CN114725401A - Preparation method of metal oxide catalyst for lithium-oxygen battery - Google Patents
Preparation method of metal oxide catalyst for lithium-oxygen battery Download PDFInfo
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- CN114725401A CN114725401A CN202210338501.5A CN202210338501A CN114725401A CN 114725401 A CN114725401 A CN 114725401A CN 202210338501 A CN202210338501 A CN 202210338501A CN 114725401 A CN114725401 A CN 114725401A
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- metal oxide
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- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- -1 polypropylene Polymers 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- 229910009112 xH2O Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 229910004755 Cerium(III) bromide Inorganic materials 0.000 claims description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 2
- 229910008069 Cerium(III) iodide Inorganic materials 0.000 claims description 2
- 229910005258 GaBr3 Inorganic materials 0.000 claims description 2
- 229910005267 GaCl3 Inorganic materials 0.000 claims description 2
- 229910005263 GaI3 Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 claims description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Inorganic materials [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 2
- DWRNSCDYNYYYHT-UHFFFAOYSA-K gallium(iii) iodide Chemical compound I[Ga](I)I DWRNSCDYNYYYHT-UHFFFAOYSA-K 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- KGYONDOWIDQLMY-UHFFFAOYSA-K cerium(3+);triperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O KGYONDOWIDQLMY-UHFFFAOYSA-K 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- 229910001323 Li2O2 Inorganic materials 0.000 description 1
- ROLJWXCAVGNMAK-UHFFFAOYSA-N [Ce]=O Chemical compound [Ce]=O ROLJWXCAVGNMAK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound 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 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Classifications
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- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8853—Electrodeposition
-
- 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
-
- 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
- H01M4/8605—Porous electrodes
-
- 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
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- 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
Abstract
The invention relates to a preparation method of a metal oxide catalyst for a lithium oxygen battery. Specifically, in a pure oxygen atmosphere, metal lithium is used as a negative electrode, a carbon material is used as a positive electrode, a non-lithium metal salt solution is used as an electrolyte, constant current discharge is carried out until the cut-off voltage is reached, and the metal oxide catalyst is generated on the surface of the positive electrode.
Description
Technical Field
The invention relates to a preparation method of a metal oxide catalyst for a lithium-oxygen battery, belonging to the technical field of batteries.
Background
The lithium oxygen battery has ultrahigh energy density (3500 Wh. kg)-1) Is considered to be the next generation energy storage system with great development potential. However, the discharge product Li2O2The slow kinetics of oxygen reduction (ORR) and Oxygen Evolution (OER) reactions result in energy inefficiency in lithium oxygen batteriesShort ring life, poor rate capability, and easy decomposition of carbon-based material on positive electrode side to form Li after long-term charging under high voltage2CO3And other side reaction products. These by-products are difficult to decompose, and as the cycle progresses, they are accumulated on the surface of the positive electrode, blocking electrons and O2Eventually leading to battery failure. To solve the above problems, selection of a suitable catalyst is considered to be one of the most effective approaches.
In recent years, researchers have been working on the development of highly effective non-noble metal catalysts, where metal oxides have gained widespread acceptance at their low cost, abundant storage, high catalytic activity and stability. However, the process of synthesizing the metal oxide catalyst by an ex-situ method such as a hydrothermal method is complicated and is easily affected by external factors and the environment. In addition, the metal oxide catalyst synthesized in the non-in-situ mode is unstable, and is easy to fall off and agglomerate in the circulation process. Therefore, the research of designing a simple and rapid method for preparing the metal oxide catalyst for the anode of the lithium-oxygen battery has important significance.
Disclosure of Invention
Based on the above background, the present invention is directed to a method for preparing a metal oxide catalyst for a lithium oxygen battery, wherein the metal oxide material provided by the present invention can be used as a lithium oxygen battery anode catalyst, has the advantages of simple synthesis and low cost, and is beneficial to practical use of the lithium oxygen battery.
In one aspect, the invention provides a preparation method of a metal oxide catalyst for a lithium-oxygen battery, wherein the metal oxide catalyst is generated on the surface of a positive electrode by using metal lithium as a negative electrode, using a carbon material as a positive electrode, using a non-lithium metal salt solution as an electrolyte and performing constant current discharge until the cut-off voltage is reached in a pure oxygen atmosphere.
Preferably, the carbon material is a multi-walled carbon nanotube; a separator is arranged between the positive electrode and the negative electrode; the membrane is Whatman GF/C glass fiber membrane, polypropylene membrane, polyethylene membrane, polyimide membrane and polyamide membrane.
Preferably, the non-lithium metal salt is a salt that combines with oxygen ions to form a solid metal oxide; preferably, the reaction potential of the metal element with reduced oxygen in the non-lithium metal salt > the reaction potential of lithium metal with reduced oxygen.
Preferably, the non-lithium metal salt is at least one of a Ce salt, a Ga salt and a Sm salt; the Ce salt is Ce (ClO)4)3·6H2O、Ce(NO3)3·6H2O、Ce(Ac)3·xH2O、CeBr3、CeCl3And CeI3At least one of (a); the Ga salt is Ga (ClO)4)3、Ga(NO3)3·xH2O、GaI3、GaBr3And GaCl3At least one of; the Sm salt is selected from Sm (NO)3)3、Sm(Ac)3·xH2O、SmBr3、SmCl3、Sm(CF3O3S)3And SmI2At least one of (1). The micro-morphology of the correspondingly prepared cerium oxide is cubic, and the average particle size can be 50-600 nm, preferably 200-400 nm, and more preferably 300 nm. Ga2O3The microscopic morphology is spherical, and the average particle size can be 40-200 nm, preferably 60-100 nm, and more preferably 80 nm. Sm2O3The microscopic morphology is cubic, and the average particle size is 50-600 nm, preferably 200-400 nm, and more preferably 300 nm.
Preferably, the solvent of the non-lithium metal salt solution is an organic solvent, and the organic solvent is at least one selected from dimethyl sulfoxide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethyl carbonate, propylene carbonate and ethylene carbonate; the concentration of the non-lithium metal salt in the non-lithium metal salt solution is 0.001-5 mol/L.
Preferably, the non-lithium metal salt solution further comprises a metal lithium salt; the metal lithium salt is selected from LiTFSI, LiFSI and LiClO4、LiBF4And LiPF6At least one of; the concentration of the metal lithium salt in the non-lithium metal salt solution is 0.05-3 mol/L.
Preferably, the current density of the constant current discharge is 100 to 1500mA/g, preferably 300 to 800mA/g, and most preferably 500 mA/g.
Preferably, the cut-off voltage is 2.5 to 3.5V.
In another aspect, the present invention also provides a metal oxide catalyst for a lithium oxygen battery prepared according to the above preparation method.
Has the advantages that:
the preparation method of the metal oxide catalyst for the lithium-oxygen battery provided by the invention fully utilizes the pure oxygen atmosphere of the lithium-oxygen battery, and in the discharging process of the battery, non-lithium metal ions dissolved in organic electrolyte and oxygen molecules generate electrochemical reaction in the discharging process to form a non-lithium metal oxide solid catalyst; the preparation method has simple process and controllable process; and the prepared metal oxide catalyst has an improved effect on the catalytic performance of the lithium-oxygen battery.
Drawings
FIG. 1 is a schematic diagram of the formation of a metal oxide according to the present invention;
FIG. 2 is a constant current discharge curve provided in example 1;
FIG. 3 is a cyclic voltammogram of a lithium oxygen battery containing a soluble cerium salt;
FIG. 4 shows CeO formed in example 12The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen battery;
FIG. 5 shows CeO formed in example 22The morphology of the catalyst;
FIG. 6 shows Ga formed in example 32O3The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen battery;
FIG. 7 shows Sm obtained in example 42O3The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen battery;
FIG. 8 shows CeO formed in example 52The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen battery;
FIG. 9 shows CeO formed in example 62The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen battery;
FIG. 10 shows CeO formed in example 72The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen battery;
FIG. 11 shows CeO formed in example 82The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen cell.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The preparation process of the metal oxide catalyst provided by the invention is simple, the size of the catalyst can be regulated, the cost of raw materials is low, and the lithium oxygen battery using the catalyst shows high-efficiency catalytic performance and excellent cycle reversibility, thereby showing wide application prospects.
In the present invention, a specific soluble non-lithium metal salt is selected and added to an organic electrolyte of a lithium oxygen battery, and the lithium oxygen battery is discharged at a constant current, thereby generating a non-lithium metal oxide catalyst that is difficult to be oxidatively decomposed on the surface of an air positive electrode. The following exemplarily illustrates a method for preparing a metal oxide catalyst for a lithium oxygen battery provided by the present invention.
A specific non-lithium metal salt is selected. The non-metallic lithium salt is soluble in organic solvents and can combine with oxygen ions to form salts of solid metal oxides.
And dissolving a certain amount of non-lithium metal salt with molar concentration in the electrolyte to assemble the corresponding lithium oxygen battery. The concentration of the metal lithium salt added into the electrolyte can be 0.05-3 mol/L, and the preferable concentration is 1 mol/L. Thus, after the metal oxide catalyst is prepared, the lithium oxide catalyst can be directly used as a lithium oxygen battery for testing the electrochemical performance.
In an alternative embodiment, the solvent of the electrolyte may be at least one of dimethyl sulfoxide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethyl carbonate, propylene carbonate, and ethylene carbonate. Preferably, the solvent is selected from dimethyl sulfoxide.
And (3) carrying out constant current discharge on the lithium-oxygen battery under the pure oxygen atmosphere to cut-off voltage to obtain the metal oxide catalyst. Wherein the molar concentration of the non-lithium metal salt is as follows: 0.001 to 5mol/L, preferably 0.05 mol/L.
In the present invention, the constant discharge current density is 100mA · g-1～1500mA·g-1Preferably, the constant discharge current density is set to 500mA · g-1. The cut-off voltage can be 2.5-3.5V, and preferably the cut-off voltage is 2.8V.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also merely one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Preparing electrolyte: an electrolyte (LiClO as a metal lithium salt) of a dimethyl sulfoxide-based lithium oxygen battery is added into a glove box (moisture is less than 0.1ppm and oxygen content is less than 0.1ppm) filled with argon41moL/L) of cerium perchlorate hexahydrate Ce (ClO)4)3·6H2O, the addition amount is 0.05 mol/L.
Assembling the battery: the positive active material of the lithium oxygen battery is a carbon nano tube coated on a porous current collector, the negative electrode is a circular metal lithium sheet with the diameter of 12mm, the battery shell is of a 2032 type, the opening of the negative electrode shell is upward, and the negative electrode shell is flatly placed on the panel; placing the spring piece into the negative electrode shell; clamping the gasket on the spring plate, and then clamping the lithium plate in the middle of the gasket; clamping a diaphragm to cover a lithium sheet, and dropping the electrolyte on the diaphragm (Whatman GF/C glass fiber diaphragm) by using a liquid moving machine; and (3) clamping the positive plate in the middle of the diaphragm, clamping the porous positive shell by using tweezers to cover, and pressing by using a button cell packaging machine to obtain the button lithium oxygen cell, wherein the addition amount of the electrolyte in the button cell is 80 mu L.
And (3) synthesis of metal oxide: the assembled cell was left to stand in an oxygen glove box (moisture < 0.1ppm) for 6 hours, and then set at 500mA · g-1Discharging current density to 2.75V to form CeO on the surface of the positive electrode2A catalyst.
FIG. 1 is a schematic diagram of the process of forming a metal oxide according to the present invention. The method is characterized in that metal salt is added into electrolyte of the lithium oxygen battery, metal cations react with reduced oxygen on the surface of a positive electrode to generate metal oxide particles in the discharging process, and the metal oxide can be used as a positive electrode catalyst of the lithium oxygen battery to improve the electrochemical performance of the lithium oxygen battery.
FIG. 2 shows the addition of Ce (ClO) to the sample 14)3·6H2The constant-current discharge curve of the O lithium oxygen battery has an obvious platform before 2.75V, and is a cerium oxygen reaction platform before lithium oxygen reaction.
FIG. 3 shows the addition of Ce (ClO) to the solution of example 14)3·6H2The cyclic voltammogram of the lithium oxygen battery of O shows that a distinct cathode peak, which is a cerium oxide reaction peak, appears between 2.75 and 3.2V before the lithium oxide reaction.
FIG. 4 shows CeO formed in example 12The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen battery, from the results, it is seen that the metal salt Ce (ClO) is added4)3·6H2O, then forming cubic CeO on the surface of the positive electrode2Particles with a size of-300 nm, and a lithium oxygen battery using the catalyst can reach 1000 mAh.g-1Has a stable circulation at 490 times and at 5000mAh g-1Is stably circulated for 35 times under the ultrahigh cut-off capacity.
Example 2
An electrolyte (LiClO as a metal lithium salt) of a dimethyl sulfoxide-based lithium oxygen battery is added into a glove box (moisture is less than 0.1ppm and oxygen content is less than 0.1ppm) filled with argon41mol/L of cerium nitrate hexahydrate is added3)3·6H2O, the addition amount is 0.05 mol/L. A lithium oxygen battery was assembled using the electrolyte solution in the same manner as in example 1.
The assembled cell was left to stand in an oxygen glove box (moisture < 0.1ppm) for 6 hours and then at 500mA · g-1Current density discharge, i.e. formation of CeO on the surface of the positive electrode2A catalyst.
FIG. 5 shows CeO formed in example 22The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen battery, it is seen from the results that the metal salt Ce (NO) is added to the electrolyte3)3·6H2After O, it forms cubic CeO on the surface of the positive electrode2Particles with a size of-300 nm, and a lithium oxygen battery using the catalyst can reach 1000 mAh.g -1460 times of stable cycling at the cut-off capacity.
Example 3
Preparing electrolyte: an electrolyte (LiClO as a metal lithium salt) of a dimethyl sulfoxide-based lithium oxygen battery is added into a glove box (moisture is less than 0.1ppm and oxygen content is less than 0.1ppm) filled with argon4Gallium triiodide (GaI) is added into the solution with the concentration of 1mol/L3) The amount of addition was 0.05 mol/L.
And (3) synthesis of metal oxide: the assembled cell was left to stand in an oxygen glove box (moisture < 0.1ppm) for 6 hours and then at 500mA · g-1Discharging current density to 3.0V to form preposed Ga on the surface of the positive electrode2O3A catalyst.
FIG. 6 shows Ga formed in example 32O3The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen battery, it is seen from the results that the metal salt GaI is added3Then, it forms spherical Ga on the surface of the positive electrode2O3The lithium oxygen battery applying the catalyst can stably cycle for 100 circles (> 400 hours) under the condition of keeping low overpotential, and maintains higher energy efficiency (75%).
Example 4
An electrolyte (LiClO as a metal lithium salt) of a dimethyl sulfoxide-based lithium oxygen battery is added into a glove box (moisture is less than 0.1ppm and oxygen content is less than 0.1ppm) filled with argon4Adding samarium nitrate Sm (NO) into the solution with the concentration of 1mol/L3)3The amount of addition was 0.1 mol/L. A lithium oxygen battery was assembled using the electrolyte solution in the same manner as in example 3.
The assembled cell was left to stand in an oxygen glove box (moisture < 0.1ppm) for 6 hours and then at 500mA · g-1Discharging current density to 2.5V to form Sm on the surface of the positive electrode2O3A catalyst.
FIG. 7 shows Sm as formed in example 42O3The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen battery, it is seen from the results that the metal salt Sm (NO) is added to the electrolyte3)3Then, it forms a cube Sm on the surface of the positive electrode2O3Particles with a size of-300 nm, and a lithium oxygen battery using the catalyst can reach 1000 mAh.g-1Stable 115 cycles at cutoff capacity.
Example 5
The assembly of the lithium oxygen cell in this example 5 is as in example 1 except that: cerium perchlorate hexahydrate Ce (ClO) in electrolyte4)3·6H2O, the addition amount is 0.01 mol/L.
FIG. 8 shows CeO formed in example 52Morphology of the catalyst and corresponding cycle performance of the lithium oxygen cell, as seen by the results, when Ce (ClO) in the electrolyte4)3·6H2When the amount of O added is 0.01mol/L, CeO is formed on the surface of the positive electrode2The number of particles is small, and the lithium oxygen battery using the catalyst is 1000 mAh.g-1 Stable cycle 170 times at cut-off capacity.
Example 6
The assembly of a lithium-oxygen battery in this example 6 is as in example 1, except that: cerium perchlorate hexahydrate Ce (ClO) in electrolyte4)3·6H2O, the addition amount is 0.3 mol/L.
FIG. 9 shows CeO formed in example 62Morphology of the catalyst and corresponding cycle performance of the lithium oxygen cell, as seen by the results, when Ce (ClO) in the electrolyte4)3·6H2When the amount of O added is 0.3mol/L, CeO is formed on the surface of the positive electrode2The quantity of the particles is large, and the lithium oxygen battery using the catalyst is 1000 mAh.g-1Stable 320 cycles at the cut-off capacity of (d).
Example 7
The assembly of a lithium-oxygen battery in this example 7 is as in example 1, except that: at 100mA · g-1Discharging the current density to 2.75V, i.e. forming on the surface of the positive electrodeCeO2A catalyst.
FIG. 10 shows CeO formed in example 72The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen cell, it is seen from the results that, under otherwise identical conditions, when the discharge current density is reduced to 100mA g-1CeO formed on the surface of the positive electrode2The particle is bigger, the size is 600nm, and the lithium oxygen battery using the catalyst is 1000 mAh.g-1 Stable cycle 180 times at cut-off capacity.
Example 8
The assembly of a lithium oxygen battery in this example 8 is as in example 1, except that: at 1500mA · g-1Discharging current density to 2.75V to form CeO on the surface of the positive electrode2A catalyst.
FIG. 11 shows CeO formed in example 82The morphology of the catalyst and the corresponding cycle performance of the lithium oxygen cell, it is seen from the results that, under otherwise identical conditions, when the discharge current density is increased to 1500mA g-1CeO formed on the surface of the positive electrode2The particle size is small and is about 50nm, and the lithium oxygen battery using the catalyst has the density of 1000 mAh.g-1 Stable cycle 75 times at cut-off capacity.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (9)
1. A preparation method of a metal oxide catalyst for a lithium-oxygen battery is characterized in that in a pure oxygen atmosphere, metal lithium is used as a negative electrode, a carbon material is used as a positive electrode, a non-lithium metal salt solution is used as an electrolyte, constant current discharge is carried out until the cut-off voltage is reached, and the metal oxide catalyst is generated on the surface of the positive electrode.
2. The production method according to claim 1, wherein the carbon material is a multi-walled carbon nanotube; a separator is arranged between the positive electrode and the negative electrode; the membranes include Whatman GF/C glass fiber membranes, polypropylene membranes, polyethylene membranes, polyimide membranes, and polyamide membranes.
3. The method according to claim 1, wherein the non-lithium metal salt is a salt that combines with oxygen ions to form a solid metal oxide; preferably, the reaction potential of the metal element with reduced oxygen in the non-lithium metal salt > the reaction potential of lithium metal with reduced oxygen.
4. The production method according to claim 3, wherein the non-lithium metal salt is at least one of a Ce salt, a Ga salt, and a Sm salt; the Ce salt is Ce (ClO)4)3·6H2O、Ce(NO3)3·6H2O、Ce(Ac)3·xH2O、CeBr3、CeCl3And CeI3At least one of; the Ga salt is Ga (ClO)4)3、Ga(NO3)3·xH2O、GaI3、GaBr3And GaCl3At least one of; the Sm salt is selected from Sm (NO)3)3、Sm(Ac)3·xH2O、SmBr3、SmCl3、Sm(CF3O3S)3And SmI2At least one of (a).
5. The method according to claim 1, wherein the solvent of the non-lithium metal salt solution is an organic solvent or water, and the organic solvent is at least one selected from the group consisting of dimethyl sulfoxide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethyl carbonate, propylene carbonate, and ethylene carbonate; the concentration of the non-lithium metal salt in the non-lithium metal salt solution is 0.001-5 mol/L.
6. The method of claim 1, wherein the non-lithium metal salt solution further comprises a metal lithium salt; the lithium metal salt is selected from LiTFSI, LiFSI and LiClO4、LiBF4And LiPF6At least one of; the concentration of the metal lithium salt in the non-lithium metal salt solution is 0.05-3 mol/L.
7. The method according to claim 1, wherein the constant current discharge has a current density of 100 to 1500 mA/g.
8. The method according to any one of claims 1 to 7, wherein the cut-off voltage is 2.5 to 3.5V.
9. A metal oxide catalyst for a lithium oxygen battery prepared according to the preparation method of any one of claims 1 to 8.
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