CN101060172B - Nano-sized nickel hydroxide/carbon composite material and its manufacture method and purpose - Google Patents
Nano-sized nickel hydroxide/carbon composite material and its manufacture method and purpose Download PDFInfo
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- CN101060172B CN101060172B CN2007100518082A CN200710051808A CN101060172B CN 101060172 B CN101060172 B CN 101060172B CN 2007100518082 A CN2007100518082 A CN 2007100518082A CN 200710051808 A CN200710051808 A CN 200710051808A CN 101060172 B CN101060172 B CN 101060172B
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Abstract
The disclosed preparation method for nano Ni(OH)3/C composite material comprises: on condition of ultrasonic vibrating, fast reacting the soluble nickel salt and strong base to generate the nano-size Ni(OH)3 and attach on carbon material uniformly. The product has super conductivity and charge/discharge performance. This invention is simple, high efficient, and low cost.
Description
Technical field
The present invention relates to a kind of nano-sized nickel hydroxide/carbon composite material and its production and use, belong to the nano composite material technical field.
Background technology
Urgent day by day global energy resource problem impels the research of electric automobile to enter a unprecedented upsurge.In to electric automobile research and development process, storage battery receives much attention as the key factor of restriction electric automobile development.Metal nickel hydride (MH/Ni) battery with its high specific energy, long-life, be fit to large current charge and discharge, excellent comprehensive characteristic such as pollution-free, be described as first-selected electric vehicle power accumulator.But this system is when being used for hybrid-power electric vehicle, and its high rate during charging-discharging also needs further to improve.
In order further to improve the performance of MH/Ni battery, to its positive electrode active materials Ni (OH)
2Development in, the researcher is on the one hand on the ball-shape nickel hydroxide basis of maturation, improving its performance by it being carried out means such as inside doping, finishing, then is to improve its performance by the novel nickel hydroxide for preparing different size, pattern on the other hand.Study on the modification to ball-shape nickel hydroxide is very ripe, and its effect mainly is can strengthen its conductivity, improve oxygen evolution potential, improve high-temperature charging efficient etc.But under the high current charge-discharge condition, electrochemical reaction mainly concentrates on micron-size spherical Ni (OH) fast
2Carry out on the top layer of particle, and this will inevitably cause the active material of particle depths can't be fully utilized under this kind condition, also just means the reduction of the specific capacity that discharges and recharges.To studies show that of novel nickel hydroxide (mainly being nano-sized nickel hydroxide), compare with common micron ball-shape nickel hydroxide, have bigger specific area, higher protolysis speed, littler grain resistance, activating velocity and higher electrochemistry capacitance etc. faster, show that the less relatively nano-sized nickel hydroxide of particle diameter is a kind of very promising material that can effectively solve the existing problem of positive electrode aspect high power applications.But, since have that the resistance of nickel hydroxide nano intergranule of characteristic of semiconductor is very big, the nano-sized nickel hydroxide material is easily reunited and when assembled battery nano-sized nickel hydroxide particle and conductive agent particle size ratio factor such as do not match, be difficult to mix, causing separately by nano-sized nickel hydroxide is not very desirable as the performance of the battery of active material assembling.So, make nano material characteristic be effectively played, must solve its problems referred to above that in the middle of battery applications, exist.
Summary of the invention
The object of the present invention is to provide a kind of nano-sized nickel hydroxide/carbon composite material that is suitable as the alkaline battery positive active material and its production and use, this nano-sized nickel hydroxide/carbon composite material has high power capacity, advantage that high rate during charging-discharging is strong, and the preparation method is simple, cost is low.
The technical scheme that realizes the object of the invention is a kind of Powdered composite material that nano-sized nickel hydroxide is arranged in powder carbon material surface uniform load for this nano-sized nickel hydroxide/carbon composite material.
And the weight percent content of nano-sized nickel hydroxide is 5%～95% in this composite material, and the weight percent content of material with carbon element is 95%～5%.
The preparation method of this nano-sized nickel hydroxide/carbon composite material provided by the invention is under the condition of ultrasonic vibration, react the yardstick that is generated rapidly by soluble nickel salt and highly basic and be attached to carbon material surface equably at nano level nickel hydroxide particulate, thereby obtain a kind of composite material of nano-sized nickel hydroxide/carbon, specifically comprise the steps:
(1) in the percentage by weight of material with carbon element in the middle of composite material is 95%～5% ratio, getting an amount of powder formed carbon material joins in the middle of the aqueous solution of soluble nickel salt that concentration is 0.01-5mol/L, 0.5%～5% the organic solvent that adds volume simultaneously and be above-mentioned liquor capacity is made dispersant, is that 20～50KHz, ultrasonic power are greater than 2W/cm with the mixed solution supersonic frequency that forms
2Ultrasonic vibration 5 to 180 minutes, wherein soluble nickel salt is a kind of in nickelous sulfate, nickel nitrate, nickel chloride or the nickel acetate;
(2) adding molar ratio with nickel salt then is 2～5: 1 strong base solution, continues with ultrasonic vibration 5 to 180 minutes;
(3) wash with water 2-5 time at last,, promptly obtain nano-sized nickel hydroxide/carbon composite material in 40--200 ℃ of dry 5--24 hour.
Wherein, used strong base solution is KOH, NaOH or LiOH. solution, and solution concentration is 0.1-5mol/L.
Used powder formed carbon material is a particle size at 0.001～50 micron acetylene black, carbon black, graphite or indefinite form carbon.
Used dispersant is one or more the mixing in methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol or acetone, the butanone.
Be especially suitable for use as the positive electrode active materials of alkaline battery with the nano-sized nickel hydroxide/carbon composite material of method for preparing.
By technical method provided by the invention as can be known, the present invention be utilize nano-sized nickel hydroxide particulate that the method for ultrasonic Treatment generates the scene in liquid phase directly equably spread loads in nanometer to micron-sized carbon back microparticle material surface, make both become a kind of compound material, so not only solved the nano-sized nickel hydroxide active material that exists in the prior art and disperseed difficult problem, and its conductivity problems also is resolved.So, the nano-meter characteristic of nano-sized nickel hydroxide just can be good at embodying, and confirms that by test it has excellent large current density electrical characteristics, and the utilance of active material also is improved.The effect of ultrasonic Treatment has two aspects among the present invention: be that the carbon carrier powder of adding can be disperseed fully on the one hand, thereby guarantee that nano-sized nickel hydroxide can generate on the surface of single carbon particulate uniformly, be the generation of guaranteeing nano-sized nickel hydroxide on the other hand, and can avoid prepared nano-sized nickel hydroxide to reunite.
One of advantage of the present invention is to adopt simple method to prepare nano-sized nickel hydroxide/carbon composite material, and this kind preparation method is fit to large-scale operation.Two of advantage of the present invention has solved scattering problem, the conductivity problems of nano-sized nickel hydroxide with being to settle at one go, saved the mixed process of nano-sized nickel hydroxide active material and conductive agent when electrode preparation, the process of sizing mixing is simplified greatly, thereby also can be reduced running cost.Electro-chemical test shows, this nano-sized nickel hydroxide composite material discharge and recharge good reversibility, cycle performance is good, and conductivity is significantly improved than the general spherical shape nickel hydroxide active material.When nano-sized nickel hydroxide/carbon composite material was used for nickel electrode, the capacity of nickel electrode and high current charge-discharge ability all were significantly improved.
Description of drawings
Fig. 1 is to be XRD (X-ray diffraction) figure of the nano-sized nickel hydroxide/carbon composite material (50wt%) of substrate with acetylene black, and the peak that * marks among the figure is the diffraction maximum of nickel hydroxide, and the peak that marks is the diffraction maximum of acetylene black substrate.
Fig. 2 is SEM (scanning electron microscopy) figure of acetylene black substrate.
Fig. 3 is SEM (scanning electron microscopy) figure of nano-sized nickel hydroxide/carbon composite material.
Fig. 4 is to be the cyclic voltammogram of the nano-sized nickel hydroxide/carbon composite material of substrate with acetylene black (50wt%).
Fig. 5 is to be the cyclic voltammogram of the nano-sized nickel hydroxide/carbon composite material of substrate with acetylene black (66.7wt%).
Fig. 6 is to be the cyclic voltammogram of the nano-sized nickel hydroxide/carbon composite material of substrate with acetylene black (33.3wt%).
Fig. 7 is the cyclic voltammogram of commercialization ball-shape nickel hydroxide.
Fig. 8 be commercialization ball-shape nickel hydroxide and carbon in the ratio of 50wt%: 50wt% directly mixed the cyclic voltammogram of composite material.
Fig. 9 is to be the cyclic voltammogram of the different cycles of nano-sized nickel hydroxide/carbon composite material of substrate with acetylene black (50wt%).
Embodiment
Nano-sized nickel hydroxide/carbon composite material provided by the invention is a kind of Powdered composite material that nano-sized nickel hydroxide is arranged in powder carbon material surface uniform load, the weight percent content of nano-sized nickel hydroxide is 5%～95% in the composite material, and the weight percent content of material with carbon element is 95%～5%.Material with carbon element is a particle size at 0.001～50 micron acetylene black, carbon black, graphite or indefinite form carbon, and the shared ratio of carbon support material is big more, and nano-sized nickel hydroxide is in its just easy more even dispersion of surface.But, when the material with carbon element too high levels and nickel hydroxide content when low, the volume and capacity ratio of active material will inevitably decrease, so should comprehensively weigh the appropriate adding proportion of material with carbon element, respectively be respectively 50% to be that example is described in detail only below, but the weight percent content of material with carbon element, nano-sized nickel hydroxide all can conversion between 5%～95% as required with the weight percent content of material with carbon element, nano-sized nickel hydroxide.
Embodiment 1: the weight percent content of nano-sized nickel hydroxide is the preparation of 50% nano-sized nickel hydroxide/carbon composite material.
Substrate raw material of wood-charcoal material can select for use particle size at 0.001～50 micron acetylene black, carbon black, graphite or indefinite form carbon, is example with acetylene black in the present embodiment.
1) compound concentration is the NiCl of 0.01-5.0mol/L
2Solution for later use also can be nickelous sulfate, nickel acetate or nickel nitrate solution with concentration;
2) compound concentration is the KOH solution of 0.1-5.0mol/L, also can be NaOH or LiOH solution with concentration;
3) preparation of nano-sized nickel hydroxide/carbon composite material: in proportion acetylene black is joined above-mentioned NiCl
2The aqueous solution in the middle of, add volume simultaneously and be above-mentioned liquor capacity 0.5%～5% ethanol or methyl alcohol, propyl alcohol, butanols, isopropyl alcohol, acetone, butanone is made dispersant, is that 20～50KHz, ultrasonic power are greater than 2W/cm with supersonic frequency
2Ultrasonic echography vibration after 5--180 minute, is the KOH solution for preparing that 2～5: 1 ratio adds in the middle of the above-mentioned mixed solution in the mol ratio with nickel salt, continued ultrasonic 5--180 minute, filter, after washing 2-5 time with water, can obtain nano-sized nickel hydroxide/carbon composite material of the present invention in 40-200 ℃ of dry 5--24 hour.The XRD of prepared nano-sized nickel hydroxide/carbon composite material, SEM figure respectively as shown in figures 1 and 3; Fig. 2 is the SEM figure of acetylene black substrate.From XRD figure, can significantly distinguish the typical diffraction maximum of carbon substrate and nickel hydroxide.In SEM figure, sized nickel hydroxide/carbon composite material is the single-size that particle diameter is about 90-100nm, and its particle diameter is significantly increased than the particle diameter of base material (about 50-60nm).Show that thus nano level nickel hydroxide particle is carried on the acetylene black surface of the about 50-60nm of particle diameter equably.
Embodiment 2: the weight percent content of nano-sized nickel hydroxide is the preparation of 33.3% nano-sized nickel hydroxide/carbon composite material.
The nano-sized nickel hydroxide weight percent content that with acetylene black is substrate is that the weight percent content of the preparation process of 33.3% nano-sized nickel hydroxide/carbon composite material and nano-sized nickel hydroxide is that the preparation process of 50% nano-sized nickel hydroxide/carbon composite material is identical, just the ratio difference of required reactant in the middle of preparation process.The weight of the acetylene black that adds in this preparation process is the weight twice of the nano-sized nickel hydroxide that generates in this preparation process.The circulation of the prepared nano-sized nickel hydroxide/carbon composite material curve (Fig. 5) of bending over the desk shows that the oxidation peak current potential of nickel is 0.460V, and the reduction peak current potential is 0.336V, and the spike potential difference is 0.124V, illustrates that this kind material also shows good conductivity and invertibity.Test after making simulated battery with this nano-sized nickel hydroxide composite material, its 1C discharge capacity is 288.7mAh (g-Ni (OH)
2)
-1
Embodiment 3: the weight percent content of nano-sized nickel hydroxide is the preparation of 66.7% nano-sized nickel hydroxide/carbon composite material.
The nano-sized nickel hydroxide weight percent content that with acetylene black is substrate is that the weight percent content of the preparation process of 66.7% nano-sized nickel hydroxide/carbon composite material and nano-sized nickel hydroxide is that the preparation process of 50% nano-sized nickel hydroxide/carbon composite material is identical, just the ratio difference of required reactant in the middle of preparation process.The weight of the acetylene black that adds in this preparation process be the nano-sized nickel hydroxide that generates in this preparation process weight half.The circulation of the prepared nano-sized nickel hydroxide composite material curve (Fig. 6) of bending over the desk shows that the oxidation peak current potential of nickel is 0.457V, and the reduction peak current potential is 0.334V, and the spike potential difference is 0.123V, illustrates that this kind material also shows good conductivity and invertibity.Test after making simulated battery with this nano-sized nickel hydroxide composite material, its 1C discharge capacity is 282.2mAh (g-Ni (OH)
2)
-1
What the performance verification of the nano-sized nickel hydroxide/carbon composite material of the present invention's preparation adopted is the cyclic voltammetric test, electrolytic cell is classical three-electrode system, and work electrode is 50 microns a microcavity electrode, is the nickel sheet to electrode, reference electrode is the Hg/HgO electrode, and electrolyte is the KOH solution of 6mol/L.The reason of microcavity electrode is selected in cyclic voltammetric test: avoid other additives such as binding agent to effect of material performance, the more essential chemical property to material characterizes.What discharge and recharge the experiment use also is three-electrode system, and negative pole is a commercialization hydrogen bearing alloy pole piece, and reference electrode is the Hg/HgO electrode, and electrolyte is the KOH solution of 6mol/L.
With embodiment 1 prepared nano-sized nickel hydroxide/carbon composite material is tested object, using diameter is that 50 microns microcavity electrode is as work electrode, with the nickel sheet is to electrode, and the Hg/HgO electrode is a reference electrode, carries out the cyclic voltammetric test in the middle of the KOH of 6mol/L solution.Fig. 4 is the cyclic voltammogram that records.As can be seen from the figure, the oxidation peak current potential of nickel hydroxide is 0.455V, and the reduction peak current potential is 0.341V, and the spike potential difference is 0.114V; And testing in the cyclic voltammogram (Fig. 7) of the pure commercialization ball-shape nickel hydroxide that records under the identical condition with above-mentioned cyclic voltammogram, the oxidation peak current potential of nickel hydroxide, reduction peak current potential and spike potential difference are respectively 0.575V, 0.326V and 0.249V.Clearly, compare with pure commercialization ball-shape nickel hydroxide, the electrochemical reaction of this kind nano-sized nickel hydroxide/carbon composite material is subjected to mass transport affects very little, and the invertibity of reaction obviously improves, and the conductivity of material also increases significantly.
In order further to verify the advantage that nano particle showed in the nano-sized nickel hydroxide/carbon composite material of the present invention, to with also carried out the cyclic voltammetric test by micron ball-shape nickel hydroxide and carbon by the composite material that 1: 1 mixed forms, the result as shown in Figure 8, the test condition of the cyclic voltammetric of its test condition and described nano-sized nickel hydroxide/carbon composite material is identical.From Fig. 8 and Fig. 7 more as can be known, add material with carbon element after, the conductivity of micron ball-shape nickel hydroxide also is significantly improved.But, with nano-sized nickel hydroxide/carbon composite material comparatively speaking, there are tangible broadening in the oxidation peak and the reduction peak of micron ball-shape nickel hydroxide/carbon composite, this oxidation peak and reduction peak broadening also just mean, on the one hand oarse-grained nickel hydroxide is difficult in the short time and finishes in the middle of charge and discharge process, and this will be unfavorable to high current charge-discharge; On the other hand in the middle of charging process, broadening oxidation peak with analyse the oxygen peak and easily produce overlapping, the adverse effect of oxygen evolution reaction is strengthened.Thus, nano-sized nickel hydroxide/carbon composite material of the present invention can demonstrate fully the electrochemistry advantage of nano material, preferably and big electric current discharge and recharge application.
In order to further specify the material cycle performance, (Fig. 9) is determined for the cyclic voltammetric of the different cycles of nano-sized nickel hydroxide/carbon composite material.Among the figure, the oxidation peak of nickel hydroxide and the spike potential of reduction peak remain unchanged substantially, have verified that material has good invertibity and cycle performance.By the efficiency for charge-discharge of represented this kind active material of the area ratio of reduction peak in the cyclic voltammogram of Fig. 4 and oxidation peak up to 93.01%.Test after making simulated battery with this nano-sized nickel hydroxide/carbon composite material, its 1C discharge capacity is 288.2mAh/g-Ni (OH)
2As seen this nano-sized nickel hydroxide/carbon composite material is especially suitable for use as the positive electrode active materials of alkaline battery.
Claims (6)
1. the preparation method of a nano-sized nickel hydroxide/carbon composite material, it is characterized in that under the condition of ultrasonic vibration, react the yardstick that is generated rapidly by soluble nickel salt and highly basic and be attached to carbon material surface equably at nano level nickel hydroxide particulate, thereby obtain a kind of nano-sized nickel hydroxide/carbon composite material, specifically comprise the steps:
(1) in the percentage by weight of material with carbon element in the middle of composite material is 95%～5% ratio, getting an amount of powder formed carbon material joins in the middle of the aqueous solution of soluble nickel salt that concentration is 0.01-5mol/L, 0.5%～5% the organic solvent that adds volume simultaneously and be above-mentioned liquor capacity is made dispersant, is that 20～50KHz, ultrasonic power are greater than 2W/cm with the mixed solution supersonic frequency that forms
2Ultrasonic vibration 5 to 180 minutes, wherein soluble nickel salt is a kind of in nickelous sulfate, nickel nitrate, nickel chloride or the nickel acetate;
(2) adding molar ratio with nickel salt then is 2～5: 1 strong base solution, continues with ultrasonic vibration 5 to 180 minutes;
(3) wash with water 2-5 time at last,, promptly obtain nano-sized nickel hydroxide/carbon composite material in 40--200 ℃ of dry 5--24 hour.
2. the preparation method of nano-sized nickel hydroxide/carbon composite material according to claim 1, it is characterized in that: strong base solution is KOH, NaOH or LiOH. solution, and solution concentration is 0.1-5mol/L.
3. the preparation method of nano-sized nickel hydroxide/carbon composite material according to claim 1 is characterized in that: the powder formed carbon material is a particle size at 0.001～50 micron acetylene black, carbon black, graphite or indefinite form carbon.
4. the preparation method of nano-sized nickel hydroxide/carbon composite material according to claim 1 is characterized in that: dispersant is one or more the mixing in methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol or acetone, the butanone.
5. the nano-sized nickel hydroxide/carbon composite material of the preparation method of the described nano-sized nickel hydroxide/carbon composite material of claim 1 preparation, it is characterized in that: it is a kind of Powdered composite material that nano-sized nickel hydroxide is arranged in powder carbon material surface uniform load, the weight percent content of nano-sized nickel hydroxide is 5%～95% in the composite material, and the weight percent content of material with carbon element is 95%～5%.
6. the described nano-sized nickel hydroxide/carbon composite material of claim 5 is as the positive electrode active materials of alkaline battery.
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| JP6178554B2 (en) * | 2012-09-03 | 2017-08-09 | 日本ケミコン株式会社 | Method for producing composite material of metal oxide and conductive carbon |
| CN104600277B (en) * | 2015-02-11 | 2017-03-29 | 武汉大学 | A kind of sized nickel hydroxide/carbon nano composite material of doping zinc and cobalt and its preparation method and application |
| CN109786767A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of zinc-nickel single flow battery positive electrode and its preparation and application |
| CN108054361A (en) * | 2017-12-11 | 2018-05-18 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of the carbon containing ball-shape nickel hydroxide composite material of alkaline secondary cell |
| CN110016337B (en) * | 2019-01-22 | 2021-10-26 | 复旦大学 | Preparation method of metal hydroxide quantum dots |
| CN112002564B (en) * | 2020-08-26 | 2021-09-07 | 郑州航空工业管理学院 | Electrode material of super capacitor, preparation method and application |
| CN112802689B (en) * | 2021-02-22 | 2022-08-16 | 重庆大学 | Porous activated carbon and alpha-Ni (OH) 2 Nanocomposite and method for preparing same |
| CN113120978B (en) * | 2021-04-19 | 2022-07-01 | 贵州源驰新能源科技有限公司 | A kind of Ni (OH)2And method for preparing the same |
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