CN118352546A - Ni-Ru bimetallic catalyst and preparation method and application thereof - Google Patents
Ni-Ru bimetallic catalyst and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 71
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
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- 238000000034 method Methods 0.000 claims description 14
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
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- 239000011261 inert gas Substances 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
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- 230000000052 comparative effect Effects 0.000 description 20
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
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- 230000000694 effects Effects 0.000 description 10
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Abstract
The invention relates to the technical field of new energy, in particular to a Ni-Ru bimetallic catalyst, a preparation method and application thereof, wherein the Ni-Ru bimetallic catalyst comprises a substrate doped with nitrogen element, and nickel catalytic sites and ruthenium catalytic sites supported on the surface of the substrate; the matrix is reduced graphene oxide; the nickel catalytic sites are supported on the surface of the matrix in the form of monoatoms and/or clusters, and the ruthenium catalytic sites are supported on the surface of the matrix in the form of at least one of monoatoms, clusters and nanoparticles. According to the invention, reduced graphene oxide is used as a matrix, nickel catalytic sites and ruthenium catalytic sites are loaded on the matrix, and nitrogen elements are introduced at the same time so as to improve the internal defect degree of the material. The catalyst is used for catalyzing a positive electrode material of a lithium-oxygen battery, and can obviously reduce the charge overpotential, increase the discharge capacity and prolong the cycle life of the battery due to the existence of the synergic catalysis of the Ni-Ru bimetallic catalyst; and the Ni-Ru bimetallic catalyst can act on both the positive and negative sides.
Description
Technical Field
The invention relates to the technical field of new energy, in particular to a Ni-Ru bimetallic catalyst and a preparation method and application thereof.
Background
The recyclable lithium-oxygen (Li-O 2) battery is known as a 'holy cup' in the battery industry, and has attracted worldwide attention (11.6 kWh kg -1) due to its ultrahigh theoretical energy density compared with the traditional lithium ion battery, so that the battery can be used for future energy storage on a power grid scale and becomes an important structure of a novel renewable energy device.
A typical rechargeable organic-based lithium-oxygen battery contains a lithium metal negative electrode, an electrolyte-impregnated glass fiber separator, and an oxygen positive electrode. Oxygen is introduced as an active material during discharge of the battery, which is significantly different from conventional lead-acid battery systems or lithium ion battery systems. Lithium-oxygen batteries produce an electric current through oxidation of lithium at the negative electrode and reduction of oxygen at the positive electrode, which occurs during discharge of the battery, i.e., an oxygen reduction reaction; in the charging process, an oxygen evolution reaction occurs, that is, the discharge product Li 2O2 or LiO 2 is decomposed on the positive electrode side, and the standard oxidation-reduction potential of the above chemical reaction approaches 3.0V (vs. Li/Li +).
Currently, the development of lithium-oxygen batteries is severely limited by problems including large overpotential, low rate capability, and poor cycling stability, with significant charge overpotential being one of the major challenges that prevent long-term operation and commercial use of lithium-oxygen batteries. High charge overpotential increases the likelihood of electrolyte decomposition and other side reactions, and the resulting byproducts can continuously exacerbate the charge overpotential and passivate the entire battery system. In addition, high overpotential also reduces the cycle efficiency and coulombic efficiency of the battery. It is well known that charge overpotential is usually induced by slow OER reaction kinetics due to the nature of multiple electron transfer. Thus, various electrocatalysts including pure metals, metal oxides and metal complexes are introduced sequentially to reduce the lithium-oxygen cell overpotential and to improve other electrochemical properties. However, for practical use of lithium-oxygen batteries, most of the charging potentials remain high.
In order to solve the above problems, in the positive electrode, researchers have focused on exploring high-efficiency electrocatalysts with better kinetics of aerobic reduction/oxygen precipitation reactions, and current efforts have been mainly focused on carbon materials, noble metals, transition metal oxides, metal nitrides, metal sulfides, metal carbides, and the like; meanwhile, various stabilization strategies are also proposed in the aspect of the anode, such as construction of alternative novel lithium-containing anode, application of electrolyte additives/modification, construction of protective layer, and the like. However, attention has been paid to a single metal catalyst, which has a limitation effect on further improving the catalytic activity thereof, resulting in a large gap from practical applications, and the negative electrode of a lithium-oxygen battery has various problems due to a complicated system.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide a Ni-Ru bimetallic catalyst and a preparation method and application thereof, and aims to solve the problems that the catalytic activity of the existing single metal catalyst is limited and the like.
The technical scheme of the invention is as follows:
A Ni-Ru bimetallic catalyst comprises a substrate doped with nitrogen, and nickel catalytic sites and ruthenium catalytic sites supported on the surface of the substrate; the matrix is reduced graphene oxide; the nickel catalytic sites are supported on the surface of the matrix in the form of monoatoms and/or clusters, and the ruthenium catalytic sites are supported on the surface of the matrix in the form of at least one of monoatoms, clusters and nanoparticles.
The Ni-Ru bimetallic catalyst, wherein the particle size of the nickel catalytic site and the ruthenium catalytic site are both smaller than 5nm.
The total mass of the ruthenium catalytic site is 0.235-0.717 wt% of the mass of the Ni-Ru bimetallic catalyst.
The Ni-Ru bimetallic catalyst comprises 1.11-4.18 wt% of nitrogen doped in reduced graphene oxide.
A preparation method of a Ni-Ru bimetallic catalyst comprises the following steps:
Mixing nickel salt with water to obtain nickel salt solution;
mixing ruthenium salt with water to obtain ruthenium salt solution;
mixing the nickel salt solution, the ruthenium salt solution and a graphene oxide aqueous solution subjected to ultrasonic treatment in advance to obtain a precursor solution;
transferring the precursor solution into a hydrothermal reaction kettle for hydrothermal reaction to obtain gel;
and (3) annealing the gel under the atmosphere containing ammonia gas to obtain the Ni-Ru bimetallic catalyst.
The preparation method of the Ni-Ru bimetallic catalyst comprises the step of selecting one or more of nickel salts from NiCl2·6H2O、Ni(NO3)2·6H2O、Ni(CH3COO)2·4H2O; the ruthenium salt is selected from one or more of RuCl 3·3H2O、RuCl3·xH2O、Ru(CH3COO)3.
The preparation method of the Ni-Ru bimetallic catalyst comprises the steps of enabling the concentration of the nickel salt solution to be 0.8mg/l-1.2mg/ml; the concentration of the ruthenium salt solution is 0.8mg/l-1.2mg/ml.
The preparation method of the Ni-Ru bimetallic catalyst comprises the steps of carrying out hydrothermal reaction at 170-190 ℃ for 5-7 h.
The preparation method of the Ni-Ru bimetallic catalyst comprises the following steps of carrying out annealing treatment under the mixed atmosphere of inert gas and ammonia gas; the temperature of the annealing treatment is 850-950 ℃, the heating rate of the annealing treatment is 4-6 ℃/min, and the time of the annealing treatment is 1-2 h.
An application of Ni-Ru bimetallic catalyst in lithium-oxygen battery.
The beneficial effects are that: the invention provides a Ni-Ru bimetallic catalyst, a preparation method and application thereof, wherein the Ni-Ru bimetallic catalyst comprises a substrate doped with nitrogen element, and nickel catalytic sites and ruthenium catalytic sites supported on the surface of the substrate; the matrix is reduced graphene oxide; the nickel catalytic sites are supported on the surface of the matrix in the form of monoatoms and/or clusters, and the ruthenium catalytic sites are supported on the surface of the matrix in the form of at least one of monoatoms, clusters and nanoparticles. The invention adopts a hydrothermal-high temperature thermal reduction method to prepare a bimetallic catalyst (NiRu-N/rGO) with coexistence of single atom-cluster-nano particles, which takes reduced graphene oxide as a matrix, loads nickel catalytic sites and ruthenium catalytic sites on the matrix, and introduces nitrogen elements to improve the internal defect degree of the material. Compared with a single metal catalyst, the Ni-Ru bimetallic catalyst has the advantages that the Ni-Ru bimetallic catalyst has synergistic catalysis effect, so that the charge overpotential can be obviously reduced, the discharge capacity can be increased, and the cycle life of the battery can be prolonged. Meanwhile, the composite lithium metal negative electrode prepared by loading the composite lithium metal negative electrode on the surface of lithium metal endows a lithium-oxygen battery with good high-rate cycle stability, effectively delays corrosion of a battery system to lithium metal, and improves safety. And the Ni-Ru bimetallic catalyst can act on both the positive and negative sides.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a Ni-Ru bimetallic catalyst according to the invention;
FIG. 2 is a schematic process flow diagram of the preparation of Ni-Ru bimetallic catalyst according to examples 1-4;
FIG. 3 is a graph of a spherical aberration transmission electron microscope (EDS) -Mapping of NiRu 3 -N/rGO bimetallic catalyst prepared in example 3 and Ru monometal catalyst prepared in comparative example 1;
FIG. 4 is an X-ray diffraction pattern of NiRu 3 -N/rGO bimetallic catalyst prepared in example 3 and Ru monometal catalyst prepared in comparative example 1;
FIG. 5 is an X-ray photoelectron spectrum of NiRu 3 -N/rGO bimetallic catalyst prepared in example 3 and Ru monometal catalyst prepared in comparative example 1;
FIG. 6 is a Fourier transform extended X-ray absorption fine structure diagram of NiRu 3 -N/rGO bimetallic catalyst prepared in example 3;
FIG. 7 is a graph showing the first-cycle discharge capacity of lithium-oxygen batteries of the catalytic positive electrode prepared by the bimetallic catalyst prepared in examples 1-4 and the monometallic catalyst prepared in comparative example 1;
FIG. 8 is a graph showing charge and discharge performance of lithium oxygen batteries in which a catalytic cathode was prepared using the bimetallic catalyst prepared in example 3 and the single metal catalyst prepared in comparative example 1;
FIG. 9 is a graph showing the rate performance of lithium-oxygen batteries in which the bimetallic catalyst prepared in example 3 and the single metal catalyst prepared in comparative example 1 are used to prepare a catalytic cathode;
FIG. 10 is a graph showing the cycling stability of lithium oxygen batteries in which the bimetallic catalyst prepared in examples 1-4 and the single metal catalyst prepared in comparative example 1 are used to prepare a catalytic positive electrode;
fig. 11 is a graph showing the cycling stability of a lithium-oxygen battery using the bimetallic catalyst prepared in example 3 to catalyze the positive electrode and the negative electrode of the composite lithium metal.
Detailed Description
The invention provides a Ni-Ru bimetallic catalyst and a preparation method and application thereof, and the invention is further described in detail below for the purpose, technical scheme and effect of the invention to be clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It will be understood by those skilled in the art that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
For practical use of lithium-oxygen batteries, most of the charging potentials are still high; the prior Chinese patent document CN111370714A discloses an octahedral Ni-N-C composite material and a preparation method of inverse microemulsion thereof. The Ni-N-C composite material prepared by the method is used as a lithium air battery anode catalyst material, has lower overpotential, and the preparation method is simple and has better prospect. In addition, for example, the Chinese patent document CN111348640A relates to a porous carbon-Fe 3O4 nanometer air anode material, and the porous carbon-Fe 3O4 nanometer material obtained by hydrothermal and calcination has large specific surface area, can provide more catalytic active sites, has better catalytic activity, and can provide more space for stacking discharge products of lithium-air batteries. However, attention has been paid to a single metal catalyst, which may have a limitation in further improving its catalytic activity, resulting in a large gap from practical applications, and the negative electrode of a lithium-oxygen battery has various problems due to a complicated system.
The prior art is therefore still in need of improvement and development. Nanostructured bimetallic catalysts have demonstrated remarkable electronic and chemical catalysis in many fields, such as fuel cells, nitrogen production, biomass fuel conversion, and the like, over the past decades. The improvement in catalytic performance of nanostructured bimetallic catalysts can be attributed to the formation of bonds between heterogeneous atoms on the metal surface and to the change in local bonding morphology. The former affects the electronic environment of the surface atoms and their reactivity, while the latter affects the electronic structure of the metal. Therefore, the composition and the structure of the nano-structure bimetallic catalyst can be regulated so as to meet the actual application requirement of the lithium-oxygen battery.
Based on the above, the invention provides a Ni-Ru bimetallic catalyst, which comprises a substrate doped with nitrogen element, and nickel catalytic sites and ruthenium catalytic sites supported on the surface of the substrate; the matrix is reduced graphene oxide; the nickel catalytic sites are supported on the surface of the matrix in the form of monoatoms and/or clusters, and the ruthenium catalytic sites are supported on the surface of the matrix in the form of at least one of monoatoms, clusters and nanoparticles.
In the embodiment, the reduced graphene oxide doped with nitrogen is taken as a matrix, so that the internal defect contrast of the material can be improved, a coordination structure is formed with metal sites, the catalytic activity is generated, and the overall catalytic performance of the material and the affinity to lithium are enhanced; ni/Ru bimetallic catalytic sites are loaded on the surface of the matrix, ru exists in the form of at least one of single atoms, clusters and nano particles, and Ni exists in the form of single atoms and/or clusters. Meanwhile, the Ni-Ru bimetallic catalyst has rich pore structures and specific surface areas, increases the contact area between an electrode and electrolyte, shortens the transmission path of ions and electrons, effectively improves the problem of three-phase interfaces, and provides more sites for accommodating discharge products.
Specifically, the Ni-Ru bimetallic catalyst has larger specific surface area and higher pore volume, the high specific surface area can promote the infiltration of electrolyte, increase three-phase reaction boundary, promote the electron transmission and the dissolution of ions in the electrolyte, and improve the charge and discharge performance of the battery; in addition, the large pore volume can also promote the positive electrode to contain more discharge products, increase the capacity of the battery and the like. In the Ni-Ru bimetallic catalyst, the electronic environment and the reactivity of surface atoms and the electronic structure of metal are influenced through the formation of heteroatomic bonds and the change of local bonding morphology on the surface of metal, so that the synergistic catalytic operation of an atomic-level Ni active site and a Ru active site is emphasized, and further the lithium-oxygen battery with more excellent performance is realized.
In some embodiments, the nickel catalytic sites and the ruthenium catalytic sites each have a particle size of less than 5nm. The atomic nickel catalytic site and the ruthenium catalytic site can play a role in synergistic catalysis, so that a lithium-oxygen battery with more excellent performance is realized. In addition, due to the existence of the synergistic catalysis effect, the charge overpotential can be obviously reduced, the discharge capacity can be increased, and the cycle life of the battery can be prolonged.
In some embodiments, the total mass of the ruthenium catalytic sites is 0.235wt% to 0.717wt% of the mass of the Ni-Ru bimetallic catalyst. The nitrogen-doped reduced graphene oxide is used as a matrix, and ruthenium active sites with the mass fraction of 0.235-0.717 wt% are loaded, so that the active sites and nickel catalytic sites can play a role in synergistic catalysis, the charge overpotential can be remarkably reduced, the discharge capacity can be increased, and the cycle life of the battery can be prolonged.
In some embodiments, the reduced graphene oxide has a mass percentage of doped nitrogen element of 1.11wt% to 4.18wt%. The nitrogen element is introduced into the reduced graphene oxide, so that the internal defect degree of the material can be improved.
In addition, as shown in FIG. 1, the invention also provides a preparation method of the Ni-Ru bimetallic catalyst, which comprises the following steps:
step S10: mixing nickel salt with water to obtain nickel salt solution;
step S20: mixing ruthenium salt with water to obtain ruthenium salt solution;
Step S30: mixing the nickel salt solution, the ruthenium salt solution and a graphene oxide aqueous solution subjected to ultrasonic treatment in advance to obtain a precursor solution;
step S40: transferring the precursor solution into a hydrothermal reaction kettle for hydrothermal reaction to obtain gel;
Step S50: and (3) annealing the gel under the atmosphere containing ammonia gas to obtain the Ni-Ru bimetallic catalyst.
In the embodiment, a hydrothermal-high temperature thermal reduction method is adopted to prepare a bimetallic catalyst (NiRu-N/rGO) with coexistence of single atoms, clusters and nano particles, reduced graphene oxide is taken as a matrix, nickel catalytic sites and ruthenium catalytic sites are loaded on the reduced graphene oxide, and nitrogen elements are introduced to improve the internal defect degree of the material.
Specifically, nitrogen doping is introduced into an ammonia decomposition product, the structure and conductivity of graphene are greatly improved, meanwhile, uneven distribution of atomic charge density in the doping process is beneficial to promoting oxygen adsorption and material activity, generated defects and disorder provide active sites for oxygen and lithium ion adsorption in a lithium-oxygen battery, and the density of reactive active sites is increased, so that the discharge voltage and discharge capacity are improved in the lithium-oxygen battery discharge process.
In some embodiments, the nickel salt is selected from one or more of NiCl2·6H2O、Ni(NO3)2·6H2O、Ni(CH3COO)2·4H2O; the ruthenium salt is selected from one or more of RuCl 3·3H2O、RuCl3·xH2O、Ru(CH3COO)3. The nickel salt and the ruthenium salt are easy to dissolve in water, and form a precursor solution with uniformly dispersed solutes with the graphene oxide aqueous solution treated by ultrasonic in advance, so that the nickel element and the ruthenium element are favorable for loading on the graphene oxide surface.
In some embodiments, the nickel salt solution has a concentration of 0.8mg/l to 1.2mg/ml; the concentration of the ruthenium salt solution is 0.8mg/l-1.2mg/ml.
In some embodiments, the volume ratio of the nickel salt solution to the ruthenium salt solution is 1 (4-39).
In some embodiments, the concentration of the graphene oxide aqueous solution is 2mg/ml.
In some embodiments, the pre-sonicated graphene oxide aqueous solution is specifically pre-sonicated for 3 hours.
In some embodiments, in the step S30, the nickel salt solution, the ruthenium salt solution and the graphene oxide aqueous solution that is treated by ultrasonic treatment in advance are magnetically stirred for 0.5h, and then are sonicated for 0.5h, so as to obtain a uniform and stable precursor solution.
In some embodiments, in step S40, after transferring the precursor solution into a hydrothermal reaction kettle, sealing and placing in a blast drying oven, performing a hydrothermal reaction to obtain a black cylindrical regular gel sample, and soaking and cleaning the black cylindrical regular gel sample with deionized water three times for 30min each time for standby.
In some embodiments, the temperature of the hydrothermal reaction is 170 ℃ to 190 ℃ and the time of the hydrothermal reaction is 5h to 7h.
In a preferred embodiment, the temperature of the hydrothermal reaction is 180 ℃ and the time of the hydrothermal reaction is 6 hours.
In some embodiments, the gel is freeze-dried for 60-72 hours to remove moisture entrained in the gel prior to annealing.
In some embodiments, the annealing treatment is performed under a mixed atmosphere of inert gas and ammonia gas; the temperature of the annealing treatment is 850-950 ℃, the heating rate of the annealing treatment is 4-6 ℃/min, and the time of the annealing treatment is 1-2 h.
In a preferred embodiment, the annealing treatment is performed under an Ar (150 sccm)/NH 3 (50 sccm) atmosphere.
In some embodiments, the mixed atmosphere has a gas flow of 100ml/min.
In a preferred embodiment, the temperature of the annealing treatment is 900 ℃, the temperature rise rate of the annealing treatment is 5 ℃/min, and the time of the annealing treatment is 1h.
In addition, the invention also provides application of the Ni-Ru bimetallic catalyst in a lithium-oxygen battery.
In the embodiment, nitrogen element doping is introduced into an ammonia decomposition product, the structure and conductivity of graphene are greatly improved, meanwhile, uneven distribution of atomic charge density in the doping process is beneficial to promoting oxygen adsorption and material activity, generated defects and disorder provide active sites for oxygen and lithium ion adsorption in a lithium-oxygen battery, and the density of reactive active sites is increased, so that discharge voltage and discharge capacity are improved in the lithium-oxygen battery discharge process. Meanwhile, the composite lithium metal negative electrode prepared by loading the composite lithium metal negative electrode on the surface of lithium metal endows a lithium-oxygen battery with good high-rate cycle stability, effectively delays corrosion of a battery system to lithium metal, and improves safety. The ni—ru bimetallic catalyst can function on both the positive and negative electrode sides.
The following examples are further given to illustrate the invention in detail. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure.
Examples 1 to 4
Examples 1 to 4 each provide a ni—ru bimetallic catalyst, as shown in fig. 2, with the following specific steps:
Step 1: 50mg of NiCl 2·6H2 O is dissolved in 50mL of deionized water, and the solution is magnetically stirred for 1h until the solution is completely dissolved, so as to obtain nickel salt solution;
Step 2: dissolving 50mg of RuCl 3·3H2 O in 50mL of deionized water, and magnetically stirring for 1h until the RuCl 3·3H2 O is completely dissolved to obtain ruthenium salt solution;
Step 3: according to Table 1, a certain amount of the nickel salt solution, ruthenium salt solution and deionized water are added into 50mL of graphene oxide aqueous solution (2 mg/mL) which is subjected to ultrasonic treatment for 3 hours in advance according to a certain proportion, and then are subjected to magnetic stirring for 0.5 hour, and four uniform and stable precursor solutions are obtained after ultrasonic treatment for 0.5 hour for later use;
Step 4: transferring the four precursor solutions into a hydrothermal reaction kettle respectively, sealing and placing in a blast drying box, performing hydrothermal reaction for 6 hours at the temperature of 180 ℃ to obtain a black cylindrical regular gel sample, soaking and cleaning the sample with deionized water for three times for 30 minutes each time for later use;
Step 5: the above-mentioned black gel sample after washing was freeze-dried for 72 hours to remove the water content, and then transferred to a tube furnace for high temperature annealing treatment, and heated to 900 ℃ at a heating rate of 5 ℃ min -1 under an atmosphere of Ar (150 sccm)/NH 3 (50 sccm) mixed gas, and calcined at a high temperature for 1 hour, wherein the gas flow rate of the mixed gas is 100ml min-1, and cooled to room temperature to obtain NiRu 1 -N/rGO of example 1, niRu 2 -N/rGO of example 2, niRu 3 -N/rGO of example 3, niRu 4 -N/rGO of example 4, respectively.
Comparative example 1
The comparative example was prepared in the same manner as in example 3 except that the addition amount of the nickel salt solution and the deionized water were not changed in step 3, as shown in Table 1.
TABLE 1
The spherical transmission electron microscope image and EDS-Mapping image of the NiRu 3 -N/rGO bimetallic catalyst prepared in example 3 and the Ru monometal catalyst prepared in comparative example 1 are shown in FIG. 3, wherein (a) in FIG. 3 is the spherical transmission electron microscope image of the NiRu 3 -N/rGO bimetallic catalyst prepared in example 3, and it can be seen from the image that bimetallic catalytic sites are uniformly dispersed on the whole grapheme carbon material matrix in the form of coexistence of single atoms, clusters and nano particles; ni exists in the form of monoatomic + clusters; FIG. 3 (b) is a spherical aberration transmission electron microscope image of the Ru single metal catalyst prepared in comparative example 1, in which Ru is uniformly dispersed on the whole graphene carbon material matrix in the form of single atom, cluster, nanoparticle coexistence; the EDS-Mapping diagram of NiRu 3 -N/rGO bimetallic catalyst and Ru monometallic catalyst in FIG. 3 shows that the interior of the material, including particle-to-particle, particle-to-cluster and the like, is composed of Ni element and Ru element, and the Ni element and the Ru element play a role in synergic catalysis on the subsequent lithium-oxygen battery.
To verify the effect of atomic-scale Ni active sites on the microstructure of the composite, X-ray diffraction tests (XRD) were performed on example 3 and comparative example 1, and as shown in fig. 4, when a trace amount of atomic-scale Ni element was added, the main peak of Ru around 44 ° was shifted to a high angle, demonstrating that the interaction between Ni-Ru dissimilar metal atoms occurred, and the smaller Ni atoms were incorporated into the larger Ru atoms, and the two interacted to cause the Ru atoms to shrink in lattice, resulting in the shift of its characteristic peak to a high angle, changing the structure inside the material, producing a Ni-Ru solid solution phase, thereby affecting the final properties of the material.
To further illustrate the effect of interactions between dissimilar metal atoms on the internal structure of the material, and since the electronic structure of the material directly affects the catalytic performance of the material, the surface element compositions and chemical states of example 3 and comparative example 1 were then characterized using X-ray photoelectron spectroscopy (XPS), as shown in fig. 5, and as can be seen in fig. 5, the characteristic peaks of Ru 3p 3/2 and Ru 3p 1/2 are clearly observed in both sets of samples, and can be classified into 0-valent Ru (Ru 0) and Ru +, and as can be seen from the peak areas, ru 0 dominates, proving that Ru nanoparticles ensure the basic catalytic performance of both materials. When the trace Ni element is added, the Ru 0 characteristic peak shifts to the high binding energy by about 0.8eV, the Ru + characteristic peak shifts to the high binding energy by about 2.23eV, and the XRD diffraction peak shifts, as shown by the combination, in the NiRu 3 -N/rGO bimetallic composite material (example 3), the trace Ni element can cause the change of the internal electronic structure of the composite material, and electrons are transferred to the Ni element from the Ru element to form a part of Ni-Ru solid solution, so that the bimetallic synergistic catalytic effect is generated, the catalytic performance of the material is enhanced, and conditions are provided for the application of lithium-oxygen batteries.
The extended X-ray absorption fine structure diagram of the bimetallic catalyst NiRu 3 -N/rGO prepared in example 3 is shown in fig. 6, and it can be seen from fig. 6 that most of the bimetallic catalyst is Ru-Ru coordination, trace Ru-N coordination exists, meanwhile Ru-Ni coordination exists, no Ru-O coordination exists, and it is proved that bonding and bonding occur between Ni and Ru, which intuitively explains the XRD/XPS result, and further, a bimetallic synergistic catalytic effect is generated.
1. The Ni-Ru bimetallic catalyst prepared in examples 1-4 and the Ru single metal catalyst prepared in comparative example 1 are used as catalytic positive electrode materials in lithium-oxygen batteries, and the specific steps are as follows:
1) Preparing a positive plate of the lithium-oxygen battery: uniformly dispersing the Ni-Ru bimetallic catalyst prepared in examples 1-4 and the Ru single metal catalyst prepared in comparative example 1 and the conductive ketjen black and a 6% polytetrafluoroethylene binder in an isopropanol solution according to a mass ratio of 6:3:1, wherein the mass ratio of the Ni-Ru bimetallic catalyst or the Ru single metal catalyst to the ketjen black and the mass ratio of the Ru single metal catalyst to the isopropanol are 1:120, and sequentially carrying out magnetic stirring for 0.5h and ultrasonic treatment for 3h to obtain uniform slurry; and (3) uniformly coating 50 mu L of the slurry on a carbon paper substrate, and vacuum drying at 90 ℃ for 12 hours to obtain positive pole pieces, wherein the active material load (catalyst+KB) of each positive pole piece is 0.3mg/cm 2.
2) Lithium-oxygen battery assembly and testing: and (3) assembling the battery in a glove box filled with high-purity argon, wherein the H 2O、O2 content is less than 0.1ppm, taking metal lithium (purity is more than 99.9%) as a negative electrode, taking a glass fiber film (GF/D) as a diaphragm, taking a solution of lithium bistrifluoromethyl sulfinate in tetraethylene glycol dimethyl ether as electrolyte (the concentration is 1 mol/L), using 230 mu L of the electrolyte, and assembling the CR2032 button battery. Transferring the assembled battery into a lithium-oxygen battery test box, standing at room temperature for 3 hours, introducing oxygen with 1 atmosphere, standing for 6 hours in an oxygen atmosphere, and introducing oxygen for the second time. And (3) performing electrochemical performance test on the treated lithium oxygen battery, wherein the test equipment is a Land battery test system (5V, 1 MA), and the test voltage range is 2.0-4.5/5.0V.
The first-turn discharge capacity curve of the battery at the current density of 200mA/g is shown in FIG. 7, and as can be seen from FIG. 7, the first-turn discharge capacities of the lithium-oxygen batteries of the catalytic anodes prepared by using the bimetallic catalysts prepared in examples 1-4 and the monometal catalyst prepared in comparative example 1 respectively reach 9032, 9581, 11748, 5680 and 7337mAh/g.
The charge-discharge performance curve of the battery under the current density of 100mAh/g and 500mAh/g is shown in fig. 8, and as can be seen from fig. 8, the overpotential of the lithium-oxygen battery of the catalytic anode prepared by using the bimetallic catalyst prepared in example 3 is only 0.92V, and the overpotential of the lithium-oxygen battery of the catalytic anode prepared by using the monometal catalyst prepared in comparative example 1 is 1.13V.
The rate performance curves of the battery under the conditions of 500mAh/g limiting capacity and different current densities are shown in fig. 9, and as can be seen from fig. 9, the lithium-oxygen battery prepared by utilizing NiRu 3 -N/rGO of the embodiment 3 has the advantages that the discharge platform is almost unchanged along with the gradual increase of the current density (100 mAg -1～500mAg-1), the charging platform is slowly and orderly increased, when the current density reaches 600mAg -1～900mAg-1, the discharge platform is gradually decreased, the charging platform is still slowly and orderly increased, the battery is in a normal and stable running state, but when the current density is increased to 1000mAg -1, the discharge platform is about 2V, the actual running effect of the battery is poor under the parameters, and the maximum bearing capacity is exceeded. And when the current is reduced again, the battery charging and discharging platforms are restored to the original size, and the NiRu 3 -N/rGO prepared lithium-oxygen battery with the catalytic anode in the embodiment 3 has excellent multiplying power performance. Meanwhile, for comparison, the multiplying power performance of Ru-N/rGO (comparative example 1) electrodes is tested under the same conditions, and as a result, when the current density is increased to 700mAg -1, the battery discharging platform starts to be remarkably reduced, the discharging voltage after three cycles is lower than 2V, the battery degradation is obvious, the battery cannot normally operate under the current density of 800mAg -1～1000mA g-1, and even if the current is reduced and returns to the normal state, the multiplying power performance of the lithium-oxygen battery of the catalytic anode prepared by Ru-N/rGO of comparative example 1 is still poor.
The cycling stability curves of this cell at a defined capacity of 500mAh/g and a current density of 200mA/g are shown in FIG. 10. As can be seen from FIG. 10, the lithium oxygen cells of the catalyst preparation catalytic anodes of examples 1-4 and comparative example 1 can be cycled steadily for 67, 78, 139, 154 and 220 cycles.
2. The NiRu 3 -N/rGO bimetallic catalyst prepared in example 3 is used as a negative electrode material for a lithium-oxygen battery, and the specific steps are as follows:
1) Preparation of a lithium-oxygen battery composite lithium metal anode: uniformly dispersing the Ni-Ru bimetallic catalyst prepared in the embodiment 3 and the conductive agent ketjen black in tetraethylene glycol dimethyl ether according to the mass ratio of 2:1, wherein the mass ratio of the Ni-Ru bimetallic catalyst to the ketjen black to the tetraethylene glycol dimethyl ether is 1:120, and sequentially carrying out magnetic stirring for 0.5h and ultrasonic treatment for 3h to obtain a uniform mixed solution; and taking 70 mu L of the mixed solution to uniformly coat on the surface of a lithium sheet in a glove box filled with high-purity argon, and drying at 60 ℃ for 12 hours to obtain the composite lithium metal with the protective layer.
2) Lithium-oxygen battery assembly and testing: and (3) assembling the obtained composite lithium metal into a glove box filled with high-purity argon, wherein the H2O, O2 content is less than 0.1ppm, taking the composite lithium metal as a negative electrode, and keeping the rest assembling modes and testing conditions consistent with the above.
The cycling stability curve of the battery at 500mAh/g limited capacity and 500mA/g current density is shown in FIG. 11, and as can be seen from FIG. 11, the NiRu 3 -N/rGO prepared lithium oxygen battery of example 3 can stably cycle for more than 180 circles (80 circles of single positive electrode).
In summary, the Ni-Ru bimetallic catalyst provided by the invention, as well as the preparation method and application thereof, comprises a substrate doped with nitrogen element, and nickel catalytic sites and ruthenium catalytic sites supported on the surface of the substrate; the matrix is reduced graphene oxide; the nickel catalytic sites are supported on the surface of the matrix in the form of monoatoms and/or clusters, and the ruthenium catalytic sites are supported on the surface of the matrix in the form of at least one of monoatoms, clusters and nanoparticles. The invention adopts a hydrothermal-high temperature thermal reduction method to prepare a bimetallic catalyst (NiRu-N/rGO) with coexistence of single atom-cluster-nano particles, which takes reduced graphene oxide as a matrix, loads nickel catalytic sites and ruthenium catalytic sites on the matrix, and introduces nitrogen elements to improve the internal defect degree of the material. Compared with a single metal catalyst, the Ni-Ru bimetallic catalyst has the advantages that the Ni-Ru bimetallic catalyst has synergistic catalysis effect, so that the charge overpotential can be obviously reduced, the discharge capacity can be increased, and the cycle life of the battery can be prolonged. Meanwhile, the composite lithium metal negative electrode prepared by loading the composite lithium metal negative electrode on the surface of lithium metal endows a lithium-oxygen battery with good high-rate cycle stability, effectively delays corrosion of a battery system to lithium metal, and improves safety. And the Ni-Ru bimetallic catalyst can act on both the positive and negative sides.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. The Ni-Ru bimetallic catalyst is characterized by comprising a substrate doped with nitrogen element, and nickel catalytic sites and ruthenium catalytic sites supported on the surface of the substrate; the matrix is reduced graphene oxide; the nickel catalytic sites are supported on the surface of the matrix in the form of monoatoms and/or clusters, and the ruthenium catalytic sites are supported on the surface of the matrix in the form of at least one of monoatoms, clusters and nanoparticles.
2. The Ni-Ru bimetallic catalyst of claim 1, wherein the particle size of both the nickel catalytic sites and the ruthenium catalytic sites is less than 5nm.
3. The Ni-Ru bimetallic catalyst of claim 1, wherein the total mass of ruthenium catalytic sites is from 0.235wt% to 0.717wt% of the mass of the Ni-Ru bimetallic catalyst.
4. The Ni-Ru bimetallic catalyst of claim 1, wherein the mass percent of nitrogen element doped in the reduced graphene oxide is between 1.11wt% and 4.18wt%.
5. A method for preparing the Ni-Ru bimetallic catalyst as in any one of claims 1-4, comprising the steps of:
Mixing nickel salt with water to obtain nickel salt solution;
mixing ruthenium salt with water to obtain ruthenium salt solution;
mixing the nickel salt solution, the ruthenium salt solution and a graphene oxide aqueous solution subjected to ultrasonic treatment in advance to obtain a precursor solution;
transferring the precursor solution into a hydrothermal reaction kettle for hydrothermal reaction to obtain gel;
and (3) annealing the gel under the atmosphere containing ammonia gas to obtain the Ni-Ru bimetallic catalyst.
6. The method for preparing a Ni-Ru bimetallic catalyst as claimed in claim 5, wherein the nickel salt is selected from one or more of NiCl2·6H2O、Ni(NO3)2·6H2O、Ni(CH3COO)2·4H2O; the ruthenium salt is selected from one or more of RuCl 3·3H2O、RuCl3·xH2O、Ru(CH3COO)3.
7. The method for preparing a Ni-Ru bimetallic catalyst according to claim 5, wherein the concentration of the nickel salt solution is 0.8mg/l-1.2mg/ml; the concentration of the ruthenium salt solution is 0.8mg/l-1.2mg/ml.
8. The method for preparing a Ni-Ru bimetallic catalyst according to claim 5, wherein the temperature of the hydrothermal reaction is 170 ℃ to 190 ℃ and the time of the hydrothermal reaction is 5h to 7h.
9. The method for producing a Ni-Ru bimetallic catalyst as claimed in claim 5, wherein the annealing treatment is performed in a mixed atmosphere of inert gas and ammonia gas; the temperature of the annealing treatment is 850-950 ℃, the heating rate of the annealing treatment is 4-6 ℃/min, and the time of the annealing treatment is 1-2 h.
10. Use of the Ni-Ru bimetallic catalyst of any of claims 1-4 in a lithium oxygen battery.
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