CN113913972A - Preparation method of metal-doped porous carbon fiber/graphene composite material with interconnected macropores - Google Patents
Preparation method of metal-doped porous carbon fiber/graphene composite material with interconnected macropores Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 46
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 40
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000009987 spinning Methods 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
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- 239000006185 dispersion Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 150000001868 cobalt Chemical class 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract description 2
- 150000002505 iron Chemical class 0.000 abstract description 2
- 150000002815 nickel Chemical class 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 8
- 229920001021 polysulfide Polymers 0.000 description 7
- 239000005077 polysulfide Substances 0.000 description 7
- 150000008117 polysulfides Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000011068 loading method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
- D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- D01F1/10—Other agents for modifying properties
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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Abstract
The invention discloses a preparation method of a metal-doped porous carbon fiber/graphene composite material with interconnected macropores, which is characterized in that the porous carbon fiber/graphene composite material is prepared by an electrostatic spinning method; dispersing graphene into PVP spinning solution, then spinning the uniform mixed solution by using an electrostatic spinning method, finally pre-oxidizing an electrostatic spinning product, and then firing to obtain a porous carbon fiber/graphene composite material; in order to improve the electrochemical performance of the lithium-sulfur battery, cobalt salt, iron salt, nickel salt and the like can be added into the spinning solution to form monatomic doping so as to promote the catalytic conversion reaction of the lithium-sulfur battery.
Description
Technical Field
The invention relates to the technical field of sulfur host materials, in particular to a preparation method of a metal-doped porous carbon fiber/graphene composite material with interconnected macropores.
Background
Because large-scale electric vehicles put new demands on secondary batteries with high power density and high energy density, the traditional lithium cobaltate and ternary cathode materials can not meet the requirements far away. The elementary sulfur is used as the LSBs anode material, and the theoretical specific capacity of the elementary sulfur reaches 1675 mAh.g-1The theoretical specific energy can reach 2600 Wh.kg-1And the elemental sulfur has the advantages of abundant reserves, low cost, environmental friendliness and the like. Therefore, LSBs have been greatly developed in recent years.
However, sulfur as a positive electrode still has many problems to be solved, such as poor conductivity of sulfur results in low utilization rate of sulfur, and polysulfide dissolution and shuttling effect in electrolyte results in continuous loss of sulfur.
The method mainly adopted for solving the problems is to compound a carbon material (porous carbon, graphene and the like) and a sulfur simple substance so as to improve the conductivity and the adsorption of the material. However, carbon materials have less adsorption properties for polysulfides as non-polar materials and sulfur loading is limited by the specific surface area of the carbon material. However, interconnected macroporous carbon materials generally exhibit poor pore structure stability.
Disclosure of Invention
The invention aims to provide a preparation method of a metal-doped porous carbon fiber/graphene composite material with interconnected macropores, and aims to solve the problems of low sulfur load and low polysulfide adsorption performance.
In order to improve the adsorption conversion capacity of the load material to polysulfide, the porous metal-doped carbon nanofiber/graphene composite material with a large specific surface area is prepared by an electrostatic spinning method. The porous carbon fiber improves the load of sulfur simple substance, the metal single atom is doped to enhance the catalytic conversion reaction of polysulfide, and the graphene constructs a three-dimensional conductive network to improve the conductivity and structural stability of the fiber and has a physical barrier effect on the polysulfide.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a metal-doped porous carbon fiber/graphene composite material with interconnected macropores comprises the following specific steps:
s1 carbon source dispersion: adding graphene into the treatment liquid A, carrying out ultrasonic treatment, and carrying out ultrasonic dispersion to obtain a graphene dispersion liquid;
preparation of S2 spinning solution: adding nitrate and melamine into the graphene dispersion liquid obtained in the step S1 and stirring; then adding PVP, stirring for 3-6 h, adding the polytetrafluoroethylene emulsion after fully dissolving, and stirring for 1-3 h; finally, electrostatic spinning is carried out under the voltage of 18-25 kV and the glue pushing speed of 0.5-2 ml/h, and drying is carried out to obtain dry fibers;
s3 preparation of the interconnected macroporous metal-doped porous carbon fiber/graphene composite material: pre-oxidizing the dry fiber prepared in the step S2 in a tubular furnace at 180-250 ℃ to form a stable carbon fiber structure; and heating at 800-1000 ℃ in Ar atmosphere to volatilize the polytetrafluoroethylene at high temperature, leaving a cavity in the carbon fiber, and forming a stable chemical structure by the metal atoms and the nitrogen atoms at high temperature to obtain the metal-doped porous carbon fiber/graphene composite material.
Preferably, the treating solution a in step S1 is one of deionized water and ethanol/DMF mixed solution.
Preferably, the volume ratio of ethanol/DMF is 1: 1.
Preferably, 10mg of graphene is added into 3-5g of deionized water for ultrasonic treatment for 2h, and ultrasonic dispersion is carried out.
Preferably, the nitrate in step S2 is one or more of cobalt nitrate, nickel nitrate, and iron nitrate.
Preferably, the molecular weight of the PVP is 130 ten thousand, 20mg of cobalt nitrate and 100mg of melamine are added into the graphene dispersion liquid and stirred; then, 1g of PVP is added and stirred for 3-6 h.
Compared with the prior art, the invention has the beneficial effects that: the porous carbon fiber/graphene composite material is prepared by an electrostatic spinning method. And dispersing graphene into PVP spinning solution, then spinning the uniform mixed solution by using an electrostatic spinning method, and finally pre-oxidizing and firing an electrostatic spinning product to obtain the porous carbon fiber/graphene composite material. In order to improve the electrochemical performance of the lithium-sulfur battery, cobalt salt, iron salt, nickel salt and the like can be added into the spinning solution to form monatomic doping so as to promote the catalytic conversion reaction of the lithium-sulfur battery.
The preparation process is controllable, and the specific surface area of the porous carbon fiber is controlled by controlling the amount of the template; the prepared carbon fiber has interconnected macropores, so that the loading capacity of S can be improved; polytetrafluoroethylene is added as a pore-forming agent, subsequent treatments such as activation and etching are not needed, and the method is environment-friendly, efficient and suitable for commercial production; the larger specific surface area is helpful for increasing the reactive active sites and adsorbing polysulfide; the graphene increases the stability of the porous carbon fiber structure and improves the conductivity, and the performance of the lithium-sulfur battery can be synergistically improved by the monatomic doping of the metal-nitrogen-carbon structure, the high-conductivity and high-mechanical-property network formed by the graphene and the high specific surface area of the porous carbon fiber.
(1) The invention utilizes the electrostatic spinning technology, and the polymer solution or melt is subjected to jet spinning in a strong electric field. Under the action of an electric field, liquid drops at the needle head are changed into a conical shape from a spherical shape, namely a Taylor cone, fiber filaments are obtained by extending from the tip of the cone, namely polymer micro jet flow, can run for a long distance and are finally solidified into fibers, electrostatic spinning is carried out, filaments rather than liquid drops are pulled out from the needle head, and finally the interconnected macroporous metal-doped carbon fiber/graphene composite material is prepared by utilizing an electrostatic spinning technology.
(2) According to the invention, the carbon fiber subjected to pure PVP heat treatment has poor conductivity, the graphene is completely wrapped in the carbon nanofiber, the graphene can be connected with each hole of the fiber in the fiber, a three-dimensional conductive network is formed in the cavity to improve the conductivity and the structural stability of the material, and in addition, the excellent mechanical property of the graphene can also improve the overall structural stability of the carbon fiber.
(3) Various metal salts added can form metal doping, the catalytic conversion effect of Lithium Sulfur Batteries (LSBs) is improved, and the addition of melamine into the spinning solution is beneficial to forming a metal-nitrogen-carbon structure and improving the stability of metal sites.
Drawings
FIG. 1 is an SEM image of a Co-doped porous carbon fiber/graphene-0.5 composite prepared in example 1;
FIG. 2 is an SEM image of a Co-doped porous carbon fiber/graphene-1 composite prepared in example 2;
FIG. 3 is an SEM image of a Co-doped porous carbon fiber/graphene-2 composite prepared in example 3;
FIG. 4 is an SEM image of a Co-doped porous carbon fiber/graphene-3 composite prepared in example 4;
FIG. 5 is a graph of performance of a lithium sulfur battery with Co-doped porous carbon fiber-3;
figure 6 is Co-doped porous carbon fiber/graphene-3 lithium sulfur battery performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the specific techniques or conditions are not indicated in the examples, and the techniques or conditions are described in the literature in the field or according to the product specification; the reagents and materials, both of which are analytically pure reagents, are commercially available without specific reference.
Example 1
A preparation method of a Co-doped porous carbon fiber/graphene composite material comprises the following steps:
s1 graphene Dispersion
And adding 10mg of graphene into 3-5g of deionized water for ultrasonic treatment for 2 hours, and performing ultrasonic dispersion.
S2 preparation of spinning solution
20mg of cobalt nitrate and 100mg of melamine were added to the graphene dispersion and stirred. Then adding 1g of PVP with the molecular weight of 130 ten thousand, stirring for 3-6 h, fully dissolving, adding into 3g of polytetrafluoroethylene emulsion, and finally stirring for 2 h. And finally, carrying out electrostatic spinning at the voltage of 18-25 kV and the glue pushing speed of 0.5-2 ml/h.
S3 preparation of Co-doped porous carbon fiber/graphene composite material
Heating the dried fiber to 180-250 ℃ in a tube furnace at a heating rate of 2 ℃/min, and pre-oxidizing for 1 hour to form a stable carbon fiber structure; heating to 800-1000 ℃ at the heating rate of 5 ℃/min under the Ar atmosphere for 3 hours, so as to volatilize the polytetrafluoroethylene at high temperature and leave a cavity in the carbon fiber; and at high temperature, the metal atoms and the nitrogen atoms form a stable chemical structure.
Examples 2 to 4
The process steps were identical to example 1, except that the amounts of polytetrafluoroethylene were adjusted to 1g, 2g and 3 g.
Comparative example 1
A preparation method of Co-doped porous carbon fibers comprises the following steps:
adding 20mg of cobalt nitrate and 100mg of melamine into 5g of water, stirring, then adding 1g of PVP (polyvinyl pyrrolidone), stirring for 3-6 h, adding into 3g of polytetrafluoroethylene emulsion after fully dissolving, and finally stirring for 2 h. And finally, carrying out electrostatic spinning at the voltage of 18-25 kV and the glue pushing speed of 0.5-2 ml/h.
Heating the dried fiber to 180-250 ℃ in a tube furnace at a heating rate of 2 ℃/min, and pre-oxidizing for 1 hour to form a stable carbon fiber structure; heating to 800-1000 ℃ at the heating rate of 5 ℃/min under the Ar atmosphere for 3 hours, so as to volatilize the polytetrafluoroethylene at high temperature and leave a cavity in the carbon fiber; and at high temperature, the metal atoms and the nitrogen atoms form a stable chemical structure.
As can be seen from fig. 1 to 4, the metal-doped porous carbon fiber/graphene composite material with interconnected macropores is successfully prepared, the prepared carbon fiber has larger pores, the metal-nitrogen-carbon structure of the invention is doped with single atoms, and the graphene forms a high-conductivity and high-mechanical-property network, and the morphology of the fiber is maintained.
FIG. 5 is a graph showing the rate performance of a lithium-sulfur battery made of Co-doped porous carbon fibers, wherein the discharge capacities at current densities of 0.1C, 0.3C,0.5C,1C,3C and 5C are 1086, 621, 254, 160, 129 and 96mA h g-1。
FIG. 6 is a graph of rate performance of a Co-doped porous carbon fiber/graphene-3 lithium-sulfur battery, wherein the discharge capacities at current densities of 0.1C, 0.3C,0.5C,1C,3C, and 5C are 1320, 908, 729, 502, 229, 121mA h g, respectively-1。
The sample in fig. 6 is added with more graphene than that in fig. 5, and from comparison of fig. 5 to fig. 6, as for the electrode material, the rate performance can be enhanced by improving the conductivity, so the rate performance of the Co-doped porous carbon fiber/graphene-3 is good under the same current density, and the utilization rate of S is improved by adding the graphene, so the discharge capacity of the first circle is greatly increased.
In conclusion, the performance of the lithium-sulfur battery can be synergistically improved through the monatomic doping of the metal-nitrogen-carbon structure, the high-conductivity high-mechanical-property network formed by the graphene and the high specific surface area of the porous carbon fiber.
As an example, in the step of the S1 experiment, graphene may be replaced by carbon nanotube or MXene.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts in the embodiments are referred to each other. The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A preparation method of a metal-doped porous carbon fiber/graphene composite material with interconnected macropores is characterized by comprising the following specific steps:
s1 carbon source dispersion: adding graphene oxide into the treatment liquid A, carrying out ultrasonic treatment, and carrying out ultrasonic dispersion to obtain a graphene oxide dispersion liquid;
preparation of S2 spinning solution: adding nitrate and melamine into the graphene oxide dispersion liquid obtained in the step S1, and stirring; then adding PVP, stirring for 3-6 h, adding the polytetrafluoroethylene emulsion after fully dissolving, and stirring for 1-3 h; finally, electrostatic spinning is carried out under the voltage of 18-25 kV and the glue pushing speed of 0.5-2 ml/h, and drying is carried out to obtain dry fibers;
s3 preparation of the metal-doped porous carbon fiber/graphene composite material: pre-oxidizing the dry fiber prepared in the step S2 in a tubular furnace at 180-250 ℃ to form a stable carbon fiber structure; and heating at 800-1000 ℃ in Ar atmosphere to volatilize the polytetrafluoroethylene at high temperature, leaving a cavity in the carbon fiber, and forming a stable chemical structure by the metal atoms and the nitrogen atoms at high temperature to obtain the metal-doped porous carbon fiber/graphene composite material.
2. The method of claim 1, wherein the treating solution A in step S1 is one of deionized water and ethanol/DMF mixture.
3. The method of claim 2, wherein the volume ratio of ethanol to DMF is 1: 1.
4. The preparation method of claim 1, wherein 10mg of graphene oxide is added into 3-5g of deionized water for ultrasonic treatment for 2h, and ultrasonic dispersion is performed.
5. The method according to claim 1, wherein the nitrate in step S2 is one or more of cobalt nitrate, nickel nitrate, and iron nitrate.
6. The preparation method according to claim 1, wherein the molecular weight of the PVP is 130 ten thousand, 20mg of cobalt nitrate and 100mg of melamine are added into the graphene dispersion liquid and stirred; then, 1g of PVP is added and stirred for 3-6 h.
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