CN106410227A - Copper oxide and preparation method thereof - Google Patents
Copper oxide and preparation method thereof Download PDFInfo
- Publication number
- CN106410227A CN106410227A CN201611138641.9A CN201611138641A CN106410227A CN 106410227 A CN106410227 A CN 106410227A CN 201611138641 A CN201611138641 A CN 201611138641A CN 106410227 A CN106410227 A CN 106410227A
- Authority
- CN
- China
- Prior art keywords
- cupric oxide
- peak
- oxygen
- characteristic peak
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
Abstract
The invention relates to a copper oxide and preparation method thereof. The X-ray photoelectron spectroscopy of the copper oxide contains an O1s characteristic peak and a Cu2p3/2 characteristic peak. The amplitude ratio between the O1s characteristic peak and the Cu2p3/2 characteristic peak is 1.2 to 5. The copper oxide has excellent catalytic property.
Description
Technical field
The invention belongs to Material Field is and in particular to a kind of cupric oxide and preparation method thereof.
Background technology
Metal-air battery, is a kind of strong candidate of New Generation of Electric Vehicle electrokinetic cell.Metal-air
, generally using metal as anode electrochemical active material, the oxygen of in the air is as electroactive cathode material for battery.Due to
Oxygen is directed to air without being stored in inside battery so that metal-air battery has very high theoretical specific energy.
Metal-air battery is possible to realize the device energy density of more than 1000Wh/kg, close with gasoline.
The anode active material of metal-air battery can be alkali metal, alkaline-earth metal or other active metal (for example
Zn).In numerous anode active materials, lithium metal has relatively negative electrode potential (- 3.04V vs.SHE) and less density
(6.95g·mol-1), be conducive to the raising of the specific capacity of battery, be the focus of current research.Lithium metal is as GND material
Material has about 3.81Ahg-1Theoretical specific capacity, now, the energy density theoretical value of lithium-air battery is possible to reach 3505Wh/
kg.Under this energy density, the electric automobile course continuation mileage being equipped with lithium-air battery can reach more than 600 kilometers.
In order to improve the performance of metal-air battery, technical staff person uses the negative electrode of catalyst metal-air battery
Reaction, such as oxygen reduction reaction (Oxygen Reductive Reaction, ORR) and/or oxygen evolution reaction (Oxygen
Evolution Reaction, OER).The species of catalyst mainly includes noble metal and its alloy, metal oxide, functionalization
Material with carbon element etc..
Content of the invention
It is an object of the present invention to provide a kind of high cupric oxide of catalysis activity, it is also another object of the present invention to provide
A kind of high cupric oxide of copper valence state, it is also another object of the present invention to provide a kind of high cupric oxide of absorption oxygen content；This
The further object of invention is the cupric oxide providing a kind of absorption oxygen reactivity high；It is also another object of the present invention to provide one
Kind of the absorption high cupric oxide of oxygen adsorption strength, further object of the present invention be provide one kind can effectively catalytic oxidation-reduction reaction with/
Or the cupric oxide of oxygen evolution reaction, further object of the present invention be find a kind of cupric oxide be used for catalytic oxidation-reduction reaction and/or
The purposes of oxygen evolution reaction, further object of the present invention is to provide a kind of metal-air battery.
Inventor finds, the cupric oxide of the present invention has the absorption oxygen of high-load, and this cupric oxide can be catalyzed oxygen effectively
Reduction reaction and/or oxygen evolution reaction.The cupric oxide of the present invention is as the cathod catalyst of metal-air battery, it is possible to increase gold
Belong to the rate capability of air cell, improve its high current charge-discharge ability.
First aspect present invention provides a kind of cupric oxide, its x-ray photoelectron energy spectrum diagram (X-ray photoelectron
Spectroscopy, XPS) include O1s characteristic peak and Cu2p3/2 characteristic peak, the peak of O1s characteristic peak and Cu2p3/2 characteristic peak
Area ratio value is 1.2～5, such as 1.5～5, more such as 2～5, more such as 3～5, more such as 3～4, more such as 1.2,1.3,
1.4、1.5、1.6、1.7、1.8、1.9、2、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、3、3.1、3.2、3.3、
3.4th, 3.5,3.6,3.7,3.8,3.9,4,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9 or 5.
The O1s characteristic peak of this cupric oxide is higher with the ratio of the peak area of Cu2p3/2 characteristic peak, and this CuO surface is described
Absorption oxygen content higher.The raising of absorption oxygen content is conducive to the raising of copper oxide catalyzation activity.
In one embodiment, the cupric oxide of any one of the present invention, the corresponding combination of described Cu2p3/2 feature peak-to-peak value
Can be 933.0～935.5eV, such as 934～935eV, more such as 934.5～935eV, more such as 934.2～934.8eV, then
Such as 934.6～934.8eV.
The corresponding combination of Cu2p3/2 feature peak-to-peak value of this cupric oxide can be higher, illustrates that on this CuO surface, chemistry is inhaled
The activity of attached oxygen is high.The raising of the activity of the oxygen of chemisorbed is conducive to the raising of copper oxide catalyzation activity.
In one embodiment, the cupric oxide of any one of the present invention, described O1s characteristic peak includes that peak value combines can be
Characteristic peak in the range of 525～537eV, such as peak value combine can characteristic peak in the range of 530～535eV, more such as peak value
In conjunction with can characteristic peak in the range of 530～533eV；
Preferably, described O1s characteristic peak includes two characteristic peaks；
Preferably, described O1s characteristic peak include peak value combination can for 530～531.9eV (such as 530～531eV, for example
530.1～530.3eV) characteristic peak and peak value combination can for 532～534eV (such as 522～533eV, such as 532.1～
532.3eV) characteristic peak；
Preferably, described O1s characteristic peak includes the characteristic peak that peak value combination can be 530.3eV and 532.3eV, such as peak value
In conjunction with the characteristic peak that can be 530.1eV and 532.3eV, more such as peak value combination can be the characteristic peak of 530.3eV and 532.3eV.
In one embodiment, the cupric oxide of any one of the present invention, described O1s characteristic peak is by Lattice Oxygen characteristic peak and suction
Attached oxygen characteristic peak is formed by stacking；
Preferably, Lattice Oxygen characteristic peak and absorption oxygen characteristic peak are to fit peak；
Preferably, described Lattice Oxygen characteristic peak and the ratio of the peak area of described Cu2p3/2 characteristic peak are about 1；
Preferably, described absorption oxygen characteristic peak and the ratio of the peak area of described Cu2p3/2 characteristic peak are 0.2～3.2, example
As 0.5～3, more such as 1～2.8, more such as 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,
1.4、1.5、1.6、1.7、1.8、1.9、2、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、3；
Preferably, the corresponding combination of described Lattice Oxygen feature peak-to-peak value can be 530～532eV, such as 530～531eV, example
As 530.1～530.5eV, e.g., from about 530.3eV；
Preferably, the described absorption corresponding combination of oxygen feature peak-to-peak value can be 531～533eV, such as 532～533eV, example
As 531～532.5eV, such as 531.3eV and 532.1eV.
In one embodiment, the cupric oxide of any one of the present invention, the X ray diffracting spectrum of described cupric oxide includes 2 θ
Angle is the diffraction of 32.5-33.5 ° (such as 32.8 °), 34.8-35.8 ° (such as 35.5 °) and 37.5-38.5 ° (such as 38.3 °)
Peak.
In one embodiment, the cupric oxide of any one of the present invention, described cupric oxide is in the size of at least one dimension
Less than or equal to 1 micron, preferably lower than or equal to 500 nanometers, more preferably less than or be equal to 100 nanometers, further preferably for 5～1000
Nanometer, further preferably for 30～1000 nanometers, such as 300～500 nanometers.
In one embodiment, the cupric oxide of any one of the present invention, it has following one or more feature：
X) described cupric oxide is nano particle, the granularity of described nano particle be preferably 80～1000 nanometers (such as 100～
500 nanometers)；
Y) described cupric oxide is nanometer rods, and the length of described nanometer rods is preferably 30～1000 nanometers (such as 300～500
Nanometer), the diameter of described nanometer rods is preferably 10～100 nanometers (such as 30～50 nanometers)；
Z) described cupric oxide is nano wire, and the length of described nano wire is preferably 1～50 micron (such as 10～20 microns),
The diameter of described nano wire is preferably 50～200 nanometers (preferably 100～150 nanometers).
In one embodiment, the cupric oxide of any one of the present invention is nano cupric oxide.
In one embodiment, in order to improve the electric conductivity of cupric oxide, electro-deposition, photo-reduction or chemistry can first be adopted also
Former method is deposited on elemental copper on the carrier of porous, such as porous carbon, porous tin-antimony oxide electro-conductive glass, multi-layer graphene
On, then carry out caustic corrosion again, prepare corresponding cupric oxide, such as copper oxide nano material.
Second aspect present invention provides a kind of porous material, including porous carrier, described porous carrier has been also loaded this
The cupric oxide of any one of invention.
In one embodiment, the porous material of any one of the present invention, described porous carrier is conductive.
In one embodiment, the porous material of any one of the present invention, described porous carrier is porous carbon, porous tin antimony
Oxide or multi-layer graphene.
In one embodiment, in order to lift oxygen adsorption capacity further and improve electric conductivity, cupric oxide can be with other
Oxide is used in mixed way, or preparation oxidation copper based mixed oxide catalyst, such as cupric oxide-Sb2O3, cupric oxide-CeO2, oxidation
Copper-Ni2O3, cupric oxide-Co3O4, cupric oxide-RuO2, more such as cupric oxide-Co3O4-RuO2, cupric oxide-Co3O4-RuO2Deng.
Third aspect present invention provides a kind of composition, including the cupric oxide of any one of the present invention.
In one embodiment, the composition of any one of the present invention, it also includes Sb2O3、CeO2、Ni2O3、Co3O4With
RuO2One or more of；
Preferably, described composition is by the cupric oxide of any one of the present invention, Co3O4And RuO2Constitute.
Fourth aspect present invention provides a kind of preparation method of cupric oxide, and it comprises the following steps：
A) a Copper substrate part is placed in alkaline aqueous solution, a part exposes in atmosphere, reaction, or by alkaline water
Solution puts on the surface of Copper substrate, reaction；
Preferably, the time of reaction is 10 minutes to 30 days, preferably 30 minutes to 3 days, further preferably 1～2 day；
Preferably, the temperature of reaction is 0～90 DEG C, such as 20～50 DEG C；
Preferably, described Copper substrate is the porous carrier that copper is covered on copper sheet, copper powder or surface.
In one embodiment, the method for any one of the present invention, described alkaline aqueous solution contains water-soluble alkali；
Preferably, concentration in alkaline aqueous solution for the described water-soluble alkali is 0.1～10mol/L, preferably 0.1～5mol/L
(such as 0.1mol/L, 1mol/L or 3mol/L)；
Preferably, described water-soluble alkali is included selected from one or more of LiOH, KOH or NaOH.
In one embodiment, the method for any one of the present invention, described alkaline aqueous solution contains additive, described interpolation
Agent include selected from ethanol, ammoniacal liquor, hexamethylenetetramine, dodecyl sodium sulfate, lauryl sodium sulfate, potassium chloride, sodium chloride,
One or more in lithium chloride, tween, glycerine, ethylene glycol；
In one embodiment, the method for any one of the present invention, described alkaline aqueous solution contains additive, described interpolation
Agent is included selected from ethanol, hexamethylenetetramine, dodecyl sodium sulfate, lauryl sodium sulfate, potassium chloride, sodium chloride, chlorination
One or more in lithium, tween, glycerine, ethylene glycol；
In one embodiment, the method for any one of the present invention, described alkaline aqueous solution contains additive, described interpolation
Agent is included selected from lauryl sodium sulfate, sodium chloride or glycerine；
Preferably, described additive in alkaline aqueous solution concentration be 0.0001-0.2mol/L, preferably 0.01～
0.1mol/L.
In one embodiment, the method for any one of the present invention, described alkaline aqueous solution contain 1mol/L KOH,
0.1mol/L LiOH and 0.01mol/L KCl.
In one embodiment, the method for any one of the present invention, described alkaline aqueous solution contain 0.1mol/L LiOH and
0.1mmol/L dodecyl sodium sulfate.
In one embodiment, the method for any one of the present invention, described alkaline aqueous solution contain 3mol/L KOH and
0.1mmol/L glycerine
In one embodiment, the method for any one of the present invention, does not contain oxidant in described alkaline aqueous solution；
Preferably, described oxidant is selected from one or more of hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate.
In one embodiment, the method for any one of the present invention, does not contain NH in described alkaline aqueous solution4 +, preferably not
Containing ammoniacal liquor.
In one embodiment, the method for any one of the present invention, also includes after step a)：
B) product of step a) is heat-treated in oxygen-containing atmosphere；
Preferably, the temperature of heat treatment is 100～400 DEG C, preferably 250～350 DEG C；
Preferably, the time of heat treatment is 1～5 hour, preferably 2～4 hours；
Preferably, described oxygen-containing atmosphere is air atmosphere.
In one embodiment, the method for any one of the present invention, the one or multi-step comprising the following steps：
I) clean Copper substrate；
Ii) a Copper substrate part is placed in alkaline aqueous solution, a part exposes in atmosphere, reaction, or by alkalescence
The aqueous solution puts on the surface of Copper substrate, reaction；
Alternatively, also include step iii)
Iii) heat treatment step ii) product；
Iv) wash, be dried.
In one embodiment, the method for any one of the present invention, the time of reaction is 10 minutes to 30 days, preferably 30 points
Clock to 3 days, such as 12h, 24h, 36h or 48h.
In one embodiment, the method for any one of the present invention, described cupric oxide is the cupric oxide of any one of the present invention.
Fifth aspect present invention provides a kind of cupric oxide, and it is obtained by the method for fourth aspect present invention.
Sixth aspect present invention provides cupric oxide, the porous material of any one of the present invention or the present invention of any one of the present invention
The composition of any one is used for catalytic oxidation-reduction reaction and/or the purposes of oxygen evolution reaction；
Preferably, described oxygen reduction reaction is 4Li+O2+2H2O→4Li++4OH-；
Preferably, described oxygen evolution reaction is 4OH-→O2+2H2O+4e-；
Preferably, described oxygen reduction reaction is 4Li+O2+4H+→4Li++2H2O；
Preferably, described oxygen evolution reaction is 2H2O→O2+4H++4e-.
Seventh aspect present invention provides a kind of metal-air battery, appoints including the cupric oxide of any one of the present invention, the present invention
The porous material of one and/or the composition of any one of the present invention；
Preferably, the negative electrode of described metal-air battery includes the cupric oxide of any one of the present invention, any one of the present invention
Porous material and/or the composition of any one of the present invention.
In one embodiment, the metal-air battery of any one of the present invention, the anode bag of described metal-air battery
Include：One or more of active metal simple substance, active metallic ion, active metal alloy and active metal insert material；
Preferably, described active metal is included selected from one or more of K, Na, Li, Mg, Ca, Ba and Zn；
Preferably, described active metal includes Li；
Preferably, described metal-air battery is lithium-air battery, sodium air cell, zinc-air battery, calcium air cell
Or magnesium air cell.
In one embodiment, the metal-air battery of any one of the present invention, including anode electrochemical active component and
Cathode electrochemical Iy active component.
In one embodiment, the metal-air battery of any one of the present invention, its anode electrochemical active component includes：
One or more of active metal simple substance, active metallic ion, active metal alloy and active metal insert material
In one embodiment, the metal-air battery of any one of the present invention, active metal includes alkali metal, alkaline earth gold
One or more of genus and transition metal.
In one embodiment, the metal-air battery of any one of the present invention, active metal include selected from Li, Na, K,
One or more of Ca, Mg, Ba, Zn；Preferably active metal includes Li.
In one embodiment, active metallic ion is included selected from Li+、Na+、K+、Ca2+、Mg2+、Ba2+、Zn2+In one
Plant or multiple.
In one embodiment, the metal-air battery of any one of the present invention, active metal alloy includes：Containing Li,
The alloy of one or more of Na, K, Ca, Mg, Ba, Zn element；Preferably include by Li, Na, K, Ca, Mg, Ba, Zn
One or more element and in Sn, Si, Zn, Al, Sb, Ge, Pb, Mg, Ca, As, Bi, Pt, Ag, Au, Cd, Hg etc.
The alloy more than binary of kind or various metals composition or ternary；Preferably include selected from lithium-aluminium alloy, Li-Si alloy, lithium-tin alloy
One or more of with lithium silver alloy.
In one embodiment, the metal-air battery of any one of the present invention, active metal insert material is carbon or lithium
Carbon compound.
In one embodiment, the metal-air battery of any one of the present invention, its cathode electrochemical Iy active component includes
Oxygen.
In one embodiment, the metal-air battery of any one of the present invention, its cathode electrochemical Iy active component includes
Air.
In one embodiment, the metal-air battery of any one of the present invention, the negative electrode of this metal-air battery also wraps
Include electronic conductor, described electronic conductor includes material with carbon element and binding agent.
In one embodiment, material with carbon element is carbon black (Super P, Ketjen Black, Vulcan XC-72 etc.), carbon
Nanotube and Graphene etc..
In one embodiment, binding agent is Nafion of PVDF, PTFE or lithiumation etc..
In one embodiment, the metal-air battery of any one of the present invention is lithium-air battery, and lithium-air battery is excellent
Elect organic electrolyte system lithium-air battery, organic-water combination electrolyte system lithium-air battery, water solution system lithium air as
Battery or all solid state electrolyte system lithium-air battery.
In one embodiment, the metal-air battery of any one of the present invention, in the discharged condition, negative electrode is positive pole,
Anode is negative pole.
Beneficial effects of the present invention
The content that the CuO surface of the present invention adsorbs oxygen is higher, is conducive to improving the catalysis activity of cupric oxide.Additionally, should
The copper of cupric oxide has high oxidation state, more than+divalent；And O1s characteristic peak and Cu2p3/2 characteristic peak in XPS analysis
The ratio of peak area is more than 1.It follows that the oxygen content of the chemisorbed of this CuO surface is higher.General according to catalysis
Principle, the oxygen of chemisorbed has than physical absorption compared with high reaction activity, and the absorption oxygen that these have high reaction activity can
The catalysis activity of lifting cupric oxide, and then improve the reaction rate of CuO surface oxygen reduction reaction and/or oxygen evolution reaction.
Some embodiments of the invention has following one or more beneficial effect：
(1) catalysis activity of the cupric oxide of some embodiments is high；
(2) the copper valence state of the cupric oxide of some embodiments is higher；
(3) surface of the cupric oxide of some embodiments, the content of absorption oxygen is higher, especially the content of chemically adsorbing oxygen
Higher；
(4) surface of the cupric oxide of some embodiments, the adsorption strength of absorption oxygen is higher；
(5) surface of the cupric oxide of some embodiments, the reactivity of absorption oxygen is higher；
(6) cupric oxide of some embodiments has more defect sturcture, and these defect sturctures are conducive to improving oxygen suction
Attached amount；
(7) cupric oxide of some embodiments can more efficiently catalytic oxidation-reduction react and/or oxygen evolution reaction；
(8) some embodiments prepare cupric oxide method is simple, preparation process environmental friendliness, cost of material is low, easily
In large-scale production；
(9) cupric oxide of some embodiments has inexpensive, eco-friendly advantage, is conducive to business application, helps
In the large-scale production realizing metal-air battery and application；
(10) metal-air battery of some embodiments has the high rate performance of improvement, the heavy-current discharge energy improving
Power.
Brief description
Accompanying drawing described herein is used for providing a further understanding of the present invention, constitutes the part of the application, this
Bright schematic description and description is used for explaining the present invention, does not constitute limitation of the invention.In the accompanying drawings：
Fig. 1 is the electron scanning micrograph of the cupric oxide of embodiment 1；
Fig. 2 is the X ray diffracting spectrum of the cupric oxide of embodiment 1；
Fig. 3 is the XPS collection of illustrative plates of the cupric oxide of embodiment 1.Wherein, (a) is：O 1s photoelectron spectral line, empty circles line 1 is
Initial data spectral line, heavy black 2 is the spectral line according to initial data line shape fitting, and thin black line 3 is matching peak；B () is Cu 2p3/
2 photoelectron spectral lines；
Fig. 4 is the electron scanning micrograph of the cupric oxide of embodiment 2；
Fig. 5 is the electron scanning micrograph of cupric oxide and the X ray diffracting spectrum of embodiment 2；
Fig. 6 is the transmission electron microscope photo of the cupric oxide of embodiment 3, and illustration is this transmission electron microscope photo
Fourier transformation image；
Fig. 7 is the electron scanning micrograph of the cupric oxide of embodiment 3.
Specific embodiment
Referred to specific embodiments of the present invention in detail now.The example of specific embodiments is illustrated in the drawings.To the greatest extent
Pipe describes the present invention with reference to these specific embodiments, it is appreciated that being not intended to limit the invention to these specific embodiment parties
Case.On the contrary, these embodiments are intended to cover the replacement that may include in the spirit and scope being defined by the claims, change
Become or equivalent embodiments.In the following description, a large amount of details are elaborated to provide complete understanding of the present invention.
The present invention can be carried out in the case of these details not part or all of.In other cases, in order to not make this
Bright unnecessarily obscure, be not described in known to technological operation.
When with this specification and the appended claims in " inclusion ", " method includes ", " device includes " or similar language
When being used in combination, singulative " certain ", " certain ", " being somebody's turn to do " include plural reference, unless the context clearly dictates otherwise.Unless it is another
It is usual that outer definition, all technology used herein and scientific terminology have general technical staff of the technical field of the invention
The identical meanings understanding.
The instrument that following examples use and test condition are as shown in table 1 below：
Table 1
| Instrument | Producer's trade mark |
| SEM | JSM-6330F, Shimadzu |
| TEM | JEM-2010HR, JEOL |
| XPS | ESCALab 250 |
Preparation and the sign of cupric oxide are described below by specific embodiment：
Embodiment 1
1st, the preparation of cupric oxide
(1) with copper sheet as presoma, first copper sheet is first cleaned by ultrasonic 5 minutes in the HCl solution of 0.1mol/L, then uses
Deionized water rinsing, then soaks 1 minute, finally deionized water is rinsed again in acetone soln.
(2) the copper sheet part after cleaning is placed in alkaline aqueous solution, a part exposes in atmosphere, alkaline aqueous solution
Containing 1mol/L KOH, 0.1mol/L LiOH and 0.01mol/L KCl, after reacting 5 days at room temperature, whole copper sheet surface becomes
Black.Take out copper sheet, deionized water is cleaned, and is then dried.
(3) dried copper sheet is heat-treated 5 hours at 300 DEG C, air atmosphere, obtains the copper that surface is covered with cupric oxide
Piece.
2nd, characterize
(1) surface be covered with the copper sheet of cupric oxide SEM (SEM) photo as shown in Figure 1.Grow on copper sheet
A lot of nanometer rods, nanorod diameter is about 30 nanometers, a length of 300-500 nanometer.The rough surface of nanometer rods.
(2) X-ray diffraction analysis (XRD) are carried out to the copper sheet being covered with cupric oxide, X ray diffracting spectrum is as shown in Figure 2.2θ
Angle is 32.8 °, the peak of 35.5 ° and 38.3 ° is the diffraction maximum of cupric oxide, and 2 θ angles are 43.2 ° and 50.7 ° of peak is spreading out of copper-based bottom
Penetrate peak.The diffraction peak intensity of cupric oxide is weak and wider, illustrates that the degree of crystallinity of cupric oxide is relatively low.XRD data confirm that, copper sheet surface
Nanometer rods be cupric oxide.
From SEM and XRD data, this cupric oxide has coarse surface and low degree of crystallinity, and this illustrates this cupric oxide
There is substantial amounts of defect sturcture, these defect sturctures are conducive to improving the amount of oxygen absorption.
(3) copper sheet being covered with cupric oxide has been carried out with X-ray photoelectron spectroscopic analysis (XPS) analysis, result is shown in Fig. 3, its
In, (a) is：O 1s photoelectron spectral line, empty circles line 1 is initial data spectral line, and heavy black 2 is to be intended according to initial data spectral line
The spectral line closing, carefully black spectral line 3 is matching peak；B () is Cu 2p3/2 photoelectron spectral line.Display O1s is special for x-ray photoelectron energy spectrum diagram
Levy the corresponding combination of peak-to-peak value and can be respectively 530.3eV and 532.3eV, the corresponding combination of Cu2p3/2 feature peak-to-peak value can be
934.8eV.O1s characteristic peak is 2.8 with the ratio of the ratio of the peak area of Cu2p3/2 characteristic peak.Swarming plan is carried out to O1s characteristic peak
With, by O1s characteristic peak divide into Lattice Oxygen characteristic peak and absorption oxygen characteristic peak.The corresponding combination of Lattice Oxygen feature peak-to-peak value can be
530.3eV, the absorption corresponding combination of oxygen feature peak-to-peak value can be 531.3eV and 532.1eV.According to XPS data, Lattice Oxygen feature
The ratio of peak and the ratio of the peak area of Cu2p3/2 characteristic peak is 1.01, absorption oxygen characteristic peak and Cu2p3/2 characteristic peak peak face
The ratio of long-pending ratio is 1.79.
Using XPS Peak 41 software, according to Gauss-Lorentz lorentz's mixed function fitting theory, calculated by XPS data
Know, CuO surface oxygen is up to 2.8 with the atomic ratio of copper, remove the oxygen of 1 ratio and copper is combined outward with the chemical formula of cupric oxide,
Remaining 1.8 parts of oxygen, belong to absorption oxygen.The content of absorption oxygen is higher.
Additionally, the combination of the Cu2p3/2 characteristic peak of this cupric oxide can be higher, up to 934.8eV, illustrate that copper has height
Oxidation state, more than+divalent.It follows that oxygen is in the adsorbed state not only bag physical absorption of CuO surface, also inclusion
Learn absorption, and the oxygen of chemisorbed has higher adsorption strength.Due to adsorbing reactivity and its adsorption strength positive of oxygen
Close, adsorption strength is higher, and reactivity is also higher, the absorption oxygen of therefore this CuO surface has higher reactivity.
This cupric oxide has higher catalysis activity, can effectively catalytic oxidation-reduction react and/or oxygen evolution reaction.
Therefore, the cupric oxide of embodiment 1 can effectively catalytic oxidation-reduction reaction and/or oxygen evolution reaction carrying out.Enter
One step, using the cupric oxide of embodiment 1 as metal-air battery cathod catalyst.Now, this cupric oxide being capable of catalytic cell
Electrochemical cathode reaction (oxygen reduction reaction and/or oxygen evolution reaction), and then improve the high rate performance of this metal-air battery,
Improve its high current charge-discharge ability.
Embodiment 2
1st, the preparation of cupric oxide
(1) with copper sheet for copper presoma, copper sheet is first cleaned by ultrasonic 5 minutes in the HCl solution of 0.1mol/L, then uses
Deionized water rinsing, then soaks 1 minute, finally deionized water is rinsed again in acetone soln.
(2) by cleaning after copper sheet be placed in alkaline aqueous solution, alkaline aqueous solution contain 0.1mol/LLiOH and
0.1mmol/L dodecyl sodium sulfate, after reacting 1 day at room temperature, copper sheet surface stain.Take out copper sheet, deionized water is clear
Wash, be dried, obtain the copper sheet that surface is covered with cupric oxide.
2nd, characterize
(1) surface is covered with SEM (SEM) photo of the copper sheet of cupric oxide as shown in Figure 4 and Figure 5, Fig. 4's
Scale is 2 μm, and the scale of Fig. 5 is 500nm.As shown in Figure 4 and Figure 5, the surface of copper sheet is covered with copper oxide nanometer particle, particle
Granularity is about 200～400 nanometers (such as 300 nanometers), the rough surface of particle.(2) surface is covered with the copper sheet transmission of cupric oxide
Electronic Speculum (TEM) photo is as shown in Figure 6.The internal no obvious lattice fringe in crystalline state of this copper oxide particle.Fig. 6 upper right corner
Illustration is the Fourier transformation figure of this TEM photo, and the point diffraction of this in figure is in halation feature.TEM photo and its Fourier transformation
Figure all shows the low-crystallinity of sample.
(3) copper sheet that surface is covered with cupric oxide carries out X-ray diffraction analysis (XRD), and the curve in Fig. 5 is XRD spectra,
2 θ angles are the diffraction maximum that 35.5 ° and 37.8 ° of peak is cupric oxide, and 2 θ angles are the diffraction that 43.5 ° and 50.8 ° of peak is copper-based bottom
Peak.The diffraction peak intensity of cupric oxide is weak and wider, shows that the degree of crystallinity of cupric oxide is low.
From SEM, TEM and XRD data, this cupric oxide has coarse surface and low degree of crystallinity, and this illustrates this oxygen
Change copper and there is substantial amounts of defect sturcture, these defect sturctures are conducive to oxygen to adsorb.
(4) copper sheet being covered with cupric oxide has been carried out with X-ray photoelectron spectroscopic analysis (XPS) analysis.X-ray photoelectron energy
Spectrogram shows, the corresponding combination of O1s feature peak-to-peak value can be 530.1eV and 532.3eV, and Cu2p3/2 feature peak-to-peak value is corresponding
In conjunction with can be 934.2eV.O1s characteristic peak is 3.2 with the ratio of the peak area of Cu2p3/2 characteristic peak.O1s characteristic peak is carried out point
Peak fits, and O1s characteristic peak be divide into Lattice Oxygen characteristic peak and absorption oxygen characteristic peak.Lattice Oxygen characteristic peak and Cu2p3/2 feature
The ratio of the peak area at peak is 1.03, absorption oxygen characteristic peak and Cu2p3/2 characteristic peak the ratio of peak area be 2.17.Oxidation
Copper Surface Oxygen is up to 3.2 with the atomic ratio of copper, removes the oxygen of 1 ratio and copper is combined outward with the chemical formula of cupric oxide, remaining
2.2 parts of oxygen, belong to absorption oxygen.The content of absorption oxygen is higher.
Additionally, the combination of the Cu2p3/2 characteristic peak of this cupric oxide can be higher, up to 934.2eV element has high oxidation valency
State, more than+divalent.It follows that oxygen, in the adsorbed state not only bag physical absorption of CuO surface, also includes chemisorbed, and
The oxygen of chemisorbed has higher adsorption strength.Due to adsorbing reactivity and its adsorption strength positive correlation of oxygen, absorption is strong
Degree is higher, and reactivity is also higher, and the absorption oxygen of therefore this CuO surface has higher reactivity.This cupric oxide has
There is higher catalysis activity, can effectively catalytic oxidation-reduction react and/or oxygen evolution reaction.
Embodiment 3
1st, the preparation of cupric oxide
(1) with copper sheet for copper presoma, copper sheet is first cleaned by ultrasonic 5 minutes in the HCl solution of 0.1mol/L, then uses
Deionized water rinsing, then soaks 1 minute, finally deionized water is rinsed again in acetone soln.
(2) alkaline aqueous solution is put on the copper sheet surface after cleaning, alkaline aqueous solution contain 3mol/L KOH and
0.1mmol/L glycerine, reacts 30 minutes at room temperature, and copper sheet surface becomes blue.Take out sample, deionized water is cleaned, be dried.
(3) dried copper sheet is heat-treated 5 hours at 300 DEG C, air atmosphere, sample blackening after heat treatment, obtains table
Face is covered with the copper sheet of cupric oxide.
2nd, characterize
(1) surface is covered with the electron scanning micrograph of the copper sheet of cupric oxide as shown in fig. 7, the epontic oxygen of copper sheet
Change copper is nano wire, and a diameter of about 100 nanometers of nano wire, length is about 1～50 micron (such as 10～20 microns).
(2) copper sheet being covered with cupric oxide has been carried out with X-ray photoelectron spectroscopic analysis (XPS) analysis.X-ray photoelectron energy
Spectrogram shows, the corresponding combination of O1s characteristic peak can be 530.3eV and 532.3eV, the corresponding knot of Cu2p3/2 feature peak-to-peak value
Closing can be 934.6eV.O1s characteristic peak is 3.8 with the ratio of the peak area of Cu2p3/2 characteristic peak.Swarming is carried out to O1s characteristic peak
Fit, O1s characteristic peak be divide into Lattice Oxygen characteristic peak and absorption oxygen characteristic peak.Lattice Oxygen characteristic peak and Cu2p3/2 characteristic peak
The ratio of peak area be 1.02, absorption oxygen characteristic peak and Cu2p3/2 characteristic peak the ratio of peak area be 2.78.
Using XPS Peak 41 software, according to Gauss-Lorentz lorentz's mixed function fitting theory, calculated by XPS data
Know that CuO surface oxygen and the atomic ratio of copper are up to 3.8, remove the oxygen of 1 ratio and copper is combined outward with the chemical formula of cupric oxide,
Remaining 2.8 parts of oxygen, belong to absorption oxygen.The content of absorption oxygen is higher.
Additionally, the combination of the Cu2p3/2 characteristic peak of this cupric oxide can be higher, up to 934.6eV, illustrate that copper has height
Oxidation state, more than+divalent.It follows that oxygen is in the adsorbed state not only bag physical absorption of CuO surface, also inclusion
Learn absorption, and the oxygen of chemisorbed has higher adsorption strength.Due to adsorbing reactivity and its adsorption strength positive of oxygen
Close, adsorption strength is higher, and reactivity is also higher, the absorption oxygen of therefore this CuO surface has higher reactivity.
This cupric oxide has higher catalysis activity, can effectively catalytic oxidation-reduction react and/or oxygen evolution reaction.
Finally it should be noted that：Above example is only not intended to limit in order to technical scheme to be described；To the greatest extent
Pipe has been described in detail to the present invention with reference to preferred embodiment, and those of ordinary skill in the art should be understood：Still
The specific embodiment of the present invention can be modified or equivalent is carried out to some technical characteristics；Without deviating from this
The spirit of bright technical scheme, it all should be covered in the middle of the technical scheme scope that the present invention is claimed.
Claims (20)
1. a kind of cupric oxide, its x-ray photoelectron energy spectrum diagram includes O1s characteristic peak and Cu2p3/2 characteristic peak, O1s characteristic peak
Ratio with the peak area of Cu2p3/2 characteristic peak is 1.2～5, such as 1.5～5, more such as 2～5, more such as 3～5, more for example
3～4.
2. the cupric oxide of claim 1, the corresponding combination of described Cu2p3/2 feature peak-to-peak value can be 933.0～935.5eV, example
As 934～935eV.
3. the cupric oxide of claim 1, described O1s characteristic peak includes that peak value combines can feature in the range of 525～537eV
Peak, such as peak value combine can characteristic peak in the range of 530～535eV, more such as peak value combine can be in 530～533eV scope
Interior characteristic peak；
Preferably, described O1s characteristic peak includes that peak value combination can be the characteristic peak of 530～531.9eV and peak value combination can be 532
The characteristic peak of～534eV.
4. the cupric oxide of claim 1, described O1s characteristic peak is formed by stacking by Lattice Oxygen characteristic peak and absorption oxygen characteristic peak；
Preferably, described Lattice Oxygen characteristic peak and the ratio of the peak area of described Cu2p3/2 characteristic peak are about 1；
Preferably, the ratio of the peak area of described absorption oxygen characteristic peak and described Cu2p3/2 characteristic peak is 0.2～3.2 (for example
1.5～3)；
Preferably, the corresponding combination of described Lattice Oxygen feature peak-to-peak value can be 530～532eV；
Preferably, the described absorption corresponding combination of oxygen feature peak-to-peak value can be 531～533eV.
5. the cupric oxide of claim 1, it is 32.5-33.5 °, 34.8- that the X ray diffracting spectrum of described cupric oxide includes 2 θ angles
35.8 ° and 37.5-38.5 ° of diffraction maximum.
6. the cupric oxide of claim 1, described cupric oxide being smaller in size than or equal to 1 micron at least one dimension, preferably little
In or be equal to 500 nanometers, more preferably less than or be equal to 100 nanometers, further preferably for 5～1000 nanometers, further preferably for 30～1000
Nanometer.
7. the cupric oxide of any one of claim 1～6, it has following one or more feature：
X) described cupric oxide is nano particle, and the granularity of described nano particle is preferably 50～1000 nanometers (such as 100～500
Nanometer)；
Y) described cupric oxide is nanometer rods, and (such as 300～1000 receive preferably 30～2000 nanometers of the length of described nanometer rods
Rice), the diameter of described nanometer rods is preferably 10～100 nanometers (such as 30～50 nanometers)；
Z) described cupric oxide is nano wire, and the length of described nano wire is preferably 1～50 micron (such as 10～20 microns), described
The diameter of nano wire is preferably 50～200 nanometers (preferably 100～150 nanometers).
8. a kind of porous material, including porous carrier, described porous carrier is also loaded the oxygen of any one of requirement 1～7 of having the right
Change copper.
9. the porous material of claim 8, described porous carrier is porous carbon, porous tin-antimony oxide or multi-layer graphene.
10. a kind of composition, including the cupric oxide of any one of claim 1～7.
The composition of 11. claims 10, it also includes Sb2O3、CeO2、Ni2O3、Co3O4And RuO2One or more of.
A kind of 12. metal-air batteries, including the cupric oxide of any one of claim 1～7, any one of claim 8～9 many
Porous materials and/or the composition of any one of claim 10～11；
Preferably, the negative electrode of described metal-air battery includes the cupric oxide of any one of claim 1～7, claim 8～9
The porous material of any one and/or the composition of any one of claim 10～11.
The metal-air battery of 13. claims 12, the anode of described metal-air battery includes：Active metal simple substance, activity
One or more of metal ion, active metal alloy and active metal insert material；
Preferably, described active metal is included selected from one or more of K, Na, Li, Mg, Ca, Ba and Zn；
Preferably, described active metal includes Li；
Preferably, described metal-air battery is lithium-air battery, sodium air cell, zinc-air battery, calcium air cell or magnesium
Air cell.
The cupric oxide of 14. any one of claim 1～7, the porous material of any one of claim 8～9 or claim 10～
The composition of 11 any one is used for catalytic oxidation-reduction reaction and/or the purposes of oxygen evolution reaction；
Preferably, described oxygen reduction reaction is 4Li+O2+2H2O→4Li++4OH-；
Preferably, described oxygen evolution reaction is 4OH-→O2+2H2O+4e-；
Preferably, described oxygen reduction reaction is 4Li+O2+4H+→4Li++2H2O；
Preferably, described oxygen evolution reaction is 2H2O→O2+4H++4e-.
A kind of 15. preparation methods of cupric oxide, it comprises the following steps：
A) a Copper substrate part is placed in alkaline aqueous solution, a part exposes in atmosphere, reaction；Or alkaline aqueous solution is applied
It is added on the surface of Copper substrate, reaction；
Preferably, the time of reaction is 10 minutes to 30 days, preferably 30 minutes to 3 days, further preferably 1～2 day；
Preferably, the temperature of reaction is 0～90 DEG C, such as 20～50 DEG C；
Preferably, described Copper substrate is the porous carrier that copper is covered on copper sheet, copper powder or surface.
The method of 16. claims 15, described alkaline aqueous solution contains water-soluble alkali；
Preferably, concentration in alkaline aqueous solution for the described water-soluble alkali is 0.1～10mol/L, preferably 0.1～5mol/L；
Preferably, described water-soluble alkali is included selected from one or more of LiOH, KOH or NaOH.
The method of 17. claims 15, described alkaline aqueous solution contains additive, described additive include selected from ethanol, ammoniacal liquor,
Hexamethylenetetramine, dodecyl sodium sulfate, lauryl sodium sulfate, potassium chloride, sodium chloride, lithium chloride, tween, glycerine,
One or more in ethylene glycol；
Preferably, described additive in alkaline aqueous solution concentration be 0.0001-0.2mol/L, preferably 0.01～
0.1mol/L.
The method of 18. claims 15, does not contain oxidant in described alkaline aqueous solution；
Preferably, described oxidant is selected from one or more of hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate.
The method of 19. claims 15, also includes after step a)：
B) product of step a) is heat-treated in oxygen-containing atmosphere；
Preferably, the temperature of heat treatment is 100～400 DEG C, preferably 250～350 DEG C；
Preferably, the time of heat treatment is 1～5 hour, preferably 2～4 hours；
Preferably, described oxygen-containing atmosphere is air atmosphere.
The method of 20. any one of claim 15～19, the one or multi-step comprising the following steps：
I) clean Copper substrate；
Ii) the Copper substrate part after cleaning is placed in alkaline aqueous solution, a part exposes in atmosphere, reaction；Or by alkali
Property the aqueous solution put on the surface of Copper substrate, reaction；
Alternatively, also include step iii)
Iii) heat treatment step ii) product；
Iv) wash, be dried.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611138641.9A CN106410227B (en) | 2016-12-12 | 2016-12-12 | A kind of copper oxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611138641.9A CN106410227B (en) | 2016-12-12 | 2016-12-12 | A kind of copper oxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106410227A true CN106410227A (en) | 2017-02-15 |
| CN106410227B CN106410227B (en) | 2019-01-15 |
Family
ID=58085365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611138641.9A Active CN106410227B (en) | 2016-12-12 | 2016-12-12 | A kind of copper oxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106410227B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555466A (en) * | 2017-09-21 | 2018-01-09 | 华中农业大学 | A kind of preparation method of copper oxide nano fiber |
| CN108358234A (en) * | 2018-05-29 | 2018-08-03 | 吉林大学 | A kind of hydroxy copper chloride nanometer sheet and preparation method thereof |
| CN109640411A (en) * | 2019-01-29 | 2019-04-16 | 长沙暖宇新材料科技有限公司 | A kind of graphene constant temperature electric heating film and preparation method thereof |
| TWI703237B (en) * | 2018-09-29 | 2020-09-01 | 鴻海精密工業股份有限公司 | Nanoporous copper supported copper oxide nanosheet array composite material and method thereof |
| CN112520779A (en) * | 2020-12-07 | 2021-03-19 | 贵州理工学院 | Porous copper oxide nanowire material and preparation method thereof |
| US11196035B2 (en) | 2018-09-29 | 2021-12-07 | Tsinghua University | Anode of lithium battery, method for fabricating the same, and lithium battery using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380914A (en) * | 1999-09-29 | 2002-11-20 | 欧罗巴金属公开有限公司 | Electrochemical method for forming inorganic covering layer on surface of copper material |
| US20040224229A1 (en) * | 2003-05-09 | 2004-11-11 | Mansuetto Michael F. | Alkaline cell with copper oxide cathode |
| CN102231435A (en) * | 2011-05-20 | 2011-11-02 | 合肥工业大学 | Method for preparing electrode material CuO (cupric oxide) film of lithium ion battery on copper substrate |
| CN105618778A (en) * | 2015-12-29 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method for copper nanotube with copper oxide nano-particles embedded therein |
-
2016
- 2016-12-12 CN CN201611138641.9A patent/CN106410227B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380914A (en) * | 1999-09-29 | 2002-11-20 | 欧罗巴金属公开有限公司 | Electrochemical method for forming inorganic covering layer on surface of copper material |
| US20040224229A1 (en) * | 2003-05-09 | 2004-11-11 | Mansuetto Michael F. | Alkaline cell with copper oxide cathode |
| CN102231435A (en) * | 2011-05-20 | 2011-11-02 | 合肥工业大学 | Method for preparing electrode material CuO (cupric oxide) film of lithium ion battery on copper substrate |
| CN105618778A (en) * | 2015-12-29 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method for copper nanotube with copper oxide nano-particles embedded therein |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555466A (en) * | 2017-09-21 | 2018-01-09 | 华中农业大学 | A kind of preparation method of copper oxide nano fiber |
| CN108358234A (en) * | 2018-05-29 | 2018-08-03 | 吉林大学 | A kind of hydroxy copper chloride nanometer sheet and preparation method thereof |
| TWI703237B (en) * | 2018-09-29 | 2020-09-01 | 鴻海精密工業股份有限公司 | Nanoporous copper supported copper oxide nanosheet array composite material and method thereof |
| US11196035B2 (en) | 2018-09-29 | 2021-12-07 | Tsinghua University | Anode of lithium battery, method for fabricating the same, and lithium battery using the same |
| CN109640411A (en) * | 2019-01-29 | 2019-04-16 | 长沙暖宇新材料科技有限公司 | A kind of graphene constant temperature electric heating film and preparation method thereof |
| CN109640411B (en) * | 2019-01-29 | 2021-05-25 | 长沙暖宇新材料科技有限公司 | Graphene constant-temperature electrothermal film and preparation method thereof |
| CN112520779A (en) * | 2020-12-07 | 2021-03-19 | 贵州理工学院 | Porous copper oxide nanowire material and preparation method thereof |
| CN112520779B (en) * | 2020-12-07 | 2023-09-15 | 贵州理工学院 | Porous copper oxide nanowire material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106410227B (en) | 2019-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106410227B (en) | A kind of copper oxide and preparation method thereof | |
| Davari et al. | Bifunctional electrocatalysts for Zn–air batteries | |
| Bu et al. | Coupled spd exchange in facet-controlled Pd3Pb tripods enhances oxygen reduction catalysis | |
| JP6155327B2 (en) | All solid state secondary battery | |
| Davari et al. | Manganese-cobalt mixed oxide film as a bifunctional catalyst for rechargeable zinc-air batteries | |
| Patil et al. | Bifunctional catalytic activity of Ni–Co layered double hydroxide for the electro-oxidation of water and methanol | |
| US9676034B2 (en) | Method of manufacturing powder having high surface area | |
| Meng et al. | Spent alkaline battery-derived manganese oxides as efficient oxygen electrocatalysts for Zn–air batteries | |
| WO2013039602A1 (en) | Catalytic cathode for lithium-air batteries | |
| Xiong et al. | Sequentially electrodeposited MnOX/Co-Fe as bifunctional electrocatalysts for rechargeable zinc-air batteries | |
| Feng et al. | Agni-catalyzed anode for direct borohydride fuel cells | |
| Tahira et al. | An efficient bifunctional electrocatalyst based on a nickel iron layered double hydroxide functionalized Co 3 O 4 core shell structure in alkaline media | |
| Madan et al. | Enhancing the oxygen evolution activity of nitrogen-doped graphitic carbon shell-embedded nickel/nickel oxide nanoparticles by surface dissolution | |
| WO2021104106A1 (en) | Graphene-supported platinum-based alloy nanoparticle catalyst and preparation method therefor | |
| Rong et al. | ZnO@ Ag microspheres used as the anodic materials of superior alkaline rechargeable Zn–Ni batteries | |
| CN105874632A (en) | Positive electrode for lithium air battery and lithium air battery comprising same | |
| WO2004066421A1 (en) | Closed nickel-hydrogen storage battery and its production method | |
| de Souza Dias et al. | Transition metal chalcogenides carbon-based as bifunctional cathode electrocatalysts for rechargeable zinc-air battery: An updated review | |
| Hsiao et al. | Facile synthesis of ammonium-decorated cobalt molybdenum fluoride as electroactive material of supercapacitor | |
| Zhang et al. | A review of the Al-gas batteries and perspectives for a “Real” Al-air battery | |
| Ali et al. | Binary metal selenide nanowires wrapped over carbon fibers for a binder-free anode of sodium-ion batteries | |
| JP6508990B2 (en) | Porous metal, method of manufacturing the same, and power storage device | |
| Li et al. | Surface-Pt-rich AgPtAu trimetallic nanotrough arrays for boosting alcohol electrooxidation | |
| JP7156258B2 (en) | Aqueous battery | |
| Poonam et al. | A review of magnesium air battery systems: from design aspects to performance characteristics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |