CN111916774B - Load Pd @ Pd4S hollow carbon nanosphere and preparation method and application thereof - Google Patents

Load Pd @ Pd4S hollow carbon nanosphere and preparation method and application thereof Download PDF

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CN111916774B
CN111916774B CN202010717934.2A CN202010717934A CN111916774B CN 111916774 B CN111916774 B CN 111916774B CN 202010717934 A CN202010717934 A CN 202010717934A CN 111916774 B CN111916774 B CN 111916774B
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hollow carbon
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CN111916774A (en
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张进涛
刘晓猛
黄启顺
许浩然
王俊
赵兰玲
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Shandong University
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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
    • H01M4/92—Metals of platinum group
    • H01M4/923—Compounds thereof with non-metallic elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite

Abstract

The invention provides a load Pd @ Pd4S hollow carbon nanospheres and a preparation method and application thereof. The obtained supported Pd @ Pd4The hollow carbon nanosphere of S has high conductivity and excellent catalytic activity, and the hollow porous structure effectively solves the problem of volume expansion caused by accumulation and decomposition of discharge products in the charge-discharge process, so that the hollow carbon nanosphere has good cycle performance. Meanwhile, the production process is simple and reliable, easy to amplify and produce, free of toxic and harmful byproducts in the reaction process, green and safe, and beneficial assistance is provided for the practical industrial application of the lithium oxygen battery.

Description

Load Pd @ Pd4S hollow carbon nanosphere and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrocatalysis of lithium oxygen batteries, and particularly relates to a Pd @ Pd supported battery4S hollow carbon nanospheres and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The lithium oxygen battery has ultrahigh theoretical energy density (up to 3505 Wh.kg)-1) Become the research focus of scientists. However, lithium oxygen batteries are currently still under development, and slow oxygen reduction and oxygen evolution reaction kinetics lead to overpotential excess, poor rate capability and limited cycle life, which are problematicFurther applications of the lithium oxygen battery are contemplated. Therefore, it is imperative to develop efficient positive catalysts to accelerate the electrochemical process during charging and discharging of lithium oxygen batteries.
Studies have shown that noble metal materials have excellent electrocatalytic activity and excellent durability, and are considered as ideal positive electrode catalyst materials. Among them, Pt-based materials show excellent performance of a lithium oxygen battery when used as a cathode catalyst, but Pt is too expensive, thereby limiting a wide range of applications thereof. The noble metal Pd, which is also a platinum group, and the compound thereof also exhibit excellent electrocatalytic properties and are considerably less expensive than the metal Pt, and thus have received much attention from researchers.
The realization of stable cyclic charge and discharge is an important precondition for the practical application of the lithium-oxygen battery, and the inventor finds that although the research on the application of the Pd-carbon composite material to the anode catalytic material of the lithium-oxygen battery has made a certain progress, the serious defects of small specific surface area, poor conductivity and low stability still exist. The technical problem to be solved is to provide an electrocatalyst capable of improving the cycle stability of a lithium oxygen battery.
Disclosure of Invention
Aiming at solving the problem of the existing preparation method for preparing carbon-supported Pd4The S catalyst still has the defects of small specific surface area, poor conductivity and low cycle life of the lithium-oxygen battery caused by easy collapse of the catalyst structure in the charging and discharging processes, and the invention provides the Pd @ Pd supported catalyst4S hollow carbon nanosphere, preparation method and application thereof, and Pd @ Pd supported on nanosphere4The hollow carbon nanosphere of S has higher specific surface area and high-efficiency catalytic performance, can effectively promote the generation of lithium peroxide and provide sufficient storage space when being used as a positive catalytic material of a lithium-oxygen battery during discharging, and Pd @ Pd during charging4The S heterojunction is beneficial to the high-efficiency decomposition of lithium peroxide, and the porous carbon structure provides a good material transmission channel in the charging and discharging processes. In addition, the invention loads Pd @ Pd4The preparation method of the hollow carbon nanosphere of S is simple, the production cost is low, special equipment and harsh conditions are not needed, and the material can be produced on a large scale and can be practically applied to a lithium-oxygen batteryIt is possible.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the invention, the invention provides a Pd @ Pd supported catalyst4The preparation method of the hollow carbon nanosphere of S comprises the following steps:
s1, preparing hollow carbon nanospheres;
s2, in-situ preparation of palladium nanoparticles: mixing the hollow carbon nanospheres obtained in the step S1 with a divalent palladium salt solution and a hexadecyl trimethyl ammonium chloride solution, and adding a reducing agent solution to obtain a suspension of the hollow carbon nanospheres loaded with palladium nanoparticles;
s3, preparing load Pd @ Pd4Hollow carbon nanoball of S: sulfurizing the hollow carbon nanosphere loaded with palladium nanoparticles obtained in S2 in inert atmosphere to prepare Pd @ Pd4S hollow carbon nanoball.
In a second aspect of the invention, the invention provides a Pd @ Pd supported4The hollow carbon nanosphere of S adopts the Pd @ Pd loaded4S is prepared by the preparation method of the hollow carbon nanosphere.
In a third aspect of the invention, the invention provides a Pd @ Pd supported catalyst4The application of the hollow carbon nanosphere of S is to load the Pd @ Pd4The hollow carbon nanospheres of S are used for catalyzing the oxygen reduction reaction of the lithium-oxygen battery.
In a fourth aspect of the present invention, the present invention provides a lithium oxygen battery comprising a supported Pd @ Pd as described above4S hollow carbon nanoball.
Compared with the prior art, one or more technical schemes of the invention have the following beneficial effects:
(1) the method adopts the mode of protective atmosphere vulcanization after solution reduction to grow Pd @ Pd on the surface of the hollow carbon nanosphere in situ4The S particles are simple in method, do not need special experimental environment and conditions in the synthetic process, and are easy to operate.
(2) The inventor finds that when the hollow carbon spheres are used for in-situ loading of the Pd nanoparticles, the Pd nanoparticles are difficult to aggregate and accumulate, so that the pore structure of the carbon spheres is blocked, the utilization rate of the high specific surface area of the hollow carbon spheres is influenced, and the material transmission efficiency is reduced; meanwhile, the binding force of the divalent palladium salt on the surface of the carbon sphere is weaker, so that the inventor adds the hexadecyl trimethyl ammonium chloride solution after mixing the carbon sphere with the divalent palladium salt solution, which not only can avoid Pd nanoparticle aggregation, but also can enhance the binding force of the divalent palladium salt and the surface of the carbon sphere.
(3) The inventor also finds that when the hollow carbon nanosphere is used as a carrier, the catalytic activity is poor due to low loading of the active catalyst, and in order to improve the loading of the Pd nanoparticles, a hexadecyl trimethyl ammonium chloride solution is added while a divalent palladium salt is added, so that the loading of the active substance is greatly improved, and the method becomes a key for improving the catalyst activity and the stability of the lithium-oxygen battery.
(4) The invention prepares the load Pd @ Pd4The hollow carbon nanosphere has the advantages that the material has larger specific surface area and good conductivity, the heterojunction particles are uniformly distributed, so that the material has excellent electrocatalysis performance, the porous structure of the carbon matrix can provide abundant substance transmission channels, meanwhile, the volume change caused by accumulation and decomposition of products in the charging and discharging process is relieved, the original structure can be still maintained in the charging and discharging process, and the cyclicity stability of the battery is improved.
(5) In order to improve the circulation stability of the lithium-oxygen battery under the high current density, the invention prepares the load Pd @ Pd for the first time4The hollow carbon nanospheres of the S further improve the battery performance of the lithium-oxygen battery through the hierarchical porous structure of the hollow carbon nanospheres; effectively promote the generation of lithium peroxide during discharging and provide sufficient storage space during charging with Pd @ Pd4The S heterojunction is beneficial to the high-efficiency decomposition of lithium peroxide, and the porous carbon structure provides a good material transmission channel in the charging and discharging processes, and the experiment proves that the current density is 200 mA-g-1The specific capacity is limited to 1000 mAh.g-1May be cycled for 52 cycles.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is a SAED diagram of a hollow carbon nanoball synthesized by example 1;
FIG. 2 is a TEM image of the synthesized hollow carbon nanoball of example 1;
fig. 3 is an SEM image of the synthesized hollow carbon nanoball of example 1;
FIG. 4 is a Pd @ Pd supported catalyst synthesized in example 14TEM image of the hollow carbon nanoball of S;
FIG. 5 is a Pd @ Pd supported catalyst synthesized in example 14SEM image of the hollow carbon nanoball of S;
FIG. 6 is a Pd @ Pd supported catalyst synthesized in example 14XRD pattern of the hollow carbon nanoball of S;
FIG. 7 shows a Pd @ Pd supported catalyst synthesized in example 14An element distribution map of the hollow carbon nanosphere of S;
FIG. 8 shows a Pd @ Pd supported catalyst synthesized in example 14A nitrogen adsorption and desorption isotherm diagram of the hollow carbon nanosphere of S;
FIG. 9 shows a Pd @ Pd supported catalyst prepared in example 14The hollow carbon nanosphere of S is used for a cycle performance chart of a lithium oxygen battery.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Carbon-supported Pd prepared by the present preparation method as described in the background of the invention4The S catalyst still has the defects of small specific surface area, poor conductivity and low stability, and the defect of short cycle life of the lithium-oxygen battery in the charging and discharging processes is overcome4S hollow carbon nanospheres and a preparation method and application thereof.
In the embodiment of the invention, the Pd @ Pd is loaded4The preparation method of the hollow carbon nanosphere of S comprises the following steps:
s1, preparing hollow carbon nanospheres;
s2, in-situ preparation of palladium nanoparticles: mixing the hollow carbon nanospheres obtained in the step S1 with a divalent palladium salt solution and a hexadecyl trimethyl ammonium chloride solution, and adding a reducing agent solution to obtain a suspension of the hollow carbon nanospheres loaded with palladium nanoparticles;
s3, preparing load Pd @ Pd4Hollow carbon nanoball of S: sulfurizing the hollow carbon nanosphere loaded with palladium nanoparticles obtained in S2 in inert atmosphere to prepare Pd @ Pd4S hollow carbon nanoball.
In an embodiment of the present invention, in step S2, the divalent palladium salt includes Pd (NO)3)2、PdCl2、PdSO4·2H2O、H2PdCl4、K2PdCl4、Na2PdCl4One of (1); preferably, the divalent palladium salt is H2PdCl4。
In the embodiment of the present invention, in step S2, the reducing agent is used to reduce palladium ions on the surface of the hollow carbon nanosphere in situ to obtain palladium nanoparticles, and the reducing agent is preferably ascorbic acid.
In the embodiment of the present invention, in step S3, the sulfurization process includes mixing the hollow carbon nanoball loaded with palladium nanoparticles with a compound containing elemental sulfur, and then calcining at high temperature; the compound containing sulfur element comprises metal sulfide, polysulfide, sodium hydrosulfite and thiosulfate; the compound containing elemental sulfur is preferably sodium thiosulfate.
In the embodiment of the invention, the Pd @ Pd is loaded4The preparation method of the hollow carbon nanosphere of S specifically comprises the following steps:
s1, preparing hollow carbon nanospheres: firstly, hydrolyzing Tetraethoxysilane (TEOS) in an alcohol/water system by taking ammonia water as a catalyst to prepare a silicon dioxide ball; then, adding resorcinol and formaldehyde into the prepared silicon dioxide spheres, uniformly mixing, collecting the product, sintering at high temperature in an inert atmosphere, corroding with hydrofluoric acid, collecting the product, and drying in vacuum to obtain the hollow carbon nanospheres;
s2, in-situ preparation of palladium nanoparticles: dispersing the hollow carbon nanospheres obtained in S1 in water, performing ultrasonic treatment, and adding H2PdCl4Uniformly mixing the solution and a hexadecyl trimethyl ammonium chloride solution, and then adding an ascorbic acid solution for reaction to obtain a suspension of the hollow carbon nanospheres loaded with the palladium nanoparticles;
s3, preparing load Pd @ Pd4Hollow carbon nanoball of S: na was added to the suspension of the hollow carbon nanoball supporting palladium nanoparticles obtained in S22S2O3·5H2Continuously stirring the solution O, collecting and drying a precipitate product, and calcining the precipitate product at a high temperature in an inert atmosphere to obtain the Pd @ Pd4S hollow carbon nanoball.
In another embodiment of the present invention, in step S1, the alcohol/water system refers to a mixed solvent with a volume ratio of anhydrous ethanol to deionized water of 5-10:0.5-1.5, wherein the volume ratio range can avoid agglomeration of silica spheres, so as to ensure high dispersibility of silica spheres and maintain the diameter of the silica spheres within the range of 200-300 nm; preferably, the volume ratio of the absolute ethyl alcohol to the deionized water is 7: 1.
In another specific embodiment of the present invention, in step S1, the mass percentage concentration of the ammonia water is 18 to 35%, and within this mass percentage concentration range, the sufficient hydrolysis of ethyl orthosilicate can be achieved, the resource utilization rate can be improved, and the uniformity of the silica spheres can be maintained; preferably, the mass percentage concentration of the ammonia water is 25%.
In another embodiment of the present invention, in step S1, the mass of the resorcinol is 0.2 to 0.8g, and the mass percentage concentration of formaldehyde is 30 to 45%, within this range, the resorcinol and formaldehyde can be sufficiently reacted, and the thickness of the carbon layer can be controlled within a reasonable range; preferably, the mass of the resorcinol is 0.4g, and the mass percentage concentration of the formaldehyde is 37%.
In another embodiment of the present invention, in step S1, the inert gas includes nitrogen or argon.
In another embodiment of the present invention, in step S1, the temperature of the high-temperature sintering is 600-; preferably, the high-temperature sintering temperature is 700 ℃, and the high-temperature sintering time is 2 h.
In another embodiment of the present invention, in step S1, the mass percentage concentration of the hydrofluoric acid is 30-50%, and the hydrofluoric acid is in the mass percentage concentration range, which not only can effectively ensure that the silica sphere template is completely etched, but also can prevent the hollow carbon sphere from being etched by the hydrofluoric acid with too high concentration, resulting in collapse of the hollow carbon sphere structure; preferably, the mass percentage concentration of the hydrofluoric acid is 40%.
In another embodiment of the present invention, in step S2, the ultrasonic treatment time is 5-10min, and the hollow carbon nanospheres can be well dispersed in water within this time range; preferably, the ultrasonic time is 7 min.
In still another embodiment of the present invention, in step S2, H is2PdCl4The concentration of the solution is 5-15mmol L-1，H2PdCl4The volume of the solution is 10-25mL, and the solution can be extracted in the rangeSufficient palladium is supplied and excessive palladium is prevented to reduce the conductivity of the carbon material; preferably, said H2PdCl4The concentration of the solution was 10mmol L-1，H2PdCl4The volume of the solution was 15 mL.
In another embodiment of the present invention, in step S2, the concentration of the cetyltrimethylammonium chloride solution is 5-15mmol L-1The volume of the hexadecyl trimethyl ammonium chloride solution is 8-15 mL.
In another embodiment of the present invention, in step S2, the concentration of the ascorbic acid solution is 90 to 120mmol L-1The volume of the ascorbic acid solution is 1-4ml, and the palladium ions in the solution system can be effectively reduced on the surface of the hollow carbon nanospheres in situ in the range; preferably, the concentration of the ascorbic acid solution is 100mmol L-1The volume of the ascorbic acid solution was 2 ml.
In still another embodiment of the present invention, in step S3, the Na content is2S2O3·5H2The concentration of the O solution is 5-15mmol L-1Said Na2S2O3·5H2The volume of the O solution is 0.5-5ml, and the O solution can not only realize the full vulcanization of palladium, but also prevent excessive sulfur from etching the carbon nano material in the high-temperature section burning process; preferably, the Na is2S2O3·5H2The concentration of the O solution was 10mmol L-1Said Na2S2O3·5H2The volume of the O solution was 1 ml.
In another embodiment of the present invention, in step S3, the high-temperature calcination temperature is 600-2The carbon nanospheres are further etched by the corrosive acid gas, so that abundant holes are provided, and the specific surface area of the carbon nanospheres is favorably improved; preferably, the high-temperature calcination temperature is 800 ℃, and the sintering time is 2 h.
Conventional preparation of carbon-supported Pd4The method of S is that Pd is firstly prepared4S, and then calcining the obtained product with a carbon source at high temperature to obtain the carbon-supported Pd4The S material has small specific surface area, and the carbon layer is easy to remove Pd4S active site coverage, resulting in inefficient utilization of the active site Pd4S, severe reduction of carbon-supported Pd4The electrochemical performance of S is not beneficial to improving the cycle performance of the lithium oxygen battery. According to the implementation mode of the invention, the hollow carbon nanosphere template is prepared firstly, then in-situ reduction is carried out to obtain the palladium nanoparticles, and finally the supported Pd @ Pd is prepared by vulcanization4S hollow carbon nanoball. The unique design can ensure Pd4The S active sites are fully exposed on the surface of the carbon sphere, so that the adsorption of electrochemical active substances is facilitated, the overpotential is reduced, the electrochemical catalytic activity is improved, meanwhile, the palladium nanoparticles are reduced in situ on the surface of the carbon sphere, the bonding force between the palladium particles and the surface of the carbon sphere can be improved, and the problems of target spot falling and morphology collapse in the charging and discharging process of the battery are effectively solved.
In another embodiment of the invention, a Pd @ Pd supported catalyst is provided4S hollow carbon nanosphere adopting any one of Pd @ Pd supported on4S is prepared by the preparation method of the hollow carbon nanosphere. The load Pd @ Pd4The hollow carbon nanosphere of S takes the hollow carbon nanosphere as a carrier, palladium nanoparticles are reduced in situ on the surface of the hollow carbon nanosphere by ascorbic acid, and then Pd @ Pd evenly distributed on the hollow carbon nanosphere is obtained by sulfurization4And S, by utilizing an in-situ growth method, the binding force between the metal nano particles and the carbon substrate is enhanced, and the falling of the metal particles is effectively avoided. The Pd @ Pd supported catalyst prepared in this example4The S hollow carbon nanosphere has good oxygen reduction performance, high electrocatalysis efficiency and large specific surface area, and has potential industrial application prospect.
In another embodiment of the invention, a Pd @ Pd supported catalyst is provided4The application of the hollow carbon nanosphere of S is to load the Pd @ Pd4The hollow carbon nanospheres of S are used for catalyzing the oxygen reduction reaction of the lithium-oxygen battery. The Pd @ Pd supported catalyst prepared in this example4Hollow carbon nanosphere of SThe lithium-oxygen battery has good oxygen reduction performance, high electrocatalysis efficiency and large specific surface area, and can greatly prolong the cycle life of the lithium-oxygen battery.
In another embodiment of the invention, a lithium oxygen battery is provided, which comprises the supported Pd @ Pd as described above4S hollow carbon nanoball. The lithium oxygen cell obtained in this example was loaded with Pd @ Pd4The hollow carbon nanosphere of S is a positive electrode catalyst, and the Pd @ Pd is loaded by the uniformly distributed heterojunction particles4The hollow carbon nanosphere of the S has excellent electrocatalytic performance, and the porous spherical shell structure of the carbon matrix can provide a substance transmission channel and relieve volume change caused by product accumulation and decomposition in the charging and discharging process, so that the original structure can be still maintained in the charging and discharging process, and the cycling stability of the battery is improved.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
Load Pd @ Pd4S hollow carbon nanoball prepared by the following steps:
(1) preparation of hollow carbon nanospheres
Uniformly mixing 70mL of absolute ethyl alcohol, 10mL of deionized water and 3mL of 25% ammonia water by mass, dropwise adding 3.46mL of ethyl orthosilicate, magnetically stirring for about 15min, adding 0.4g of resorcinol and 0.56mL of 37% formaldehyde, magnetically stirring for 24h, centrifugally collecting a product, washing the product with deionized water for three times, drying the product in vacuum at 60 ℃ for 6h, and precipitating the precipitate in N2At 2 ℃ min under an atmosphere-1Heating to 700 ℃ at the heating rate, keeping the temperature for 2h, putting the obtained black powder into 50mL of hydrofluoric acid solution with the mass fraction of 40%, corroding for 3h, centrifugally washing for 5 times by deionized water, and then drying in vacuum at 60 ℃ for 12 h.
(2) Preparation H2PdCl4Solutions of
0.1774g PdCl2The solubility of the product is 0.4 mol.L when the product is dissolved in 10mL-1Stirring the mixture until the mixture is completely dissolved in the hydrochloric acid,then diluted with deionized water to a constant volume of 100mL, thereby obtaining a concentration of 10 mmol. multidot.L-1H of (A) to (B)2PdCl4A solution;
(3) in situ preparation of palladium nanoparticles
Ultrasonically dispersing 65mg of black powder obtained in the step (1) into 120mL of deionized water, and adding 15mL of 10 mmol.L-1H of (A) to (B)2PdCl4Solution and 10mL of 10 mmol. L-1Cetyl trimethyl ammonium chloride solution is magnetically stirred for 30min, 2mL of 0.1mol L is added-1The ascorbic acid solution is magnetically stirred for 10 min;
(4) preparation of Pd @ Pd4Hollow carbon nanosphere of S
Adding 1mL of the black turbid solution obtained in the step (3) with a concentration of 10 mmol.L-1Na of (2)2S2O3·5H2O solution and continuous stirring for 10h, three centrifugal washes with water, collection of product and drying at 60 ℃ for 6h, and application of the resulting black powder to N2At 5 deg.C for min under atmosphere-1Heating to 800 ℃ at a heating rate, keeping the temperature for 2 hours, and cooling along with the furnace to obtain the load Pd @ Pd4S hollow carbon nanoball.
Fig. 1 is a SAED picture of the hollow carbon nanoball synthesized in step 1 of example 1, and fig. 2 and 3 are TEM and SEM photographs thereof, respectively, which clearly show the hierarchical porous structure of the hollow spherical shell, the thickness of the spherical shell being about 20nm, and the diameter of the spherical shell being about 300 nm. FIGS. 4 and 5 are views showing the Pd @ Pd supported on the catalyst synthesized in step 4 of the process of this example4TEM and SEM pictures of the hollow carbon nanosphere of S can clearly observe Pd @ Pd from the morphology picture4The S nano particles are uniformly loaded on the hollow carbon nano spherical shell, the original appearance of the carbon matrix is not changed, and the grading porous structure is clear and visible. FIG. 6 shows Pd @ Pd as a support4The XRD spectrogram of the hollow carbon nanosphere of S clearly confirms Pd and Pd4And (4) successfully synthesizing S. FIG. 7 shows Pd @ Pd as a support4The element distribution picture of the hollow carbon nanosphere of S shows that the carbon element, the palladium element and the sulfur element are uniformly distributed. FIG. 8 shows Pd @ Pd as a support4The nitrogen adsorption and desorption isotherm and the pore distribution condition chart of the hollow carbon nanosphere of S are calculated according to the BET theory to obtain the specific surface areaUp to 162.7m2g-1The pores are mainly in the form of mesopores and macropores.
The supported Pd @ Pd obtained in example 1 is used4The hollow carbon nanoball of S was fabricated into an electrode and tested for its performance in a lithium oxygen battery as follows:
the material obtained in example 1, ketjen black and PTFE were weighed in a weight ratio of 4:4:2, then an appropriate amount of isopropanol was added, an ultrasonic dispersion was performed to form a uniformly mixed suspension, which was uniformly sprayed on round carbon paper, and vacuum-dried at 120 ℃ for 10 hours. The lithium oxygen battery for testing is a 2032 type button battery, a metal lithium sheet is taken as a negative electrode, a carbon paper sheet containing the material is taken as a positive electrode, and an electrolyte contains 1 mol.L-1LiTFSI in TEGDME, the membrane being a glass fiber. The battery assembly is carried out in a glove box filled with argon, and then the battery is placed in a pure oxygen environment at room temperature for constant-current charge and discharge test, and the test equipment is a LAND CT 2001A multi-channel battery tester. FIG. 9 shows the results of 200mA g of the material prepared in example 1 when used as a positive electrode catalyst material for a lithium oxygen battery-1Current density of 1000mAh g-1The limited specific capacity test condition of (2), which can stably cycle for 52 circles.
Example 2
(1) Preparation of hollow carbon nanospheres
Uniformly mixing 80mL of absolute ethyl alcohol, 10mL of deionized water and 3mL of ammonia water with the mass fraction of 18%, dropwise adding 3.46mL of ethyl orthosilicate, magnetically stirring for about 15min, adding 0.2g of resorcinol and 0.56mL of formaldehyde with the mass fraction of 30%, magnetically stirring for 24h, centrifugally collecting a product, washing the product with deionized water for three times, drying the product in vacuum at 60 ℃ for 6h, and precipitating the precipitate in N2At 2 deg.C/min under atmosphere-1Heating to 800 ℃ at the heating rate, keeping the temperature for 2.5h, putting the obtained black powder into 50mL of hydrofluoric acid solution with the mass fraction of 40%, corroding for 3h, centrifugally washing for 5 times by deionized water, and then drying in vacuum at 60 ℃ for 12 h.
(2) Preparation H2PdCl4Solutions of
0.1774g PdCl2The solubility of the product is 0.4 mol.L when the product is dissolved in 10mL-1Is stirred until the hydrochloric acid is completely dissolvedAfter the decomposition, the mixture was diluted with deionized water to a constant volume of 100mL, whereby a concentration of 10 mmol. multidot.L was obtained-1H of (A) to (B)2PdCl4A solution;
(3) in situ preparation of palladium nanoparticles
Ultrasonically dispersing 65mg of black powder obtained in the step (1) into 120mL of deionized water, and adding 12mL of 25 mmol.L-1H of (A) to (B)2PdCl4Solution and 10mL of 10 mmol. L-1Cetyl trimethyl ammonium chloride solution is magnetically stirred for 30min, 3mL of 0.1mol L is added-1The ascorbic acid solution is magnetically stirred for 10 min;
(4) preparation of Pd @ Pd4Hollow carbon nanosphere of S
Adding 0.5mL of 9 mmol. multidot.L into the black turbid liquid obtained in the step (3)-1Na of (2)2S2O3·5H2O solution and continuous stirring for 10h, three centrifugal washes with water, collection of product and drying at 60 ℃ for 6h, and application of the resulting black powder to N2At 5 deg.C for min under atmosphere-1Heating to 600 ℃ at a heating rate, keeping the temperature for 2 hours, and cooling along with the furnace to obtain the load Pd @ Pd4S hollow carbon nanoball.
Example 3
(1) Preparation of hollow carbon nanospheres
Uniformly mixing 70mL of absolute ethyl alcohol, 10mL of deionized water and 3mL of 35% ammonia water by mass, dropwise adding 3.46mL of ethyl orthosilicate, magnetically stirring for about 15min, adding 0.2g of resorcinol and 0.56mL of 40% formaldehyde, magnetically stirring for 24h, centrifugally collecting a product, washing the product with deionized water for three times, drying the product in vacuum at 60 ℃ for 6h, and precipitating the precipitate in N2At 2 ℃ min under an atmosphere-1Heating to 850 ℃ at the heating rate, keeping the temperature for 2 hours, putting the obtained black powder into 50mL of hydrofluoric acid solution with the mass fraction of 45%, corroding for 3 hours, centrifugally washing for 5 times by deionized water, and then drying in vacuum at 60 ℃ for 12 hours.
(2) Preparation H2PdCl4Solutions of
0.1774g PdCl2The solubility of the product is 0.4 mol.L when the product is dissolved in 10mL-1Is stirred until the hydrochloric acid is completely dissolved, and then the mixture is usedDiluting with deionized water to 100mL constant volume to obtain a concentration of 10 mmol.L-1H of (A) to (B)2PdCl4A solution;
(3) in situ preparation of palladium nanoparticles
Ultrasonically dispersing 65mg of black powder obtained in the step (1) into 120mL of deionized water, and adding 25mL of 15 mmol.L-1H of (A) to (B)2PdCl4Solution and 10mL10 mmol. multidot.L-1Cetyl trimethyl ammonium chloride solution is magnetically stirred for 30min, 3mL of 0.11mol L is added-1The ascorbic acid solution is magnetically stirred for 10 min;
(4) preparation of Pd @ Pd4Hollow carbon nanosphere of S
Adding 2.5mL of the black turbid solution obtained in the step (3) to the solution with a concentration of 12 mmol.L-1Na of (2)2S2O3·5H2O solution and continuous stirring for 10h, three centrifugal washes with water, collection of product and drying at 60 ℃ for 6h, and application of the resulting black powder to N2At 5 deg.C for min under atmosphere-1Heating to 900 ℃ at the heating rate, keeping the temperature for 2 hours, and cooling along with the furnace to obtain the load Pd @ Pd4S hollow carbon nanoball.
Example 4
(1) Preparation of hollow carbon nanospheres
Uniformly mixing 70mL of absolute ethyl alcohol, 10mL of deionized water and 3mL of 25% ammonia water by mass, dropwise adding 3.46mL of ethyl orthosilicate, magnetically stirring for about 15min, adding 0.6g of resorcinol and 0.56mL of 36% formaldehyde, magnetically stirring for 24h, centrifugally collecting a product, washing the product with deionized water for three times, drying the product in vacuum at 60 ℃ for 6h, and precipitating the precipitate in N2At 2 ℃ min under an atmosphere-1Heating to 750 ℃ at the heating rate, keeping the temperature for 2 hours, putting the obtained black powder into 50mL of hydrofluoric acid solution with the mass fraction of 50%, corroding for 3 hours, centrifugally washing for 5 times by deionized water, and then drying in vacuum at 60 ℃ for 12 hours.
(2) Preparation H2PdCl4Solutions of
0.1774g PdCl2The solubility of the product is 0.4 mol.L when the product is dissolved in 10mL-1Is stirred until the hydrochloric acid is completely dissolved, and then deionized water is used for dissolvingDiluting to 100mL constant volume, thereby obtaining a concentration of 10 mmol. L-1H of (A) to (B)2PdCl4A solution;
(3) in situ preparation of palladium nanoparticles
Ultrasonically dispersing 65mg of black powder obtained in the step (1) into 120mL of deionized water, and adding 20mL of 13 mmol.L-1H of (A) to (B)2PdCl4Solution and 8mL of 5 mmol. L-1Cetyl trimethyl ammonium chloride solution and magnetic stirring for 30min, adding 1.5mL of 0.1mol L-1The ascorbic acid solution is magnetically stirred for 10 min;
(4) preparation of Pd @ Pd4Hollow carbon nanosphere of S
Adding 5mL of 10 mmol. L to the black turbid solution obtained in the step (3)-1Na of (2)2S2O3·5H2O solution and continuous stirring for 10h, three centrifugal washes with water, collection of product and drying at 60 ℃ for 6h, and application of the resulting black powder to N2At 5 deg.C for min under atmosphere-1Heating to 850 ℃ at the heating rate, keeping the temperature for 2 hours, and cooling along with the furnace to obtain the load Pd @ Pd4S hollow carbon nanoball.
Example 5
(1) Preparation of hollow carbon nanospheres
Uniformly mixing 70mL of absolute ethyl alcohol, 10mL of deionized water and 3mL of 25% ammonia water by mass, dropwise adding 3.46mL of ethyl orthosilicate, magnetically stirring for about 15min, adding 0.4g of resorcinol and 0.56mL of 37% formaldehyde, magnetically stirring for 24h, centrifugally collecting a product, washing the product with deionized water for three times, drying the product in vacuum at 60 ℃ for 6h, and precipitating the precipitate in N2At 2 ℃ min under an atmosphere-1Heating to 750 ℃ at the heating rate, keeping the temperature for 2 hours, putting the obtained black powder into 50mL of hydrofluoric acid solution with the mass fraction of 40%, corroding for 3 hours, centrifugally washing for 5 times by deionized water, and then drying in vacuum at 60 ℃ for 12 hours.
(2) Preparation H2PdCl4Solutions of
0.1774g PdCl2The solubility of the product is 0.4 mol.L when the product is dissolved in 10mL-1Is stirred until the hydrochloric acid is completely dissolved, and then is diluted to 100mL by deionized waterConstant volume, thereby obtaining a concentration of 10 mmol.L-1H of (A) to (B)2PdCl4A solution;
(3) in situ preparation of palladium nanoparticles
Ultrasonically dispersing 65mg of black powder obtained in the step (1) into 120mL of deionized water, and adding 16mL of 10 mmol.L-1H of (A) to (B)2PdCl4Solution and 15mL of 5 mmol. L-1Cetyl trimethyl ammonium chloride solution is magnetically stirred for 30min, 2mL of 0.1mol L is added-1The ascorbic acid solution is magnetically stirred for 10 min;
(4) preparation of Pd @ Pd4Hollow carbon nanosphere of S
Adding 0.5mL of a solution having a concentration of 20 mmol.L to the black turbid solution obtained in the step (3)-1Na of (2)2S2O3·5H2O solution and continuous stirring for 10h, three centrifugal washes with water, collection of product and drying at 60 ℃ for 6h, and application of the resulting black powder to N2At 5 deg.C for min under atmosphere-1Heating to 850 ℃ at the heating rate, keeping the temperature for 2 hours, and cooling along with the furnace to obtain the load Pd @ Pd4S hollow carbon nanoball.
Example 6
(1) Preparation of hollow carbon nanospheres
Uniformly mixing 70mL of absolute ethyl alcohol, 10mL of deionized water and 3mL of 25% ammonia water by mass, dropwise adding 3.46mL of ethyl orthosilicate, magnetically stirring for about 15min, adding 0.4g of resorcinol and 0.56mL of 40% formaldehyde, magnetically stirring for 24h, centrifugally collecting a product, washing the product with deionized water for three times, drying the product in vacuum at 60 ℃ for 6h, and precipitating the precipitate in N2At 2 ℃ min under an atmosphere-1Heating to 800 ℃ at the heating rate, keeping the temperature for 2 hours, putting the obtained black powder into 50mL of hydrofluoric acid solution with the mass fraction of 40%, corroding for 3 hours, centrifugally washing for 5 times by deionized water, and then drying in vacuum at 60 ℃ for 12 hours.
(2) Preparation H2PdCl4Solutions of
0.1774gPdCl2The solubility of the product is 0.4 mol.L when the product is dissolved in 10mL-1Is stirred until the hydrochloric acid is completely dissolved, and then diluted to 100mL constant volume by deionized water, thereby obtaining the solutionThe concentration obtained was 10 mmol. L-1H of (A) to (B)2PdCl4A solution;
(3) in situ preparation of palladium nanoparticles
Ultrasonically dispersing 65mg of black powder obtained in the step (1) into 120mL of deionized water, and adding 20mL of 7 mmol.L-1H2PdCl4Solution and 15mL of 15 mmol. L-1Cetyl trimethyl ammonium chloride solution is magnetically stirred for 30min, 2mL of 0.1mol L is added-1The ascorbic acid solution is magnetically stirred for 10 min;
(4) preparation of Pd @ Pd4Hollow carbon nanosphere of S
Adding 0.5mL of a solution having a concentration of 10 mmol.L to the black turbid solution obtained in the step (3)-1Na of (2)2S2O3·5H2O solution and continuous stirring for 10h, three centrifugal washes with water, collection of product and drying at 60 ℃ for 6h, and application of the resulting black powder to N2At 5 deg.C for min under atmosphere-1Heating to 850 ℃ at the heating rate, keeping the temperature for 2 hours, and cooling along with the furnace to obtain the load Pd @ Pd4S hollow carbon nanoball.
Example 7
(1) Preparation of hollow carbon nanospheres
Uniformly mixing 70mL of absolute ethyl alcohol, 10mL of deionized water and 3mL of 25% ammonia water by mass, dropwise adding 3.46mL of ethyl orthosilicate, magnetically stirring for about 15min, adding 0.4g of resorcinol and 0.56mL of 37% formaldehyde, magnetically stirring for 24h, centrifugally collecting a product, washing the product with deionized water for three times, drying the product in vacuum at 60 ℃ for 6h, and precipitating the precipitate in N2At 2 ℃ min under an atmosphere-1Heating to 800 ℃ at the heating rate, keeping the temperature for 2 hours, putting the obtained black powder into 50mL of hydrofluoric acid solution with the mass fraction of 40%, corroding for 3 hours, centrifugally washing for 5 times by deionized water, and then drying in vacuum at 60 ℃ for 12 hours.
(2) Preparation H2PdCl4Solutions of
0.1774g PdCl2The solubility of the product is 0.4 mol.L when the product is dissolved in 10mL-1Is stirred until the solution is completely dissolved, and then diluted to 100mL constant volume by deionized water, thereby obtaining the concentration of 10 mmol.L-1H of (A) to (B)2PdCl4A solution;
(3) in situ preparation of palladium nanoparticles
Ultrasonically dispersing 65mg of black powder obtained in the step (1) into 120mL of deionized water, and adding 20mL of 10 mmol.L-1H of (A) to (B)2PdCl4Solution and 10mL of 10 mmol. L-1Cetyl trimethyl ammonium chloride solution is magnetically stirred for 30min, 2mL of 0.1mol L is added-1The ascorbic acid solution is magnetically stirred for 10 min;
(4) preparation of Pd @ Pd4Hollow carbon nanosphere of S
Adding 0.5mL of a solution having a concentration of 20 mmol.L to the black turbid solution obtained in the step (3)-1Na of (2)2S2O3·5H2O solution and continuous stirring for 10h, three centrifugal washes with water, collection of product and drying at 60 ℃ for 6h, and application of the resulting black powder to N2At 5 deg.C for min under atmosphere-1Heating to 850 ℃ at the heating rate, keeping the temperature for 2 hours, and cooling along with the furnace to obtain the load Pd @ Pd4S hollow carbon nanoball.
Test example 8
(1) Preparation of hollow carbon nanospheres
Uniformly mixing 70mL of absolute ethyl alcohol, 10mL of deionized water and 3mL of 25% ammonia water by mass, dropwise adding 3.46mL of ethyl orthosilicate, magnetically stirring for about 15min, adding 0.4g of resorcinol and 0.56mL of 37% formaldehyde, magnetically stirring for 24h, centrifugally collecting a product, washing the product with deionized water for three times, drying the product in vacuum at 60 ℃ for 6h, and precipitating the precipitate in N2At 2 ℃ min under an atmosphere-1Heating to 700 ℃ at the heating rate, keeping the temperature for 2h, putting the obtained black powder into 50mL of hydrofluoric acid solution with the mass fraction of 40%, corroding for 3h, centrifugally washing for 5 times by deionized water, and then drying in vacuum at 60 ℃ for 12 h.
(2) Preparation H2PdCl4Solutions of
0.1774g PdCl2The solubility of the product is 0.4 mol.L when the product is dissolved in 10mL-1Is stirred until the solution is completely dissolved, and then diluted to 100mL constant volume by deionized water, thereby obtaining the concentration of 10 mmol.L-1H of (A) to (B)2PdCl4A solution;
(3) in situ preparation of palladium nanoparticles
Ultrasonically dispersing 65mg of black powder obtained in the step (1) into 120mL of deionized water, and adding 15mL of 10 mmol.L-1H of (A) to (B)2PdCl4The solution was magnetically stirred for 30min, 2mL of 0.1mol L was added-1The ascorbic acid solution is magnetically stirred for 10 min;
(4) preparation of Pd @ Pd4Hollow carbon nanosphere of S
Adding 1mL of the black turbid solution obtained in the step (3) with a concentration of 10 mmol.L-1Na of (2)2S2O3·5H2O solution and continuous stirring for 10h, three centrifugal washes with water, collection of product and drying at 60 ℃ for 6h, and application of the resulting black powder to N2At 5 deg.C for min under atmosphere-1Heating to 800 ℃ at a heating rate, keeping the temperature for 2 hours, and cooling along with the furnace to obtain the load Pd @ Pd4S hollow carbon nanoball.
The supported Pd @ Pd obtained in test example 8 was used4The hollow carbon nanoball of S was fabricated into an electrode and tested for its performance in a lithium oxygen battery as follows:
the material obtained in example 1, ketjen black and PTFE were weighed in a weight ratio of 4:4:2, then an appropriate amount of isopropanol was added, an ultrasonic dispersion was performed to form a uniformly mixed suspension, which was uniformly sprayed on round carbon paper, and vacuum-dried at 120 ℃ for 10 hours. The lithium oxygen battery for testing is a 2032 type button battery, a metal lithium sheet is taken as a negative electrode, a carbon paper sheet containing the material is taken as a positive electrode, and an electrolyte contains 1 mol.L-1LiTFSI in TEGDME, the membrane being a glass fiber. The battery assembly is carried out in a glove box filled with argon, and then the battery is placed in a pure oxygen environment at room temperature for constant-current charge and discharge test, and the test equipment is a LAND CT 2001A multi-channel battery tester.
Test example 8 the obtained material was used as a positive electrode catalyst material for a lithium oxygen battery at 200mA g-1Current density of 1000mAh g-1The test can stably circulate for 12 circles under the specific capacity limiting test condition. The charge-discharge cycle stability was much lower than that of the battery of example 1, demonstrating hexadecyltrimethylammonium chlorideThe solution plays an important role in improving the performance of the lithium oxygen battery.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (25)

1. Load Pd @ Pd4The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps:
s1, preparing hollow carbon nanospheres: firstly, hydrolyzing tetraethoxysilane in an alcohol/water system by taking ammonia water as a catalyst to prepare silicon dioxide spheres; then, adding resorcinol and formaldehyde into the prepared silicon dioxide spheres, uniformly mixing, collecting the product, sintering at high temperature in an inert atmosphere, corroding with hydrofluoric acid, collecting the product, and drying in vacuum to obtain the hollow carbon nanospheres;
s2, preparing palladium nanoparticles in situ: dispersing the hollow carbon nanospheres obtained in S1 in water, performing ultrasonic treatment, and adding H2PdCl4 Uniformly mixing the solution and a hexadecyl trimethyl ammonium chloride solution, and then adding an ascorbic acid solution for reaction to obtain a suspension of the hollow carbon nanospheres loaded with the palladium nanoparticles;
s3 preparation of load Pd @ Pd4Hollow carbon nanoball of S: na was added to the suspension of the hollow carbon nanoball supporting palladium nanoparticles obtained in S22S2O3•5H2Continuously stirring the O solution, collecting and drying a precipitate product, and calcining the precipitate product at a high temperature in an inert atmosphere to obtain the negative Pd @ Pd4S hollow carbon nanoball.
2. The Pd @ Pd supported catalyst as claimed in claim 14Hollow of SThe preparation method of the carbon nanosphere is characterized by comprising the following steps:
in step S1, the alcohol/water system refers to absolute ethyl alcohol and deionized water in a volume ratio of
5-10: 0.5-1.5.
3. The Pd @ Pd supported catalyst as claimed in claim 24The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: the volume ratio of the absolute ethyl alcohol to the deionized water is 7: 1.
4. The Pd @ Pd supported catalyst as claimed in claim 14The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: in step S1, the mass percentage concentration of the ammonia water is 18-35%.
5. The Pd @ Pd supported catalyst as claimed in claim 44The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: the mass percentage concentration of the ammonia water is 25%.
6. The Pd @ Pd supported catalyst as claimed in claim 14The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: in step S1, the mass of the resorcinol is 0.2-0.8g, and the mass percentage concentration of the formaldehyde is 30-45%.
7. The Pd @ Pd supported catalyst as claimed in claim 64The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: the mass of the resorcinol is 0.4g, and the mass percentage concentration of the formaldehyde is 37%.
8. The Pd @ Pd supported catalyst as claimed in claim 14The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: in step S1, the inert atmosphere includes nitrogen or argon.
9. The Pd @ Pd supported catalyst as claimed in claim 14The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: step (ii) ofIn S1, the high-temperature sintering temperature is 600-900 ℃, and the high-temperature sintering time is 1-3 h.
10. The Pd @ Pd supported catalyst as claimed in claim 94The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: the high-temperature sintering temperature is 700 ℃, and the high-temperature sintering time is 2 h.
11. The Pd @ Pd supported catalyst as claimed in claim 14The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: in step S1, the hydrofluoric acid has a mass percentage concentration of 30-50%.
12. The Pd @ Pd supported as claimed in claim 114The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: the mass percentage concentration of the hydrofluoric acid is 40%.
13. The Pd @ Pd supported catalyst as claimed in claim 14The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: in step S2, the ultrasonic treatment time is 5-10 min.
14. The Pd @ Pd supported as claimed in claim 134The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: the ultrasonic time is 7 min.
15. The Pd @ Pd supported catalyst as claimed in claim 14The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: in step S2, H2PdCl4 The concentration of the solution is 5-15mmol L-1, H2PdCl4The volume of the solution was 10-25 mL.
16. The Pd @ Pd supported as claimed in claim 154The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: said H2PdCl4The concentration of the solution was 10mmol L-1，
H2PdCl4The volume of the solution was 15 mL.
17. The Pd @ Pd supported catalyst as claimed in claim 14The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: in step S2, the concentration of the ascorbic acid solution is 90-120mmol L-1And the volume of the ascorbic acid solution is 1-4 ml.
18. The Pd @ Pd supported as claimed in claim 174The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: the concentration of the ascorbic acid solution is 100mmol L-1The volume of the ascorbic acid solution was 2 ml.
19. The Pd @ Pd supported catalyst as claimed in claim 14The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps:
in step S3, the Na2S2O3•5H2The concentration of the O solution is 5-15mmol L-1Said Na2S2O3•5H2The volume of the O solution is 0.5-5 ml.
20. The Pd @ Pd supported as claimed in claim 194The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: the Na is2S2O3•5H2The concentration of the O solution was 10mmol L-1Said Na2S2O3•5H2The volume of the O solution was 1 ml.
21. The Pd @ Pd supported catalyst as claimed in claim 14The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: in step S3, the temperature of the high-temperature calcination is 600-900 ℃, and the sintering time is 1-3 h.
22. The Pd @ Pd supported as claimed in claim 214The preparation method of the S hollow carbon nanosphere is characterized by comprising the following steps: the high temperature calcinationThe temperature of (2) is 800 ℃ and the sintering time is 2 h.
23. Load Pd @ Pd4S hollow carbon nanosphere, characterized in that the Pd @ Pd is supported4Hollow carbon nanosphere of S using the Pd @ Pd supported as described in any of claims 1-224S is prepared by the preparation method of the hollow carbon nanosphere.
24. Load Pd @ Pd4Use of the hollow carbon nanosphere of S, wherein the Pd @ Pd supported by the catalyst of claim 234The hollow carbon nanospheres of S are used for catalyzing the oxygen reduction reaction of the lithium-oxygen battery.
25. A lithium oxygen cell comprising the supported Pd @ Pd of claim 234S hollow carbon nanoball.
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