CN101982402A - Multi-element doped nano alpha-Ni(OH)2 material and preparation method thereof - Google Patents
Multi-element doped nano alpha-Ni(OH)2 material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multi-element doped nano alpha-Ni(OH)2 material and a preparation method thereof. The multi-element doped nano alpha-Ni(OH)2 material is prepared by using an ultrasonic co-precipitation method and simultaneously doping 2 to 5 kinds of metal ions to substitute nickel ions; a reactor is placed in an ultrasonic cleaner vibrating cavity, and the whole reaction process of reactants containing multiple metal ions is performed in an ultrasonic vibrating environment so that the generated nano particles have small particle size, narrow distribution, good dispersity and high activity; 8 weight percent of four-element doped nano alpha-Ni(OH)2 prepared by the method and industrial micro nickel spheres are mixed to prepare a composite electrode, the 0.5C discharge capacity of the composite electrode is 346mAh/g and is 9mAh/g higher than the 0.1C discharge capacity, and other various electrochemical performance indexes of the composite electrode such as discharge platform, cycle life and the like are superior to those of a low-element doped electrode; and the multi-element doped nano alpha-Ni(OH)2 is suitable to be used as a nickel-hydrogen battery anode active material, and particularly suitable to be used as an anode material for high-power rechargeable batteries of electric vehicles, electric tools and the like.
Description
Technical field
The present invention relates to α phase nano-sized nickel hydroxide of a kind of multi-element doping and preparation method thereof, belong to nano composite material and advanced field of energy source materials.
Background technology
As the nickel hydroxide of anode of nickel-metal hydride battery active material, two kinds of crystal formations of α type and β type are arranged.Because β-Ni (OH)
2Theoretical capacity be 289mAh/g only, and easy generating electrodes expands when overcharging, and α-Ni (OH)
2Theoretical capacity be 482mAh/g, and in electrode charge and discharge process, be difficult for expanding, therefore receive the more concern of people in recent years.But, α-Ni (OH)
2Poor stability in the alkaline electrolyte of high concentration is converted into β-Ni (OH) easily
2, and because of its surperficial dangling bonds are many, particle is easily reunited, and therefore bad dispersibility is not applied in the production so far.Solving stability problem mainly is the method that other metal ions of employing partly replace nickel ion, synthetic α-Ni (OH)
2Stability improves in highly basic.Single at present the doping and binary doped nanometer α-Ni (OH)
2Existing patent report is as patent ZL 200510050318.1, CN 1322677A and CN1772629A etc.But single doping or binary (low unit) doping only is suitable for low range and discharges and recharges, and the chemical property of electrode is no longer stable during high magnification, is easy to degenerate, and discharge capacity sharply reduces.On the other hand, with conventional preparation nanometer α-Ni (OH)
2The nano particle that makes of method (precipitation method, solid phase method etc.) easily reunite, for solving above-mentioned two aspect problems, the present invention proposes new method.
Though nanometer α-Ni (OH)
2Very high activity is arranged, but its tap density is low, because the battery of certain specification, its volume is certain, so should not be with pure nanometer α-Ni (OH)
2Make the active material of electrode.Therefore adopt with certain proportion nanometer α-Ni (OH)
2Be incorporated in the industrial micron order ball nickel and make compound nickel electrode, like this, make nanometer α-Ni (OH)
2High activity and two advantage mutual superposition of high density of industrial ball nickel, thereby improve the discharge capacity of electrode.
Summary of the invention
The object of the present invention is to provide the nanometer α-Ni (OH) of a kind of epigranular, active high, high rate during charging-discharging is good, the overcharging resisting ability is strong multiple element doping
2Material and preparation method thereof.Replace α-Ni (OH) at unit or low unit
2The problem of high magnification chemical property difference, the present invention proposes to prepare nanometer α-Ni (OH) with the method for mixing multiple metallic element simultaneously
2, the nanometer α of this multi-element doping-Ni (OH)
2Have desirable fault of construction, it is with after industrial ball nickel mixes, and the high-rate charge-discharge capability of its electrode is significantly increased when mixing than low unit.Multiple doping nano α-Ni (OH)
2Material is prepared from by the ultrasonic wave coprecipitation, this method is that reaction vessel is inserted in the ultrasonic cleaner vibration cavity, reactant is all carried out in the ultrasonic vibration environment in entire reaction course, by ultrasonic cavitation effect, fuel factor and mechanical effect, acceleration nucleus generating rate also suppresses the coalescent of crystal grain and grows up, under the synergy of ultrasonic wave and solution dispersant, make the nanometer α-Ni (OH) of generation
2Particle is tiny, even, good dispersion and Stability Analysis of Structures.
A kind of multiple doping nano α-Ni provided by the invention (OH)
2Material mixes 2～5 kinds of metallic elements simultaneously, and the metallic element that mixes is any combination of Al, Co, Zn, Y, Ca, Cu, Mg, Fe, and the total content of metal ion accounts for 5%～60% of nickelous molal quantity.
Embodiment of the present invention are described below:
One, the ultrasonic wave coprecipitation prepares multiple doping nano α-Ni (OH)
2The method of material has following steps:
(1) be the commercial nickel salting liquid of 0.05～1.0mol/l and the salting liquid of 0.05～1.0mol/l doped chemical M with the deionized water configuration concentration, wherein nickel salt is a kind of in nickel nitrate, nickelous sulfate or the nickel chloride, doped chemical M is 2～5 kinds among Al, Co, Zn, Y, Ca, Cu, Mg, the Fe, slaine is chlorate or nitrate or sulfate, and the mol ratio of doping is: M
N+/ Ni
2+=5～60%; Add the dispersant that accounts for nickel hydroxide theoretical yield 1%～5% mass percent again, make the mixed solution of nickel salt;
(2) with the deionized water configuration concentration be the industrial caustic solution of 0.1～2.0mol/l, in the caustic-alkali aqueous solution adding alkali lye with an amount of ammoniacal liquor or ammonium, stir, make the caustic-alkali aqueous solution that contains ammonia or ammonium 0.1～2.0mol/l;
(3) two kinds of aqueous solution making in step (1) and the step (2) are gone into to place reaction vessel in the ultrasonic cleaner vibration cavity with 15～30 speed of per minute and drip, entire reaction course is all carried out in the ultrasonic vibration environment, keep temperature of reaction system, pH value and mixing speed constant simultaneously, wherein temperature remains on certain value, pH value certain value between 8～11 of room temperature～60 ℃, and mixing speed is certain value of 150～1000 rev/mins; After reactant drips, continue stir about 5 hours until reacting completely, still aging then washing and filtering is dried to constant weight with 60～100 ℃, takes out nanometer α-Ni (OH) that grinding obtains multi-element doping
2Powder.
Dispersant in the above-mentioned steps (1) is a kind of in polyethylene glycol or the Tween-80.
Industrial caustic alkali in the above-mentioned steps (2) is a kind of in NaOH or the potassium hydroxide.
Ultrasonic power in the above-mentioned steps (3) is 50～80W, and frequency is 40～100KHz.
Two, combination electrode preparation and discharge and recharge experimental procedure:
(1) multiple doping nano α-Ni (OH) that embodiment one is prepared
2Sample mixes with 85%～90% (mass ratio) industrial micron order ball nickel and conductive agent, binding agent and distilled water with 5%～10% (mass ratio) and loads on the electrode base sheet, dry compressing tablet then and make positive plate for nickel-hydrogen cell, the negative plate preparation method is identical with positive plate, and its slurry is the homogeneous mixture of hydrogen bearing alloy, conductive agent, binding agent and distilled water.
(2) positive and negative plate and diaphragm paper the are sandwiched open simulated battery of type, it is excessive to get negative pole, simulated battery is placed electrolyte, and electrolyte is the aqueous solution of 6～8mol/l KOH or the mixed solution of 6～8mol/l KOH and 0.5～1.0mol/l LiOH.
(3) change into: with 0.1C electric current constant-current charge, 0.1C is discharged to 1.0V then, carries out 3 activation under the room temperature, makes battery capacity reach stable.
(4) discharge and recharge setting: the activation finish after to electrode carry out 0.1C, 0.2C respectively, 0.5C discharges and recharges experiment.Overcharge 10%～20% of theoretical capacity, again with the different multiplying constant-current discharge to 1.0V.Cycle-index 100～300 is set.For reducing systematic error and objective condition error, guarantee that data are reliable, the electrode of the same terms is surveyed 5 groups simultaneously under same multiplying power.
Three, cyclic voltammetric characteristic (CV) and AC impedance (EIS) testing procedure:
(1) test anodal cyclic voltammetric characteristic with automatic sensitivity and different scanning speed, its voltage range is-0.2～0.7V.
(2) zero volt voltage conditions is tested anodal ac impedance spectroscopy (EIS) down, and charged state is 100%, frequency range 100～100000Hz.
Description of drawings
Fig. 1 is multiple doping nano α-Ni (OH)
2The X-ray diffraction of sample (XRD) collection of illustrative plates.A:Co, Al mix; B:Co, Al, Y mix; C:Co, Al, Y, Zn mix.
Fig. 2 is the particle size distribution figure of c sample.
Fig. 3 is anodal A, B, the cyclic voltammetric characteristic curve of C under the sweep speed of 0.1V/s that a, b, c sample are mixed and made into 8% ratio and industrial ball nickel respectively.
Fig. 4 is the cyclic voltammetric characteristic curve that A, B, C electrode record under different scanning speed.
Fig. 5 is that A, B, C anodizing peak current density change figure with 1/2 power of sweep speed.
Fig. 6 is the ac impedance spectroscopy of A, B, C electrode.
Fig. 7 is A, B, the charging and discharging curve of C electrode under the 0.1C multiplying power.
Fig. 8 is A, B, the charging and discharging curve of C electrode under the 0.5C multiplying power.
Fig. 9 is A, B, the C electrode cycle life relation under 0.5C multiplying power discharging condition.
Figure 10 adds ultrasonic wave and does not add Co, the Al dopen Nano α-Ni (OH) that makes under the ultrasonic wave situation
2The XRD figure spectrum of sample.E is the sample that makes under the 60W ultrasonic wave condition, and f is the sample when not adding ultrasonic wave.
Figure 11 is nanometer α-Ni (OH) that the Co, the Al that prepare under the different pH condition mix
2The XRD figure spectrum of sample.The pH value of sample g, h, i is respectively 8,9,10.
The specific embodiment
Below in conjunction with embodiment the present invention is described in further detail, the present invention is not limited to these examples.
Prepared two, three respectively, four kind of nanometer α-Ni (OH) that metallic element mixes simultaneously
2Powder, and its structure, particle diameter and chemical property carried out the system testing analysis.
(1) sample preparation and structure and testing graininess
By the mol ratio of embodiment one step preparation Ni: Al: Co 1: 0.25: 0.24 0.5mol/l Ni (Cl)
26H
2O, Al
2(SO
4)
318H
2O and Co (NO
3)
26H
2O solution 50ml, and add 0.15g (mass ratio 2%)) Tween-80.Na (OH) the solution 50ml of preparation 1.4mol/l also adds 3ml ammoniacal liquor and the 0.06g natrium carbonicum calcinatum.Above two kinds of solution and drip be added to place (power 60W in the ultrasonic cleaner vibration cavity, frequency 60KHz) stirs in the reaction vessel and constantly, control rate of addition (30 droplets/minute) and mixing speed (400 rev/mins), make temperature of charge remain on 50 ± 2 ℃, the pH value remains on 9.00 ± 0.10.After being added dropwise to complete, continue to stir 5 hours.Still aging then washing and filtering, takes out synthetic grinding and obtains sample a more than 18 hours with 90 ℃ of dryings.It is 1: 0.25: 0.24 that same employing said method prepares mol ratio Ni: Al: Co: Y respectively: 0.05 sample b and mol ratio Ni: Al: Co: Y: Zn are 1: 0.25: 0.24: 0.05: 0.05 sample c, wherein aluminium, cobalt, yttrium, zinc salt are respectively aluminum sulfate, cobalt nitrate, yttrium chloride and zinc sulfate.Fig. 1 is the XRD spectrum of three samples.As seen from the figure, diffraction maximum broadening degree is c, b, a successively, and relative intensity is a, b, c, and c is in the diffraction maximum complete obiteration of (015) crystal face, and b is difficult for differentiating, and a then obviously as seen.Hence one can see that, and the sample grain size of four kinds of element dopings during than three kinds of element dopings is little, and degree of crystallinity is poor, and three kinds of element dopings are littler than two kinds of element doping grain sizes, and degree of crystallinity is poor.By present research theory, the defective of crystal structure or imperfection will help improving electrode in highly basic stability and improve chemical property.The laser particle size test result of c sample as shown in Figure 2.Among the figure as seen, narrow particle size distribution (uniform particles), average grain diameter is 49.3nm.The average grain diameter that records a, b sample with quadrat method is respectively 61.1,59.4nm.
(2) electrode preparation
By (1) step in the embodiment two, respectively sample a, b, c are made combination electrode A, B, C with the industrial ball nickel of 8% (mass ratio) and 88% (mass ratio) and conductive agent, binding agent, distilled water after mixing.
(3) electrochemical property test
Respectively cyclic voltammetric characteristic, ac impedance spectroscopy, discharge capacity and the cycle life of electrode A, B, C are tested by the method that embodiment two, three is described.
Fig. 3 is the cyclic voltammetric characteristic curve that three kinds of electrodes record under the sweep speed of 0.1V/s.List in the table 1 by the electrode parameter that curve records.Table 1 as seen, the difference Δ E of oxidation peak voltage and reduction peak voltage
OR(V) size order is: electrode C＜electrode B＜electrode A, and analyse the poor (E of oxygen peak voltage and oxidation peak voltage
OER-E
O) size order is: electrode C＞electrode B＞electrode A.This shows that electrode C has higher invertibity and charge efficiency, and B takes second place, and A is the poorest.
Table 1
The cyclic voltammetric characteristic curve that three kinds of electrodes record under different scanning speed as shown in Figure 4, along with the increase of sweep speed, oxidation peak moves and reduction peak moves to negative direction slightly to positive direction.Fig. 5 is the 1/2 power mappings of three kinds of anodizing peak current density to sweep speed, and the result is a straight line, and this illustrates that this system is the reversible system of diffusing step control.Its straight slope electrode C maximum, B takes second place, the A minimum.Hence one can see that, and corresponding diffusion of protons coefficient magnitude is in proper order: electrode C＞electrode B＞electrode A.
The ac impedance spectroscopy of three kinds of electrodes as shown in Figure 6.Show three electrode solution resistance R among the figure
LMuch at one, and charge transfer resistance R
tA great difference is arranged, and (diameter of figure line semicircle is big more, R
tBig more), the result is R
T, C＜R
T, B＜R
T, ATherefore electrode C has maximum diffusion of protons coefficient and minimum charge transfer resistance, and this illustrates that being added with of multiple element is beneficial to the electrochemical behavior that improves nickel hydroxide electrode.
Fig. 7 is the high specific capacity charging and discharging curves of three kinds of electrodes under the 0.1C multiplying power.As can be seen, the charge efficiency of electrode C is the highest among the figure, and discharge capacity is also the highest, reaches 337mAh/g, and other two electrodes are smaller.The discharge platform of going back show electrode C among the figure also is higher than A, B electrode.
Fig. 8 is the high specific capacity charging and discharging curves of three kinds of electrodes under the 0.5C multiplying power.Among the figure as can be seen, the charge efficiency of electrode C far above the back both, the electrode parameter of C-V characteristic in the table 1 test has also well confirmed this point.It should be noted that, increase discharge-rate, the specific discharge capacity of electrode C does not only reduce to increase on the contrary, and its 0.5C discharge capacity reaches 346mAh/g, than increasing 9mAh/g under the 0.1C discharge-rate condition, A, B electrode then increase discharge capacity with discharge-rate and sharply reduce.
Fig. 9 is the cycle life relations of three kinds of electrodes under the 0.5C multiplying power.As seen from the figure, through 40 circulations, electrode A, the capacitance fade rate R of B and C
dBe respectively 13%, 6.3% and 3.5%, visible electrode C has the highest electric capacity conservation rate, and B takes second place, and A is the poorest.
The present embodiment explanation, nanometer α-Ni (OH) that quaternary is mixed
2Account for the combination electrode of 8wt.%, its every chemical property index all electrode when containing binary or ternary doping is good, especially more demonstrates the superiority of multi-element doping under the high magnification.
Embodiment 2
In order to determine ultrasonic wave to the physical characteristic of material and the influence of chemical property, present embodiment is two groups of samples of (other conditions are identical) preparation under adding ultrasonic wave and not adding two kinds of situations of ultrasonic wave respectively, and its structure and specific discharge capacity have been done test and contrast.
By the mol ratio of embodiment one step preparation Ni: Al: Co 1: 0.10: 0.17 0.5mol/l Ni (Cl)
26H
2O, Al
2(SO
4)
318H
2O and Co (NO
3)
26H
2O solution 50ml also adds 0.12g (mass ratio 2%) Tween-80.Na (OH) the solution 50ml of preparation 1.4mol/l also adds ammoniacal liquor 3ml and the 0.06g natrium carbonicum calcinatum.Two kinds of solution and drip are added to and place (power 60W in the ultrasonic cleaner vibration cavity, frequency 60KHz) stirs in the reaction vessel and constantly, control rate of addition (30 droplets/minute) and mixing speed (500 rev/mins), make that the solution reaction temperature remains on 50 ± 2 ℃ in the reaction vessel, the pH value remains on 9.00 ± 0.10.After being added dropwise to complete, continue to stir 5 hours.Leave standstill the battle arrayization washing and filtering then, synthetic with 90 ℃ of dryings 18 hours, is taken out to grind and obtains sample e.As a comparison case, other conditions are same as described above, and different is that whole experiment does not add ultrasonic wave, and the sample that makes is designated as f.Figure 10 is e, the XRD figure spectrum of f sample.As seen, e sample diffraction maximum has tangible broadening than f among the figure, illustrates that adding ultrasonic wave energy makes powder granule become tiny.Table 2 is interplanar distances of the main crystal face that calculated by Figure 10, and the sample that data further specify under the ultrasonic wave condition in the table has less crystal particle diameter.Make combination electrode by embodiment two steps, discharge and recharge under the 0.2C multiplying power, the maximum specific discharge capacity of combination electrode that records the e sample respectively is 308mAh/g, and the combination electrode of f sample is 294mAh/g.As seen, add ultrasonic wave energy and make the particle of generation tiny, the dispersed raising, thus active high, the electrode specific capacity is increased.
Table 2
| Sample | d 003/nm | d 006/nm | d 012/nm | d 113/nm |
| e(60w) | 1.0815 | 0.6901 | 0.5628 | 0.9006 |
| f(0w) | 1.1982 | 1.0144 | 0.7752 | 1.1231 |
Present embodiment has been studied doping ratio to nanometer α-Ni (OH)
2The influence of material discharging capacity.
Prepare Ni: Al: Co: Y=1 with embodiment 1: 0.25: 0.24: 0.05 step is identical with other conditions, different is the ratio that changes Co, be Ni: Al: Co: Y=1: 0.25: 0.12: 0.05, the sample that makes is designated as j, corresponding combination electrode is J, recording its maximum specific discharge capacity is 321mAh/g (charge-discharge magnification 0.2C), and B electrode maximum specific discharge capacity under same multiplying power is 330mAh/g among the embodiment 1.As seen, doped chemical ratio difference, specific discharge capacity can change thereupon.
Present embodiment has been studied the pH value to dopen Nano α-Ni (OH)
2The physics of material and the influence of chemical property
Identical with other conditions and the step of embodiment 2, the pH value of conditioned reaction solution is 8,9,10 respectively, and the sample of producing is g, h, and i, its XRD figure spectrum is as shown in figure 11.As seen from the figure, the diffraction maximum of h sample is than g, and i has obvious broadening, and the intensity at peak is less than g, i, and this shows that pH is that 9 o'clock sample has smaller particles particle diameter and relatively poor degree of crystallinity.Prepare combination electrode G, H and the I of three samples respectively by embodiment two, three, record maximum specific discharge capacity and be respectively 299,308,302mAh/g.As seen, it is more excellent conditions that the pH value gets 9, reflects that also crystal defect that nano particle is suitable and smaller particles degree help improving the discharge capacity of its electrode simultaneously.
The above results shows, prepares multiple doping nano α-Ni (OH) with the ultrasonic wave precipitation method
2, not only can make tiny even, the active height of good dispersion of particle of generation, and can obtain desirable fault of construction and keep Stability Analysis of Structures, thereby every chemical property index of its electrode is all improved a lot; Mix the nanometer α of multi-element doping-Ni (OH) relatively with unit or low unit
2Charge-discharge performance is superior under high magnification, and stability is high, and the overcharging resisting ability is strong.In the present embodiment, contain nanometer α-Ni (OH) that quaternary (Al, Co, Y, Zn) is mixed
2Account for the combination electrode of 8wt.%, its 0.5C discharge capacity (346mAh/g) also exceeds 9mAh/g than 0.1C discharge capacity, this result that discharge capacity goes up not down under high magnification is difficult the generation under unit or low first doping situation, yet there are no the research report.Therefore, the multiple doping nano α-Ni (OH) for preparing with the inventive method
2Be suitable as the active material of anode of nickel-metal hydride battery, especially be fit to be applied to the positive electrode of great-power chargeable batteries such as electric motor car, electric tool.
Claims (5)
1. a multiple doping nano α-Ni (OH)
2Material is characterized in that mixing simultaneously 2～5 kinds of metallic elements, and the metallic element that mixes is any combination of Al, Co, Zn, Y, Ca, Cu, Mg, Fe, and the total content of metal ion accounts for 5%～60% of nickelous molal quantity.
2. the described multiple doping nano α-Ni of claim 1 (OH)
2Preparation methods is characterized in that this method has following steps:
(1) be the commercial nickel salting liquid of 0.05～1.0mol/l and the salting liquid of 0.05～1.0mol/l doped chemical M with the deionized water configuration concentration, wherein nickel salt is a kind of in nickel nitrate, nickelous sulfate or the nickel chloride, doped chemical M is 2～5 kinds among Al, Co, Zn, Y, Ca, Cu, Mg, the Fe, slaine is chlorate or nitrate or sulfate, and the mol ratio of doping is: M
N+/ Ni
2+=5～60%; Add the dispersant that accounts for nickel hydroxide theoretical yield 1%～5% mass percent again, make the mixed solution of nickel salt;
(2) with the deionized water configuration concentration be the industrial caustic solution of 0.1～2.0mol/l, in the caustic-alkali aqueous solution adding alkali lye with an amount of ammoniacal liquor or ammonium, stir, make the caustic-alkali aqueous solution that contains ammonia or ammonium 0.1～2.0mol/l;
(3) two kinds of aqueous solution making in step (1) and the step (2) are gone into to place reaction vessel in the ultrasonic cleaner vibration cavity with 15～30 speed of per minute and drip, entire reaction course is all carried out in the ultrasonic vibration environment, keep temperature of reaction system, pH value and mixing speed constant simultaneously, wherein temperature remains on certain value, pH value certain value between 8～11 of room temperature～60 ℃, and mixing speed is certain value of 150～1000 rev/mins; After reactant drips, continue to stir 5 hours until reacting completely, still aging then washing and filtering is dried to constant weight with 60～100 ℃, takes out nanometer α-Ni (OH) that grinding obtains multi-element doping
2Powder.
3. preparation method according to claim 2 is characterized in that: the dispersant in the above-mentioned steps (1) is a kind of in polyethylene glycol or the Tween-80.
4. preparation method according to claim 2 is characterized in that: the industrial caustic alkali in the above-mentioned steps (2) is a kind of in NaOH or the potassium hydroxide.
5. preparation method according to claim 2 is characterized in that: the ultrasonic power in the above-mentioned steps (3) is 50～80W, and frequency is 40～100KHz.
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| CN102637868A (en) * | 2011-06-08 | 2012-08-15 | 广东工业大学 | Nano multiphase nickel hydroxide containing rare-earth elements and synthetic method of nano multiphase nickel hydroxide |
| CN102931396A (en) * | 2012-11-05 | 2013-02-13 | 湖南丰日电源电气股份有限公司 | Anode material for high-performance alkaline batteries and method for preparing anode material |
| CN103553152A (en) * | 2013-10-22 | 2014-02-05 | 金天能源材料有限公司 | High-density spherical nickel-cobalt-aluminum precursor material and preparation method thereof |
| CN104716377A (en) * | 2013-12-17 | 2015-06-17 | 远景能源（江苏）有限公司 | Alternating current charging and discharging cell |
| CN105070512A (en) * | 2015-08-06 | 2015-11-18 | 太原理工大学 | Mg-doped nano spherical flower-shaped alpha-Ni(OH)2 electrode material and preparation method thereof |
| CN106783219A (en) * | 2017-03-13 | 2017-05-31 | 黄冈师范学院 | A kind of laminar nickel doping nickel hydroxide electrode material and its preparation method and the application in ultracapacitor is prepared |
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| CN102637868A (en) * | 2011-06-08 | 2012-08-15 | 广东工业大学 | Nano multiphase nickel hydroxide containing rare-earth elements and synthetic method of nano multiphase nickel hydroxide |
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