CN1609008A - Nickel hydroxide nanotube and its prepn and application - Google Patents
Nickel hydroxide nanotube and its prepn and application Download PDFInfo
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- CN1609008A CN1609008A CNA2004100723863A CN200410072386A CN1609008A CN 1609008 A CN1609008 A CN 1609008A CN A2004100723863 A CNA2004100723863 A CN A2004100723863A CN 200410072386 A CN200410072386 A CN 200410072386A CN 1609008 A CN1609008 A CN 1609008A
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Abstract
The present invention relates to nickel hydroxide nanotube and its preparation and application. The nickel hydroxide nanotube has open-mouthed needle nanometer crystal structure and great specific surface area, and has length of 50-60 microns, outer diameter of 180-220 nm and tube wall thickness of 20-30 nm. The nickel hydroxide nanotube of the present invention is one excellent kind of reversible charging and discharging matter, and when used in electrochemical oxidation and reduction, it has fast charging and discharging speed, high electrochemical capacity and long circulating life. It may be used in raising specific discharging capacity, high multiplying factor and high temperature discharging performance of nickel electrode and may be used in developing new type of secondary alkali battery.
Description
Technical field
The present invention relates to a kind of preparation, particularly nickel hydroxide nano-tube and preparation method and application thereof of novel electrode materials.Have the acicular nanometer crystal structure through the prepared nickel hydroxide nano-tube of room temperature chemical reaction, its length is 50～60 μ m, and external diameter is 180-220nm, thickness of pipe 20～30nm.Nickel hydroxide nano-tube as electrode materials, can be improved specific discharge capacity, high magnification and the high temperature discharge performance of nickel electrode effectively, thereby can be applicable to the exploitation of novel alkaline secondary cell.
Background technology
In recent years, because developing rapidly of global information industry, various small portable electronic device such as mobile communication, notebook computer are to the demand surge of battery, make secondary cell occupy more and more important position in daily life, as widely used cadmium/nickel (Cd-Ni), iron/nickel (Fe-Ni), zinc/nickel (Zn-Ni), metal hydride/nickel nickel such as (MH-Ni) series alkaline secondary cell.Because the positive pole in this series battery all is a nickel electrode, thus to high reactivity, heavy body, high comprehensive performance nickel positive active material---the research of nickel hydroxide has important practical significance.
The chemical reaction that nickel electrode is taken place in charge and discharge process is mainly:
, that is to say electrode Ni (OH) when charging
2Be transformed into NiOOH, Ni
2+Be oxidized to Ni
3+And NiOOH is reverse into Ni (OH) when discharge
2, i.e. Ni
3+Be reduced into Ni
2+According to Faraday's law, Ni (OH)
2In charge and discharge process, be accompanied by Ni
2+With Ni
3+The theoretical loading capacity that the phase co-conversion is produced is 289mAh/g.Yet the chemical reaction that nickel electrode is taken place in actual charge and discharge process is quite complicated, is comprising the phase co-conversion of multiple crystal formation, comprises α, the Ni of β type (OH)
2And the NiOOH of beta, gamma type.And α-Ni (OH)
2Can also be oxidized to γ-NiOOH, produce simultaneously than β-Ni (OH)
2The specific discharge capacity that/β-NiOOH is higher, this is owing to contain Ni among γ-NiOOH
4+Existence, the average Oxidation Number of its Ni surpasses due to 3.
In order to improve the performance of nickel electrode material nickel hydroxide, people pay close attention to spherical Ni (OH) always
2And the research and development [M.Oshitani of related compound material, M.Watada, T.Tanaka, T.Iida, Hydrogen and Metal HydrideBatteries, Vol.94-27, ed.P.D.Bennett and T.Sakai, p.303, The Electrochem.Soc.Inc., Pennington, NJ (1994); J.Chen, D.H.Bradhurst, S.X.Dou, H.K.Liu, Nickel Hydroxide as anactive material for the positive electrode in rechargeable alkaline batteries J.Electrochem.Soc.1999,146,3606.; I.Zhitomirsky, Composite Nickel Hydroxide-Polyelectrolyte FilmsPrepared by Cathodic Electrosynthesis J.Appl.Electrochem.2004,34,235-240.].On the one hand, spherical Ni (OH)
2Have high relatively density and good filling flowability, can improve the unit volume loading level of electrode, thereby also with regard to the corresponding electrode capacity that improved.And from another point of view, since diffusional resistance, spherical Ni (OH)
2The core under higher charge-discharge magnification and higher working temperature, still present inertia.、
In recent years, nanometer Ni (OH)
2Particle as a kind of novel, battery material has caused many investigators' concern [X.Wang efficiently, H.Luo, P.V. Parkhutik, et al.Studies of the Performance of NanostructuralMultiphase Nickel Hydroxide J.Power Sources 2003,115,153-160.].Nanometer Ni (OH)
2The particle diameter of particle is little, specific surface area is big, has increased and the contacting of electrolyte solution, and has reduced the diffusion length of proton in solid phase, thereby improves the diffusion of proton.And nanotube is because its unique microtexture, and by and the distinguished optics that produces, performances such as magnetics and electrochemistry demonstrate the potential application prospect at aspects such as nanometer energy storage, nano-catalytics.In the synthetic and technology of preparing of numerous nanotubes, template is an effective technology of synthesis of nano pipe, and its characteristics are exactly to have good controllability, promptly can make the nanotube of desired structure.Therefore: explore high purity N i (OH)
2The preparation of nanotube has crucial meaning undoubtedly.
In addition, remove this problem about Ni (OH)
2The preparation of nanotube and as the research of anode of basic secondary battery active material outer [F. S.Cai, G.Y. Zhang, J.Chen, et al.Ni (OH)
2Tubes with Mesoscale Dimensions asPositive-Electrode Materials of Alkaline Rechargeable Batteries Angew.Chem.Int.Ed.2004,43,4212-4216], Ni (OH)
2The preparation of nanotube and performance study thereof yet there are no report at home and abroad.Therefore, the preparation of nickel hydroxide nano-tube and Electrochemical Properties thereof are of very high actual application value for the research and development of novel alkaline secondary cell.
Summary of the invention
The purpose of this invention is to provide a kind of nickel hydroxide nano-tube and preparation method and application thereof, it is novel electrode materials.The present invention is the nickel hydroxide nano-tube that adopts template to prepare high-purity, opening, have acicular structure, and realizes the good controllability to material structure, and the application of exploitation nickel hydroxide nano-tube aspect the anode of basic secondary battery active material.
Nickel hydroxide nano-tube of the present invention is a kind of opening nanotube of being made up of the acicular nanometer crystalline substance, and its length is 50～60 μ m, and external diameter is 180-220nm, thickness of pipe 20～30nm.The length of nanotube is consistent with the thickness of used porous alumina formwork) aperture of external diameter and used alumina formwork is consistent.
The preparation method of nickel hydroxide nano-tube of the present invention comprises the steps:
1) at room temperature alumina formwork is put into the soluble nickel salts solution and soaked 0.5-1 hour, make Ni
2+On the inwall attached to the alumina formwork micropore.
2) dropping ammonia solution on alumina formwork, under gravity and wicking action, ammoniacal liquor infiltrates the template micropore and sees through template, and generates Ni (OH) attached to the reaction of the bivalent nickel ion on the template micropore inwall
2
3) behind the repeating step (1)-(2) 3～4 times, water flushing template.
4) with the 2-6M aqueous sodium hydroxide solution alumina formwork is dissolved, collect the solid that obtains after the template dissolving, water cleaned the back at 60-90 ℃ of dry 30-60 minute, was prepared Ni (OH)
2Nanotube.
The diameter 47mm of described alumina formwork, aperture 200nm, thickness 60 μ m (commodity alumina formwork, Whatman International Ltd.); Described nickel salt solution is single nickel salt, nickelous nitrate or nickelous chloride; Described ammonia soln is the ammonia soln of 0.2-1M.
Described nickel hydroxide nano-tube is used for the positive electrode active materials of alkaline secondary cell.
The concentration that the present invention controls bivalent nickel ion and ammoniacal liquor is most important: as the concentration of ammoniacal liquor hour (less than 0.2M), bivalent nickel ion (Ni
2+) easily generate Ni (OH) with ammoniacal liquor at template surface
2, cause the obstruction of template micropore easily; And when the concentration of ammoniacal liquor is excessive (greater than 1M), bivalent nickel ion (Ni
2+) and NH
3Coordination generates Ni (NH easily
3)
6 2+, influence forms needed Ni (OH)
2Have only when the two concentration ratio is suitable and could neither generate nickel hydroxide, be difficult for forming the coordination product again at template surface.Therefore, adopt 0.4M nickel chloride solution and 1M ammoniacal liquor to react can to obtain opening, high-purity needle-like nickel hydroxide nano-tube, the output of nanotube accounts for more than 99% of total product.In addition, repeating step 1) and 2) 3～4 times to guarantee the formation of nanotube in the template micropore, makes that prepared nano tubular structure is more stable.
Because diffusional resistance, the core of general spherical shape nickel hydroxide (as more than 40 ℃) under higher charge-discharge magnification (more than 3C) and higher working temperature still presents inertia, in addition, because there is the phase co-conversion of multiple crystal formation in nickel electrode in charge and discharge process, therefore can cause the expansion of nickel electrode volume, reduced the effective contact between the active material particle, increased the reaction resistance of electrode, that particularly embodies under the situation of high temperature, high power charging-discharging is more obvious.And the constructional feature of nanotube opening, hollow makes that the diffusion of protons process is easier to carry out in the electrode reaction, and speed is faster, and then has improved high magnification, the high temperature discharge performance of nickel electrode; And the tubular structure of nickel hydroxide nano-tube uniqueness makes it have certain deformation recovery ability, can reduce nickel electrode in charge and discharge process since volumetric expansion to structure cause than havoc, thereby improved the reaction reversibility of nickel electrode.Therefore, the opening nickel hydroxide nano-tube is used for nickel electrode can significantly improve its chemical property, and vast potential for future development and range of application are arranged.
The chemical property of nickel hydroxide nano-tube adopts three-electrode system to measure among the present invention, be about to nickel hydroxide nano-tube and be wrapped in and be made into positive plate (working electrode) in the nickel foam collector, the hydrogen-bearing alloy powder that loading capacity is surpassed positive discharge capacity 200% (for example: the mixed rare earth hydrogen storage alloy MmNi that Inner Mongol AudioCodes in seventy years of age company produces
3.8Co
0.5Mn
0.4Al
0.3) as negative material, the Hg/HgO electrode is as reference electrode, the 6M KOH aqueous solution is electrolytic solution.Adopt computer-controlled battery test system to carry out electrochemical property test.For the performance with nickel hydroxide nano-tube compares, adopt identical method that ball-shape nickel hydroxide is made into electrode slice and test.
The invention has the advantages that and adopt template to prepare high-purity nickel hydroxide nano-tube, realize good controllability the structure of material; Nickel hydroxide nano-tube is used for nickel electrode, specific discharge capacity, high magnification and the high temperature discharge performance of nickel electrode be can improve effectively, whole nickel series (cadmium/nickel, iron/nickel improved greatly, zinc/nickel, metal hydride/nickel) over-all properties of alkaline secondary cell.
Description of drawings
Fig. 1 prepares the process flow diagram of nickel hydroxide nano-tube for template.
Fig. 2 is Ni (OH)
2The XRD figure of nanotube.
Fig. 3 is Ni (OH)
2The scanning electron microscope analysis of nanotube.
Fig. 4 is Ni (OH)
2The transmission electron microscope of nanotube and high resolving power TEM (transmission electron microscope) analysis.
Fig. 5 is Ni (OH)
2Nanotube and spherical Ni (OH)
2Discharge curve at 20 ℃.
Fig. 6 is nanotube Ni (OH)
2Electrode and spherical Ni (OH)
2The specific discharge capacity contrast of electrode under differing temps and different current density.
The synoptic diagram of transformation mutually that Fig. 7 is a nickel electrode in charging and discharge process, nanotube Ni (OH)
2Electrode and spherical Ni (OH)
2Electrode is compared has more γ-NiOOH and β-Ni (OH)
2Between mutual conversion.
Embodiment
Embodiment 1: high-purity N i (OH)
2The preparation of nanotube.
Experimental procedure: (1) with alumina formwork (diameter 47mm, aperture 200nm, thickness 60 μ m, Whatman England) puts into 0.4M NiCl
2Soak half an hour in the solution, make NiCl
2Solution fully immerses in the template micropore; (2) from NiCl
2Take out template in the solution, oven dry.Slowly drip the ammoniacal liquor that concentration is 1M to template surface, ammoniacal liquor infiltration into microporous and see through template under gravity and wicking action is and attached to the NiCl on the template hole wall
2Reaction generates Ni (OH)
2Under visible light, human eye can be observed the color of template by becoming light green in vain gradually.(3) after repeating step (1) and (2) 4 times, use the distilled water flushing template, and template is dissolved in the 2M NaOH solution.(4) collect template and all dissolve the remaining green solid in back, use distilled water and absolute ethanol washing repeatedly,, promptly obtain Ni (OH) 60 ℃ of following vacuum-dryings 1 hour
2Nanotube.Fig. 1 prepares the process flow diagram of nickel hydroxide nano-tube for template.Generate Ni (OH)
2The included above-mentioned chemical equation of nanotube is as follows:
According to the prepared Ni of aforesaid method (OH)
2The XRD figure of nanotube as shown in Figure 2.Calculating unit cell parameters according to characteristic peak positions in the spectrogram and intensitometer is a=b=0.3127nm, and c=0.4606nm belongs to hexagonal structure, with β-Ni (OH)
2(a=b=0.3126nm, c=0.4605nm, ICCD-JCPDS No.14-0117) matches, and do not have the dephasign diffraction peak, illustrates that product is the very high β-Ni of purity (OH)
2The broadening of diffraction peak is because product is a nano level, and crystal grain is very tiny to be caused.
Fig. 3 is Ni (OH)
2The scanning electron microscope analysis of nanotube.Find out that from figure the microscopic appearance of product is the fibrous of a branch of bundle, length approximately is 50～60 μ m, matches with the thickness of porous alumina formwork used in the preparation process.Further transmission electron microscope and high resolving power TEM (transmission electron microscope) analysis (Fig. 4) illustrate that product is a hollow tubular structure, and the external diameter of nanotube is about 200nm, and is also consistent with the aperture of template.Tube wall is very smooth, thick 20～30nm.And as can be seen from the figure prepared Ni (OH)
2Nanotube is by the brilliant be combined into of atomic little acicular nanometer.
Embodiment 2:
According to the prepared nanotube Ni (OH) of embodiment 1
2Or the commodity ball-shape nickel hydroxide (Tanaka Chemical is a positive active material Japan), is conductive agent with the carbon black, and polytetrafluoroethylene (PTFE) is a caking agent, and nickel foam is that collector is made positive plate.Active substance Ni (OH)
2, carbon black, PTFE mass percent be Ni (OH)
2: carbon black: PTFE=85: 10: 5.Accurately take by weighing each component, it is fully ground, mixes,, and it is coated on the nickel foam base material equably mixture furnishing pasty state with an amount of dehydrated alcohol, being pressed into thickness after 1 hour with tabletting machine in 80 ℃ of dryings is that cathode film about 0.4mm is as positive plate.Hydrogen-bearing alloy powder (the mixed rare earth hydrogen storage alloy MmNi that Inner Mongol AudioCodes in seventy years of age company produces that surpasses positive electrode capacity 200% with loading capacity
3.8Co
0.5Mn
0.4Al
0.3, Mm is a lanthanum rich mischmetal) and as negative pole, the Hg/HgO electrode is as reference electrode, and the 6M KOH aqueous solution is electrolytic solution.(the blue electric Electronics Co., Ltd. in Wuhan LAND2001CT-10mA) carries out the charge-discharge performance test to adopt computer-controlled battery test system.Fig. 5 is Ni (OH)
2Nanotube and spherical Ni (OH)
2At 20 ℃ of discharge curves with the current density discharge of 50mA/g.Find out nanotube Ni (OH) from figure
2Electrode is than spherical Ni (OH)
2Electrode has the sparking voltage of a longer discharge platform and Geng Gao, thereby nanotube Ni (OH)
2Electrode has higher specific storage (nanotube Ni (OH)
2Electrode is 315mAh/g, and spherical Ni (OH)
2Electrode is 265mAh/g).
Embodiment 3:
Nanotube Ni (OH) according to embodiment 2 preparations
2Electrode and spherical Ni (OH)
2Electrode differing temps (20,40,60 ℃) and different current density (50,100, carry out discharge test under 150mA/g).Fig. 6 nanotube Ni (OH)
2Electrode and spherical Ni (OH)
2The specific discharge capacity contrast of electrode under differing temps and different current density.Fig. 6 has reflected the specific discharge capacity performance of differing temps and different following two kinds of electrodes of current density.Find out that from figure the specific discharge capacity of two kinds of electrodes all reduces with the rising of temperature and the increase of current density, but under uniform temp and current density, nanotube Ni (OH)
2The specific discharge capacity of electrode always is higher than spherical Ni (OH)
2The specific discharge capacity of electrode.For example, when 20 ℃ of current densities with 150mA/g are discharged, nanotube Ni (OH)
2The electrode discharge specific storage is 265mAh/g, is 84.1% of its peak capacity; And spherical Ni (OH)
2The specific discharge capacity of electrode only is 203mAh/g, is 76.6% of its peak capacity.And when 60 ℃ of current densities with 150mA/g are discharged, nanotube Ni (OH)
2The specific discharge capacity of electrode still has 205mAh/g, and corresponding spherical Ni (OH)
2Electrode then has only 123mAh/g, and this has illustrated nanotube Ni (OH)
2Electrode has excellent high-temperature and high-rate discharge ability.
Embodiment 4:
Nanotube Ni (OH) according to embodiment 2 preparations
2Electrode and spherical Ni (OH)
2Electrode carries out the charge and discharge cycles test under the current density of 20 ℃ and 100mA/g.Experiment shows after 500 charge/discharge cycle nanotube Ni (OH)
2The capacity attenuation of electrode only 5%, and spherical Ni (OH)
2The capacity of electrode then decays 25%.Therefore, prepared nanotube Ni (OH)
2Electrode has good cycle life.
By to prepared nanotube Ni (OH)
2Electrode and spherical Ni (OH)
2Electrode carries out electrochemical property test relatively, as can be seen, and with nanotube Ni (OH)
2As positive electrode material, no matter on the reversibility of electrode reaction, still on high magnification, high temperature discharge ability all than spherical Ni (OH)
2Bigger advantage is arranged, and these attributes all derive from the hollow structure of nanotube uniqueness, make that the diffusion of protons process is easy to carry out in the electrode reaction, and then have improved high magnification, the high temperature discharge performance of nickel electrode.And nanotube Ni (OH)
2Electrode and spherical Ni (OH)
2Electrode is compared, and the higher electrochemistry capacitance that shows is owing to contain Ni among γ-NiOOH
4+Existence, the average Oxidation Number of Ni is surpassed due to 3.As shown in Figure 7, Fig. 7 nickel electrode is illustrated nanotube Ni (OH) in charging with the transformation mutually in the discharge process
2Electrode and spherical Ni (OH)
2Electrode is compared has more γ-NiOOH and β-Ni (OH)
2Between mutual conversion.
In charge and discharge process, because nanotube Ni (OH)
2Electrode has more γ-NiOOH and β-Ni (OH)
2Between mutual conversion, make nanotube electrode have higher electrochemistry capacitance; And on the other hand, because nanotube Ni (OH)
2The cannulated structure that it is unique makes it have better ability of anti-deformation, also just reduced nickel electrode in charge and discharge process since volumetric expansion to structure cause than havoc, thereby improved the reversibility and the cyclicity of electrode reaction.
Claims (7)
1, a kind of nickel hydroxide nano-tube is characterized in that it by the brilliant opening nanotube of forming of acicular nanometer, and its length is 50～60 μ m, and external diameter is 180-220nm, thickness of pipe 20～30nm.
2, the preparation method of the described nickel hydroxide nano-tube of claim 1 is characterized in that it comprises the steps:
1) at room temperature alumina formwork is put into the soluble nickel salts solution and soaked 0.5-1 hour, make Ni
2+On the inwall attached to the alumina formwork micropore;
2) dropping ammonia solution on alumina formwork, ammoniacal liquor infiltrate the template micropore and see through template, and generate Ni (OH) attached to the reaction of the bivalent nickel ion on the template micropore inwall
2
3) repeating step 1)-2) after 3～4 times, water flushing template;
4) with the 2-6M aqueous sodium hydroxide solution alumina formwork is dissolved, collect the solid that obtains after the template dissolving, water cleaned the back at 60-90 ℃ of dry 30-60 minute, was prepared Ni (OH)
2Nanotube.
3,, it is characterized in that the diameter 47mm of described alumina formwork, aperture 200nm, thickness 60 μ m according to the preparation method of the described nickel hydroxide nano-tube of claim 2.
4,, it is characterized in that described nickel salt solution is single nickel salt, nickelous nitrate or nickelous chloride according to the preparation method of the described nickel hydroxide nano-tube of claim 2.
5,, it is characterized in that described ammonia soln is the ammonia soln of 0.2-1M according to the preparation method of the described nickel hydroxide nano-tube of claim 2.
6,, it is characterized in that described nickel salt solution is the 0.4M nickel chloride solution according to the preparation method of the described nickel hydroxide nano-tube of claim 2; Described ammoniacal liquor is the ammonia soln of 1M.
7, the described nickel hydroxide nano-tube of claim 1 is used for the positive electrode active materials of alkaline secondary cell.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425539C (en) * | 2006-10-31 | 2008-10-15 | 山东师范大学 | Synthesis method of nickel hydroxide nano-tube |
| CN103579628A (en) * | 2012-07-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Zinc-nickel single-fluid cell anode, preparation method of zinc-nickel single-fluid cell anode, and zinc-nickel single-fluid cell |
| CN103896344A (en) * | 2014-04-01 | 2014-07-02 | 淮安信息职业技术学院 | Method for synthesizing nickel hydroxide/nickel oxide nanometer hollow tube by using nickel plating wastewater |
| CN107123555A (en) * | 2017-05-19 | 2017-09-01 | 中国科学技术大学 | Empty nanotube and its preparation method and application in a kind of metal hydroxides |
| CN109603840A (en) * | 2018-12-30 | 2019-04-12 | 武汉理工大学 | Classifying porous hydroxy nickel oxide nano-tube array and its preparation method and application |
| CN115321615A (en) * | 2022-08-12 | 2022-11-11 | 北京科技大学 | Ni (OH) 2 ·0.75H 2 O hollow tube catalyst material and preparation method thereof |
-
2004
- 2004-10-26 CN CNB2004100723863A patent/CN1267357C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425539C (en) * | 2006-10-31 | 2008-10-15 | 山东师范大学 | Synthesis method of nickel hydroxide nano-tube |
| CN103579628A (en) * | 2012-07-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Zinc-nickel single-fluid cell anode, preparation method of zinc-nickel single-fluid cell anode, and zinc-nickel single-fluid cell |
| CN103579628B (en) * | 2012-07-25 | 2016-02-03 | 中国科学院大连化学物理研究所 | Zinc-nickel single flow battery positive pole and preparation and zinc-nickel single flow battery |
| CN103896344A (en) * | 2014-04-01 | 2014-07-02 | 淮安信息职业技术学院 | Method for synthesizing nickel hydroxide/nickel oxide nanometer hollow tube by using nickel plating wastewater |
| CN103896344B (en) * | 2014-04-01 | 2015-04-01 | 淮安信息职业技术学院 | Method for synthesizing nickel hydroxide/nickel oxide nanometer hollow tube by using nickel plating wastewater |
| CN107123555A (en) * | 2017-05-19 | 2017-09-01 | 中国科学技术大学 | Empty nanotube and its preparation method and application in a kind of metal hydroxides |
| CN107123555B (en) * | 2017-05-19 | 2018-11-13 | 中国科学技术大学 | Empty nanotube and its preparation method and application in a kind of metal hydroxides |
| CN109603840A (en) * | 2018-12-30 | 2019-04-12 | 武汉理工大学 | Classifying porous hydroxy nickel oxide nano-tube array and its preparation method and application |
| CN109603840B (en) * | 2018-12-30 | 2022-03-11 | 武汉理工大学 | Hierarchical porous nickel oxyhydroxide nanotube array and preparation method and application thereof |
| CN115321615A (en) * | 2022-08-12 | 2022-11-11 | 北京科技大学 | Ni (OH) 2 ·0.75H 2 O hollow tube catalyst material and preparation method thereof |
| CN115321615B (en) * | 2022-08-12 | 2023-07-21 | 北京科技大学 | Ni (OH) 2 ·0.75H 2 O hollow tube catalyst material and preparation method thereof |
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|---|---|
| CN1267357C (en) | 2006-08-02 |
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