CN117254049A - Co for lithium air battery 3 O 4 /CeO 2 Preparation method of nanosphere composite material - Google Patents
Co for lithium air battery 3 O 4 /CeO 2 Preparation method of nanosphere composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000002077 nanosphere Substances 0.000 title claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 235000011187 glycerol Nutrition 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 11
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000002243 precursor Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000004729 solvothermal method Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- -1 cobalt cerium glycerin Chemical compound 0.000 abstract description 2
- 239000013590 bulk material Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 239000003273 ketjen black Substances 0.000 description 6
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Hybrid Cells (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses Co for a lithium air battery 3 O 4 /CeO 2 A method for preparing nanosphere composite material. The invention adopts Co (NO) 3 ) 2 ·6H 2 O is cobalt source, ce (NO) 3 ) 3 ·6H 2 O is a cerium source, isopropanol and glycerin are used as solvents, and a nanometer spherical regular cobalt cerium glycerin precursor is obtained through solvothermal reaction, and the obtained precursor is obtainedAnnealing the bulk material at high temperature to obtain Co 3 O 4 /CeO 2 Nanosphere composite materials. The method prepares Co 3 O 4 /CeO 2 The nanosphere composite material has simple method and controllable morphology and size, and is prepared from Co 3 O 4 And CeO 2 The catalyst material has good catalytic performance and very high specific capacitance as the catalyst material of organic lithium air battery.
Description
Technical Field
The invention relates to the field of preparation of catalyst materials for lithium air batteries, in particular to Co 3 O 4 /CeO 2 A solvothermal preparation method of a nanosphere composite material.
Background
In order to solve the energy crisis and environmental pollution caused by excessive combustion of fossil fuel, popularization of electric automobiles is an important way for realizing sustainable development of human society. However, the power source widely used in the electric automobile at present is a lithium ion battery, and the theoretical energy density is low, so that the driving mileage and further application of the electric automobile are limited. Lithium air batteries are considered ideal alternatives to mainstream lithium ion batteries with their highest energy density and environmental friendliness.
However, there are still many problems in the current lithium air battery in practical industrial application, such as small practical specific capacity, high overpotential and poor cycle performanceSlow oxygen reduction (ORR), oxygen Evolution (OER), etc., while lithium air battery positive catalysts directly affect these properties. Common lithium air catalysts include carbon materials, noble metals, metal oxides, and the like. Metal oxides are widely used in lithium air battery catalysts due to their redox stability and variable valence state, where Co 3 O 4 Metal oxide catalysts for lithium air batteries have dual catalytic activity, however, co 3 O 4 Poor conductivity itself affects its catalytic activity. CeO (CeO) 2 Not only has high oxygen ion conductivity, but also can be used as an oxygen storage medium. Based on the strategy, the invention develops Co for the lithium air battery 3 O 4 /CeO 2 Nanosphere composite materials. Co (Co) 3 O 4 /CeO 2 The nanosphere composite material provides more catalytic sites, thereby improving the capacity and cycle performance of the lithium air battery. The common mixed solvent of isopropanol and glycerin and other mixed alcohol solvents is used as the solvothermal reaction, chinese patent CN113948690A uses the mixed solvent of isopropanol and glycerin to carry out the solvothermal reaction to prepare hollow ball-shaped CuO/Co 3 O 4 The composite material is used as a lithium ion battery cathode material, and Chinese patent CN107658527A uses a mixed alcohol solution as a solvent to carry out solvothermal reaction to prepare the transition metal oxide hollow sphere material.
Disclosure of Invention
The invention aims to improve the Co of a lithium air battery 3 O 4 The problems of low conductivity of the catalyst and the like provide Co for a lithium air battery 3 O 4 /CeO 2 A solvothermal preparation method of a nanosphere composite material.
Co for lithium air battery 3 O 4 /CeO 2 The preparation method of the nanosphere composite material comprises the following steps: dissolving cobalt source and cerium source in mixed solvent of isopropanol and glycerin, stirring and mixing to obtain uniform solution, transferring the solution into a reaction kettle, placing into a baking oven at a certain temperature for reacting for a period of time to obtain the product, centrifuging, separating, washing, and drying the product in a constant temperature drying oven at 60deg.C for 12 hrCalcining in air atmosphere when the temperature is raised to a certain temperature to obtain the Co 3 O 4 /CeO 2 Nanosphere composite materials.
Further, the cobalt source is cobalt nitrate hexahydrate; the cerium source is cerium nitrate hexahydrate; the mole ratio of cobalt nitrate hexahydrate to cerium nitrate hexahydrate is as follows: 10-1:1.
Further, the mixture is placed in an oven at a certain temperature for reaction for a period of time to obtain a product, wherein the certain temperature is 160-220 ℃, and the reaction period of time is 3-24 hours.
Further, the calcination process specifically comprises the following steps: the temperature rise is at a rate of 1-5 ℃/min, the calcination temperature is 400-600 ℃, and the calcination time is 1-10h.
The invention provides a Co 3 O 4 /CeO 2 The nanosphere composite material is prepared by adopting the method.
The invention also provides a Co 3 O 4 /CeO 2 The application of the nanosphere composite material in the electrode material of the lithium air battery.
The invention has the beneficial effects that: co prepared by the invention 3 O 4 /CeO 2 The nanosphere composite material adopts a solvothermal method, is convenient and simple, and has strong experimental repeatability. The invention prepares Co by solvent thermal reaction of mixed solvent of isopropanol and glycerin 3 O 4 /CeO 2 The nanosphere composite material can regulate and control Co by regulating and controlling the molar ratio of raw material metal cobalt salt and cerium salt, the volume of solvent, the reaction time and the reaction temperature 3 O 4 /CeO 2 Morphology and size of the nanosphere composite; the composite material can effectively solve the problem of Co 3 O 4 Poor conductivity by Co 3 O 4 And CeO 2 The synergistic effect improves the catalytic capability and improves the capacity of the lithium air battery.
Drawings
FIG. 1 is Co prepared in example 1 3 O 4 /CeO 2 XRD pattern of the nanosphere composite;
FIG. 2 is Co prepared in example 1 3 O 4 /CeO 2 NanospheresSEM profile of the composite;
FIG. 3 is Co prepared in example 1 3 O 4 /CeO 2 The nanosphere composite material is used as a positive electrode catalyst of a lithium air battery, and a first constant current charge-discharge curve map of the battery is assembled.
Detailed Description
The invention will be further described with reference to the drawings and specific examples of the invention.
Example 1
Co for lithium air battery 3 O 4 /CeO 2 The preparation method of the nanosphere composite material comprises the following specific steps:
weigh 0.5mmol Co (NO) 3 ) 2 ·6H 2 O and 0.5mmol Ce (NO) 3 ) 3 ·6H 2 O is dissolved in a mixed solvent of 50mL of isopropanol and 10mL of glycerol, and the mixture is magnetically stirred at room temperature for 6-9h to obtain pink clear liquid. The liquid was then transferred to a 100mL autoclave, the autoclave was placed in an oven, heated to 180 ℃ and incubated for 8 hours, cooled to room temperature after completion of the reaction, the precipitate was centrifuged, washed five times with absolute ethanol at 9000rpm, and then placed in an oven at 60 ℃ and dried for 12 hours. Placing the dried precursor in air atmosphere, heating to 500 ℃ at a heating rate of 1 ℃/min, and calcining for 2 hours to obtain Co 3 O 4 /CeO 2 Nanosphere composite materials.
FIG. 1 is Co 3 O 4 /CeO 2 SEM pictures of nanosphere composite materials show that the particle size of the particles synthesized by the method is about 400nm and the size is uniform. FIG. 2 is Co 3 O 4 /CeO 2 XRD spectrum of the nanosphere composite material is compared with standard card, and the obtained product is Co 3 O 4 /CeO 2 Nanosphere composites and no other impurities.
Co obtained in example 1 3 O 4 /CeO 2 The nanosphere composite material is prepared into an electrode and assembled into a lithium air battery according to the following method:
specifically, co is weighed according to the mass ratio of 3:6:1 respectively 3 O 4 /CeO 2 The nanosphere composite material, ketjen black and polyvinylidene fluoride are dissolved in N-methyl pyrrolidone, stirred and mixed uniformly, then the mixture is coated on carbon paper uniformly to prepare an electrode, a metal lithium sheet is taken as a negative electrode, and electrolyte is 1mol/L lithium triflate (LiCF) 3 SO 3 ) The membrane is made of glass fiber membrane, and the battery is assembled in a glove box. Fig. 3 is a graph of the first charge and discharge test under the following conditions: current density 100mA g -1 The discharge cutoff voltage was 2.2V, and the charge cutoff voltage was 4.4V. The test results show that: co is adopted 3 O 4 /CeO 2 The lithium air anode prepared by the nanosphere composite material catalyst has good electrochemical performance, and the first discharge capacity reaches 8868mAh g -1 。
Example 2
Co for lithium air battery 3 O 4 /CeO 2 The preparation method of the nanosphere composite material comprises the following specific steps:
weigh 0.8mmol Co (NO) 3 ) 2 ·6H 2 O and 0.2mmol Ce (NO) 3 ) 3 ·6H 2 O is dissolved in a mixed solvent of 50mL of isopropanol and 10mL of glycerol, and the mixture is magnetically stirred at room temperature for 6-9h to obtain pink clear liquid. The liquid was then transferred to a 100mL autoclave, the autoclave was placed in an oven, heated to 180 ℃ and incubated for 8 hours, cooled to room temperature after completion of the reaction, the precipitate was centrifuged, washed five times with absolute ethanol at 9000rpm, and then placed in an oven at 60 ℃ and dried for 12 hours. Placing the dried precursor in air atmosphere, heating to 500 ℃ at a heating rate of 1 ℃/min, and calcining for 2 hours to obtain Co 3 O 4 /CeO 2 Nanosphere composite materials.
Co obtained in example 2 3 O 4 /CeO 2 The nanosphere composite material is prepared into an electrode and assembled into a lithium air battery according to the following method:
specifically, co is weighed according to the mass ratio of 3:6:1 respectively 3 O 4 /CeO 2 The nanosphere composite material, ketjen black and polyvinylidene fluoride are dissolved in N-methyl pyrrolidone and stirred and mixed uniformlyThen uniformly coating the electrode on carbon paper, taking a metal lithium sheet as a negative electrode, and taking 1mol/L lithium triflate (LiCF) as electrolyte 3 SO 3 ) The membrane is made of glass fiber membrane, and the membrane is assembled into a battery in a glove box and subjected to a first charge and discharge test under the following conditions: current density 100mA g -1 The discharge cutoff voltage was 2.2V, and the charge cutoff voltage was 4.4V. The first discharge capacity of the battery reaches 8583mAh g -1 。
Example 3
Co for lithium air battery 3 O 4 /CeO 2 The preparation method of the nanosphere composite material comprises the following specific steps:
weigh 0.5mmol Co (NO) 3 ) 2 ·6H 2 O and 0.5mmol Ce (NO) 3 ) 3 ·6H 2 O is dissolved in a mixed solvent of 60mL of isopropanol and 10mL of glycerol, and the mixture is magnetically stirred at room temperature for 6-9h to obtain pink clear liquid. The liquid was then transferred to a 100mL autoclave, the autoclave was placed in an oven, heated to 180 ℃ and incubated for 8 hours, cooled to room temperature after completion of the reaction, the precipitate was centrifuged, washed five times with absolute ethanol at 9000rpm, and then placed in an oven at 60 ℃ and dried for 12 hours. Placing the dried precursor in air atmosphere, heating to 500 ℃ at a heating rate of 1 ℃/min, and calcining for 2 hours to obtain Co 3 O 4 /CeO 2 Nanosphere composite materials.
Co obtained in example 3 3 O 4 /CeO 2 The nanosphere composite material is prepared into an electrode and assembled into a lithium air battery according to the following method:
specifically, co is weighed according to the mass ratio of 3:6:1 respectively 3 O 4 /CeO 2 The nanosphere composite material, ketjen black and polyvinylidene fluoride are dissolved in N-methyl pyrrolidone, stirred and mixed uniformly, then the mixture is coated on carbon paper uniformly to prepare an electrode, a metal lithium sheet is taken as a negative electrode, and electrolyte is 1mol/L lithium triflate (LiCF) 3 SO 3 ) Tetraethylene glycol dimethyl ether solution (TEGDME) of (A), the diaphragm is a glass fiber diaphragm, and the battery is assembled and carried out in a glove boxThe first charge and discharge test is carried out under the following conditions: current density 100mA g -1 The discharge cutoff voltage was 2.2V, and the charge cutoff voltage was 4.4V. The first discharge capacity of the battery is 8190mAh g -1 。
Example 4
Co for lithium air battery 3 O 4 /CeO 2 The preparation method of the nanosphere composite material comprises the following specific steps:
weigh 0.6mmol Co (NO) 3 ) 2 ·6H 2 O and 0.4mmol Ce (NO) 3 ) 3 ·6H 2 O is dissolved in a mixed solvent of 50mL of isopropanol and 10mL of glycerol, and the mixture is magnetically stirred at room temperature for 6-9h to obtain pink clear liquid. The liquid was then transferred to a 100mL autoclave, the autoclave was placed in an oven, heated to 180 ℃ and incubated for 6 hours, cooled to room temperature after completion of the reaction, the precipitate was centrifuged, washed five times with absolute ethanol at 9000rpm, and then placed in an oven at 60 ℃ and dried for 12 hours. Placing the dried precursor in air atmosphere, heating to 500 ℃ at a heating rate of 1 ℃/min, and calcining for 2 hours to obtain Co 3 O 4 /CeO 2 Nanosphere composite materials.
Co obtained in example 4 3 O 4 /CeO 2 The nanosphere composite material is prepared into an electrode and assembled into a lithium air battery according to the following method:
specifically, co is weighed according to the mass ratio of 3:6:1 respectively 3 O 4 /CeO 2 The nanosphere composite material, ketjen black and polyvinylidene fluoride are dissolved in N-methyl pyrrolidone, stirred and mixed uniformly, then the mixture is coated on carbon paper uniformly to prepare an electrode, a metal lithium sheet is taken as a negative electrode, and electrolyte is 1mol/L lithium triflate (LiCF) 3 SO 3 ) The membrane is made of glass fiber membrane, and the membrane is assembled into a battery in a glove box and subjected to a first charge and discharge test under the following conditions: current density 100mA g -1 The discharge cutoff voltage was 2.2V, and the charge cutoff voltage was 4.4V. The first discharge capacity of the battery reaches 8233mAh g -1 。
Example 5
Co for lithium air battery 3 O 4 /CeO 2 The preparation method of the nanosphere composite material comprises the following specific steps:
weigh 0.8mmol Co (NO) 3 ) 2 ·6H 2 O and 0.2mmol Ce (NO) 3 ) 3 ·6H 2 O is dissolved in a mixed solvent of 50mL of isopropanol and 10mL of glycerol, and the mixture is magnetically stirred at room temperature for 6-9h to obtain pink clear liquid. The liquid was then transferred to a 100mL autoclave, the autoclave was placed in an oven, heated to 190 ℃ and incubated for 6 hours, cooled to room temperature after completion of the reaction, the precipitate was centrifuged, washed five times with absolute ethanol at 9000rpm, and then placed in an oven at 60 ℃ and dried for 12 hours. Placing the dried precursor in air atmosphere, heating to 500 ℃ at a heating rate of 1 ℃/min, and calcining for 2 hours to obtain Co 3 O 4 /CeO 2 Nanosphere composite materials.
Co obtained in example 5 3 O 4 /CeO 2 The nanosphere composite material is prepared into an electrode and assembled into a lithium air battery according to the following method:
specifically, co is weighed according to the mass ratio of 3:6:1 respectively 3 O 4 /CeO 2 The nanosphere composite material, ketjen black and polyvinylidene fluoride are dissolved in N-methyl pyrrolidone, stirred and mixed uniformly, then the mixture is coated on carbon paper uniformly to prepare an electrode, a metal lithium sheet is taken as a negative electrode, and electrolyte is 1mol/L lithium triflate (LiCF) 3 SO 3 ) The membrane is made of glass fiber membrane, and the membrane is assembled into a battery in a glove box and subjected to a first charge and discharge test under the following conditions: current density 100mA g -1 The discharge cutoff voltage was 2.2V, and the charge cutoff voltage was 4.4V. The first discharge capacity of the battery reaches 8366mAh g -1 。
Example 6
Co for lithium air battery 3 O 4 /CeO 2 The preparation method of the nanosphere composite material comprises the following specific steps:
weigh 0.5mmol Co (NO) 3 ) 2 ·6H 2 O and 0.5mmol Ce (NO) 3 ) 3 ·6H 2 O is dissolved in a mixed solvent of 50mL of isopropanol and 10mL of glycerol, and the mixture is magnetically stirred at room temperature for 6-9h to obtain pink clear liquid. The liquid was then transferred to a 100mL autoclave, the autoclave was placed in an oven, heated to 180 ℃ and incubated for 8 hours, cooled to room temperature after completion of the reaction, the precipitate was centrifuged, washed five times with absolute ethanol at 9000rpm, and then placed in an oven at 60 ℃ and dried for 12 hours. Placing the dried precursor in air atmosphere, heating to 600 ℃ at a heating rate of 1 ℃/min, and calcining for 2 hours to obtain Co 3 O 4 /CeO 2 Nanosphere composite materials.
Co obtained in example 6 3 O 4 /CeO 2 The nanosphere composite material is prepared into an electrode and assembled into a lithium air battery according to the following method:
specifically, co is weighed according to the mass ratio of 3:6:1 respectively 3 O 4 /CeO 2 The nanosphere composite material, ketjen black and polyvinylidene fluoride are dissolved in N-methyl pyrrolidone, stirred and mixed uniformly, then the mixture is coated on carbon paper uniformly to prepare an electrode, a metal lithium sheet is taken as a negative electrode, and electrolyte is 1mol/L lithium triflate (LiCF) 3 SO 3 ) The membrane is made of glass fiber membrane, and the membrane is assembled into a battery in a glove box and subjected to a first charge and discharge test under the following conditions: current density 100mA g -1 The discharge cutoff voltage was 2.2V, and the charge cutoff voltage was 4.4V. The first discharge capacity of the battery reaches 8569mAh g -1 。
Claims (6)
1. Co for lithium air battery 3 O 4 /CeO 2 The preparation method of the nanosphere composite material is characterized by comprising the following steps: dissolving cobalt source and cerium source in mixed solvent of isopropanol and glycerin, stirring and mixing to obtain uniform solution, transferring the solution into a reaction kettle, placing into a baking oven at a certain temperature for reacting for a period of time to obtain a product, centrifuging, separating and washing the obtained product, drying the product in a constant-temperature drying oven at 60 ℃ for 12h, and heating to a certain temperatureCalcining in air atmosphere to obtain the Co 3 O 4 /CeO 2 Nanosphere composite materials.
2. Co for lithium air batteries according to claim 1 3 O 4 /CeO 2 The preparation method of the nanosphere composite material is characterized by comprising the following steps: the cobalt source is cobalt nitrate hexahydrate; the cerium source is cerium nitrate hexahydrate; the mole ratio of cobalt nitrate hexahydrate to cerium nitrate hexahydrate is as follows: 10-1:1.
3. Co for lithium air batteries according to claim 1 3 O 4 /CeO 2 The preparation method of the nanosphere composite material is characterized by comprising the following steps: and (3) placing the mixture in an oven at a certain temperature for reaction for a period of time to obtain a product, wherein the certain temperature is 160-220 ℃, and the reaction period of time is 3-24 hours.
4. Co for lithium air batteries according to claim 1 3 O 4 /CeO 2 The preparation method of the nanosphere composite material is characterized by comprising the following steps: the calcination process specifically comprises the following steps: the temperature rise is at a rate of 1-5 ℃/min, the calcination temperature is 400-600 ℃, and the calcination time is 1-10h.
5. Co (cobalt) 3 O 4 /CeO 2 The nanosphere composite material is characterized in that the nanosphere composite material is prepared by the method of any one of claims 1-4.
6. Co according to claim 5 3 O 4 /CeO 2 The application of the nanosphere composite material in the electrode material of the lithium air battery.
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| CN117691131A (en) * | 2024-02-01 | 2024-03-12 | 新乡学院 | MoO for lithium air battery 2 /CeO 2 Nanosphere composite material and preparation method thereof |
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