CN106410227B - A kind of copper oxide and preparation method thereof - Google Patents

A kind of copper oxide and preparation method thereof Download PDF

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Publication number
CN106410227B
CN106410227B CN201611138641.9A CN201611138641A CN106410227B CN 106410227 B CN106410227 B CN 106410227B CN 201611138641 A CN201611138641 A CN 201611138641A CN 106410227 B CN106410227 B CN 106410227B
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copper oxide
peak
characteristic peak
copper
oxygen
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CN106410227A (en
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钟宽
田静
李影
李乾乾
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Gree Electric Appliances Inc of Zhuhai
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Gree Electric Appliances Inc of Zhuhai
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00Hybrid cells; Manufacture thereof
    • H01M12/04Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06Hybrid 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9016Oxides, hydroxides or oxygenated metallic salts

Abstract

The present invention relates to a kind of copper oxide and preparation method thereof.It include O1s characteristic peak and Cu2p3/2 characteristic peak in the x-ray photoelectron spectroscopy figure of the copper oxide, the ratio of the peak area of O1s characteristic peak and Cu2p3/2 characteristic peak is 1.2~5.The copper oxide has preferable catalytic performance.

Description

A kind of copper oxide and preparation method thereof
Technical field
The invention belongs to Material Fields, and in particular to a kind of copper oxide and preparation method thereof.
Background technique
Metal-air battery is a kind of strong candidate of New Generation of Electric Vehicle power battery.Metal-air Battery is usually using metal as anode electrochemical active material, and the oxygen in air is as electroactive cathode material.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 1000Wh/kg or more, close with gasoline.
The anode active material of metal-air battery can be alkali metal, alkaline-earth metal or other active metals (such as Zn).In numerous anode active materials, lithium metal has relatively negative electrode potential (- 3.04V vs.SHE) and lesser density (6.95g·mol-1), be conducive to the raising of the specific capacity of battery, be the hot spot of current research.Lithium metal is as battery cathode material Material has about 3.81Ahg-1Theoretical specific capacity, at this point, the energy density theoretical value of lithium-air battery is possible to up to 3505Wh/ kg.Under this energy density, the electric car course continuation mileage for being equipped with lithium-air battery can achieve 600 kilometers or more.
In order to improve the performance of metal-air battery, technical staff person uses the cathode 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 type of catalyst mainly includes noble metal and its alloy, metal oxide, functionalization Carbon material etc..
Summary of the invention
It is an object of the present invention to provide a kind of copper oxide that catalytic activity is high, it is also another object of the present invention to provide A kind of copper oxide that copper valence state is high, it is also another object of the present invention to provide a kind of copper oxide that absorption oxygen content is high;This The further object of invention is to provide a kind of copper oxide that absorption oxygen reactivity is high;It is also another object of the present invention to provide one Kind of the high copper oxide of absorption oxygen adsorption strength, further object of the present invention be to provide it is a kind of can effectively catalytic oxidation-reduction reaction and/ Or the copper oxide of oxygen evolution reaction, further object of the present invention be find a kind of copper oxide for catalytic oxidation-reduction reaction and/or The purposes of oxygen evolution reaction, further object of the present invention are to provide a kind of metal-air battery.
Inventors have found that copper oxide of the invention has the absorption oxygen of high-content, which can effectively be catalyzed oxygen Reduction reaction and/or oxygen evolution reaction.The cathod catalyst of copper oxide of the invention as metal-air battery, can be improved gold The rate capability for belonging to air cell, improves its high current charge-discharge ability.
First aspect present invention provides a kind of copper oxide, x-ray photoelectron spectroscopy figure (X-ray photoelectron Spectroscopy, XPS) in 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, then such as 2~5, then such as 3~5, then such as 3~4, then 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、 3.4,3.5,3.6,3.7,3.8,3.9,4,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9 or 5.
The O1s characteristic peak and the ratio of the peak area of Cu2p3/2 characteristic peak of the copper oxide are higher, illustrate the CuO surface Absorption oxygen content it is higher.The raising of absorption oxygen content is conducive to the active raising of copper oxide catalyzation.
In one embodiment, the copper oxide of any one of present invention, the corresponding combination of the Cu2p3/2 feature peak-to-peak value It can be 933.0~935.5eV, such as 934~935eV, then such as 934.5~935eV, then 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 the copper oxide can be higher, illustrates chemistry suction on the CuO surface The activity of attached oxygen is high.The active raising of the oxygen of chemisorption is conducive to the active raising of copper oxide catalyzation.
In one embodiment, the copper oxide of any one of present invention, the O1s characteristic peak include that peak value combines can be Characteristic peak within the scope of 525~537eV, such as combine can be in the characteristic peak within the scope of 530~535eV for peak value, then such as peak value In conjunction with can be in the characteristic peak within the scope of 530~533eV;
Preferably, the O1s characteristic peak includes two characteristic peaks;
Preferably, the O1s characteristic peak include peak value combination can be 530~531.9eV (such as 530~531eV, such as 530.1~530.3eV) characteristic peak and peak value combination can be 532~534eV (such as 522~533eV, such as 532.1~ 532.3eV) characteristic peak;
Preferably, the 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, then the characteristic peak that such as peak value combination can be 530.3eV and 532.3eV.
In one embodiment, the copper oxide of any one of present invention, the 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, the ratio of the peak area of the Lattice Oxygen characteristic peak and the Cu2p3/2 characteristic peak is about 1;
Preferably, the ratio of the peak area of the absorption oxygen characteristic peak and the Cu2p3/2 characteristic peak is 0.2~3.2, example Such as 0.5~3, then such as 1~2.8, then 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 the Lattice Oxygen feature peak-to-peak value can be 530~532eV, such as 530~531eV, example Such as 530.1~530.5eV, for example, about 530.3eV;
Preferably, the corresponding combination of the absorption oxygen feature peak-to-peak value can be 531~533eV, such as 532~533eV, example Such as 531~532.5eV, such as 531.3eV and 532.1eV.
In one embodiment, the copper oxide of any one of present invention, the X ray diffracting spectrum of the copper oxide include 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 copper oxide of any one of present invention, size of the copper oxide at least one dimension Less than or equal to 1 micron, preferably lower than or equal to 500 nanometers, be further preferably 5~1000 more preferably less than or equal to 100 nanometers Nanometer, is further preferably 30~1000 nanometers, such as 300~500 nanometers.
In one embodiment, the copper oxide of any one of present invention, with following one or more features:
X) copper oxide is nano particle, the granularity of the nano particle be preferably 80~1000 nanometers (such as 100~ 500 nanometers);
Y) copper oxide is nanometer rods, and the length of the nanometer rods is preferably 30~1000 nanometers (such as 300~500 Nanometer), the diameter of the nanometer rods is preferably 10~100 nanometers (such as 30~50 nanometers);
Z) copper oxide is nano wire, and the length of the nano wire is preferably 1~50 micron (such as 10~20 microns), The diameter of the nano wire is preferably 50~200 nanometers (preferably 100~150 nanometers).
In one embodiment, the copper oxide of any one of present invention is nano cupric oxide.
In one embodiment, in order to improve the electric conductivity of copper oxide, electro-deposition, photo-reduction or chemistry can first be used also Former method is deposited on elemental copper on porous carrier, such as porous carbon, porous tin-antimony oxide electro-conductive glass, multi-layer graphene On, caustic corrosion is then carried out again, prepares corresponding copper oxide, such as copper oxide nano material.
Second aspect of the present invention provides a kind of porous material, including porous carrier, this has been also loaded on the porous carrier Invent the copper oxide of any one.
In one embodiment, the porous material of any one of present invention, the porous carrier is conductive.
In one embodiment, the porous material of any one of present invention, the porous carrier are porous carbon, porous tin antimony Oxide or multi-layer graphene.
In one embodiment, in order to further enhance oxygen adsorption capacity and raising electric conductivity, copper oxide can be with other Oxide is used in mixed way, or preparation oxidation copper based mixed oxide catalyst, such as copper oxide-Sb2O3, copper oxide-CeO2, oxidation Copper-Ni2O3, copper oxide-Co3O4, copper oxide-RuO2, then such as copper oxide-Co3O4-RuO2, copper oxide-Co3O4-RuO2Deng.
Third aspect present invention provides a kind of composition, including copper oxide any one of of the invention.
In one embodiment, the composition of any one of present invention, further includes Sb2O3、CeO2、Ni2O3、Co3O4With RuO2One of or it is a variety of;
Preferably, the composition is by copper oxide any one of of the invention, Co3O4And RuO2It constitutes.
Fourth aspect present invention provides a kind of preparation method of copper oxide comprising following steps:
A) Copper substrate a part is placed in alkaline aqueous solution, a part exposure in air, reaction, or by alkaline water Solution is applied to 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, the 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 present invention, the alkaline aqueous solution contain water-soluble alkali;
Preferably, concentration of the water-soluble alkali in alkaline aqueous solution is 0.1~10mol/L, preferably 0.1~5mol/L (such as 0.1mol/L, 1mol/L or 3mol/L);
Preferably, the water-soluble alkali includes selected from one of LiOH, KOH or NaOH or a variety of.
In one embodiment, the method for any one of present invention, the alkaline aqueous solution contain additive, the addition Agent include selected from ethyl alcohol, ammonium hydroxide, hexamethylenetetramine, dodecyl sodium sulfate, lauryl sodium sulfate, potassium chloride, sodium chloride, It is lithium chloride, tween, glycerine, one or more in ethylene glycol;
In one embodiment, the method for any one of present invention, the alkaline aqueous solution contain additive, the addition Agent includes being selected from ethyl alcohol, hexamethylenetetramine, dodecyl sodium sulfate, lauryl sodium sulfate, potassium chloride, sodium chloride, chlorination It is lithium, tween, glycerine, one or more in ethylene glycol;
In one embodiment, the method for any one of present invention, the alkaline aqueous solution contain additive, the addition Agent includes being selected from lauryl sodium sulfate, sodium chloride or glycerine;
Preferably, concentration of the additive in alkaline aqueous solution be 0.0001-0.2mol/L, preferably 0.01~ 0.1mol/L。
In one embodiment, the present invention any one of method, the alkaline aqueous solution contain 1mol/L KOH, 0.1mol/L LiOH and 0.01mol/L KCl.
In one embodiment, the present invention any one of method, the alkaline aqueous solution contain 0.1mol/L LiOH and 0.1mmol/L dodecyl sodium sulfate.
In one embodiment, the present invention any one of method, the alkaline aqueous solution contain 3mol/L KOH and 0.1mmol/L glycerine
In one embodiment, the method for any one of present invention does not contain oxidant in the alkaline aqueous solution;
Preferably, the oxidant is selected from one of hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate or a variety of.
In one embodiment, the method for any one of present invention does not contain NH in the alkaline aqueous solution4 +, preferably not Contain ammonium hydroxide.
In one embodiment, the method for any one of present invention, after step a) further include:
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, the oxygen-containing atmosphere is air atmosphere.
In one embodiment, the method for any one of present invention, the one or more steps included the following steps:
I) Copper substrate is cleaned;
Ii) Copper substrate a part is placed in alkaline aqueous solution, a part exposure in air, is reacted, or will be alkaline Aqueous solution is applied to the surface of Copper substrate, reaction;
It optionally, further include step iii)
Iii) heat treatment step ii) product;
Iv it) washs, is dry.
In one embodiment, the method for any one of present invention, the time of reaction are 10 minutes to 30 days, preferably 30 points Clock to 3 days, such as 12h, for 24 hours, 36h or 48h.
In one embodiment, the method for any one of present invention, the copper oxide are copper oxide any one of of the invention.
Fifth aspect present invention provides a kind of copper oxide, is made by the method for fourth aspect present invention.
Sixth aspect present invention provides the porous material or the present invention of any one of the copper oxide of any one of present invention, present invention The composition of any one is reacted for catalytic oxidation-reduction and/or the purposes of oxygen evolution reaction;
Preferably, the oxygen reduction reaction is 4Li+O2+2H2O→4Li++4OH-
Preferably, the oxygen evolution reaction is 4OH-→O2+2H2O+4e-
Preferably, the oxygen reduction reaction is 4Li+O2+4H+→4Li++2H2O;
Preferably, the oxygen evolution reaction is 2H2O→O2+4H++4e-
Seventh aspect present invention provides a kind of metal-air battery, appoints including copper oxide any one of of the invention, the present invention One porous material and/or the composition of any one of the present invention;
Preferably, the cathode of the metal-air battery includes any one of copper oxide any one of of the invention, the present invention The composition of porous material and/or any one of the present invention.
In one embodiment, the metal-air battery of any one of present invention, the anode packet of the metal-air battery Include: one of active metal simple substance, active metallic ion, active metal alloy and active metal insert material are a variety of;
Preferably, the active metal includes selected from one of K, Na, Li, Mg, Ca, Ba and Zn or a variety of;
Preferably, the active metal includes Li;
Preferably, the metal-air battery is lithium-air battery, sodium air cell, zinc-air battery, calcium air cell Or magnesium air battery.
In one embodiment, the present invention any one of metal-air battery, including anode electrochemical active component and Cathode electrochemical Iy active component.
In one embodiment, the metal-air battery of any one of present invention, anode electrochemical active component include: One of active metal simple substance, active metallic ion, active metal alloy and active metal insert material are a variety of
In one embodiment, the metal-air battery of any one of present invention, active metal include alkali metal, alkaline earth gold One of category and transition metal are a variety of.
In one embodiment, the present invention any one of metal-air battery, active metal include selected from Li, Na, K, One of Ca, Mg, Ba, Zn or a variety of;It is preferred that active metal includes Li.
In one embodiment, active metallic ion includes being selected from Li+、Na+、K+、Ca2+、Mg2+、Ba2+、Zn2+In one Kind is a variety of.
In one embodiment, the present invention any one of metal-air battery, active metal alloy include: containing Li, The alloy of one of Na, K, Ca, Mg, Ba, Zn or multiple element;It preferably includes by Li, Na, K, Ca, Mg, Ba, Zn One or more elements and in Sn, Si, Zn, Al, Sb, Ge, Pb, Mg, Ca, As, Bi, Pt, Ag, Au, Cd, Hg etc. one The alloy more than binary or ternary that kind or various metals are constituted;It preferably includes selected from lithium-aluminium alloy, Li-Si alloy, lithium-tin alloy With one of lithium silver alloy or a variety of.
In one embodiment, the metal-air battery of any one of present invention, active metal insert material are carbon or lithium Carbon compound.
In one embodiment, the metal-air battery of any one of present invention, cathode electrochemical Iy active component include Oxygen.
In one embodiment, the metal-air battery of any one of present invention, cathode electrochemical Iy active component include Air.
In one embodiment, the metal-air battery of any one of present invention, the cathode of the metal-air battery also wrap Electronic conductor is included, the electronic conductor includes carbon material and binder.
In one embodiment, carbon material is carbon black (Super P, Ketjen Black, Vulcan XC-72 etc.), carbon Nanotube and graphene etc..
In one embodiment, binder PVDF, PTFE or the Nafion of lithiumation etc..
In one embodiment, the metal-air battery of any one of present invention is lithium-air battery, and lithium-air battery is excellent It is selected as organic electrolyte system lithium-air battery, organic-water combination electrolyte system lithium-air battery, water solution system lithium air Battery or all solid state electrolyte system lithium-air battery.
In one embodiment, the metal-air battery of any one of present invention, in the discharged condition, cathode are anode, Anode is cathode.
Beneficial effects of the present invention
The content of CuO surface absorption oxygen of the invention is higher, is conducive to the catalytic activity for improving copper oxide.In addition, should The copper of copper oxide has high oxidation state, is greater than+divalent;And O1s characteristic peak and Cu2p3/2 characteristic peak in XPS analysis The ratio of peak area is greater than 1.It follows that the oxygen content of the chemisorption of the CuO surface is higher.According to the general of catalysis Principle, oxygen the having compared with high reaction activity than physical absorption of chemisorption, these absorption oxygen with high reaction activity can The catalytic activity of copper oxide is promoted, and then improves the reaction rate of CuO surface oxygen reduction reaction and/or oxygen evolution reaction.
Some embodiments of the invention have it is following one or more the utility model has the advantages that
(1) catalytic activity of the copper oxide of some embodiments is high;
(2) the copper valence state of the copper oxide of some embodiments is higher;
(3) surface of the copper oxide of some embodiments, the content for adsorbing oxygen is higher, especially the content of chemically adsorbing oxygen It is higher;
(4) surface of the copper oxide of some embodiments, the adsorption strength for adsorbing oxygen are higher;
(5) surface of the copper oxide of some embodiments, the reactivity for adsorbing oxygen are higher;
(6) copper oxide of some embodiments has more defect sturcture, these defect sturctures are conducive to improve oxygen suction Attached amount;
(7) copper oxide of some embodiments can more efficiently catalytic oxidation-reduction reaction and/or oxygen evolution reaction;
(8) method for preparing copper oxide of some embodiments is simple, preparation process is environmental-friendly, and cost of material is low, easily In large-scale production;
(9) copper oxide of some embodiments has the advantages that inexpensive, environmental-friendly, is conducive to business application, helps In the large-scale production and application of realizing metal-air battery;
(10) metal-air battery of some embodiments has the heavy-current discharge energy of improved high rate performance, improvement Power.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes part of this application, this hair Bright illustrative embodiments and their description are used to explain the present invention, and are not constituted a limitation of the invention.In the accompanying drawings:
Fig. 1 is the electron scanning micrograph of the copper oxide of embodiment 1;
Fig. 2 is the X ray diffracting spectrum of the copper oxide of embodiment 1;
Fig. 3 is the XPS map of the copper oxide of embodiment 1.Wherein, (a) are as follows: O 1s photoelectron spectral line, empty circles line 1 are Initial data spectral line, heavy black 2 are the spectral line according to initial data line shape fitting, and thin black line 3 is fitting peak;It (b) is Cu 2p3/ 2 photoelectron spectral lines;
Fig. 4 is the electron scanning micrograph of the copper oxide of embodiment 2;
Fig. 5 is the electron scanning micrograph and X ray diffracting spectrum of the copper oxide of embodiment 2;
Fig. 6 is the transmission electron microscope photo of the copper oxide of embodiment 3, and illustration is the transmission electron microscope photo Fourier transformation image;
Fig. 7 is the electron scanning micrograph of the copper oxide of embodiment 3.
Specific embodiment
It will refer to specific embodiments of the present invention in detail now.The example of specific embodiment is illustrated in the drawings.To the greatest extent Pipe combines these specific embodiments description present invention, 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 may include substitution in the spirit and range being defined by the claims, change Change or equivalent embodiments.In the following description, elaborate a large amount of details in order to provide complete understanding of the present invention. The present invention can be carried out in the case where not partly or entirely these details.In other cases, in order not to making this hair It is bright unnecessarily to obscure, it is not described in well known technological operation.
When with " comprising ", " method includes ", " device includes " or the similar language in this specification and the appended claims When being used in combination, singular " certain ", " some ", "the" include plural reference, unless the context clearly dictates otherwise.Unless another Outer definition, all technical and scientific terms used herein have general technical staff of the technical field of the invention usual The identical meanings of understanding.
The instrument and test condition that following embodiment uses 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
Illustrate the preparation and characterization of copper oxide below by specific embodiment:
Embodiment 1
1, the preparation of copper oxide
(1) using copper sheet as presoma, first copper sheet is first cleaned by ultrasonic 5 minutes in the HCl solution of 0.1mol/L, is then used Deionized water is rinsed, and is then impregnated 1 minute in acetone soln, is finally rinsed again with deionized water.
(2) copper sheet a part after cleaning is placed in alkaline aqueous solution, a part exposes in air, alkaline aqueous solution Containing 1mol/L KOH, 0.1mol/L LiOH and 0.01mol/L KCl, after reacting 5 days at room temperature, entire copper sheet surface becomes It is black.Copper sheet is taken out, is cleaned with deionized water, is then dried.
(3) copper sheet after drying is heat-treated 5 hours at 300 DEG C, air atmosphere obtains to surface and is covered with the copper of copper oxide Piece.
2, it characterizes
(1) surface be covered with the copper sheet of copper oxide scanning electron microscope (SEM) photo it is as shown in Figure 1.It is grown on copper sheet Many nanometer rods, nanorod diameter is about 30 nanometers, 300-500 nanometers a length of.The rough surface of nanometer rods.
(2) X-ray diffraction analysis (XRD) is carried out to the copper sheet for being covered with copper oxide, X ray diffracting spectrum is as shown in Figure 2.2θ The peak that angle is 32.8 °, 35.5 ° and 38.3 ° is the diffraction maximum of copper oxide, and the peak that 2 angles θ are 43.2 ° and 50.7 ° is spreading out for copper-based bottom Penetrate peak.The diffraction peak intensity of copper oxide is weak and wider, illustrates that the crystallinity of copper oxide is lower.XRD data confirm that, copper sheet surface Nanometer rods be copper oxide.
By SEM and XRD data it is found that the copper oxide has coarse surface and low crystallinity, this illustrates the copper oxide With a large amount of defect sturcture, these defect sturctures are conducive to improve the amount of oxygen absorption.
(3) X-ray photoelectron spectroscopic analysis (XPS) analysis has been carried out to the copper sheet for being covered with copper oxide, has as a result seen Fig. 3, In, (a) are as follows: O 1s photoelectron spectral line, empty circles line 1 are initial data spectral line, and heavy black 2 is quasi- according to initial data spectral line The spectral line of conjunction, thin black spectral line 3 are fitting peak;It (b) is Cu 2p3/2 photoelectron spectral line.X-ray photoelectron spectroscopy figure shows O1s spy Levying the corresponding combination of peak-to-peak value can be respectively 530.3eV and 532.3eV, and the corresponding combination of Cu2p3/2 feature peak-to-peak value can be 934.8eV.The ratio of the ratio between the peak area of O1s characteristic peak and Cu2p3/2 characteristic peak is 2.8.It is quasi- that swarming is carried out to O1s characteristic peak With, by O1s characteristic peak be divided 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 corresponding combination of absorption oxygen feature peak-to-peak value can be 531.3eV and 532.1eV.According to XPS data, Lattice Oxygen feature The ratio of the ratio between the peak area of peak and Cu2p3/2 characteristic peak is 1.01, adsorbs the peak face of oxygen characteristic peak and Cu2p3/2 characteristic peak The ratio of the ratio between product is 1.79.
It is calculated according to Gauss-Lorentz lorentz's mixed function fitting theory by XPS data using 41 software of XPS Peak Know, the atomic ratio of CuO surface oxygen and copper is up to 2.8, remove the oxygen of 1 ratio and copper with the chemical formula of copper oxide in conjunction with it is outer, Remaining 1.8 parts of oxygen, belongs to absorption oxygen.The content for adsorbing oxygen is higher.
In addition, the combination of the Cu2p3/2 characteristic peak of the copper oxide can be higher, up to 934.8eV illustrates that copper has height Oxidation state, be greater than+divalent.It follows that adsorbed state not only packet physical absorption of the oxygen in CuO surface, further including It learns and adsorbs, and the oxygen of chemisorption adsorption strength with higher.Due to the reactivity and its adsorption strength positive of absorption oxygen It closes, adsorption strength is higher, and reactivity is also higher, therefore the absorption oxygen reactivity with higher of the CuO surface. Copper oxide catalytic activity with higher, being capable of effective catalytic oxidation-reduction reaction and/or oxygen evolution reaction.
Therefore, the copper oxide of embodiment 1 being capable of effectively catalytic oxidation-reduction reaction and/or the progress of oxygen evolution reaction.Into One step, using the copper oxide of embodiment 1 as the cathod catalyst of metal-air battery.At this point, the copper oxide being capable of catalytic cell Electrochemical cathode react (oxygen reduction reaction and/or oxygen evolution reaction), and then improve the high rate performance of the metal-air battery, Improve its high current charge-discharge ability.
Embodiment 2
1, the preparation of copper oxide
(1) using copper sheet as copper presoma, copper sheet is first cleaned by ultrasonic 5 minutes in the HCl solution of 0.1mol/L, is then used Deionized water is rinsed, and is then impregnated 1 minute in acetone soln, is finally rinsed again with deionized water.
(2) copper sheet after cleaning is 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.Copper sheet is taken out, it is clear with deionized water It washes, it is dry, it obtains to surface and is covered with the copper sheet of copper oxide.
2, it characterizes
(1) surface be covered with the copper sheet of copper oxide scanning electron microscope (SEM) photo it is 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 copper oxide Electronic Speculum (TEM) photo is as shown in Figure 6.Without the lattice fringe for being obviously in crystalline state inside the copper oxide particle.The upper right corner Fig. 6 Illustration is the Fourier transformation figure of the TEM photo, and the point diffraction in the figure is in halation feature.TEM photo and its Fourier transformation Figure has all shown the low-crystallinity of sample.
(3) copper sheet for being covered with copper oxide to surface carries out X-ray diffraction analysis (XRD), and the curve in Fig. 5 is XRD spectra, The peak that 2 angles θ are 35.5 ° and 37.8 ° is the diffraction maximum of copper oxide, and the peak that 2 angles θ are 43.5 ° and 50.8 ° is the diffraction at copper-based bottom Peak.The diffraction peak intensity of copper oxide is weak and wider, shows that the crystallinity of copper oxide is low.
By SEM, TEM and XRD data it is found that the copper oxide has coarse surface and low crystallinity, this illustrates the oxygen Changing copper has a large amount of defect sturcture, these defect sturctures are conducive to oxygen absorption.
(4) X-ray photoelectron spectroscopic analysis (XPS) analysis has been carried out to the copper sheet for being covered with copper oxide.X-ray photoelectron energy Spectrogram shows that 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.The ratio of the peak area of O1s characteristic peak and Cu2p3/2 characteristic peak is 3.2.O1s characteristic peak is divided Peak fits, and O1s characteristic peak is divided 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, and the ratio of the peak area of absorption oxygen characteristic peak and Cu2p3/2 characteristic peak is 2.17.Oxidation The atomic ratio of copper Surface Oxygen and copper is up to 3.2, remove the oxygen of 1 ratio and copper with the chemical formula of copper oxide in conjunction with it is outer, it is remaining 2.2 parts of oxygen, belong to absorption oxygen.The content for adsorbing oxygen is higher.
In addition, the combination of the Cu2p3/2 characteristic peak of the copper oxide can be higher, up to 934.2eV element has high oxidation valence State is greater than+divalent.It follows that adsorbed state not only packet physical absorption of the oxygen in CuO surface, further includes chemisorption, and The oxygen of chemisorption adsorption strength with higher.Since the reactivity of absorption oxygen and its adsorption strength are positively correlated, absorption is strong Degree is higher, and reactivity is also higher, therefore the absorption oxygen reactivity with higher of the CuO surface.Copper oxide tool There is higher catalytic activity, it being capable of effective catalytic oxidation-reduction reaction and/or oxygen evolution reaction.
Embodiment 3
1, the preparation of copper oxide
(1) using copper sheet as copper presoma, copper sheet is first cleaned by ultrasonic 5 minutes in the HCl solution of 0.1mol/L, is then used Deionized water is rinsed, and is then impregnated 1 minute in acetone soln, is finally rinsed again with deionized water.
(2) by alkaline aqueous solution be applied to cleaning after copper sheet surface on, alkaline aqueous solution contain 3mol/L KOH and 0.1mmol/L glycerine reacts 30 minutes at room temperature, and copper sheet surface becomes blue.Sample is taken out, is cleaned with deionized water, it is dry.
(3) copper sheet after drying is heat-treated 5 hours at 300 DEG C, air atmosphere, sample blackening, obtains table after heat treatment Face is covered with the copper sheet of copper oxide.
2, it characterizes
(1) surface is covered with the electron scanning micrograph of the copper sheet of copper oxide as shown in fig. 7, the oxygen that copper sheet surface is grown Change copper is nano wire, and the diameter of nano wire is about 100 nanometers, and length is about 1~50 micron (such as 10~20 microns).
(2) X-ray photoelectron spectroscopic analysis (XPS) analysis has been carried out to the copper sheet for being covered with copper oxide.X-ray photoelectron energy Spectrogram shows that 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 Conjunction can be 934.6eV.The ratio of the peak area of O1s characteristic peak and Cu2p3/2 characteristic peak is 3.8.Swarming is carried out to O1s characteristic peak It fits, O1s characteristic peak is divided into Lattice Oxygen characteristic peak and absorption oxygen characteristic peak.Lattice Oxygen characteristic peak and Cu2p3/2 characteristic peak Peak area ratio be 1.02, absorption oxygen characteristic peak and Cu2p3/2 characteristic peak peak area ratio be 2.78.
It is calculated according to Gauss-Lorentz lorentz's mixed function fitting theory by XPS data using 41 software of XPS Peak Know that the atomic ratio of CuO surface oxygen and copper is up to 3.8, remove the oxygen of 1 ratio and copper with the chemical formula of copper oxide in conjunction with it is outer, Remaining 2.8 parts of oxygen, belongs to absorption oxygen.The content for adsorbing oxygen is higher.
In addition, the combination of the Cu2p3/2 characteristic peak of the copper oxide can be higher, up to 934.6eV illustrates that copper has height Oxidation state, be greater than+divalent.It follows that adsorbed state not only packet physical absorption of the oxygen in CuO surface, further including It learns and adsorbs, and the oxygen of chemisorption adsorption strength with higher.Due to the reactivity and its adsorption strength positive of absorption oxygen It closes, adsorption strength is higher, and reactivity is also higher, therefore the absorption oxygen reactivity with higher of the CuO surface. Copper oxide catalytic activity with higher, being capable of effective catalytic oxidation-reduction reaction and/or oxygen evolution reaction.
Finally it should be noted that: the above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof;To the greatest extent The present invention is described in detail with reference to preferred embodiments for pipe, it should be understood by those ordinary skilled in the art that: still It can modify to a specific embodiment of the invention or some technical features can be equivalently replaced;Without departing from this hair The spirit of bright technical solution should all cover within the scope of the technical scheme claimed by the invention.

Claims (64)

  1. It include O1s characteristic peak and Cu2p3/2 characteristic peak, O1s characteristic peak in x-ray photoelectron spectroscopy figure 1. a kind of copper oxide Ratio with the peak area of Cu2p3/2 characteristic peak is 1.2~5.
  2. 2. copper oxide according to claim 1, the ratio of the peak area of O1s characteristic peak and Cu2p3/2 characteristic peak is 1.5~ 5。
  3. 3. the ratio of the peak area of copper oxide according to claim 1, O1s characteristic peak and Cu2p3/2 characteristic peak is 2~5.
  4. 4. the ratio of the peak area of copper oxide according to claim 1, O1s characteristic peak and Cu2p3/2 characteristic peak is 3~5.
  5. 5. the ratio of the peak area of copper oxide according to claim 1, O1s characteristic peak and Cu2p3/2 characteristic peak is 3~4.
  6. 6. copper oxide according to claim 1, the corresponding combination of the Cu2p3/2 feature peak-to-peak value can for 933.0~ 935.5eV。
  7. 7. copper oxide according to claim 1, the corresponding combination of the Cu2p3/2 feature peak-to-peak value can for 934~ 935eV。
  8. 8. copper oxide according to claim 1, the O1s characteristic peak includes peak value combination can be within the scope of 525~537eV Characteristic peak.
  9. 9. copper oxide according to claim 1, the O1s characteristic peak includes peak value combination can be within the scope of 530~535eV Characteristic peak.
  10. 10. copper oxide according to claim 1, the O1s characteristic peak includes peak value combination can be in 530~533eV range Interior characteristic peak.
  11. 11. copper oxide according to claim 1, the O1s characteristic peak includes that peak value combination can be 530~531.9eV Characteristic peak and peak value combination can be the characteristic peak of 532~534eV.
  12. 12. copper oxide according to claim 1, the O1s characteristic peak is folded by Lattice Oxygen characteristic peak and absorption oxygen characteristic peak Add.
  13. 13. copper oxide according to claim 12, the peak area of the Lattice Oxygen characteristic peak and the Cu2p3/2 characteristic peak Ratio be 1.
  14. 14. copper oxide according to claim 12, the peak area of absorption the oxygen characteristic peak and the Cu2p3/2 characteristic peak Ratio be 0.2~3.2.
  15. 15. copper oxide according to claim 12, state absorption oxygen characteristic peak and the Cu2p3/2 characteristic peak peak area it Ratio is 1.5~3.
  16. 16. copper oxide according to claim 12, the corresponding combination of the Lattice Oxygen feature peak-to-peak value can for 530~ 532eV。
  17. 17. copper oxide according to claim 12, the corresponding combination of the absorption oxygen feature peak-to-peak value can for 531~ 533eV。
  18. 18. copper oxide according to claim 1, the X ray diffracting spectrum of the copper oxide includes that 2 angles θ are 32.5- 33.5 °, 34.8-35.8 ° and 37.5-38.5 ° of diffraction maximum.
  19. 19. copper oxide according to claim 1, the copper oxide is micro- less than or equal to 1 in the size of at least one dimension Rice.
  20. 20. copper oxide according to claim 1, the copper oxide is less than or equal to 500 in the size of at least one dimension Nanometer.
  21. 21. copper oxide according to claim 1, the copper oxide is less than or equal to 100 in the size of at least one dimension Nanometer.
  22. 22. copper oxide according to claim 1, the copper oxide is 5~1000 nanometers in the size of at least one dimension.
  23. 23. copper oxide according to claim 1, the copper oxide is received in the size of at least one dimension for 30~1000 Rice.
  24. 24. described in any item copper oxide according to claim 1~23, with following one or more features:
    X) copper oxide is nano particle, and the granularity of the nano particle is 50~1000 nanometers;
    Y) copper oxide is nanometer rods, and the length of the nanometer rods is 30~2000 nanometers, and the diameter of the nanometer rods is 10 ~100 nanometers;
    Z) copper oxide is nano wire, and the length of the nano wire is 1~50 micron, the diameter of the nano wire is 50~ 200 nanometers.
  25. 25. described in any item copper oxide according to claim 1~23, with following one or more features:
    X) copper oxide is nano particle, and the granularity of the nano particle is 100~500 nanometers;
    Y) copper oxide is nanometer rods, and the length of the nanometer rods is 30~2000 nanometers 300~1000 nanometers;The nanometer The diameter of stick is 30~50 nanometers;
    Z) copper oxide is nano wire, and the length of the nano wire is 10~20 microns, the diameter of the nano wire is 100~ 150 nanometers.
  26. 26. a kind of porous material, including porous carrier, it is also loaded on the porous carrier and has the right to require any one of 1~25 institute The copper oxide stated.
  27. 27. porous material according to claim 26, the porous carrier is porous carbon, porous tin-antimony oxide or multilayer Graphene.
  28. 28. a kind of composition, including the described in any item copper oxide of claim 1~25.
  29. 29. composition according to claim 28 further includes Sb2O3、CeO2、Ni2O3、Co3O4And RuO2One of or It is a variety of.
  30. 30. a kind of metal-air battery, including the described in any item copper oxide of claim 1~25, claim 26~27 times Porous material described in one and/or the described in any item compositions of claim 28~29.
  31. 31. metal-air battery according to claim 30, the cathode of the metal-air battery include claim 1~ 25 described in any item copper oxide, the described in any item porous materials of claim 26~27 and/or claim 28~29 times Composition described in one.
  32. 32. metal-air battery according to claim 31, the anode of the metal-air battery includes: active metal list One of matter, active metallic ion, active metal alloy and active metal insert material are a variety of.
  33. 33. metal-air battery according to claim 32, the active metal includes being selected from K, Na, Li, Mg, Ca, Ba With one of Zn or a variety of.
  34. 34. metal-air battery according to claim 32, the active metal includes Li.
  35. 35. metal-air battery according to claim 32, the metal-air battery is lithium-air battery, sodium air electricity Pond, zinc-air battery, calcium air cell or magnesium air battery.
  36. 36. the described in any item porous materials of described in any item copper oxide, claim 26~27 according to claim 1~25 Or the described in any item compositions of claim 28~29 are reacted for catalytic oxidation-reduction and/or the purposes of oxygen evolution reaction.
  37. 37. purposes according to claim 36, the oxygen reduction reaction is 4Li+O2+2H2O→4Li++4OH-
  38. 38. purposes according to claim 36, the oxygen evolution reaction is 4OH-→O2+2H2O+4e-
  39. 39. purposes according to claim 36, the oxygen reduction reaction is 4Li+O2+4H+→4Li++2H2O。
  40. 40. purposes according to claim 36, the oxygen evolution reaction is 2H2O→O2+4H++4e-
  41. 41. the preparation method of the described in any item copper oxide of claim 1~25 comprising following steps:
    A) Copper substrate a part is placed in alkaline aqueous solution, a part exposure in air, is reacted;Or alkaline aqueous solution is applied It is added on the surface of Copper substrate, is reacted.
  42. 42. according to the method for claim 41, the time of reaction is 10 minutes to 30 days.
  43. 43. according to the method for claim 41, the time of reaction is 30 minutes to 3 days.
  44. 44. according to the method for claim 41, the time of reaction is 1~2 day.
  45. 45. according to the method for claim 41, the temperature of reaction is 0~90 DEG C.
  46. 46. according to the method for claim 41, the temperature of reaction is 20~50 DEG C.
  47. 47. according to the method for claim 41, the Copper substrate is the porous carrier that copper is covered on copper sheet, copper powder or surface.
  48. 48. according to the method for claim 41, the alkaline aqueous solution contains water-soluble alkali.
  49. 49. according to the method for claim 48, concentration of the water-soluble alkali in alkaline aqueous solution is 0.1~10mol/ L。
  50. 50. according to the method for claim 48, concentration of the water-soluble alkali in alkaline aqueous solution is 0.1~5mol/ L。
  51. 51. according to the method for claim 48, the water-soluble alkali include selected from one of LiOH, KOH or NaOH or It is a variety of.
  52. 52. according to the method for claim 41, the alkaline aqueous solution contains additive, the additive includes being selected from second Alcohol, ammonium hydroxide, hexamethylenetetramine, dodecyl sodium sulfate, lauryl sodium sulfate, potassium chloride, sodium chloride, lithium chloride, tween, It is one or more in glycerine, ethylene glycol.
  53. 53. method according to claim 52, concentration of the additive in alkaline aqueous solution is 0.0001- 0.2mol/L。
  54. 54. method according to claim 52, concentration of the additive in alkaline aqueous solution is 0.01~ 0.1mol/L。
  55. 55. according to the method for claim 41, not containing oxidant in the alkaline aqueous solution.
  56. 56. method according to claim 55, the oxidant is in hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate It is one or more.
  57. 57. according to the method for claim 41, after step a) further include:
    B) product of step a) is heat-treated in oxygen-containing atmosphere.
  58. 58. method according to claim 57, the temperature of heat treatment is 100~400 DEG C.
  59. 59. method according to claim 57, the temperature of heat treatment is 250~350 DEG C.
  60. 60. method according to claim 57, the time of heat treatment is 1~5 hour.
  61. 61. method according to claim 57, the time of heat treatment is 2~4 hours.
  62. 62. method according to claim 57, the oxygen-containing atmosphere is air atmosphere.
  63. 63. according to 41~62 described in any item methods, the one or more steps included the following steps:
    I) Copper substrate is cleaned;
    Ii) Copper substrate a part after cleaning is placed in alkaline aqueous solution, a part exposure in air, is reacted;Or by alkali Property aqueous solution be applied to the surface of Copper substrate, reaction;
    Iv it) washs, is dry.
  64. 64. method according to claim 63, step ii) and iv) between it is further comprising the steps of:
    Iii) heat treatment step ii) product.
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