CN104051728A - Material with surface multilevel nano micron structure, preparation method thereof and nickel-zinc cell containing the material in anode - Google Patents
Material with surface multilevel nano micron structure, preparation method thereof and nickel-zinc cell containing the material in anode Download PDFInfo
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Abstract
The invention discloses a material with surface multilevel nano micron structure. The material comprises: a porous conductive substrate, cobaltosic oxide primary rectangular micron sheet array growing on and perpendicular to the porous conductive substrate, and a plurality of villous nickel oxide secondary nanowires growing on the surface of each primary rectangular micron sheet. The invention also discloses a hydro-thermal synthesis method for preparing the material, and a cell containing the material in the anode, especially a nickel-zinc cell. The material has high specific surface area, can be used as the electrode material to improve the electrical contact performance of the electrode, thereby improving the overall electrical property of the electrode and cell containing the material.
Description
Technical field
The invention belongs to inorganic advanced technical field of nano material
Background technology
In various batteries, nickel-zinc cell has higher operating voltage, and well energy density and power density, be a kind of secondary power battery [J.Power Sources, 2000,88,202-205] of high energy environmental protection.Affecting one of key factor of battery performance is electrode material, but there are many problems in general commercial nickel-zinc cell aspect its electrode material, as easily there is Zhi Jing in zinc electrode, passivation etc. cause cycle life decay, nickel electrode also exists and expands and Poisoning Phenomenon, easily causes charge efficiency minimizing and capacitance loss etc.Still wish to have better electrode material and better nickel-zinc cell, to avoid the problems referred to above.
Summary of the invention
The material that the present invention has a multistage nanometer micrometer structure by the surface of unique design has solved the problem that general electrode material cyclicity is poor and capacity is low well, has good application aspect electrochemical energy storage.
First aspect, the present invention relates to a kind of surface and has the material of multistage nanometer micrometer structure, and it comprises:
Porous, electrically conductive substrate;
In described porous, electrically conductive substrate perpendicular to the elementary rectangle micron film of the cobaltosic oxide array of this substrate grown;
The secondary nano wire of multiple fine hair shape nickel oxide of growing on the surface of elementary rectangle micron film described in each.
Second aspect, the present invention relates to a kind of surface and has the preparation method of the material of multistage nanometer micrometer structure, and it comprises the following steps:
A. by tilting porous, electrically conductive substrate first reactor of putting into, in this reactor, add first aqueous solution that comprises solubility cobalt salt, ammonium fluoride and urea again, then airtight this reactor, heat up and under self-generated pressure, carry out hydro-thermal reaction for the first time, with the vertical elementary micro wire array of this substrate grown cobalt hydroxide on this porous, electrically conductive substrate surface;
B. take out this porous, electrically conductive substrate, wash and be dried;
C. by tilting porous, electrically conductive substrate after treatment step b second reactor of putting into, in this reactor, add second aqueous solution that comprises solubility cobalt salt and urea again, seal this reactor, heat up and also under self-generated pressure, carry out hydro-thermal reaction for the second time, make the elementary micro wire of cobalt hydroxide described in each form elementary rectangle micron film;
D. again take out this porous, electrically conductive substrate, wash and be dried;
E. by tilting porous, electrically conductive substrate after treatment steps d the 3rd reactor of putting into, in this reactor, add the 3rd aqueous solution that comprises soluble nickel salt and urea again, seal this reactor, heat up and under self-generated pressure, carry out hydro-thermal reaction for the third time, with the secondary nano wire of multiple fine hair shape nickel hydroxide of growing on the surface on the elementary rectangle micron film of each described cobalt hydroxide;
F. again take out this porous, electrically conductive substrate, wash and be dried;
G. in air, calcine this porous, electrically conductive substrate, make the elementary rectangle micron film of cobalt hydroxide change the elementary rectangle micron film of cobaltosic oxide into, and make the secondary nano wire of nickel hydroxide change the secondary nano wire of nickel oxide into.
The third aspect, the present invention relates to the material that its positive electrode of a kind of battery comprises surface of the present invention and have multistage nanometer micrometer structure.
Fourth aspect, the present invention relates to a kind of nickel-zinc cell, its positive electrode comprises surface of the present invention and has the material of multistage nanometer micrometer structure, its negative material comprises the zinc being plated in conductive substrates, and the conductive substrates comprising in the conductive substrates wherein comprising in negative material and positive electrode is identical or different.
Brief description of the drawings
Fig. 1 is the structural representation that surface of the present invention has the material of multistage nanometer micrometer structure.
Fig. 2 is the stereoscan photograph figure (SEM) of material of the present invention, wherein clearly show, the elementary rectangle micron film of cobaltosic oxide array is grown perpendicular to substrate surface, and on the surface of the elementary rectangle micron film of each cobaltosic oxide, growth has the secondary nano wire of multiple fine hair shape nickel oxide; Wherein substrate is nickel foam.
Fig. 3 is the X-ray diffractogram (XRD) of material shown in Fig. 2, and contrasting the elementary rectangle micron film composition that can pick out on material of the present invention with standard spectrogram is cobaltosic oxide crystal, and secondary nano wire composition is nickel oxide crystal.
Fig. 4 is the cyclic voltammetry curve figure of material shown in Fig. 2, records taking mercury/mercuric oxide electrode as reference electrode.
Fig. 5 is the charging and discharging curve figure of material shown in Fig. 2.
Fig. 6 is the cyclical stability figure of material shown in Fig. 2.
Fig. 7 is the stereoscan photograph figure (SEM) of the material of the present invention of another kind of form, wherein clearly show, the elementary rectangle micron film of cobaltosic oxide array is grown perpendicular to substrate surface, and the secondary nano wire of multiple fine hair shape nickel oxide of growing on the elementary rectangle micron film of each cobaltosic oxide; Wherein substrate is carbon fiber felt.
Fig. 8 is the X-ray diffractogram (XRD) of material shown in Fig. 7, and contrasting the elementary rectangle micron film composition that can pick out on material of the present invention with standard spectrogram is cobaltosic oxide crystal, and secondary nano wire composition is nickel oxide crystal.
Fig. 9 is the cyclic voltammetry curve figure of material shown in Fig. 7, records taking mercury/mercuric oxide electrode as reference electrode.
Figure 10 is the charging and discharging curve figure of material shown in Fig. 7.
Figure 11 is the cyclical stability figure of material shown in Fig. 7.
Figure 12 uses the structural representation of material of the present invention as the nickel-zinc cell of positive electrode, and wherein negative pole includes but not limited to the copper sheet of plating zinc on surface.
Figure 13 is the cyclic voltammetry curve figure of material shown in Fig. 2 as the nickel-zinc cell of positive electrode.
Figure 14 is the charging and discharging curve figure of material shown in Fig. 2 as the nickel-zinc cell of positive electrode.
Figure 15 is the multiplying power property figure of material shown in Fig. 2 as the nickel-zinc cell of positive electrode.
Figure 16 is the cyclical stability figure of material shown in Fig. 2 as the nickel-zinc cell of positive electrode.
Photo when Figure 17 is the use material of the present invention prepared in laboratory as the energising experiment of the simple and easy Soft Roll nickel-zinc cell of positive electrode, the material that wherein surface of the present invention is had to multistage nanometer micrometer structure is as positive pole, using the copper sheet of plating zinc on surface as negative pole, electrolyte is KOH solution, barrier film is Celgard type lithium battery diaphragm, and two these Soft Roll nickel-zinc cell tandem energies make lumination of light emitting diode.
Detailed Description Of The Invention
Now each aspect of the present invention is described in detail.
A first aspect of the present invention relates to surface and has the material of multistage nanometer micrometer structure.Wherein said porous, electrically conductive substrate refers to the conductive substrates with loose structure, and this substrate can be metal or carbon in material, can correspondingly be called as foam metal or porous carbon fiber felt.Wherein metal can be selected from any applicable metal, for example, in the time that metal is copper, be called foam copper, in the time that metal is nickel, is called nickel foam.About how detailed introduction and the preparation method of foam metal or porous carbon fiber felt, can be referring to existing patented technology document.Such foam metal or porous carbon fiber felt be also can be commercially available or can make by oneself according to pertinent literature content.
The elementary rectangle micron film of multiple cobaltosic oxides is the superficial growth perpendicular to this porous, electrically conductive substrate with the form of array.On the surface of the elementary rectangle micron film of each cobaltosic oxide, be the fine hair shape secondary nano wire of multiple nickel oxide of growing.Visible, material of the present invention has two-stage nanometer micrometer structure, and primary structure is micron film structure, and secondary structure is nano thread structure, this structure might as well be called " multistage nanometer micrometer structure ", has micrometer structure and the nanostructure arrangement mode of multiple ranks.
Multistage nanometer micrometer structure like this, has increased the surface area of material of the present invention undoubtedly greatly, and has improved it and electrically contact efficiency.Inventor's discovery, material of the present invention is very suitable for the positive electrode as battery, finds in the future to exist other purposes but also do not get rid of material of the present invention.
A second aspect of the present invention relates to a kind of surface and has the preparation method of the material of multistage nanometer micrometer structure, and existing to wherein each step, details are as follows:
Step a. is by tilting porous, electrically conductive substrate first reactor of putting into, in this reactor, add first aqueous solution that comprises solubility cobalt salt, ammonium fluoride and urea again, then airtight this reactor, heat up and under self-generated pressure, carry out hydro-thermal reaction for the first time, with the vertical elementary micro wire array of this substrate grown cobalt hydroxide on this porous, electrically conductive substrate surface.Preferably, this porous, electrically conductive substrate will be in advance through cleaning, to remove lip-deep dirt and impurity.Such cleaning can be ultrasonic cleaning in concentrated hydrochloric acid, is then transferred to such as in deionized water and ethanol equal solvent ultrasonic cleaning again.In this first aqueous solution, the concentration of various materials can be adjusted as required, for example, in a kind of preferred embodiment, described solubility cobalt salt concentration is 0.025-0.1 mol/L, and ammonium fluoride concentration is 0.1-0.4 mol/L, and urea concentration is 0.1-0.5 mol/L.Certainly, also can use other concentration range.The condition of described the first hydro-thermal reaction also can be adjusted as required, and for example a kind of optimum condition is: temperature is 100-120 DEG C, and the reaction time is 8-12 hour.Through the first hydro-thermal reaction, what in porous, electrically conductive substrate, obtain is the elementary micro wire of cobalt hydroxide.Change the concentration of each material or the condition of change the first hydro-thermal reaction, can adjust elementary micro wire array at this suprabasil arranging density, growing height etc., these can be tested and specifically be groped its growth rhythm by limited number of time.Wherein said solubility cobalt salt is selected from cobalt nitrate, cobaltous sulfate or cobalt chloride, or their any hydrate with the crystallization water.After this first hydro-thermal reaction finishes, after being cooled to room temperature, opens by this first reactor.
Step b. takes out this porous, electrically conductive substrate, washs and is dried.Concrete washing and drying mode are not limited, and for example, washing can be rinsed or ultrasonic cleaning with any suitable solvent such as water, ethanol etc., is dried and can adopts the mode of drying in baking oven.
Step c is by tilting porous, electrically conductive substrate after treatment step b second reactor of putting into, in this reactor, add second aqueous solution that comprises solubility cobalt salt and urea again, seal this reactor, heat up and under self-generated pressure, carry out hydro-thermal reaction for the second time, make the orthogonal micron film of the elementary micro wire continued growth of cobalt hydroxide described in each, or the elementary micro wire merging growth of multiple cobalt hydroxide closing on becomes a rectangle micron film.In described second aqueous solution, the concentration of various materials can be adjusted as required, and for example, in a kind of preferred embodiment, solubility cobalt salt concentration is 0.025-0.075 mol/L, and urea concentration is 0.1-0.5 mol/L; The condition of described the second hydro-thermal reaction also can be adjusted as required, and for example a kind of optimum condition is: temperature is 80-100 DEG C, and the reaction time is 6-10 hour.Described solubility cobalt salt is selected from cobalt nitrate, cobaltous sulfate or cobalt chloride, or their any hydrate with the crystallization water.After this second hydro-thermal reaction finishes, after being cooled to room temperature, opens by this second reactor.
Steps d. again take out this porous, electrically conductive substrate, wash and be dried.Concrete washing and drying mode are not limited, and for example, washing can be rinsed or ultrasonic cleaning with any suitable solvent such as water, ethanol etc., is dried and can adopts the mode of drying in baking oven.
Step e. is by tilting porous, electrically conductive substrate after treatment steps d the 3rd reactor of putting into, in this reactor, add the 3rd aqueous solution that comprises soluble nickel salt and urea again, seal this reactor, heat up and under self-generated pressure, carry out hydro-thermal reaction for the third time, this secondary nano wire of villous nickel hydroxide that hydro-thermal reaction can be grown numerous on the surface of aforementioned cobalt hydroxide rectangle micron film for the third time.In described the 3rd aqueous solution, the concentration of various materials can be adjusted as required, and for example, in a kind of preferred embodiment, soluble nickel salinity is 0.025-0.1 mol/L, and urea concentration is 0.1-0.5 mol/L; The condition of described the 3rd hydro-thermal reaction also can be adjusted as required, and for example a kind of optimum condition is: temperature is 80-100 DEG C, and the reaction time is 6-10 hour.Described soluble nickel salt is selected from nickel nitrate, nickelous sulfate or nickel chloride, or their any hydrate with the crystallization water.After the 3rd hydro-thermal reaction finishes, after being cooled to room temperature, opens by the 3rd reactor.
Step f. takes out this porous, electrically conductive substrate again, washs and is dried.Concrete washing and drying mode are not limited, and for example, washing can be rinsed or ultrasonic cleaning with any suitable solvent such as water, ethanol etc., is dried and can adopts the mode of drying in baking oven.
Step g. in air, calcine this porous, electrically conductive substrate, make the elementary rectangle micron film of cobalt hydroxide array change the elementary rectangle micron film of cobaltosic oxide array into, and make villous nickel hydroxide nano line change nickel oxide nanowires into.Can regulate calcining heat, calcination time and calcination atmosphere, to guarantee that calcining rear cobalt hydroxide changes cobaltosic oxide into, nickel hydroxide changes nickel oxide into.For example, one group of preferred calcination condition is: calcining heat is 250-350 DEG C, and calcination time is 2-4 hour.
Above-mentioned preparation method is synthetic under simple hydrothermal reaction condition, and method is easy, with low cost, reproducible; Do not adopt any organic solvent and surfactant, very friendly to environment; The product structure homogeneous, the ordered arrangement that obtain, this is an integral type material for what is more important, in this material, cobaltosic oxide as electrode active material is directly connected with the porous, electrically conductive substrate as collector with nickel oxide, when making without add adhesive, and novel structure, has good conduction property; In addition by kind and the concentration of cobalt salt and nickel salt in control solution, can synthesize the multistage nanometer micrometer structure with different size size and density degree, the pattern of realizing material is controlled.Such structure has been avoided general powder body material and collector loose contact, the problem of electric transmission weak effect, and due to the existence of multistage nanometer micrometer structure, the existence of especially numerous villous secondary nano wires, can greatly increase the specific area of electrode active material, improve the electrical contact performance of material, and then improved the integrated electronic performance that comprises the electrode and the battery that change material.
A third aspect of the present invention relates to the battery that a kind of its positive pole comprises the material that a first aspect of the present invention mentions.In this battery, anticathode material is not particularly limited, as long as it can mate with the positive electrode that comprises the material that a first aspect of the present invention mentions generation electromotive force.Preferred negative material is a substrate for plating zinc on surface, and the material of substrate is also not particularly limited.
A fourth aspect of the present invention relates to a kind of nickel-zinc cell, its positive electrode comprises the material described in a first aspect of the present invention, its negative material comprises the zinc being plated in conductive substrates, and the conductive substrates comprising in the conductive substrates wherein comprising in negative material and positive electrode can be identical or different.Preferably, the conductive substrates in negative material is copper sheet or titanium sheet.In such nickel-zinc cell, also can comprise barrier film and the alkali metal hydroxide aqueous solution that comprises zincic acid radical ion as electrolyte, barrier film is not had to particular/special requirement.In a kind of substituting embodiment, negative material can be not zinc-plated in advance yet, but in electrolyte, comprise soluble zinc salt, and the mode of electroplating by charging process situ, is electroplated onto zinc on the surface of negative material.Such nickel-zinc cell can be made the form of soft-package battery.
Embodiment
Further illustrate the present invention by following examples.Embodiment is only illustrative, and not restrictive.
Embodiment 1
A. by tilting nickel foam substrate first reactor of putting into, in this reactor, add the cobalt nitrate that comprises 0.05 mol/L again, first aqueous solution of the urea of the ammonium fluoride of 0.2 mol/L and 0.25 mol/L, then airtight this reactor, be warming up to 120 DEG C and under self-generated pressure, keep carrying out for 12 hours hydro-thermal reaction for the first time, with the vertical elementary micro wire array of this substrate grown cobalt hydroxide on this nickel foam substrate surface;
B. take out this nickel foam substrate, wash and be dried;
C. by tilting nickel foam substrate after treatment step b second reactor of putting into, again to second aqueous solution of urea that adds the cobalt nitrate that comprises 0.025 mol/L and 0.25 mol/L in this reactor, seal this reactor, be warming up to 100 DEG C and under self-generated pressure, keep carrying out for 10 hours hydro-thermal reaction for the second time, make the elementary micro wire of cobalt hydroxide described in each form cobalt hydroxide rectangle micron film, or the elementary micro wire merging growth of multiple cobalt hydroxide closing on become a rectangle micron film; Concrete growth mechanism is not emphasis of the present invention, controls in a word the second hydrothermal condition, can finally produce cobalt hydroxide rectangle micron film;
D. again take out this nickel foam substrate, wash and be dried;
E. by tilting nickel foam substrate after treatment steps d the 3rd reactor of putting into, again to the 3rd aqueous solution of urea that adds the nickel nitrate that comprises 0.05 mol/L and 0.25 mol/L in this reactor, seal this reactor, be warming up to 100 DEG C and under self-generated pressure, keep carrying out hydro-thermal reaction for the third time in 10 hours, make the villous nickel hydroxide nano line of growing on the elementary rectangle micron film of cobalt hydroxide described in each;
F. again take out this nickel foam substrate, wash and be dried;
G. 250 DEG C of calcining this nickel foam substrates 3 hours in air, this calcination condition can make the elementary rectangle micron film of cobalt hydroxide change the elementary rectangle micron film of cobaltosic oxide into, and makes the secondary nano wire of nickel hydroxide change the secondary nano wire of nickel oxide into.
The scanning electron microscope (SEM) photograph of the material obtaining is referring to accompanying drawing 2, and its XRD spectra is referring to accompanying drawing 3, and its cyclic voltammetry curve figure is referring to accompanying drawing 4, and its charging and discharging curve figure is referring to Fig. 5, and its cyclical stability figure is referring to accompanying drawing 6.
Embodiment 2
Referring to the method in embodiment 1, cobalt nitrate in embodiment 1 step a and step c is changed to cobalt chloride, nickel nitrate in step e is changed to nickel chloride, the material obtaining with embodiment 1 of the material obtaining is all very approaching in appearance and performance.
Embodiment 3
Referring to the method in embodiment 1, porous, electrically conductive substrate is changed to carbon fiber felt by nickel foam substrate, all the other are constant.
The scanning electron microscope (SEM) photograph obtaining is referring to accompanying drawing 7, and its XRD spectra is referring to accompanying drawing 8, and its cyclic voltammetry curve figure is referring to accompanying drawing 9, and its charging and discharging curve figure is referring to Figure 10, and its cyclical stability figure is referring to accompanying drawing 11.
Embodiment 4
The material obtaining taking embodiment 1 is anodal, taking the conductive copper sheet of plating zinc on surface as negative pole, taking the potassium hydroxide aqueous solution of 6 mol/L as electrolyte, also contains zincic acid radical ion in this electrolyte, sets up into battery.
Its cyclic voltammetry curve figure is referring to accompanying drawing 13, and its charging and discharging curve figure is referring to accompanying drawing 14, and its multiplying power property figure is referring to accompanying drawing 15, and its capacity circulating stability diagram is referring to accompanying drawing 16.
Embodiment 5
Using the battery in embodiment 4 as basis, separately adding celgard2400 type lithium battery diaphragm is barrier film, taking Copper Foil as wire, electrode material and barrier film is packed in Aluminium Foil Package, is assembled into easy soft-package battery.Two such soft-package battery series connection, can make LED lighting after charging, and can keep luminous at least one hour, referring to Figure 17.After tested, the electric property of this battery is as follows: the capacitive property of positive and negative polarities is stablized and capacity matching, and the battery after assembling electrically contacts well, excellent performance.Be under 0.33A/g in current density, capacity is 153.33mAh/g; Energy density when power density is 550W/kg is 251.33Wh/kg, after 500 constant current charge-discharge circulations, and its capacity attenuation less than 18%.This alkaline battery has larger energy density than traditional nickel zinc battery, and can under relatively high power density, work, and can keep good stability, has in actual applications considerable prospect.
Claims (9)
1. surface has a material for multistage nanometer micrometer structure, and it comprises:
Porous, electrically conductive substrate;
In described porous, electrically conductive substrate perpendicular to the elementary rectangle micron film of the cobaltosic oxide array of this substrate grown;
The secondary nano wire of multiple fine hair shape nickel oxide of growing on the surface of elementary rectangle micron film described in each.
2. the material of claim 1, wherein said porous, electrically conductive substrate is selected from: foam copper, nickel foam or porous carbon fiber felt.
3. the material of claim 1, the elementary rectangle micron film of wherein said cobaltosic oxide is of a size of: length 8-12 micron, width 1.5-2.5 micron; The secondary nano wire of described nickel oxide is of a size of: length 70-90 nanometer.
4. surface has a preparation method for the material of multistage nanometer micrometer structure, and it comprises the following steps:
A. by tilting porous, electrically conductive substrate first reactor of putting into, in this reactor, add first aqueous solution that comprises solubility cobalt salt, ammonium fluoride and urea again, then airtight this reactor, heat up and under self-generated pressure, carry out hydro-thermal reaction for the first time, with the vertical elementary micro wire array of this substrate grown cobalt hydroxide on this porous, electrically conductive substrate surface;
B. take out this porous, electrically conductive substrate, wash and be dried;
C. by tilting porous, electrically conductive substrate after treatment step b second reactor of putting into, in this reactor, add second aqueous solution that comprises solubility cobalt salt and urea again, seal this reactor, heat up and also under self-generated pressure, carry out hydro-thermal reaction for the second time, make the elementary micro wire of cobalt hydroxide described in each form elementary rectangle micron film;
D. again take out this porous, electrically conductive substrate, wash and be dried;
E. by tilting porous, electrically conductive substrate after treatment steps d the 3rd reactor of putting into, in this reactor, add the 3rd aqueous solution that comprises soluble nickel salt and urea again, seal this reactor, heat up and under self-generated pressure, carry out hydro-thermal reaction for the third time, with the secondary nano wire of multiple fine hair shape nickel hydroxide of growing on the surface on the elementary rectangle micron film of each described cobalt hydroxide;
F. again take out this porous, electrically conductive substrate, wash and be dried;
G. in air, calcine this porous, electrically conductive substrate, make the elementary rectangle micron film of cobalt hydroxide change the elementary rectangle micron film of cobaltosic oxide into, and make the secondary nano wire of nickel hydroxide change the secondary nano wire of nickel oxide into.
5. the method for claim 4, in wherein said first aqueous solution, described solubility cobalt salt concentration is 0.025-0.1 mol/L, ammonium fluoride concentration is 0.1-0.4 mol/L, urea concentration is 0.1-0.5 mol/L, the condition of described the first hydro-thermal reaction is: temperature is 100-120 DEG C, and the reaction time is 8-12 hour; In described second aqueous solution, solubility cobalt salt concentration is 0.025-0.075 mol/L, and urea concentration is 0.1-0.5 mol/L, and the condition of described the second hydro-thermal reaction is: temperature is 80-100 DEG C, and the reaction time is 6-10 hour; In described the 3rd aqueous solution, soluble nickel salinity is 0.025-0.1 mol/L, and urea concentration is 0.1-0.5 mol/L, and the condition of described the 3rd hydro-thermal reaction is: temperature is 80-100 DEG C, and the reaction time is 6-10 hour; Wherein said solubility cobalt salt is selected from cobalt nitrate, cobaltous sulfate or cobalt chloride; Described soluble nickel salt is selected from nickel nitrate, nickelous sulfate or nickel chloride.
6. the method for claim 4, in wherein said step g, calcining heat is 250-350 DEG C, calcination time is 2-4 hour.
7. a battery, its positive electrode comprises the material described in any one in claim 1-3.
8. a nickel-zinc cell, its positive electrode comprises the material described in any one in claim 1-3, and its negative material comprises the zinc being plated in conductive substrates, and the conductive substrates comprising in the conductive substrates wherein comprising in negative material and positive electrode is identical or different.
9. the nickel-zinc cell of claim 8, it also comprises barrier film and the alkali metal hydroxide aqueous solution that comprises zincic acid radical ion as electrolyte.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410218958.8A CN104051728B (en) | 2014-05-22 | 2014-05-22 | Material with surface multilevel nano micron structure, preparation method thereof and nickel-zinc cell containing the material in anode |
| PCT/CN2015/078444 WO2015176609A1 (en) | 2014-05-22 | 2015-05-07 | Material with surface having multilevel nano micron structure, preparation method thereof and nickel-zinc cell containing material in a positive electrode |
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| CN201410218958.8A CN104051728B (en) | 2014-05-22 | 2014-05-22 | Material with surface multilevel nano micron structure, preparation method thereof and nickel-zinc cell containing the material in anode |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104617307A (en) * | 2015-01-29 | 2015-05-13 | 北京化工大学 | Electrode material with surface nanometer-micrometer structure, preparation method thereof and hydrazine hydrate fuel battery containing electrode material |
| CN105084426A (en) * | 2014-05-19 | 2015-11-25 | 中国科学院过程工程研究所 | In-situ grown three-dimensional multi-structural cobaltosic oxide/carbon composite micro-nanomaterial and controllable preparation method thereof |
| WO2015176609A1 (en) * | 2014-05-22 | 2015-11-26 | 北京化工大学 | Material with surface having multilevel nano micron structure, preparation method thereof and nickel-zinc cell containing material in a positive electrode |
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