CN114709428A - Defect tungsten oxide/ruthenium nanoparticle composite catalyst and preparation method and application thereof - Google Patents
Defect tungsten oxide/ruthenium nanoparticle composite catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 230000007547 defect Effects 0.000 title claims abstract description 46
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 45
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 37
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000002950 deficient Effects 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
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- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
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- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 229910019897 RuOx Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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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
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
- H01M4/8828—Coating with slurry or ink
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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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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Abstract
The invention discloses a defective tungsten oxide/ruthenium nanoparticle composite catalyst and a preparation method and application thereof. The catalyst consists of Ru nanoparticles and WOxA nanosheet carrier; the Ru nanoparticles are uniformly dispersed in WOxThe particle size of the nano-sheet carrier is 4-5 nm; said WOxThe nanosheet carrier is W oxide with an oxygen defect structure, and the size of a single nanosheet is 100-400 nm; said WOxThe nanosheet carrier and the Ru nanoparticles are firmly combined through bonding, so that the battery stability is good, and more than 250 circles of stable circulation can be maintained; the catalyst is used for obtaining defects and compounds through a one-step method in a high-temperature reducing atmosphere on the basis of a homogeneous precipitation method. The catalyst has rich oxygen defect structures and active sites, is used as the anode catalyst of the lithium-oxygen battery, and has much higher specific discharge capacity than that of a comparative material Ru/WO3、WOxAnd WO3。
Description
Technical Field
The invention belongs to the technical field of electrocatalysis materials, and particularly relates to a defective tungsten oxide/ruthenium nanoparticle composite catalyst, and a preparation method and application thereof.
Background
Rechargeable lithium-oxygen batteries are considered to be the most potential next-generation energy storage battery system due to their high theoretical specific capacity. The negative electrode of the lithium-oxygen battery is metallic lithium, the positive active material is oxygen in the air, and an organic solvent in which a lithium salt is dissolved is used as an electrolyte. In the lithium-oxygen battery, during the reaction process of discharging and charging, the reduction of oxygen at the positive electrode, the generation and decomposition of lithium peroxide as a discharge product, and the like are involved, and the electrochemical reaction process is extremely complicated. In addition, the reaction of the positive electrode side containing oxygen has slow dynamic characteristics, which may cause the battery to show lower specific discharge capacity, poorer energy efficiency, etc., so that a catalyst with high catalytic activity needs to be used in the positive electrode material to accelerate the battery reaction, thereby improving the specific discharge capacity of the battery, reducing the discharge/charge voltage polarization, improving the long-term cycling stability, etc.
The defect oxide material has a large number of oxygen defect structures, can effectively expose catalytic active sites on the surface of the material, and simultaneously increases the carrier mobility of the material and improves the conductivity due to the characteristic of oxygen defect enrichment, so the defect oxide material is considered as a potential lithium-oxygen battery anode catalyst. Among the reported materials, CoO having an oxygen-deficient structurex、NiCo2O4-xThe catalysts are applied to the anode of the lithium-oxygen battery, however, the specific discharge capacity of the anode materials is reported to be difficult to exceed 5000mAh g-1And the circulation stability is not ideal, and the number of circulation turns is less than 150 turns. In addition, other defect oxides and composite materials thereof reported at present are difficult to realize defect formation and load formation simultaneously by a one-step method. In the conventional defect generation and load step synthesis method, the defect surface formed is easy to damage and lose activity when the defect oxide is further loaded and compositely treated. And the interface between the carrier and the substrate formed by the step-by-step synthesis method is weak, which increases charge transfer at the interfaceThe composite material is not contacted firmly, is easy to fall off and agglomerate, and reduces activity and stability. Therefore, a simple and controllable preparation method is developed, the composite catalyst of the defect oxide and the high-activity carrier can be formed at the same time, and a stable and firm interface is formed, which is important for improving the performance of the lithium-oxygen battery.
The tungsten oxide without defects reported at present has poor conductivity, poor activity when used as a lithium-air battery anode catalyst and difficult discharge specific capacity of 4000mAh g-1And the surface structure is stable and complete in coordination, so that the composite material is not suitable for being compounded with other materials. However, the morphology of the tungsten oxide is easy to control, defect sites are easy to form, high-activity catalyst (such as Pt, Ru and the like) loading can be carried out on the surface of the tungsten oxide while defects are formed, and the catalytic performance of the tungsten oxide is expected to be greatly improved. However, at present, there are few reports of defective tungsten oxides, defective tungsten oxide composites, and their applications. Therefore, the defect type tungsten oxide is firmly combined with the high-activity catalyst through bonding by designing a simple preparation method and synthesizing the tungsten oxide composite material with rich defect sites through a one-step method, and is the research focus and difficulty of the defect type tungsten oxide composite material as the lithium-air battery electrocatalyst.
Disclosure of Invention
The invention aims to overcome the problems and the defects of the prior art and provide a defective tungsten oxide/ruthenium nanoparticle composite catalyst and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the defect tungsten oxide/ruthenium nano-particle composite catalyst is characterized by comprising Ru nano-particles and WOxA nanosheet carrier; the Ru nanoparticles are uniformly dispersed in WOxThe particle size of the nano-sheet carrier is 4-5 nm; said WOxThe nanosheet carrier is W oxide with an oxygen defect structure, and the size of a single nanosheet is 100-400 nm; said WOxThe nanosheet carrier and the Ru nanoparticles are bondedThe bonding is firm, the battery stability is good, and more than 250 circles of stable circulation can be maintained; the catalyst is prepared by combining a homogeneous precipitation method and a high-temperature reduction method, wherein the homogeneous precipitation method comprises the following steps of: (4-6) mixing sodium tungstate dihydrate with hydrochloric acid with the concentration of 36% to obtain a precipitate, and then mixing the precipitate with sodium tungstate dihydrate in the following mass ratio: adding oxalic acid into oxalic acid of 1 (0.8-1.2) mol/mol, and heating to obtain a tungsten oxide precursor; the high-temperature reduction method comprises the following steps of preparing a tungsten oxide precursor material by mass: the defect oxide/ruthenium nanoparticle composite catalyst is obtained by adding ruthenium chloride trihydrate at the concentration of (0.1-0.2) g/g and synthesizing through a high-temperature reduction reaction one-step method.
A preparation method of a defective tungsten oxide/ruthenium nanoparticle composite catalyst comprises the following steps:
(1) preparing a tungsten oxide precursor material:
according to the mass/volume ratio of 1: (4-6) mol/L, dissolving sodium tungstate dihydrate in deionized water, uniformly stirring, and then mixing according to a mass/volume ratio of 1: (0.8-1.2) adding hydrochloric acid with the concentration of 36% into the solution per liter to obtain a bright yellow precipitate; centrifugally cleaning the precipitate with deionized water for multiple times, dissolving the precipitate in deionized water with the same volume again, and uniformly stirring; sodium tungstate dihydrate according to the mass ratio: oxalic acid is 1: (0.8-1.2) adding oxalic acid into the mixture in mol/mol ratio, mixing, heating the mixed solution to 55-65 ℃, and keeping the temperature for 20-30 hours; after the reaction is finished, centrifugally cleaning the product, and drying to obtain a tungsten oxide precursor material;
(2) ru loaded oxygen Defect WOxPreparing a composite catalyst:
according to the mass/volume ratio of 1: (80-120) g/ml, dispersing the tungsten oxide precursor material into deionized water, and uniformly stirring, wherein the mass ratio of the tungsten oxide precursor material is as follows: the ruthenium chloride trihydrate content is 1 (0.1-0.2) g/g, adding the ruthenium chloride trihydrate, and stirring and mixing uniformly; and heating the mixed solution to 38-42 ℃, stirring until drying, and carrying out high-temperature reaction in an argon/hydrogen mixed atmosphere to obtain the target catalyst.
Further, in the step (1), centrifugal cleaning is performed for 3-5 times, the rotating speed is 3000-6000 rpm, and the time is 2-5 minutes.
Further, the drying in the step (1) is oven forced air drying, and the temperature is 40-50 minutes.
Further, the argon/hydrogen mixed atmosphere in the step (2) is Ar: H according to the volume2Is 19: 1.
Further, the temperature of the high-temperature reaction in the step (2) is 450-550 ℃, and the reaction time is 0.8-1.2 h.
An application of a defective tungsten oxide/ruthenium nanoparticle composite catalyst used as a positive electrode catalyst of a lithium-oxygen battery.
An application method of a defective tungsten oxide/ruthenium nanoparticle composite catalyst comprises the steps of mixing the catalyst, conductive carbon black and polytetrafluoroethylene in a ratio of 8:1:1 by mass to prepare slurry, uniformly coating the slurry on a carbon paper current collector to obtain a positive plate, and sequentially stacking, assembling, tabletting and packaging a positive shell, the positive plate, a diaphragm (absorbing electrolyte), a lithium negative electrode, a gasket, an elastic sheet and a negative shell to obtain a lithium-oxygen battery.
Compared with the prior art, the invention has the following advantages and beneficial effects:
through a large number of explorations and experiments, the defects and the compounding are realized through a one-step method in a high-temperature reducing atmosphere, and the obtained Ru-loaded WOxThe composite catalyst has rich oxygen defect structures and active sites, the rich oxygen defect structures in the carrier improve the carrier mobility and the electron conduction capability on one hand, and the defect sites play a role in anchoring the growth of nano particles on the other hand; simultaneous vector WOxThe catalyst is bonded with the loaded Ru nanoparticles through bonding, has a certain coupling effect, adjusts electron transfer at an interface and an electronic structure on the surfaces of the Ru nanoparticles, optimizes the adsorption capacity of the catalyst on intermediate products, and improves the performance of the battery. The defect tungsten oxide/ruthenium nano-particle composite catalyst has rich active sites and a stable load structure as an electrocatalyst, and the specific discharge capacity of a lithium-oxygen battery taking the defect tungsten oxide/ruthenium nano-particle composite catalyst as a positive electrode reaches 6325mAh g-1Higher than the reference material WO3(3668mAh g-1)、WOx(4510mAh g-1) And Ru/WO3(4919mAh g-1). Shows the lowest voltage difference (1.06V,1000mA g) under different current densities-1) The method is superior to other comparative samples, the battery can keep stable circulation for more than 250 circles, and the synthesis method provided by the invention is simple and controllable and shows wide application prospects.
Drawings
FIG. 1 shows WO of comparative example 2xAnd Ru/WO in example 1xX-ray diffraction (XRD) pattern of the composite catalyst.
FIG. 2 is (a) WO of comparative example 2xAnd (b) Ru/WO in example 1xScanning Electron Microscope (SEM) images of the composite catalyst.
FIG. 3 shows Ru/WO in comparative example 13And Ru/WO in example 1xX-ray photoelectron spectroscopy (XPS) plot of the composite catalyst: (a) w4 f high-resolution spectrum, (b) O1s high-resolution spectrum, and (c) Ru 3p high-resolution spectrum.
FIG. 4 shows Ru/WO in comparative example 13WO in comparative example 2xWO in comparative example 33And Ru/WO in example 1xLithium-oxygen battery performance diagram of the composite catalyst: (a) discharge and charge performance, (b) rate capability, and (c) cycle stability.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the defect tungsten oxide/ruthenium nano-particle composite catalyst is characterized by comprising Ru nano-particles and WOxA nanosheet carrier; the Ru nanoparticles are uniformly dispersed in WOxThe particle size of the nano-sheet carrier is 4-5 nm; said WOxThe nanosheet carrier is W oxide with an oxygen defect structure, and the size of each nanosheet is 100-400 nm; said WOxThe nanosheet carrier and the Ru nanoparticles are firmly combined through bonding, so that the battery stability is good, and more than 250 circles of stable circulation can be kept; the catalyst is prepared by combining a homogeneous precipitation method and a high-temperature reduction method, wherein the homogeneous precipitation method comprises the following steps of (1): (4-6) mixing sodium tungstate dihydrate with hydrochloric acid with the concentration of 36% to obtain a precipitate, and then mixing the precipitate with sodium tungstate dihydrate in the following mass ratio: adding oxalic acid into oxalic acid of 1 (0.8-1.2) mol/mol, and heating to obtain a tungsten oxide precursor; the high-temperature reduction method comprises the following steps of preparing a tungsten oxide precursor material by mass: the defect oxide/ruthenium nanoparticle composite catalyst is obtained by adding ruthenium chloride trihydrate at the concentration of (0.1-0.2) g/g and synthesizing through a high-temperature reduction reaction one-step method.
A preparation method of a defective oxide/ruthenium nanoparticle composite catalyst comprises the following specific steps:
(1) preparing a tungsten oxide precursor material:
3.298g of sodium tungstate dihydrate (Na) were weighed out2WO4·2H2O) was dissolved in 50ml of deionized water, and after stirring uniformly, 10ml of hydrochloric acid (concentration: 36%) to yield a bright yellow precipitate. After the precipitate was washed three times by centrifugation, it was redispersed in 50ml of deionized water and stirred uniformly. 0.9g of oxalic acid is weighed and added into the mixed solution, and the mixed solution is heated to 60 ℃ and kept warm for 24 hours. And after the reaction is finished, centrifugally cleaning the product, and drying to obtain the tungsten oxide precursor material.
(2) Ru loaded oxygen Defect WOxPreparing a composite catalyst:
weighing 0.2g of the tungsten oxide precursor obtained in the step (1), dispersing into 20ml of deionized water, and uniformly stirring. 0.03g of ruthenium chloride trihydrate (RuCl) was added3·3H2O), stirring and dissolving uniformly. Heating the mixed solution to 40 ℃, stirring and drying, and finally reacting the collected product at a high temperature of 500 ℃ for 1h in an argon/hydrogen mixed atmosphere to finally obtain a target catalyst marked as Ru/WOx。
A defect tungsten oxide/ruthenium nanoparticle composite catalyst is used as a positive electrode catalyst of a lithium-oxygen battery.
An application method of a defective tungsten oxide/ruthenium nanoparticle composite catalyst comprises the steps of mixing the catalyst, conductive carbon black and polytetrafluoroethylene in a ratio of 8:1:1 by mass to prepare slurry, uniformly coating the slurry on a carbon paper current collector to obtain a positive plate, and sequentially stacking, assembling, tabletting and packaging a positive shell, the positive plate, a diaphragm (absorbing electrolyte), a lithium negative electrode, a gasket, an elastic sheet and a negative shell to obtain a lithium-oxygen battery.
Example 2:
a preparation method of a defective oxide/ruthenium nanoparticle composite catalyst comprises the following specific steps:
the difference from example 1 is that in step (1), 3.298g of sodium tungstate dihydrate (Na) was weighed2WO4·2H2O) was dissolved in 50ml of deionized water, and after stirring uniformly, hydrochloric acid (concentration: 36%) was changed to 8ml, resulting in a bright yellow precipitate. The finally obtained sample is marked as Ru/WOx-2。
Example 3:
a preparation method of a defective oxide/ruthenium nanoparticle composite catalyst comprises the following specific steps:
the difference from example 1 is that in step (1), 3.298g of sodium tungstate dihydrate (Na) was weighed2WO4·2H2O) was dissolved in 50ml of deionized water, and after stirring uniformly, hydrochloric acid (concentration: 36%) was changed to 12ml, resulting in a bright yellow precipitate. The finally obtained sample is marked as Ru/WOx-3。
Example 4:
a preparation method of a defective oxide/ruthenium nanoparticle composite catalyst comprises the following specific steps:
the difference from the example 1 is that in the step (1), the mass of oxalic acid is changed to 0.72g and added into the mixed solution, and the mixed solution is heated to 60 ℃ and kept warm for 24 h. The finally obtained sample is marked as Ru/WOx-4。
Example 5:
a preparation method of a defective oxide/ruthenium nanoparticle composite catalyst comprises the following specific steps:
the difference from the example 1 is that in the step (1), 1.08g of oxalic acid is weighed and added into the mixed solution, and the mixed solution is heated to 60 ℃ and kept warm for 24 hours. The finally obtained sample is marked as Ru/WOx-5。
Example 6:
a preparation method of a defective oxide/ruthenium nanoparticle composite catalyst comprises the following specific steps:
the difference from example 1 is that in step (2), ruthenium chloride trihydrate (RuCl) is added3·3H2The mass of O) was changed to 0.02g, and the solution was stirred to dissolve uniformly. The finally obtained sample is marked as Ru/WOx-6。
Example 7:
a preparation method of a defective oxide/ruthenium nanoparticle composite catalyst comprises the following specific steps:
the difference from example 1 is that in step (2), ruthenium chloride trihydrate (RuCl) is added3·3H2O) was changed to 0.04g, and was dissolved by stirring uniformly. The finally obtained sample is marked as Ru/WOx-7。
Example 8:
a preparation method of a defective oxide/ruthenium nanoparticle composite catalyst comprises the following specific steps:
the difference from the embodiment 1 is that in the step (2), the mixed solution is heated to 40 ℃, stirred and dried, and finally the collected product is changed into 450 ℃ at high temperature in the argon/hydrogen mixed atmosphere for reaction for 1h to finally obtain the target catalyst marked as Ru/WOx-450。
Example 9:
a preparation method of a defective oxide/ruthenium nanoparticle composite catalyst comprises the following specific steps:
the difference from the embodiment 1 is that in the step (2), the mixed solution is heated to 40 ℃, stirred and dried, and finally the collected product is changed into 550 ℃ at high temperature in the argon/hydrogen mixed atmosphere for reaction for 1h to finally obtain the target catalyst marked as Ru/WOx-550。
Comparative example 1:
Ru/WO3the preparation method of the catalyst comprises the following specific steps:
the difference from the embodiment 1 is that in the step (2), the mixed solution is heated to 40 ℃, stirred and dried, and finally the collected product is changed into a product which reacts for 1h at a high temperature of 500 ℃ under the inert atmosphere of argon, and finally the target catalyst which is marked as Ru/WO is obtained3。
Comparative example 2:
WOxthe preparation method of the catalyst comprises the following specific steps:
the difference from example 1 is that in step (2), ruthenium chloride trihydrate (RuCl)3·3H2O), weighing 0.2g of tungsten oxide precursor obtained in the step (1), directly reacting for 1h at high temperature of 500 ℃ in argon/hydrogen mixed atmosphere to finally obtain the target catalyst, and marking as WOx。
Comparative example 3:
WO3the preparation method of the catalyst comprises the following specific steps:
the difference from example 1 is that in step (2), ruthenium chloride trihydrate (RuCl) is not added first3·3H2O), weighing 0.2g of tungsten oxide precursor obtained in the step (1), and directly reacting at the high temperature of 500 ℃ for 1h in the inert atmosphere of argon to finally obtain the target catalyst, which is marked as WO3。
Performance analysis based on drawings of embodiments
FIG. 1 shows Ru/WO in example 1xComposite catalyst and comparative example WOxX-ray diffraction (XRD) pattern of (a). As can be seen from the figure, the defective oxide WOxAnd Ru/WOxAll materials exhibit the standard W20O58Crystal structure (PDF #05-0386), which indicates that W oxide having oxygen defect structure was successfully prepared. Meanwhile, the composite material does not show an obvious diffraction peak of Ru, which shows that the Ru nanoparticles on the load have smaller size and low diffraction peak intensity.
FIG. 2 shows Ru/WO in example 1xComposite catalyst and comparative example WOxScanning Electron Microscope (SEM)Figure (a). The SEM image clearly shows the micro-morphology of the catalyst, and the defect oxide WO can be seen from the imagexThe support (fig. 2a) has a nano-platelet morphology, with the size of the individual nanosheets being approximately around 200 nm. After loading the Ru nanoparticles (fig. 2b), the catalyst still maintained the nanosheet morphology.
FIG. 3 shows Ru/WO in example 1xComposite catalyst and comparative example Ru/WO3X-ray photoelectron spectroscopy (XPS) chart of (a). As can be seen from the W4 f diagram (FIG. 3a), the valence of the W element in the defect oxide can be divided into W6+And W5+This demonstrates the abundance of oxygen defect structures in the material. It can also be found from the O1s diagram (FIG. 3b) that Ru/WOxThe proportion of defective oxygen in the catalyst is greater than that in the oxygen saturated oxide, indicating that the material is rich in oxygen defects. The valence state and electronic structure of Ru nanoparticles loaded on the surface of the catalyst are shown in FIG. 3c, and the Ru 3p XPS peak is fitted to Ru0And Ru4+Wherein the presence of the high valence Ru is due to surface oxidation of the Ru nanoparticles to form RuOxAnd (5) structure. Meanwhile, Ru/WOxFitting peak position of Ru in catalyst and Ru/WO3The middle corresponding peak position has the movement in the low binding energy direction of 0.5eV, and the Ru nano particles loaded on the surface have certain interaction with the carrier, so that the surface electronic structure of the catalyst is adjusted, the adsorption state of an intermediate product is improved, and the catalytic activity is increased.
FIG. 4 shows Ru/WO in example 1xComposite catalyst and comparative example Ru/WO3、WOx、WO3Performance plots of lithium-oxygen cells. FIG. 4a shows the discharge and charge curves of a lithium-oxygen battery with a positive electrode made of a catalyst, as shown in Ru/WOxThe specific discharge capacity of the lithium-oxygen battery taking the catalyst as the anode reaches 6325mAh g-1The material is higher than other comparative samples, and the charging specific capacity and the discharging specific capacity are consistent, so that the material is proved to have excellent electrocatalytic activity and reversibility. FIG. 4b shows the rate capability of the cell, and it can be seen that Ru/WOxThe catalyst showed the lowest voltage difference at all current densities, indicating a higher energy efficiency of the cell. At 500mA g-1Electricity (D) fromFlow density, 1000mAh g-1The battery cycling performance was tested at the cut-off capacity (fig. 4c), and it can be seen that the battery was able to maintain stable cycling for more than 250 cycles.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the foregoing description is only illustrative of the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is intended to be covered by the claims. The scope of the invention is defined by the appended claims.
Claims (8)
1. The defect tungsten oxide/ruthenium nano-particle composite catalyst is characterized by comprising Ru nano-particles and WOxA nanosheet carrier; the Ru nanoparticles are uniformly dispersed in WOxThe particle size of the nano-sheet carrier is 4-5 nm; said WOxThe nanosheet carrier is W oxide with an oxygen defect structure, and the size of a single nanosheet is 100-400 nm; said WOxThe nanosheet carrier and the Ru nanoparticles are firmly combined through bonding, so that the battery stability is good, and more than 250 circles of stable circulation can be maintained; the catalyst is prepared by combining a homogeneous precipitation method and a high-temperature reduction method, wherein the homogeneous precipitation method comprises the following steps of: (4-6) mixing sodium tungstate dihydrate with hydrochloric acid with the concentration of 36% to obtain a precipitate, and then mixing the precipitate with sodium tungstate dihydrate in the following mass ratio: adding oxalic acid into oxalic acid of 1 (0.8-1.2) mol/mol, and heating to obtain a tungsten oxide precursor; the high-temperature reduction method comprises the following steps of preparing a tungsten oxide precursor material by mass: the defect oxide/ruthenium nanoparticle composite catalyst is obtained by adding ruthenium chloride trihydrate at the concentration of (0.1-0.2) g/g and synthesizing through a high-temperature reduction reaction one-step method.
2. A preparation method of a defective tungsten oxide/ruthenium nanoparticle composite catalyst is characterized by comprising the following steps:
(1) preparing a tungsten oxide precursor material:
according to the mass/volume ratio of 1: (4-6) mol/L, dissolving sodium tungstate dihydrate in deionized water, uniformly stirring, and then mixing according to the mass/volume ratio of 1: (0.8-1.2) adding hydrochloric acid with the concentration of 36% into the solution per liter to obtain a bright yellow precipitate; centrifugally cleaning the precipitate with deionized water for multiple times, dissolving the precipitate in deionized water with the same volume again, and uniformly stirring; sodium tungstate dihydrate according to the mass ratio: oxalic acid is 1: (0.8-1.2) adding oxalic acid into mol/mol, mixing, heating the mixed solution to 55-65 ℃, and keeping the temperature for 20-30 hours; after the reaction is finished, centrifugally cleaning the product, and drying to obtain a tungsten oxide precursor material;
(2) ru loaded oxygen Defect WOxPreparing a composite catalyst:
according to the mass/volume ratio of 1: (80-120) g/ml, dispersing the tungsten oxide precursor material into deionized water, and uniformly stirring, wherein the mass ratio of the tungsten oxide precursor material is as follows: the ruthenium chloride trihydrate content is 1 (0.1-0.2) g/g, adding the ruthenium chloride trihydrate, and stirring and mixing uniformly; and heating the mixed solution to 38-42 ℃, stirring until drying, and reacting at a high temperature in an argon/hydrogen mixed atmosphere to obtain the target catalyst.
3. The preparation method of the defective oxide/ruthenium nanoparticle composite catalyst according to claim 2, wherein the centrifugal cleaning in step (1) is performed 3 to 5 times at a rotation speed of 3000 to 6000 rpm for 2 to 5 minutes.
4. The preparation method of the defective oxide/ruthenium nanoparticle composite catalyst according to claim 2, wherein the drying in step (1) is oven forced air drying at a temperature of 40-50 minutes.
5. The method for preparing a defective oxide/ruthenium nanoparticle composite catalyst according to claim 2, wherein the argon/hydrogen mixed atmosphere in the step (2) is Ar: H by volume2Is 19: 1.
6. The preparation method of the defective tungsten oxide/ruthenium nanoparticle composite catalyst according to claim 2, wherein the high-temperature reaction in the step (2) is carried out at 450-550 ℃ for 0.8-1.2 h.
7. Use of the defective tungsten oxide/ruthenium nanoparticle composite catalyst according to claim 1 as a positive electrode catalyst for a lithium-oxygen battery.
8. The application method of the lithium-oxygen battery is characterized in that the lithium-oxygen battery is prepared by mixing the catalyst, the conductive carbon black and the polytetrafluoroethylene according to the mass ratio of 8:1:1 to prepare slurry, then uniformly coating the slurry on a carbon paper current collector to obtain a positive plate, and then sequentially stacking and assembling the positive plate, a diaphragm (absorbing electrolyte), the lithium negative electrode, a gasket, an elastic sheet and a negative plate, tabletting and packaging.
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