A High-Throughput Laser Synthesis Method and Application of Graphene-Supported Nanoparticles

Abstract

A high-throughput laser synthesis method and application of graphene-supported nanoparticles, belonging to the fields of nanomaterials and electrochemical technologies. The synthesis method includes the following steps: S1: In-situ conversion is carried out by using a laser to scratch a polyimide polymer film or a polyethyleneimine polymer film for the first time to obtain a graphene substrate; S2: Subsequently, a metal precursor salt solution is dropped onto the graphene substrate, and after drying treatment, laser scratching is carried out for the second time to obtain graphene-supported nanoparticles. The graphene-supported nanoparticles are used as the positive electrode material of a Li-CO2 battery, and it includes the following steps: The graphene-supported nanoparticles and a binder are mixed evenly at a mass ratio of (8-9):(1-2) to obtain a mixture; Subsequently, an NMP solvent is dropped into the mixture and ground to obtain a slurry; The slurry is dropped onto carbon paper and dried to obtain the positive electrode of the Li-CO2 battery.

Description

Technical Field

[0001] The present invention belongs to the technical fields of nanomaterials and electrochemistry, and particularly relates to a high-throughput laser synthesis method and application of graphene-supported nanoparticles. Background Art

[0002] The reduction and effective recycling of greenhouse gas CO2 have attracted wide attention. There are mainly two ways for the effective utilization of CO2: (1) converting CO2 into carbon-containing fuels with economic benefits, such as carbon monoxide, ethylene, ethanol, etc.; (2) using CO2 gas as the positive electrode reactant to form a lithium-carbon dioxide (Li-CO2) battery to provide electric energy. The Li-CO2 battery has made great progress in the past decade and has great commercial application potential, but there are still many problems with the current Li-CO2 battery, such as the lack of high-efficiency and stable positive electrode materials.

[0003] The positive electrode material, as the core of the Li-CO2 battery, plays a role in adsorbing CO2 on the one hand and can effectively improve the reaction kinetics on the other hand, mainly manifested as reducing the overpotential of the battery reaction and improving the cycle performance of the battery. High-efficiency positive electrode materials have the advantages of large specific surface area, high catalytic activity, strong cycle stability, and good electrical conductivity. The current positive electrode materials applied to Li-CO2 batteries include noble metal-based materials, transition metal-based materials, and carbon-based materials, etc. The main preparation methods of the above Li-CO2 battery positive electrode materials are hydrothermal method, chemical vapor deposition method, roasting method, and liquid phase reduction method, etc. The disadvantages of these traditional methods are long preparation time (more than 10 hours), low yield (only one material can be prepared at a time), and small output (less than 1 kg). With the rapid development of nanotechnology in recent years, some relatively new nanometer preparation methods have also been proposed, such as microwave method, induction heating method, and electron beam heating method, etc. Although the above new preparation methods have the advantages of instantaneous heating and cooling and uniform heating, they also have the disadvantage of low yield.

[0004] As a new type of rapid material preparation technology, the laser scribing method can directly in-situ convert a series of polymers such as polyimide into porous graphene under environmental conditions, with a relatively high yield and excellent crystallization quality. However, pure graphene materials usually have poor battery catalytic activity, so it is necessary to load nanoparticles with high catalytic activity and corresponding high-throughput preparation methods. Summary of the Invention

[0005] In order to overcome the above-mentioned disadvantages of the prior art, the purpose of the present invention is to provide a high-throughput laser synthesis method and application of graphene-supported nanoparticles. The synthesis method can obtain graphene-supported nanoparticles with high catalytic activity within an extremely short time (0 - 5 ms), and has the advantages of high-throughput large-scale preparation and highly adjustable composition.

[0006] To achieve the above object, the present invention is implemented by the following technical solutions:

[0007] The present invention provides a high-throughput laser synthesis method for graphene-supported nanoparticles, comprising the following steps:

[0008] S1: Using a laser to first scratch a polyimide polymer film or a polyethyleneimine polymer film for in-situ conversion to obtain a graphene substrate;

[0009] S2: Subsequently, dropping a metal precursor salt solution onto the graphene substrate, and after drying, performing a second laser scratch to obtain graphene-supported nanoparticles.

[0010] Further in the present invention, in S2, the concentration of the metal precursor salt solution is 0.01M to 1M;

[0011] The precursor salt in the metal precursor salt solution is any one or any combination of nickel nitrate hexahydrate, iron nitrate nonahydrate, cobalt nitrate hexahydrate, manganese chloride tetrahydrate, palladium chloride, ruthenium chloride, zinc chloride, copper chloride dihydrate, chromium chloride hexahydrate, molybdenum chloride, vanadium chloride, rhodium chloride hydrate, stannous chloride dihydrate, chloroplatinic acid hexahydrate, chloroauric acid tetrahydrate, ruthenium chloride trihydrate, silver nitrate, osmium chloride, iridium trichloride hydrate, and rhenium chloride.

[0012] Further in the present invention, in S1, the thickness of the polyimide polymer film or the polyethyleneimine polymer film is 20 to 200 μm.

[0013] Further in the present invention, the area of the first laser scratch and the second laser scratch is (1 to 100) × (1 to 100) cm 2 .

[0014] Further in the present invention, in S2, the drying time is 10 to 24 h, and the drying temperature is 25 to 30 °C.

[0015] Further in the present invention, the laser power of the first laser scratch and the second laser scratch is 9W - 30W, and the laser rate of the first laser scratch and the second laser scratch is 10 2 ~10 4 mm / s.

[0016] Further in the present invention, in S2, the volume dosage of the precursor salt solution is 80 to 10000 μL, and the dropping method is dropping with a manual pipette or dropping with an automatic sampling system.

[0017] The present invention also provides an application of graphene-supported nanoparticles prepared by a high-throughput laser synthesis method, wherein the graphene-supported nanoparticles are used as the cathode material of a Li-CO2 battery.

[0018] Furthermore, in the present invention, the process of using the graphene-supported nanoparticles as the cathode material of a Li-CO2 battery includes the following steps:

[0019] Mix the graphene-supported nanoparticles and the binder polyvinylidene fluoride evenly at a mass ratio of (8-9):(1-2) to obtain a mixture;

[0020] Mix the mixture with NMP solvent and then grind it to obtain a slurry;

[0021] Drop the slurry onto carbon paper and dry it to obtain the cathode of the Li-CO2 battery.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The present invention discloses a high-throughput laser synthesis method for graphene-supported nanoparticles. By using secondary laser scribing on porous graphene loaded with precursor salt solution, graphene-supported nanoparticles with high catalytic activity, including noble metal nanoparticles, alloy nanoparticles, and oxide nanoparticles, etc., can be obtained in an extremely short time (0-5 ms). Due to the diversity of precursor material selection and the fact that laser scribing can prepare multiple materials simultaneously, it also has the advantages of high throughput and large-scale preparation. The method of using laser rapid scribing to prepare graphene-supported nanoparticles in two steps. The purpose of the first scribing in the two scribings is to scribe the PI film to obtain graphene, which serves as the conductive agent in the cathode material. The second scribing is on the metal precursor salt on the graphene to obtain nanoparticles with high catalytic activity. These nanoparticles play a key role in reducing the overpotential, increasing the amplification capacity, and improving the cycle stability in battery performance, thereby further significantly improving battery performance. The metal precursor salt solution obtains nanoparticles with different catalytic activities during the second scribing, and these nanoparticles will exhibit different battery performances. The secondary laser scribing method has the advantages of instantaneous high temperature, high throughput, and in-situ preparation. The obtained cathode material has the advantages of large specific surface area, good conductivity, and high stability. The graphene-supported Pd nanoparticles prepared by laser scribing twice exhibit an extremely low overpotential (0.31 V / 50 mA / g), a high discharge capacity (>10000 mAh / g), and a long cycle life (35 cycles / 1400 h), showing excellent battery performance. Description of the Drawings

[0024] Figure 1 It is the SEM morphology diagram of the graphene-supported nanoparticles prepared by the synthesis method of the present invention;

[0025] Figure 2 XRD spectrum of the graphene-supported nanoparticles of the present invention;

[0026] Figure 3 Figures (a) and (b) in the middle are respectively the TEM morphology and high-resolution image of the graphene-supported nanoparticles of the present invention;

[0027] Figure 4 Initial charge-discharge curve of the graphene-supported nanoparticles of the present invention as the cathode material of a Li-CO2 battery at different current densities;

[0028] Figure 5 Discharge capacity curve of the graphene-supported nanoparticles of the present invention as the cathode material of a Li-CO2 battery at a current density of 100 mA / g and a cut-off voltage of 2 V;

[0029] Figure 6 Cycling curve of the graphene-supported nanoparticles of the present invention as the cathode material of a Li-CO2 battery at a current density of 50 mA / g and a cut-off capacity of 1000 mAh / g. Detailed implementation manners

[0030] To enable those skilled in the art to understand the features and effects of the present invention, the following provides a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein shall have the ordinary meaning understood by those skilled in the art for the present invention. In case of conflict, the definition in this specification shall prevail.

[0031] The theories or mechanisms described and disclosed herein, whether correct or incorrect, shall not limit the scope of the present invention in any way, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0032] In this article, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are only for the sake of brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be regarded as having covered and specifically disclosed all possible sub-ranges and individual numerical values (including integers and fractions) within the range.

[0033] In this article, unless otherwise specified, the terms "comprising", "including", "containing", "having", or similar expressions cover the meanings of "consisting of" and "consisting essentially of". For example, "A comprises a" covers the meanings of "A comprises a and others" and "A only comprises a".

[0034] In this document, for the sake of brevity of description, all possible combinations of all technical features in each implementation or embodiment are not described. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation or embodiment can be combined arbitrarily, and all possible combinations should be considered to be within the scope described in this specification.

[0035] The present invention provides a high-throughput laser synthesis method and application of graphene-supported nanoparticles.

[0036] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0037] Conventional instrument equipment in the art is used in the following embodiments. For the experimental methods without specific conditions noted in the following embodiments, they are usually carried out under conventional conditions or according to the conditions recommended by the manufacturer. Various raw materials are used in the following embodiments. Unless otherwise stated, commercially available products are used, and their specifications are conventional specifications in the art. In the specification of the present invention and the following embodiments, unless otherwise specified, "%" represents weight percentage, "parts" represents weight parts, and the ratio represents weight ratio.

[0038] This patent provides a high-throughput laser synthesis method of graphene-supported nanoparticles, including the following steps:

[0039] First, a laser engraver is used to scratch a polyimide (PI) polymer film or a polyethyleneimine polymer film for in-situ transformation to obtain a graphene substrate. Subsequently, metal precursor salt solutions with different components are dropped onto the graphene substrate obtained in-situ. Finally, the laser engraver is used for secondary scratching to obtain graphene-supported nanoparticles.

[0040] The graphene-supported nanoparticles are used as a cathode material and applied in a Li-CO2 battery.

[0041] The specific steps of the above method are as follows:

[0042] 1) A polyimide film or a polyethyleneimine polymer film with a thickness of 20 - 200 μm is adhered to a glass slide through double-sided tape, and the surface is wiped with deionized water and absolute ethanol to prevent impurity contamination.

[0043] 2) A laser engraver equipped with a 10.6 μm CO2 laser is used to scratch the polyimide film or the polyethyleneimine polymer film, and the scratched area is (1 - 100) × (1 - 100) cm 2, the laser power for the first laser scribing and the second laser scribing is 9W - 30W, and the laser speed for the first laser scribing and the second laser scribing is 10 2 ~10 4 mm / s.

[0044] 3) Prepare aqueous solutions of various precursor salts with different concentrations (0.01M - 1M). The precursor salts are any one or any combination of nickel nitrate hexahydrate (Ni(NO3)2·6H2O), iron nitrate nonahydrate (Fe(NO3)3·9H2O), cobalt nitrate hexahydrate (Co(NO3)3·6H2O), manganese chloride tetrahydrate (MnCl2·4H2O), palladium chloride (PdCl2), ruthenium chloride (RuCl3), zinc chloride (ZnCl2), copper chloride dihydrate (CuCl2·2H2O), chromium chloride hexahydrate (CrCl2·6H2O), molybdenum chloride (MoCl5), vanadium chloride (VCl3), rhodium chloride hydrate (RhCl3·xH2O), tin chloride dihydrate (SnCl2·2H2O), chloroplatinic acid hexahydrate (H2PtCl6·6H2O), chloroauric acid tetrahydrate (HAuCl4·4H2O), ruthenium chloride trihydrate (RuCl3·3H2O), silver nitrate (AgNO3), osmium chloride (OsCl3), iridium chloride hydrate (IrCl3·3H2O) and rhenium chloride (ReCl3).

[0045] Ultrasonically treat the prepared solution for 10 - 30 min.

[0046] 4) Slowly add 80 - 10000 μL of the precursor salt solution to the graphene substrate, then place it in a vacuum dryer for drying. The drying time is 10 - 24 h, and the drying temperature is room temperature or 25 - 30°C. The dropping method is dropping with a manual pipette or an automatic sampling system.

[0047] 5) After drying, take out the glass slide and use a laser engraving machine equipped with a 10.6 μm CO2 laser to scribe the graphene substrate loaded with the precursor salt. The scribing area is (1 - 100) × (1 - 100) cm 2 , the laser power is 9W - 30W, and the laser speed is 10 2 ~10 4 mm / s to obtain the positive electrode material.

[0048] The process of using the graphene - loaded nanoparticles as the positive electrode material in a Li - CO2 battery is as follows:

[0049] The obtained positive electrode material is mixed with the binder polyvinylidene fluoride (PVDF) at a mass ratio of (8-9):(1-2) to obtain a mixture. Subsequently, the mixture is uniformly dispersed in NMP organic solvent. The mixture is mixed with 500-1000 μL of NMP solvent and ground for 30-40 min to obtain a slurry. Subsequently, according to different loading requirements, 20-500 μL of the slurry is dropped onto carbon paper with a diameter of 12-16 mm, and vacuum dried at 100 °C for 24 h to dry the solvent, obtaining the positive electrode of the Li-CO2 battery.

[0050] To more clearly illustrate the technical solutions of the present invention, the drawings required for use in the experimental method will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention.

[0051] Example 1

[0052] The solution components and concentrations are as follows:

[0053] 0.05 M PdCl2 solution

[0054] The preparation process of the graphene-supported Pd nanoparticle material:

[0055] The commercial PI film is adhered to the glass slide through double-sided tape, and then the adhered PI film is placed in a CO2 laser engraving machine for the first scribing. The laser power during the scribing process is 24 W, the scanning speed is 10 3 mm / s, and the scribing area is 2.5×2.5 cm 2 , obtaining a graphene substrate. 80 μL of PdCl2 solution is dropped onto the obtained graphene substrate and dried in a vacuum at 25 °C for 10 h. Finally, the graphene substrate is laser scribed again under the CO2 laser engraving machine with a laser power of 5 W and a laser rate of 10 3 mm / s, obtaining the graphene-supported Pd nanoparticle material.

[0056] After the preparation process is completed, the binder is mixed to obtain a slurry, the battery is assembled, and the battery performance is tested, including the following steps:

[0057] 1) The obtained material is mixed with PVDF at a ratio of 9:1, uniformly dispersed in NMP organic solvent. The mixture is mixed with 700 μL of NMP solvent and ground for 30 min to obtain a slurry. Subsequently, 20 μL of the slurry is dropped onto carbon paper with a diameter of 12 mm and vacuum dried at 100 °C for 24 h to obtain the positive electrode of the Li-CO2 battery.

[0058] 2) In the glove box filled with argon, an all-solid-state battery is assembled in the order of the positive electrode case, the positive electrode, the separator, the metallic Li negative electrode, the gasket, the spring piece, and the negative electrode case. The battery model is CR2032.

[0059] 3) The battery tests were completed using a Land battery tester. The performance tests included overpotential tests, capacity tests, and cycling stability tests.

[0060] Example 2:

[0061] The solution components and concentrations were as follows:

[0062] 0.01 M MnCl2·4H2O solution

[0063] The preparation process of the graphene-supported MnO nanoparticle material:

[0064] The commercial PI film was adhered to the glass slide with double-sided tape, and then the adhered PI film was placed in a CO2 laser engraver for the first scribing. The laser power during the scribing process was 15 W, the scanning speed was 4×10 3 mm / s, and the scribing area was 2.5×2.5 cm 2 , and the scribing area was 100×100 cm 2 , to obtain a graphene substrate. 10 mL of the MnCl2·4H2O solution was dropped onto the obtained graphene substrate and dried in a vacuum at 30 °C for 20 h. Finally, the graphene substrate was laser scribed again using a CO2 laser engraver with a laser power of 16 W and a laser rate of 5×10 2 mm / s, to obtain the graphene-supported MnO nanoparticle material.

[0065] After the preparation process was completed, a slurry was obtained by mixing the binder, and a battery was assembled and its performance was tested, including the following steps:

[0066] 1) The obtained material was mixed with PVDF in a ratio of 9:1, uniformly dispersed in NMP organic solvent. The mixture was mixed with 500 μL of NMP solvent and ground for 30 min to obtain a slurry. Subsequently, 20 μL of the slurry was drop-coated onto a carbon paper with a diameter of 1 mm and dried in a vacuum at 100 °C for 24 h to obtain the positive electrode of the Li-CO2 battery.

[0067] 2) A coin cell was assembled in a glove box filled with argon in the order of the positive electrode case, positive electrode, separator, metallic Li negative electrode, gasket, shrapnel, and negative electrode case. The battery model was CR2032.

[0068] 3) The battery tests were completed using a Land battery tester. The performance tests included overpotential tests, capacity tests, and cycling stability tests.

[0069] Example 3:

[0070] The solution components and concentrations were as follows:

[0071] 0.1 M Fe(NO3)2·H2O and 0.1 M Co(NO3)2·6H2O solutions

[0072] The preparation process of the graphene-supported FeCo alloy nanoparticles material:

[0073] Attach the commercial PI film to the glass slide with double-sided tape, and then place the attached PI film in a CO2 laser engraving machine for the first engraving. The laser power during the engraving process is 19 W, the laser speed is 8×10 2 mm / s, and the engraving area is 70×70 cm 2 , to obtain a graphene substrate. Take 4 mL of the mixed solution of Fe(NO3)2·9H2O and Co(NO3)2·6H2O and titrate it onto the obtained graphene substrate, and dry it in a vacuum at 27 °C for 24 h. Finally, use the CO2 laser engraving machine to engrave the graphene substrate again. The laser power is 3 W, and the laser speed is 8×10 3 mm / s, and the graphene-supported FeCo alloy nanoparticles material is obtained.

[0074] After the preparation process is completed, a slurry is obtained by mixing binders, and battery performance tests are carried out, including the following steps:

[0075] 1) Mix the obtained material with PVDF in a ratio of 8:2, and disperse it evenly in NMP organic solvent. The mixture is mixed with 900 μL of NMP solvent and ground for 35 min to obtain a slurry. Subsequently, take 20 μL of the slurry and drop-coat it onto a carbon paper with a diameter of 12 mm, and dry it in a vacuum at 100 °C for 24 h to obtain the positive electrode of the Li-CO2 battery.

[0076] 2) Assemble a button battery in a glove box filled with argon in the order of the positive electrode case, the positive electrode, the separator, the metallic Li negative electrode, the gasket, the spring piece, and the negative electrode case. The battery model is CR2032.

[0077] 3) The battery test is completed by a Land battery tester, and the performance tests include overpotential test, capacity test, and cycle stability.

[0078] Example 4:

[0079] The solution components and concentrations are as follows:

[0080] 1 M Fe(NO3)2·9H2O and 1 M PdCl2 solutions

[0081] The preparation process of the graphene-supported PdFe alloy nanoparticles material:

[0082] Attach a commercial PI film to a glass slide with double-sided tape, and then place the attached PI film in a CO2 laser engraving machine for the first scribing. The laser power during scribing is 14 W, and the laser rate is 4×10 3 mm / s, and the scribing area is 20×20 cm 2 , obtaining a graphene substrate. Titrate 800 μL of the mixed solution of Fe(NO3)2·9H2O and PdCl2 onto the obtained graphene substrate, and dry it in a vacuum at 28 °C for 10 h. Finally, use a CO2 laser engraving machine to perform laser scribing on the graphene substrate again. The laser power is 7 W, and the laser rate is 10 4 mm / s, and the graphene-supported PdFe nanoparticle material is obtained.

[0083] After the preparation process is completed, a slurry is obtained by mixing the binder, the battery is assembled, and the battery performance is tested, including the following steps:

[0084] 1) Mix the obtained material with PVDF in a ratio of 9:1, and disperse it evenly in NMP organic solvent. The mixture is mixed with 1000 μL of NMP solvent and ground for 30 min to obtain a slurry. Subsequently, take 20 μL of the slurry and drop-coat it onto a carbon paper with a diameter of 12 mm, and dry it in a vacuum at 100 °C for 24 h to obtain the positive electrode of the Li-CO2 battery.

[0085] 2) Assemble a button battery in the order of the positive electrode case, the positive electrode, the separator, the metallic Li negative electrode, the gasket, the spring piece, and the negative electrode case in a glove box filled with argon. The battery model is CR2032.

[0086] 3) The battery test is completed by a Land battery tester. The performance test includes overpotential test, capacity test, and cycle stability.

[0087] Example 5:

[0088] The solution components and concentrations are as follows:

[0089] 0.8 M AgNO3 and 0.2 M IrCl3·3H2O solution

[0090] The preparation process of the graphene-supported AgIr alloy nanoparticle material:

[0091] Attach a commercial PI film to a glass slide with double-sided tape, and then place the attached PI film in a CO2 laser engraving machine for the first scribing. The laser power during scribing is 27 W, and the laser rate is 9×10 3 mm / s, and the scribing area is 20×20 cm 2, a graphene substrate is obtained. Take 400 μL of the mixed solution of AgNO3 and IrCl3·3H2O and titrate it onto the obtained graphene substrate, and dry it in a vacuum environment at 25 °C for 10 h. Finally, the graphene substrate is laser scribed again by a CO2 laser engraving machine, with a laser power of 28 W and a laser rate of 2×10 3 mm / s, and the graphene-supported AgIr nanoparticle material is obtained.

[0092] After the preparation process is completed, a slurry is obtained by mixing binders, a battery is assembled, and battery performance tests are carried out, including the following steps:

[0093] 1) Mix the obtained material and PVDF in a ratio of 8:2, and uniformly disperse them in NMP organic solvent. The mixture is mixed with 500 μL of NMP solvent and ground for 30 min to obtain a slurry. Subsequently, take 20 μL of the slurry and drop-coat it onto a carbon paper with a diameter of 12 mm, and dry it in a vacuum at 100 °C for 24 h to obtain the positive electrode of the Li-CO2 battery.

[0094] 2) Assemble a button battery in the order of the positive electrode case, the positive electrode, the separator, the metallic Li negative electrode, the gasket, the spring piece, and the negative electrode case in a glove box filled with argon, and the battery model is CR2032.

[0095] 3) The battery test is completed by a Land battery tester, and the performance tests include overpotential test, capacity test, and cycle stability.

[0096] Example 6:

[0097] The solution components and concentrations are as follows:

[0098] 0.2 M Fe(NO3)2·9H2O, 0.2 M Co(NO3)2·6H2O, and 0.2 M PdCl2 solution

[0099] The preparation process of the graphene-supported PdFeCo ternary alloy nanoparticle material:

[0100] Attach a commercial PI film to a glass slide with double-sided tape, and then place the attached PI film in a CO2 laser engraving machine for the first scribing. The laser power during the scribing process is 50%, the scanning speed is 50%, and the scribing area is 30×30 cm 2 , a graphene substrate is obtained. Take 1.5 mL of the mixed solution of Fe(NO3)2·9H2O, Co(NO3)2·6H2O, and PdCl2 and titrate it onto the obtained graphene substrate, and dry it in a vacuum environment at 30 °C for 15 h. Finally, the graphene substrate is laser scribed again by a CO2 laser engraving machine, with a laser power of 5 W and a laser rate of 9×10 3mm / s, thus obtaining the graphene-supported PdFeCo ternary alloy nanoparticle material.

[0101] After the preparation process is completed, a slurry is obtained by mixing the binder, and a battery is assembled for battery performance testing, including the following steps:

[0102] 1) The obtained material is mixed with PVDF in a ratio of 8:2, uniformly dispersed in NMP organic solvent. The mixture is mixed with 700 μL of NMP solvent and ground for 39 min to obtain a slurry. Subsequently, 20 μL of the slurry is dropped onto a carbon paper with a diameter of 12 mm and vacuum dried at 100 °C for 24 h to obtain the cathode of the Li-CO2 battery.

[0103] 2) Assemble a coin cell in the order of the cathode shell, cathode, separator, metallic Li anode, gasket, shrapnel, and anode shell in a glove box filled with argon. The battery model is CR2032.

[0104] 3) The battery test is completed by a Land battery tester. The performance tests include overpotential test, capacity test, and cycle stability.

[0105] Example 7:

[0106] The solution components and concentrations are as follows:

[0107] 0.2 M AgNO3, 0.2 M IrCl3·3H2O, 0.05 M RhCl3·3H2O, and 0.05 M OsCl3 solution. The preparation process of the graphene-supported AgIrRhOs quaternary alloy nanoparticle material:

[0108] The commercial PI film is adhered to the glass slide by double-sided tape, and then the adhered PI film is placed in a CO2 laser engraver for the first engraving. The laser power during the engraving process is 24 W, and the laser rate is 7×10 3 mm / s, and the engraving area is 30×30 cm 2 , obtaining a graphene substrate. Take 1.5 mL of the mixed solution of AgNO3, IrCl3·3H2O, RhCl3·3H2O, and OsCl3 and titrate it onto the obtained graphene substrate, and dry it in a vacuum environment at 30 °C for 15 h. Finally, the graphene substrate is laser engraved again by a CO2 laser engraver. The laser power is 6 W, and the laser rate is 10 2 mm / s, thus obtaining the graphene-supported AgIrRhOs ternary alloy nanoparticle material.

[0109] After the preparation process is completed, a slurry is obtained by mixing the binder, and a battery is assembled for battery performance testing, including the following steps:

[0110] 1) The obtained material was mixed with PVDF at a ratio of 8:2 and uniformly dispersed in NMP organic solvent. The mixture was mixed with 800 μL of NMP solvent and ground for 39 min to obtain a slurry. Subsequently, 20 μL of the slurry was drop-coated onto a carbon paper with a diameter of 12 mm and vacuum-dried at 100 °C for 24 h to obtain the positive electrode of the Li-CO2 battery.

[0111] 2) The coin cell was assembled in an argon-filled glove box in the order of the positive electrode case, the positive electrode, the separator, the metallic Li negative electrode, the gasket, the shrapnel, and the negative electrode case. The battery model was CR2032.

[0112] 3) The battery test was completed by a Land battery tester. The performance tests included overpotential test, capacity test, and cycle stability.

[0113] Example 8:

[0114] The solution components and concentrations were as follows:

[0115] 0.8 M Fe(NO3)2·9H2O, 0.8 M Co(NO3)2·6H2O, 0.5 M Ni(NO3)2·6H2O, 0.5 M RuCl3, and 0.4 M PdCl2 solution

[0116] The preparation process of the graphene-supported PdRuFeCoNi quinary high-entropy alloy nanoparticle material:

[0117] The commercial PI film was adhered to the glass slide with double-sided tape, and then the adhered PI film was placed in a CO2 laser engraving machine for the first engraving. The laser power during the engraving process was 10 W, the laser rate was 3×10 2 mm / s, and the engraving area was 60×60 cm 2 , to obtain a graphene substrate. 4 mL of the mixed solution of Fe(NO3)2·9H2O, Co(NO3)2·6H2O, Ni(NO3)2·6H2O, RuCl3, and PdCl2 was titrated onto the obtained graphene substrate and dried in a vacuum environment for 24 h. Finally, the graphene substrate was laser-engraved again under the CO2 laser engraving machine with a laser power of 27 W and a laser rate of 8×10 2 mm / s, and the graphene-supported PdRuFeCoNi quinary high-entropy alloy nanoparticle material was obtained.

[0118] After the preparation process was completed, the mixed binder was used to obtain a slurry, the battery was assembled, and the battery performance test was carried out, including the following steps:

[0119] 1) The obtained material was mixed with PVDF at a ratio of 9:1 and uniformly dispersed in NMP organic solvent. The mixture was mixed with 500 μL of NMP solvent and ground for 35 min to obtain a slurry. Subsequently, 20 μL of the slurry was drop-coated onto a carbon paper with a diameter of 12 mm and vacuum-dried at 100 °C for 24 h to obtain the positive electrode of the Li-CO2 battery.

[0120] 2) The coin-type battery was assembled in a glove box filled with argon in the order of the positive electrode case, positive electrode, separator, metallic Li negative electrode, gasket, shrapnel, and negative electrode case. The battery model was CR2032.

[0121] 3) The battery test was completed by a Land battery tester. The performance tests included overpotential test, capacity test, and cycle stability.

[0122] Example 9:

[0123] The solution components and concentrations were as follows:

[0124] 0.8 M ZnCl2, 0.8 M CuCl2·2H2O, 0.5 M CrCl3·6H2O, 0.5 M MoCl5, and 0.4 M VCl3 solutions

[0125] The preparation process of the graphene-supported ZnCuCrMoV quinary high-entropy alloy nanoparticle material:

[0126] The commercial polyethyleneimine polymer film was adhered to a glass slide with double-sided tape. Then, the adhered PI film was placed in a CO2 laser engraver for the first scribing. The laser power during the scribing process was 30 W, the laser rate was 7×10 3 mm / s, and the scribing area was 100×100 cm 2 , obtaining a graphene substrate. 4 mL of the mixed solution of ZnCl2, CuCl2·2H2O, CrCl3·6H2O, MoCl5, and VCl4 was titrated onto the obtained graphene substrate and dried in a vacuum environment for 24 h. Finally, the graphene substrate was laser-scribed again under a CO2 laser engraver with a laser power of 9 W and a laser rate of 4×10 2 mm / s, thus obtaining the graphene-supported ZnCuCrMoV quinary high-entropy alloy nanoparticle material.

[0127] After the preparation process was completed, a slurry was obtained by mixing the binder, the battery was assembled, and the battery performance test was carried out, including the following steps:

[0128] 1) The obtained material was mixed with PVDF at a ratio of 9:1 and uniformly dispersed in NMP organic solvent. The mixture was mixed with 1000 μL of NMP solvent and ground for 35 min to obtain a slurry. Subsequently, 20 μL of the slurry was drop-coated onto a carbon paper with a diameter of 12 mm and vacuum-dried at 100 °C for 24 h to obtain the positive electrode of the Li-CO2 battery.

[0129] 2) The button battery was assembled in a glove box filled with argon in the order of the positive electrode case, the positive electrode, the separator, the metallic Li negative electrode, the gasket, the shrapnel, and the negative electrode case. The battery model was CR2032.

[0130] 3) The battery tests were completed by a Land battery tester. The performance tests included overpotential test, capacity test, and cycle stability.

[0131] Example 10:

[0132] The components and concentrations of the solution were as follows:

[0133] 0.2 M RhCl3·3H2O, 0.2 M SnCl2·2H2O, 0.2 M H2PtCl6·6H2O, 0.2 M HAuCl4·4H2O, and 0.2 M IrCl3·3H2O solutions

[0134] The preparation process of the graphene-supported RhSnPtAuIr quinary alloy nanoparticle material:

[0135] The commercial PI film was adhered to the glass slide with double-sided tape, and then the adhered PI film was placed in a CO2 laser engraving machine for the first engraving. The laser power during the engraving process was 7 W, the laser rate was 9×10 3 mm / s, and the engraving area was 30×30 cm 2 , to obtain a graphene substrate. 1.5 mL of the mixed solution of RhCl3·3H2O, SnCl2·2H2O, H2PtCl6·6H2O, HAuCl4·4H2O, and IrCl3·3H2O was titrated onto the obtained graphene substrate and dried in a vacuum at 30 °C for 15 h. Finally, the graphene substrate was laser-engraved again under a CO2 laser engraving machine with a laser power of 16 W and a laser rate of 5×10 2 mm / s, and the graphene-supported RhSnPtAuIr quinary alloy nanoparticle material was obtained.

[0136] After the preparation process was completed, the mixed binder was used to obtain a slurry, the battery was assembled, and the battery performance tests were carried out, including the following steps:

[0137] 1) Mix the obtained material with PVDF at a ratio of 8:2, and disperse it evenly in NMP organic solvent. Mix the mixture with 600 μL of NMP solvent and grind for 39 min to obtain a slurry. Subsequently, take 20 μL of the slurry and drop-coat it onto a carbon paper with a diameter of 12 mm, and vacuum-dry it at 100 °C for 24 h to obtain the positive electrode of the Li-CO2 battery.

[0138] 2) Assemble a coin cell in the argon-filled glove box in the order of the positive electrode case, the positive electrode, the separator, the metallic Li negative electrode, the gasket, the shrapnel, and the negative electrode case. The battery model is CR2032.

[0139] 3) The battery test is completed by a Land battery tester. The performance tests include overpotential test, capacity test, and cycle stability.

[0140] Figure 1 Figure 10 is the SEM morphology photo of graphene-supported Pd nanoparticles prepared by this method. It can be seen from the figure that the graphene presents a porous structure and the nanoparticles are uniformly loaded on the graphene.

[0141] Figure 2 Figure 14 is the XRD pattern of graphene-supported Pd nanoparticles. It can be seen from the pattern that the peak corresponding to 25.8° is that of graphene, while the peaks corresponding to 40°, 46.5°, and 67.9° are the (111), (200), and (220) crystal planes of Pd nanoparticles, respectively, and there are no other impurity phases.

[0142] Figure 3 Figures (a) and (b) in the middle are the TEM morphology and high-resolution images of graphene-supported Pd nanoparticles, respectively. The transmission electron microscopy image in Figure (a) shows that the Pd nanoparticles are spherical. The high-resolution TEM image in Figure (b) further shows that the lattice fringe of Pd is 0.225 nm, corresponding to the (111) crystal plane.

[0143] Figure 4 Figure 22 is the first charge-discharge curve of graphene-supported Pd nanoparticles as the positive electrode material of the Li-CO2 battery at different current densities. It can be seen from the figure that at a current density of 50 mA / g and a cut-off capacity of 1000 mAh / g, the overpotential is 0.28 V.

[0144] Figure 5 Figure 26 is the discharge capacity curve of graphene-supported Pd nanoparticles as the positive electrode material of the Li-CO2 battery at a current density of 100 mA / g and a cut-off voltage of 2 V. It can be seen from the figure that when it is used as the positive electrode material, the capacity is 10025 mAh / g.

[0145] Figure 6The cyclic voltammetry curve of graphene-supported Pd nanoparticles as the cathode material of a Li-CO2 battery at a current density of 50 mA / g and a cut-off capacity of 1000 mAh / g. It can be seen from the graph that when used as the cathode material, it can operate stably for 35 cycles and the charging voltage is always lower than 3.5 V, which reflects the excellent bifunctional catalytic activity of graphene-supported Pd nanoparticles.

[0146] The laser-induced process described in the present invention is simple and fast, which is conducive to large-scale production. Moreover, it can achieve patterning of the target material through computer-aided automated control, facilitating the simultaneous manufacture of multiple high-yield cathode materials; this preparation method uses a commercial polymer film as the substrate and in-situ converts the polymer into multi-layer graphene, and its porous structure is beneficial to increasing ion transport and electrolyte diffusion in the battery; due to the characteristics of instantaneous high temperature and rapid quenching of this method, the high efficiency of the preparation enables it to develop into a general high-throughput experimental method.

[0147] The above content is only to illustrate the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. Any modification made on the basis of the technical solution according to the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims

1. Application of graphene-supported nanoparticles prepared by a high-throughput laser synthesis method, characterized in that, Graphene-supported nanoparticles as the positive electrode material for Li-CO2 batteries; The graphene-supported nanoparticles are any one of graphene-supported FeCo alloy nanoparticles material, graphene-supported AgIr nanoparticles material, graphene-supported AgIrRhOs quaternary alloy nanoparticles material, graphene-supported PdRuFeCoNi quinary high-entropy alloy nanoparticles material, graphene-supported ZnCuCrMoV quinary high-entropy alloy nanoparticles material, graphene-supported RhSnPtAuIr quinary alloy nanoparticles material; A high-throughput laser synthesis method for graphene-supported nanoparticles, comprising the following steps: S1: Use a laser to first scribe a polyimide polymer film or a polyethyleneimine polymer film for in-situ transformation to obtain a graphene substrate; S2: Subsequently, drop a metal precursor salt solution onto the graphene substrate, dry it, and then use a laser to scribe it a second time to obtain graphene-supported nanoparticles; In the S2, the concentration of the metal precursor salt solution is 0.01M~1M; The precursor salt in the metal precursor salt solution is any one or any combination of nickel nitrate hexahydrate, iron nitrate nonahydrate, cobalt nitrate hexahydrate, manganese chloride tetrahydrate, palladium chloride, ruthenium chloride, zinc chloride, copper chloride dihydrate, chromium chloride hexahydrate, molybdenum chloride, vanadium chloride, rhodium chloride hydrate, stannous chloride dihydrate, chloroplatinic acid hexahydrate, chloroauric acid tetrahydrate, ruthenium chloride trihydrate, silver nitrate, osmium chloride, iridium trichloride hydrate, and rhenium chloride; Engraving with a laser engraving machine equipped with a 10.6 μm CO2 laser; the full laser power is 30 W, and the full laser speed is 10 4 mm / s; the laser power for the first laser engraving and the second laser engraving is 9 W to 30 W, and the laser speed for the first laser engraving and the second laser engraving is 10 2 ~ 10 4 mm / s.

2. Use of the graphene-supported nanoparticles prepared by the high-throughput laser synthesis method according to claim 1, characterized in that, In the S1, the thickness of the polyimide polymer film or the polyethyleneimine polymer film is 20~200μm.

3. Application of graphene-supported nanoparticles prepared by the high-throughput laser synthesis method according to claim 1, characterized in that, The area of the first laser scribing and the second laser scribing is (1~100) × (1~100) cm 2 .

4. Use of the graphene-supported nanoparticles prepared by the high-throughput laser synthesis method according to claim 1, characterized in that, In S2, the drying time is 10 to 24 h, and the drying temperature is 25 to 30 o °C.

5. Use of the graphene-supported nanoparticles prepared by the high-throughput laser synthesis method according to claim 1, characterized in that, The volume dosage of the precursor salt solution is 80~10000μL.

6. Use of the graphene-supported nanoparticles prepared by the high-throughput laser synthesis method according to claim 1, characterized in that, In the S2, the dropping method is dropping with a manual pipette or dropping with an automatic sampling system.

7. Use of the graphene-supported nanoparticles prepared by the high-throughput laser synthesis method according to claim 1, characterized in that, The process of using the graphene-supported nanoparticles as the positive electrode material for Li-CO2 batteries comprises the following steps: Mix the graphene-supported nanoparticles and the binder polyvinylidene fluoride evenly at a mass ratio of (8~9):(1~2) to obtain a mixture; Mix the mixture with NMP solvent and then grind it to obtain a slurry; Drop the slurry onto carbon paper and dry it to obtain the positive electrode of the Li-CO2 battery.

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