CN111477880B - CeOx/RuO2(iii) MC and CeOx/RuO2Preparation and application of composite nanosheet material - Google Patents
CeOx/RuO2(iii) MC and CeOx/RuO2Preparation and application of composite nanosheet material Download PDFInfo
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002135 nanosheet Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 60
- 229910003320 CeOx Inorganic materials 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 23
- 239000002028 Biomass Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 150000000703 Cerium Chemical class 0.000 claims abstract description 21
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 21
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 21
- 235000005822 corn Nutrition 0.000 claims abstract description 21
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 21
- 239000010902 straw Substances 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000009489 vacuum treatment Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 241000209149 Zea Species 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical group [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 claims description 4
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 238000010306 acid treatment Methods 0.000 abstract 1
- 240000008042 Zea mays Species 0.000 description 17
- 238000010586 diagram Methods 0.000 description 13
- 238000003917 TEM image Methods 0.000 description 12
- 239000002055 nanoplate Substances 0.000 description 11
- -1 cerium ions Chemical class 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
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- 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
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- 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
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- 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
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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- H01M4/00—Electrodes
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- 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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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Abstract
The invention discloses CeOx/RuO2Composite nano-sheet of/MC and CeOx/RuO2Preparation and application of composite nanosheet material. The preparation method comprises the following steps: (1) removing hard shells of waste corn straws, crushing the waste corn straws into small particles, performing acid treatment, washing the small particles to be neutral by deionized water, filtering and drying to obtain a biomass carbon raw material; (2) preparing a mixed solution of cerium salt and ruthenium salt; (3) soaking the biomass carbon raw material in the mixed solution, sequentially carrying out ultrasonic treatment, vacuum treatment and ultrasonic treatment again in the soaking process, and then filtering and fully drying; (4) roasting the dried product in argon to obtain CeOxa/Ru/MC composite nanosheet; (5) adding CeOxRoasting the/Ru/MC composite nanosheet in the air to obtain CeOx/RuO2Composite nano-sheet of/MC or CeOx/RuO2And (3) compounding the nanosheet material. The present invention provides the CeOx/RuO2Composite nano sheet material of/MC or CeOx/RuO2The composite nanosheet material is applied as a lithium-oxygen battery anode catalyst material, has high catalytic activity, and can greatly reduce the overpotential of the OER reaction.
Description
Technical Field
The invention relates to CeOx/RuO2Composite nano-sheet of/MC and CeOx/RuO2A preparation method of the composite nanosheet material and application of the nanosheet material as a lithium-oxygen battery anode catalyst material.
Background
Lithium ion batteries, as the main energy storage devices of today, have become increasingly difficult to meet people's living and production needs. The search for the next generation of energy storage system with higher energy density is becoming more and more gradual, and the theoretical energy density of the rechargeable lithium-oxygen battery is the highest of the currently known battery systems, which is more than ten times higher than that of any currently used lithium ion battery, so the rechargeable lithium-oxygen battery is researched and paid attention to by broad scholars and enterprises. The major problems that currently impede the development of li-o batteries are their excessive overpotential, low cycle life, low round-trip efficiency, and poor rate capability. The fundamental solution to these problems is to develop a positive electrode catalyst material having excellent performance. The discharge process occurs primarily through the Oxygen Reduction Reaction (ORR), where the primary reason for limiting cell performance is the low concentration of oxygen in the cell system and slow transport. CeO (CeO)2Because lattice oxygen has high activity and fluidity, oxygen vacancies are easily caused. Thus, in most cases, CeO2In fact as CeOxIn the form of (1.5)<x<2) Which has a higher oxygen transfer capacity and more importantly, oxygen vacancies can provide additional catalytically active sites. So CeOxIs an ideal ORR catalyst in a lithium-oxygen battery. However, in addition to the limitation of the slow ORR process on lithium oxygen batteries, the excessive overpotential of the OER process is more challenging for the stable cycling of the battery. Too high an OER overpotential can lead to many side reactions, such as decomposition of the electrolyte, carbon-mediated side reactions in some materials, and the like. The existence of these side reactions is the main cause of short cycle life and poor reciprocating efficiency of the lithium-oxygen battery. A large number of studies have shown that the noble metal Ru, in particular its oxide RuO2The catalyst has excellent capability of reducing the reaction overpotential of the lithium-oxygen battery OER and has been actively explored to be applied as a catalyst material. It is not difficult to imagine that CeOxAnd RuO2The combination of the catalyst and the catalyst for the lithium-oxygen battery has great advantages. In addition to these metals or metal oxides, carbon materials are also frequently used for research on lithium-oxygen battery positive electrode catalysts because of their excellent electrical conductivity, and are mainly used as support carriers to reach dispersion levelsThe surface nano-particles and the function of enhancing the conductivity of the material. However, some research results show that carbon materials are an important part of the occurrence of side reactions in lithium-oxygen batteries, and thus the rationality of the presence of carbon remains to be considered. The invention provides a novel preparation method, which can be used for preparing CeOxAnd RuO2And the carbon material, and whether the carbon substrate is reserved or partially reserved can be selected according to the situation. The method is environment-friendly and pollution-free, adopts biomass as a raw material, has a simple process, and is very suitable for large-scale production. The invention also provides the application of the catalyst material in a lithium-oxygen battery.
Disclosure of Invention
The invention provides CeO which has simple process flow, wide raw material source and low cost and is very suitable for large-scale productionx/RuO2Composite nano sheet material of/MC and CeO with extremely low MC contentx/RuO2Preparation method of composite nanosheet material and prepared CeOx/RuO2Composite nano-sheet of/MC and CeOx/RuO2The composite nano sheet material has higher catalytic activity and can greatly reduce the overpotential of OER reaction.
It is a second object of the present invention to provide the CeOx/RuO2Composite nano-sheet material of/MC and CeOx/RuO2The composite nanosheet material is applied as a lithium-oxygen battery anode catalyst material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a CeOx/RuO2Composite nano-sheet material of/MC and CeOx/RuO2The preparation method of the composite nanosheet material comprises the following steps:
(1) removing hard shells of waste corn straws, crushing the waste corn straws into small particles, placing the small particles in an acid solution, fully stirring, washing the small particles to be neutral by using deionized water, filtering and drying to obtain a biomass carbon raw material;
(2) weighing a proper amount of cerium salt and ruthenium salt, dissolving the cerium salt and the ruthenium salt in deionized water, and fully stirring the cerium salt and the ruthenium salt to completely dissolve the cerium salt and the ruthenium salt to obtain a mixed solution with the total concentration of 5-50mM, wherein the molar ratio of the cerium salt to the ruthenium salt is 1: 0.02-1;
(3) dipping the biomass carbon raw material in the step (1) in the mixed solution prepared in the step (2), sequentially performing ultrasonic treatment, vacuum treatment and ultrasonic treatment again in the dipping process, then filtering, and fully drying the filtered product;
(4) roasting the product dried in the step (3) at the temperature of 600-900 ℃ in an argon atmosphere to obtain CeOxa/Ru/MC composite nanosheet material;
(5) the CeO obtained in the step (4) is addedxRoasting the/Ru/MC composite nano-sheet for 1-3 hours at the temperature of 200-450 ℃ in air atmosphere to obtain CeOx/RuO2Composite nano sheet material of/MC or CeOx/RuO2And (3) compounding the nanosheet material.
According to the preparation method, the adsorption of the functional groups on the surfaces of the corn straws on the cerium ions and the ruthenium ions is utilized to realize the thin-layer adhesion of the cerium ions and the ruthenium ions on the surfaces of the functional groups, so that the serious agglomeration of excessive cerium ions and ruthenium ions in the roasting process is avoided, and the ultra-small particle size and the high loading capacity are realized. The concentration of cerium ions and ruthenium ions in the impregnation liquid is crucial: excessive concentration of Ru and CeOxExcessive generation and serious agglomeration; too low concentration of Ru and CeOxToo small an amount, the catalytic action is greatly impaired. The second core of the invention is the roasting temperature in the step (4): the particles are easy to agglomerate due to the overhigh temperature; too low a temperature tends to result in incomplete carbonization of the biomass. The third core of the invention is the baking temperature and the baking time of the last step, and the combination of the two can adjust the oxidation degree of Ru and the removal degree of the carbon substrate.
Preferably, the acid solution in step (1) is sulfuric acid, hydrochloric acid or nitric acid with a concentration of 0.5 to 5 wt%; stirring at 70-100 deg.C for 1-3 hr; the drying temperature after filtration is 35-60 ℃.
Preferably, in the step (2), the cerium salt is cerium acetate, and the ruthenium salt is ruthenium trichloride, ruthenium acetate or ruthenium sulfate.
Preferably, in the step (2), the total concentration of the mixed solution is 20mM, and the molar ratio of the cerium salt to the ruthenium salt is 1: 0.2.
Preferably, the first ultrasonic treatment time in the step (3) is 20-60 minutes of ultrasonic treatment, the vacuum treatment time is 20-60 minutes, the second ultrasonic treatment time is 20-60 minutes, and the drying temperature is 35-80 ℃.
Preferably, the calcination temperature in step (4) is 600-900 deg.C (more preferably 600 deg.C), the time is 3-6 hours (more preferably 4 hours), and the temperature rise rate is 2-20 deg.C/min (more preferably 5 deg.C/min).
Preferably, the roasting temperature in the step (5) is 250-350 ℃, and the time is 2-2.5 hours; more preferably, the calcination temperature is 250 ℃ and the calcination time is 2 hours.
CeO prepared by the method of the inventionx/RuO2Composite nano-sheet material of/MC and CeOx/RuO2The composite nanosheet material has high catalytic activity, and the invention provides application of the composite nanosheet material as a lithium-oxygen battery anode catalyst material.
Compared with the prior art, the invention has the following advantages:
(1) realization of small-size RuO by adopting corn straws for the first time2And CeOxIn situ growth on mesoporous carbon.
(2) In the known CeOx/RuO2RuO of the invention in/MC Material2And CeOxThe particle size is smaller and the distribution is more uniform.
(3) Realize RuO2And CeOxThe loading capacity of the nano-crystal on the mesoporous carbon and the controllable adjustment of the grain diameter of the crystal.
(4) Firstly adopts a sacrificial biomass template method to prepare CeOx/RuO2The composite nano sheet can keep the sheet structure from collapsing after the carbon substrate is removed.
(5) The raw materials are rich and renewable, the process is simple, green and pollution-free, and the large-scale production is easy.
(6)CeOx/RuO2(MC) nanosheet and CeOx/RuO2The composite nanosheets all show good catalytic performance of the lithium-oxygen battery, and particularly the reaction overpotential in the OER process is greatly reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention.
FIG. 1 is a CeO prepared in example 1x/RuO2TG pattern of/MC nanoplates.
FIG. 2 is CeO prepared in example 1x/RuO2TEM and SEM images of/MC nanosheets.
FIG. 3 is CeO prepared in example 1x/RuO2A lithium-oxygen battery limit charge-discharge curve graph and a limited capacity charge-discharge curve graph with/MC nanosheets as the positive electrode.
FIG. 4 is CeO prepared in example 2x/RuO2TG profile of nanoplates.
FIG. 5 is CeO prepared in example 2x/RuO2TEM images of the nanoplates.
FIG. 6 is CeO prepared in example 2x/RuO2The lithium-oxygen battery with the nanosheet as the positive electrode has a limit charge-discharge curve diagram and a limited capacity charge-discharge curve diagram.
FIG. 7 is CeO prepared in example 3x/RuO2TG profile of nanoplates.
FIG. 8 is CeO prepared in example 3x/RuO2TEM images of the nanoplates.
FIG. 9 is CeO prepared in example 3x/RuO2The lithium-oxygen battery with the nanosheet as the positive electrode has a limit charge-discharge curve diagram and a limited capacity charge-discharge curve diagram.
FIG. 10 is CeO prepared in example 4x/RuO2TEM images of the nanoplates.
FIG. 11 is CeO prepared in example 4x/RuO2The lithium-oxygen battery with the nanosheet as the positive electrode has a limit charge-discharge curve diagram and a limited capacity charge-discharge curve diagram.
FIG. 12 is CeO prepared in example 5x/RuO2TEM images of the nanoplates.
FIG. 13 is CeO prepared in example 5x/RuO2Lithium-oxygen battery limit charge and discharge with nanosheet as positive electrodeGraph and defined capacity charge and discharge graph.
FIG. 14 is CeO prepared in example 6x/RuO2TEM images of the nanoplates.
FIG. 15 is CeO prepared in example 6x/RuO2The lithium-oxygen battery with the nanosheet as the positive electrode has a limit charge-discharge curve diagram and a limited capacity charge-discharge curve diagram.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but is not limited thereto:
the preparation method of the nano sheet comprises the following steps: the adsorption of the functional groups on the surface of the corn straws on cerium ions and ruthenium ions is utilized to realize the attachment of the two ions on a thin layer on the surface of the corn straws, and the thin layer of the ions is decomposed into small-size Ru and small-size CeO in the roasting processxThe nanometer crystal is loaded on the surface of the mesoporous carbon evenly to avoid serious agglomeration, and finally the nanometer crystal is roasted in the air to achieve the purposes of oxidizing Ru and removing the carbon substrate, so that CeO can be obtainedx/RuO2/MC nanosheet or CeOx/RuO2Nanosheets.
The assembly and test method of the battery in the embodiment of the invention is as follows: adding CeOx/RuO2/MC or CeOx/RuO2Mixing PVDF according to a mass ratio of 9:1, adding NMP as a solvent, stirring into a slurry, coating the slurry on carbon paper, and drying the carbon paper for 12 hours in vacuum at 120 ℃ to obtain a positive electrode material; the method comprises the steps of taking metal lithium as a negative electrode, taking glass fiber filter paper as a diaphragm, taking dimethyl sulfoxide (DMSO) solution of 1M lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) as electrolyte, assembling the battery in a glove box under the protection of argon, and testing the performance of the battery in pure oxygen atmosphere.
Example 1:
(1) removing hard shells from corn straws recovered from farms, crushing into small particles, placing the small particles in a 0.5 wt.% sulfuric acid solution, stirring at 70 ℃ for 1 hour, washing with deionized water to neutrality, and drying the filtered product at 35 ℃ to obtain a biomass carbon raw material.
(2) Weighing cerium acetate and ruthenium trichloride, dissolving in deionized water, stirring to completely dissolve the cerium acetate and ruthenium trichloride to obtain a 5mM solution, wherein the molar ratio of cerium salt to ruthenium salt is 1: 0.02.
(3) and (2) soaking the biomass carbon raw material in the step (1) in the solution prepared in the step (2), performing ultrasonic treatment for 20 minutes, performing vacuum treatment for 20 minutes, performing ultrasonic treatment for 20 minutes again, filtering, and fully drying the filtered product at the drying temperature of 35 ℃.
(4) Roasting the product dried in the step (3) for 6 hours at 600 ℃ in an argon atmosphere at the heating rate of 2 ℃/min to obtain CeOxthe/Ru/MC nanosheet material.
(5) The CeO obtained in the step (4) is addedxRoasting the/Ru/MC nanosheet in air atmosphere at the roasting temperature of 200 ℃ for 1 hour to obtain CeOx/RuO2an/MC nano-sheet.
FIG. 1 shows CeO prepared in example 1x/RuO2TG diagram of/MC nano-sheet, it can be seen that the carbon content of the nano-sheet is only about 25%, and the rest is CeOxAnd RuO2And (4) forming. FIG. 2 shows CeO prepared in example 1x/RuO2TEM image and SEM image of/MC nano sheet, and the material can be observed to be in a sheet structure in the whole, CeOxAnd RuO2The nano-crystals are uniformly distributed, and the particle size is fine and uniform and is about 3-4 nm. FIG. 3 is CeO prepared in example 1x/RuO2The limit charge-discharge curve diagram and the constant-capacity charge-discharge curve diagram of the lithium-oxygen battery assembled by taking the/MC nanosheet as the positive electrode (the capacity is limited to 500mAh/g, the current density is 200mA/g, and the voltage range is 2.25-4.5V). It can be seen that the material can contribute a specific discharge capacity in excess of 5500mAh/g with a higher coulombic efficiency. The lithium-oxygen battery assembled by the cathode material can stably cycle for more than 27 weeks, and has better cycle performance.
Example 2:
(1) removing hard shells from corn straws recovered from farms, crushing the corn straws into small particles, placing the corn straws in a 1.5 wt.% nitric acid solution, stirring the corn straws for 1 hour at 70 ℃, washing the corn straws to be neutral by deionized water, and drying the filtered corn straws at 45 ℃ to obtain a biomass carbon raw material.
(2) Weighing cerium acetate and ruthenium sulfate, dissolving in deionized water, stirring to completely dissolve the cerium acetate and ruthenium sulfate to obtain a 20mM solution, wherein the molar ratio of cerium salt to ruthenium salt is 1: 0.2.
(3) and (2) soaking the biomass carbon raw material in the step (1) in the solution prepared in the step (2), performing ultrasonic treatment for 30 minutes, performing vacuum treatment for 30 minutes, performing ultrasonic treatment for 30 minutes again, filtering, and fully drying the filtered product at the drying temperature of 60 ℃.
(4) Roasting the product dried in the step (3) for 4 hours at the temperature of 600 ℃ in the argon atmosphere, and obtaining CeO at the heating rate of 5 ℃/minxthe/Ru/MC nanosheet material.
(5) The CeO obtained in the step (4) is addedxRoasting the/Ru/MC nanosheets in air atmosphere at the roasting temperature of 250 ℃ for 2 hours to obtain CeOx/RuO2Nanosheets.
FIG. 4 shows CeO prepared in example 2x/RuO2TG pattern of nanosheets, from which it is apparent that the material consists essentially of CeOxAnd RuO2Composition, carbon is only about 5.5%. FIG. 5 shows CeO prepared in example 2x/RuO2TEM images of the nanoplates show a morphology similar to that of the material in example 1, but with a marked increase in particle size due to crystal growth caused by firing in air. FIG. 6 is CeO prepared in example 2x/RuO2The limit charge-discharge curve and the constant-capacity charge-discharge curve chart (the capacity is limited to 500mAh/g, the current density is 200mA/g, and the voltage range is 2.25-4.5V) of the lithium-oxygen battery assembled by the nanosheet as the positive electrode. It can be seen that the material can contribute a specific discharge capacity in excess of 6000mAh/g with a higher coulombic efficiency. The lithium-oxygen battery assembled by the cathode material can stably cycle for more than 50 weeks, and has good cycle performance.
Example 3:
(1) removing hard shells from corn straws recovered from farms, crushing into small particles, placing the small particles in a 2 wt.% sulfuric acid solution, stirring for 1 hour at 90 ℃, washing with deionized water to be neutral, and drying a product obtained by filtering at 50 ℃ to obtain a biomass carbon raw material.
(2) Weighing cerium acetate and ruthenium trichloride, dissolving in deionized water, stirring to completely dissolve the cerium acetate and ruthenium trichloride to obtain a 10mM solution, wherein the molar ratio of cerium salt to ruthenium salt is 1: 0.1.
(3) and (2) soaking the biomass carbon raw material in the step (1) in the solution prepared in the step (2), performing ultrasonic treatment for 30 minutes, performing vacuum treatment for 30 minutes, performing ultrasonic treatment for 30 minutes again, filtering, and fully drying the filtered product at the drying temperature of 60 ℃.
(4) Roasting the product dried in the step (3) for 4 hours at the temperature of 600 ℃ in the argon atmosphere, and obtaining CeO at the heating rate of 5 ℃/minxthe/Ru/MC nanosheet material.
(5) The CeO obtained in the step (4) is addedxRoasting the/Ru/MC nanosheets in air atmosphere at the roasting temperature of 300 ℃ for 2 hours to obtain CeOx/RuO2Nanosheets.
FIG. 7 shows CeO prepared in example 3x/RuO2TG pattern of nanosheets, from which it is apparent that the material consists essentially of CeOxAnd RuO2Composition, carbon is only about 4.5%. FIG. 8 is a CeO prepared in example 3x/RuO2TEM image of the nanoplatelets, it can be seen that the morphology is similar to the material in example 2, but the particle size is slightly increased due to crystal growth caused by firing in air, and the contrast between the particles and the background is increased in this image because the amount of carbon is small, so the background color appears weaker in TEM. FIG. 9 is CeO prepared in example 3x/RuO2The lithium-oxygen battery assembled by the nanosheet as the positive electrode has a limit charge-discharge curve and a cycling stability curve (constant-capacity charge-discharge test is adopted, the capacity is limited to 500mAh/g, the current density is 200mA/g, and the voltage range is 2.25-4.5V), so that the material can contribute to the specific discharge capacity of more than 5500mAh/g, and has higher coulombic efficiency. The lithium-oxygen battery assembled by the cathode material can stably cycle for more than 45 weeks, and has good cycle performance.
Example 4:
(1) removing hard shells from corn straws recovered from farms, crushing into small particles, placing the small particles in a 3 wt.% sulfuric acid solution, stirring for 1 hour at 90 ℃, washing with deionized water to be neutral, and drying a product obtained by filtering at 45 ℃ to obtain a biomass carbon raw material.
(2) Weighing cerium acetate and ruthenium trichloride, dissolving in deionized water, stirring to completely dissolve the cerium acetate and ruthenium trichloride to obtain a 20mM solution, wherein the molar ratio of cerium salt to ruthenium salt is 1: 0.5.
(3) and (2) soaking the biomass carbon raw material in the step (1) in the solution prepared in the step (2), performing ultrasonic treatment for 40 minutes, performing vacuum treatment for 40 minutes, performing ultrasonic treatment for 40 minutes again, filtering, and fully drying the filtered product at the drying temperature of 70 ℃.
(4) Roasting the product dried in the step (3) for 4 hours at 700 ℃ in an argon atmosphere at the heating rate of 10 ℃/min to obtain CeOxthe/Ru/MC nanosheet material.
(5) The CeO obtained in the step (4) is addedxRoasting the/Ru/MC nanosheet in air atmosphere at 350 ℃ for 2 hours to obtain CeOx/RuO2Nanosheets.
FIG. 10 shows CeO prepared in example 4x/RuO2TEM images of the nanoplates, it can be seen that the morphology is similar to the material in example 3. FIG. 11 is a CeO prepared in example 4x/RuO2The lithium-oxygen battery assembled by the nanosheet as the positive electrode has a limit charge-discharge curve and a cycling stability chart (constant-capacitance charge-discharge test is adopted, the capacity is limited to 500mAh/g, the current density is 200mA/g, and the voltage range is 2.25-4.5V), so that the material can contribute to the specific discharge capacity of more than 7000mAh/g and has higher coulombic efficiency. The lithium-oxygen battery assembled by the cathode material can stably cycle for more than 40 weeks, and has good cycle performance.
Example 5:
(1) removing hard shells from corn straws recovered from farms, crushing into small particles, placing the small particles in a 4 wt.% sulfuric acid solution, stirring at 80 ℃ for 1 hour, washing with deionized water to neutrality, and drying the filtered product at 50 ℃ to obtain a biomass carbon raw material.
(2) Weighing cerium acetate and ruthenium trichloride, dissolving in deionized water, stirring to completely dissolve the cerium acetate and ruthenium trichloride to obtain a 40mM solution, wherein the molar ratio of cerium salt to ruthenium salt is 1: 0.5.
(3) and (2) soaking the biomass carbon raw material in the step (1) in the solution prepared in the step (2), performing ultrasonic treatment for 30 minutes, performing vacuum treatment for 30 minutes, performing ultrasonic treatment for 30 minutes again, filtering, and fully drying the filtered product at the drying temperature of 80 ℃.
(4) Roasting the product dried in the step (3) for 4 hours at 800 ℃ in an argon atmosphere, and obtaining CeO at the heating rate of 5 ℃/minxthe/Ru/MC nanosheet material.
(5) The CeO obtained in the step (4) is addedxRoasting the/Ru/MC nanosheets in an air atmosphere at the roasting temperature of 400 ℃ for 2 hours to obtain CeOx/RuO2Nanosheets.
FIG. 12 is a CeO prepared in example 5x/RuO2TEM images of the nanosheets, it can be seen that the morphology is similar to the material in example 4, with a slight increase in particle size. FIG. 13 is CeO prepared in example 5x/RuO2The lithium-oxygen battery assembled by the nanosheet as the positive electrode has a limit charge-discharge curve and a cycling stability curve (constant-capacity charge-discharge test is adopted, the capacity is limited to 500mAh/g, the current density is 200mA/g, and the voltage range is 2.25-4.5V), so that the material can contribute to the specific discharge capacity of over 4500mAh/g and has higher coulomb efficiency. The lithium-oxygen battery assembled by the cathode material can stably cycle for more than 39 weeks, and has good cycle performance.
Example 6:
(1) removing hard shells from corn straws recovered from farms, crushing into small particles, placing the small particles in a 5 wt.% hydrochloric acid solution, stirring for 3 hours at 100 ℃, washing with deionized water to be neutral, and drying a product obtained by filtering at 60 ℃ to obtain a biomass carbon raw material.
(2) Weighing cerium acetate and ruthenium acetate, dissolving in deionized water, stirring to completely dissolve the cerium acetate and the ruthenium acetate to obtain a 50mM solution, wherein the molar ratio of cerium salt to ruthenium salt is 1: 1.
(3) and (2) soaking the biomass carbon raw material in the step (1) in the solution prepared in the step (2), performing ultrasonic treatment for 60 minutes, performing vacuum treatment for 60 minutes, performing ultrasonic treatment for 60 minutes again, filtering, and fully drying the filtered product at the drying temperature of 80 ℃.
(4) Roasting the product dried in the step (3) for 3 hours at 900 ℃ in an argon atmosphere at the heating rate of 20 ℃/min to obtain CeOxthe/Ru/MC nanosheet material.
(5) The CeO obtained in the step (4) is addedxRoasting the/Ru/MC nanosheet in air atmosphere at the roasting temperature of 450 ℃ for 3 hours to obtain CeOx/RuO2Nanosheets.
FIG. 14 shows CeO prepared in example 6x/RuO2TEM images of the nanoplates show a morphology similar to that of the material in example 5, but with a significant increase in particle size and little background visible, indicating that the material has a very low carbon content. FIG. 15 is CeO prepared in example 6x/RuO2The limit charge-discharge curve diagram and the circulation stability diagram of the lithium-oxygen battery assembled by the nanosheet as the positive electrode (constant-capacity charge-discharge test is adopted, the capacity is limited to 500mAh/g, the current density is 200mA/g, and the voltage range is 2.25-4.5V), so that the material can contribute to the discharge capacity exceeding 4500mAh/g and has higher coulomb efficiency. The lithium-oxygen battery assembled by the cathode material can stably cycle for more than 36 weeks, and has good cycle performance.
The above-mentioned embodiments are only a part of the preferred embodiments of the present invention, not all embodiments, and are not intended to limit the scope of the present invention, and any modifications, substitutions, etc. made under the concept and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. CeO (CeO)x/RuO2Composite nano-sheet material of/MC and CeOx/RuO2The preparation method of the composite nanosheet material comprises the following steps:
(1) removing hard shells of waste corn straws, crushing the waste corn straws into small particles, and fully stirring the small particles in an acid solution, wherein the acid solution is sulfuric acid, hydrochloric acid or nitric acid with the concentration of 0.5-5 wt%, and the stirring temperature is 70-100 ℃ and the stirring time is 1-3 hours; washing the biomass carbon raw material with deionized water to be neutral, filtering and drying to obtain a biomass carbon raw material;
(2) weighing a proper amount of cerium salt and ruthenium salt, dissolving the cerium salt and the ruthenium salt in deionized water, and fully stirring the cerium salt and the ruthenium salt to completely dissolve the cerium salt and the ruthenium salt to obtain a mixed solution with the total concentration of 5-50mM, wherein the molar ratio of the cerium salt to the ruthenium salt is 1: 0.02-1;
(3) dipping the biomass carbon raw material in the step (1) in the mixed solution prepared in the step (2), sequentially performing ultrasonic treatment, vacuum treatment and ultrasonic treatment again in the dipping process, then filtering, and fully drying the filtered product;
(4) roasting the product dried in the step (3) at the temperature of 600-900 ℃ in an argon atmosphere to obtain CeOxa/Ru/MC composite nanosheet material;
(5) the CeO obtained in the step (4) is addedxRoasting the/Ru/MC composite nano-sheet for 1-3 hours at the temperature of 200-450 ℃ in air atmosphere to obtain CeOx/RuO2Composite nano sheet material of/MC or CeOx/RuO2And (3) compounding the nanosheet material.
2. The method of claim 1, wherein: in the step (1), the drying temperature is 35-60 ℃ after filtration.
3. The method of claim 1, wherein: in the step (2), the cerium salt is cerium acetate, and the ruthenium salt is ruthenium trichloride, ruthenium acetate or ruthenium sulfate.
4. The method of claim 1, wherein: in the step (2), the total concentration of the mixed solution is 20mM, and the molar ratio of the cerium salt to the ruthenium salt is 1: 0.2.
5. The method of claim 1, wherein: in the step (3), the ultrasonic treatment time is 20-60 minutes, the vacuum treatment time is 20-60 minutes, the ultrasonic treatment time is 20-60 minutes again, and the drying temperature is 35-80 ℃.
6. The method of claim 1, wherein: in the step (4), the roasting temperature is 600-900 ℃, the time is 3-6 hours, and the heating rate is 2-20 ℃/min.
7. The method of claim 1, wherein: in the step (4), the roasting temperature is 600 ℃, the time is 4 hours, and the heating rate is 5 ℃/min.
8. The method of claim 1, wherein: in the step (5), the roasting temperature is 250-350 ℃, and the time is 2-2.5 hours.
9. The method of claim 1, wherein: in the step (5), the roasting temperature is 250 ℃, and the roasting time is 2 hours.
10. CeO produced by the production method according to claim 1x/RuO2Composite nano sheet material of/MC or CeOx/RuO2The composite nanosheet material is applied as a lithium-oxygen battery anode catalyst material.
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