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Embodiment 16
1, weighing respectively 0.0075mol purity is 98.0% Ni (NO
3)
26H
2o and 0.015mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 70ml organic reagent dimethyl formamide and 80ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A150ml, Ni in mixed salt solution A
2+and Co
2+concentration be respectively 0.4molL
-1and 0.8molL
-1.Described organic reagent is that purity is 99.5% dimethyl formamide;
2, the sodium hydroxide that is 96.0% by 0.05mol purity is dissolved in 50ml organic reagent ethylene glycol, and preparation amount of substance concentration is 1molL
-1the solution B 50ml of NaOH, described organic reagent is that purity is 99.5% dimethyl formamide;
3, the mixed salt solution A150ml at room temperature step 1 being prepared is all added drop-wise in the solution B 50ml that step 2 prepares, stir on dropping limit, limit, dropwise, continue at room temperature to stir 18h, the precursor solution that the volume ratio that obtains dimethyl formamide and deionized water is 1.5:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 24h at 60 ℃ in air dry oven;
6,, by 375 ℃ of the dry presomas of step 5, sintering 8h under atmosphere in retort furnace, obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.Resulting materials is made electrode material for super capacitor and is done charge-discharge test, can reach 374Fg than electric capacity
-1.
Embodiment 17
1, weighing respectively 0.004mol purity is 98.0% Ni (NO
3)
26H
2o and 0.008mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 20ml organic reagent ethylene glycol and 80ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution mixed salt solution A100ml, Ni in A
2+and Co
2+concentration be respectively 0.04molL
-1and 0.08molL
-1.Described organic reagent is that purity is 96.0% ethylene glycol;
2, be that 96.0% sodium hydroxide is dissolved in 60ml organic reagent ethylene glycol by 0.03mol purity, preparation amount of substance concentration is 0.5molL
-1the solution B 60ml of NaOH, described organic reagent is that purity is 96.0% ethylene glycol;
3, the mixed salt solution A100ml at 0 ℃, step 1 being prepared all transfers in the solution B 60ml that step 2 prepares by dripping, stir on dropping limit, limit, dropwise, continue to stir 48h at 0 ℃ the precursor solution that the volume ratio that obtains ethylene glycol and deionized water is 1:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 48h at 80 ℃ in air dry oven;
6, by 350 ℃ of the dry presomas of step 5, in retort furnace, under atmosphere, sintering 2h obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 15nm left and right.
Embodiment 18
1, weighing respectively 0.001mol purity is 98.0% Ni (NO
3)
26H
2o and 0.002mol purity are 99.0%Co (NO
3)
26H
2o, described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2the ratio of the amount of O is 1:2.By described Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of 20ml organic reagent ethylene glycol and 80ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, Ni in the molten A of mixed metal salt
2+and Co
2+concentration be respectively 0.01molL
-1and 0.02molL
-1.Described organic reagent is that purity is 96.0% ethylene glycol;
2, be that 96.0% sodium hydroxide is dissolved in 270ml organic reagent ethylene glycol by 0.0135mol purity, preparation amount of substance concentration is 0.05molL
-1the solution B 270ml of NaOH, described organic reagent is that purity is 96.0% ethylene glycol;
3, the mixed salt solution A100ml at room temperature step 1 being prepared is dripped and is all transferred in the solution B 270ml that step 2 prepares by dropping, stir on dropping limit, limit, dropwise, continue at room temperature to stir 48h, the precursor solution that the volume ratio that obtains ethylene glycol and deionized water is 3.625:1;
4, precursor solution step 3 being obtained separates with the rotating speed of 8000 revs/min with whizzer, uses deionized water wash three times, makes presoma;
5, presoma step 4 being made is dried 48h at 20 ℃ in air dry oven;
6,, by 300 ℃ of dry presomas, in retort furnace, under atmosphere, sintering 24h obtains nano nickel cobalt oxide.The nano nickel cobalt oxide material crystallinity that generates is good, distribution of sizes homogeneous, and particle diameter is in 10nm left and right.
Claims (7)
1. a preparation method for nano nickel cobalt oxide, is characterized in that, described preparation method comprises the following steps:
(1) by Ni (NO
3)
26H
2o and Co (NO
3)
26H
2o is dissolved in the mixed solvent of organic reagent and deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A;
(2) sodium hydroxide NaOH is dissolved in organic reagent to the solution B of preparation NaOH;
(3) the described mixed salt solution A of step (1) preparation is all added drop-wise in the described solution B of step (2) preparation, stir on dropping limit, limit, dropwises and continue to stir, and obtains precursor solution;
(4) described precursor solution whizzer step (3) being obtained separates with the rotating speed of 8000 revs/min, uses deionized water wash three times, makes presoma;
(5) described presoma step (4) being made is dry in air dry oven;
(6) dry described presoma step (5) being made in retort furnace under atmosphere sintering, obtain described nano nickel cobalt oxide;
Described organic reagent is that purity is the dimethyl formamide that 96.0% ethylene glycol or purity are 99.5%.
2. the preparation method of nano nickel cobalt oxide according to claim 1, it is characterized in that, in described organic reagent and the mixed solvent of deionized water, organic reagent is any ratio with the ratio of deionized water, and described organic reagent is that purity is the dimethyl formamide that 96.0% ethylene glycol or purity are 99.5%.
3. the preparation method of nano nickel cobalt oxide according to claim 1, is characterized in that, in described mixed salt solution A, and Ni
2+and Co
2+the ratio of amount be 1:2, Ni
2+concentration be 0.01～1molL
-1, Co
2+concentration be 0.02～2molL
-1.
4. the preparation method of nano nickel cobalt oxide according to claim 1, is characterized in that, in described solution B, and Ni(NO in NaOH and described mixed salt solution A
3)
2and Co (NO
3)
2the ratio of the total amount of substance concentration that is greater than 2, NaOH be 0.05～5molL
-1.
5. the preparation method of nano nickel cobalt oxide according to claim 1, is characterized in that, in the described precursor solution of acquisition, the volume ratio of organic reagent ethylene glycol or dimethyl formamide and water is 1～10:1.
6. the preparation method of nano nickel cobalt oxide according to claim 1, is characterized in that, in presoma preparation process, the temperature of reaction is 0～80 ℃, dropwises rear continuation and stirs 0.5～48h, and drying temperature is 20～100 ℃, and the dry time is 2～48h.
7. the preparation method of nano nickel cobalt oxide according to claim 1, is characterized in that, sintering temperature is 300～400 ℃, and the time is 2～24h.
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| CN105399149B (en) * | 2015-11-24 | 2017-09-29 | 张铭朔 | A kind of preparation method of electrode material for super capacitor |
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| CN106698527A (en) * | 2016-11-25 | 2017-05-24 | 江苏大学 | Hydrothermal method for preparing nanometer nickel cobaltate by taking ethylene glycol and water as solvent system |
| CN107459068A (en) * | 2017-08-31 | 2017-12-12 | 吕梁学院 | A kind of homogeneous precipitation method prepares NiCo2O4The method of powder and application |
| CN110395774B (en) * | 2019-07-19 | 2022-04-08 | 五邑大学 | Preparation method and application of nickel cobaltate porous material |
| CN114260014A (en) * | 2021-12-28 | 2022-04-01 | 盐城师范学院 | NiCo2O4/CeO2Composite catalyst and preparation method and application thereof |
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