CN113540464A - Preparation method of metal nanoparticle modified graphite material and three-dimensional graphite skeleton pole piece - Google Patents
Preparation method of metal nanoparticle modified graphite material and three-dimensional graphite skeleton pole piece Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000007770 graphite material Substances 0.000 title description 5
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 89
- 239000010439 graphite Substances 0.000 claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 43
- 238000001694 spray drying Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 24
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 24
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 150000002343 gold Chemical class 0.000 claims 1
- 150000003378 silver Chemical class 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 46
- 238000000151 deposition Methods 0.000 abstract description 16
- 230000008021 deposition Effects 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 238000001465 metallisation Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000009827 uniform distribution Methods 0.000 abstract description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 23
- 229910001961 silver nitrate Inorganic materials 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000001878 scanning electron micrograph Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- 230000002572 peristaltic effect Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- -1 nano-silver modified graphene Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Images
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/28—Polysaccharides or derivatives thereof
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00008—Obtaining or using nanotechnology related materials
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a nano metal modified graphite framework material, which comprises the following steps: mixing graphite, metal salt, polyvinylpyrrolidone and water, fully stirring and then carrying out ultrasonic treatment to obtain a mixed solution; and (3) spray-drying the mixed solution, annealing the obtained solid powder at 495-505 ℃, cooling and grinding to obtain the nano metal modified graphite framework material. According to the invention, the proportion of graphite, metal salt and PVP is controlled, the graphite is modified, the graphite modified by metal nano particles with uniform distribution and consistent particle size is obtained, and the obtained three-dimensional graphite skeleton pole piece has rich gaps through coating, and can accommodate the volume expansion of metal lithium. According to the invention, graphite is used as a deposition substrate, lithium is preferentially inserted into the graphite layers and then deposited on the graphite surface, and the graphite can store a part of lithium, so that a part of problems caused by lithium metal deposition are avoided, and the three-dimensional structure of the graphite pole piece is more stable.
Description
Technical Field
The invention belongs to the technical field of pole pieces, and particularly relates to a preparation method of a metal nanoparticle modified graphite skeleton material and a three-dimensional graphite skeleton pole piece.
Background
The carbon-based material has the advantages of low density, stable and controllable chemical properties, and the like, and thus is widely applied to the research of a lithium metal battery system. As one of the carbon materials, graphite is widely used as a commercial lithium ion battery due to its advantages of excellent cycle properties, a firm SEI film, and the like.
At present, researchers propose that by utilizing a graphite-metal lithium composite negative electrode, a part of lithium is stored between graphite layers in a lithium ion form and a part of lithium is stored in gaps of a graphite pole piece in a metal lithium form by utilizing the stable intercalation capability of graphite, so that the problems caused by a part of metal lithium are avoided, and the cycle stability of a lithium metal battery is improved. At present, the research on graphite-metal lithium composite negative electrodes applied to lithium metal negative electrodes is not many, for example, a large amount of lithium dendrites and dead lithium are gradually accumulated on the surface of a pure graphite-metal lithium composite negative electrode in the electrochemical cycle process; the CVD method is used for depositing a layer of nano silicon coating on the surface of graphite to effectively induce the uniform deposition of metal lithium, but the CVD method has high requirements on equipment and high cost of high-purity silane gas, when the graphite is overlapped, the silicon coating is not uniformly distributed, and when the nano silicon coating is used as a substrate material of a metal lithium cathode, huge volume change can occur in the alloying process of silicon and lithium, and the silicon coating is easy to deform and break after multiple deposition/extraction cycles of the metal lithium, so that the effect of inducing the uniform deposition of the metal lithium is eliminated, and the cycle life of the battery is short.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a metal nanoparticle modified graphite material and a three-dimensional graphite skeleton pole piece, wherein the skeleton material prepared by the method has rich voids and can accommodate volume expansion generated in a metal lithium deposition process.
The invention provides a preparation method of a nano metal modified graphite framework material, which comprises the following steps:
mixing graphite, metal salt, polyvinylpyrrolidone and water, fully stirring and then carrying out ultrasonic treatment to obtain a mixed solution; the mass ratio of the graphite substance to the metal salt substance to the polyvinylpyrrolidone is (33.5-134) mol:1mol, (3-15) mg;
spray drying the mixed solution to obtain solid powder;
and annealing the solid powder in argon at 495-505 ℃, cooling and grinding to obtain the graphite material modified by the metal nanoparticles.
According to the invention, the proportion of graphite, metal salt and PVP is controlled, the graphite is modified, metal nano particles with the same size are uniformly distributed on the surface of the graphite, and the obtained three-dimensional graphite skeleton pole piece has rich gaps through coating and can accommodate volume expansion of metal lithium. According to the invention, graphite is used as a deposition substrate, lithium is preferentially inserted into the graphite layers and then deposited on the graphite surface, and the graphite can store a part of lithium, so that a part of problems caused by lithium metal deposition are avoided, and the three-dimensional structure of the pole piece is more stable than that before modification.
The three-dimensional graphite framework material prepared by the method has good structural stability, and gaps mainly exist between graphite and graphite, so that the three-dimensional graphite framework material can play a certain confinement role in the deposition of metal lithium; after long-time multiple cycles, the three-dimensional graphite skeleton modified by the nano silver still keeps a stable structure, and higher metal lithium deposition/extraction efficiency is maintained.
The method comprises the steps of mixing graphite, metal salt, polyvinylpyrrolidone and water, fully stirring, and performing ultrasonic treatment to obtain a mixed solution. In the present invention, the mass ratio of the amount of the substance of graphite, the amount of the substance of metal salt and polyvinylpyrrolidone is (33.5 to 134) mol:1mol (3 to 15) mg, more preferably (88 to 91) mol:1mol: (8-12) mg. In the present invention, the metal salt is selected from one or more of silver salt, zinc salt, gold salt, tin salt and magnesium salt, and more preferably from one or more of silver nitrate, silver acetate, zinc nitrate hexahydrate and magnesium nitrate hexahydrate. The silver salt has a lower nucleation overpotential for lithium metal than other lithium-philic metal salts, and is more advantageous in guiding uniform deposition of lithium metal.
In the present invention, the graphite is selected from spherical graphite. The composite electrode with the metal nano particles uniformly grown on the graphite overcomes the defect of poor structural stability of silicon plated on the graphite as a host material for deposition/dissolution of the metal lithium, and can keep continuous and stable induction action on the metal lithium. The lithium metal battery can show excellent coulombic efficiency and cycling stability, which can be benefited by the extremely low nucleation overpotential of metal (such as silver) on the lithium metal and the uniform distribution of silver nano on the graphite surface, so that the lithium metal is uniformly deposited on all directions of the graphite surface. Although irreversible byproducts between the electrolyte and the metal lithium are accumulated after deposition and dissolution for many times, the nano metal modified graphite material can still maintain the induction effect on the metal lithium under the condition of high-capacity charge and discharge, thereby greatly improving the cycling stability of the metal lithium cathode.
In the invention, the time for fully stirring is 2-4 h. The ultrasonic time is 0.5-1 h.
After the mixed solution is obtained, the mixed solution is spray-dried to obtain solid powder. In the invention, the inlet temperature of the spray drying is 200-220 ℃, and the outlet temperature is 100-110 ℃. The spray drying method can evaporate the solution quickly to make the metal salt particles uniformly distributed on the graphite surface, and then annealing is carried out to decompose the metal salt at high temperature to reduce the metal nano particles. In the specific embodiment, the rotation speed of a peristaltic pump during spray drying is 25rpm, the inlet temperature of the spray drying is 220 ℃, and the outlet temperature of the spray drying is 110 ℃.
Annealing the solid powder in argon at 495-505 ℃, cooling and grinding to obtain the nano metal modified graphite framework material. In the invention, annealing is carried out at 495-505 ℃ for 110-130 min. The annealing according to the invention is preferably carried out under argon. In a tube furnace. The temperature is preferably raised to 495-505 ℃ after 100 minutes, and more preferably raised to 500 ℃. The present invention preferably ramps up to the annealing temperature at a rate of 5 deg.C/min. And heating to the required temperature, and then keeping for 110-130 min, more preferably 120 min. Naturally cooling and grinding; the graphite framework material modified by the metal nanoparticles is obtained by grinding the graphite framework material by using an agate mortar and sieving the ground graphite framework material by using a 300-mesh sieve.
The invention provides a three-dimensional graphite skeleton pole piece which comprises a nano-silver modified graphite skeleton material, conductive carbon black, sodium carboxymethylcellulose and styrene butadiene rubber in a mass ratio of 90: 3.5-4.5: 2.5-3.5.
In the specific embodiment of the invention, the mass ratio of the nano-silver modified graphite skeleton material, the conductive carbon black (super-P), the sodium carboxymethyl cellulose (CMC) and the Styrene Butadiene Rubber (SBR) is 90:4:3: 3.
After the pole piece is made of the framework material, a three-dimensional framework structure is formed, rich gaps are formed, the volume expansion generated in the deposition process of the metal lithium can be accommodated, the gaps mainly exist between graphite and graphite, and due to the structural stability of the three-dimensional framework, the volume expansion of the lithium metal can be limited to a certain extent, and the stability of the circulation of the metal lithium cathode is further ensured.
The invention provides a preparation method of a nano-silver modified graphite skeleton material, which comprises the following steps: mixing graphite, metal salt, polyvinylpyrrolidone and water, fully stirring and then carrying out ultrasonic treatment to obtain a mixed solution; the mass ratio of the graphite substance to the metal salt substance to the polyvinylpyrrolidone is (33.5-134) mol:1mol, (3-15) mg; and (3) spray-drying the mixed solution, annealing the obtained solid powder at 495-505 ℃, cooling and grinding to obtain the nano metal modified graphite framework material. According to the invention, the proportion of graphite, metal salt and PVP is controlled, the graphite is modified, the graphite modified by metal nano particles with uniform distribution and consistent particle size is obtained, and the obtained three-dimensional graphite skeleton pole piece has rich gaps through coating, and can accommodate the volume expansion of metal lithium. According to the invention, graphite is used as a deposition substrate, lithium is preferentially inserted into the graphite layers and then deposited on the graphite surface, and the graphite can store a part of lithium, so that a part of problems caused by lithium metal deposition are avoided, and the three-dimensional structure of the graphite pole piece is more stable.
Drawings
FIG. 1 is a schematic diagram of the synthesis steps for preparing silver nanoparticle modified graphite according to an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of nano-silver modified spherical graphite prepared in example 1 of the present invention;
fig. 3 is an XRD pattern of spherical graphite between silver nanoparticle modified spheres prepared in example 1 of the present invention;
FIG. 4 shows that the nano-silver modified three-dimensional spherical graphite skeleton prepared in example 1 of the present invention has a thickness of 1mAh cm as a lithium metal negative electrode-2,2mAh cm-2A cyclic coulombic efficiency map under the conditions;
FIG. 5 is a scanning electron microscope topography after the silver nanoparticle modified three-dimensional spherical graphite skeleton is cycled as a lithium metal cathode in example 1 of the present invention;
FIG. 6 is a scanning electron micrograph of CMB @ Ag-150 prepared in example 2 of the present invention;
FIG. 7 is a scanning electron micrograph of CMB @ Ag-200 prepared in example 3 of the present invention;
FIG. 8 is a scanning electron microscope image of the nano-zinc modified graphite skeleton material prepared in example 4 of the present invention;
fig. 9 is an XRD chart of the nano-zinc modified graphite skeleton material prepared in example 4 of the present invention;
FIG. 10 is an SEM image of a nano-magnesium modified graphite skeleton material prepared in example 5 of the present invention;
fig. 11 is a scanning electron microscope image of the nano-silver modified graphene framework material prepared in comparative example 1 of the present invention;
fig. 12 is an electrochemical cycle test chart of coulombic efficiency of a half-cell assembled by a nano-silver modified three-dimensional graphene framework as an electrode and a counter electrode lithium plate according to comparative example 1 of the present invention;
FIG. 13 is a scanning electron micrograph of CMB @ Ag-25 prepared in comparative example 2 of the present invention;
FIG. 14 is an electrochemical cycling test chart of coulombic efficiency of a half-cell assembled by a nano-silver modified three-dimensional graphite framework as an electrode and a counter electrode lithium plate, which are prepared in examples 2 to 3 and comparative example 2 of the present invention;
FIG. 15 is an SEM image of a nano-silver particle-modified graphite skeleton material prepared in comparative example 3 of the present invention at an annealing temperature of 450 ℃;
FIG. 16 is an SEM image of a nano-silver particle-modified graphite skeleton material prepared in comparative example 3 of the present invention at an annealing temperature of 550 ℃;
FIG. 17 is a scanning electron micrograph of a nano-silver modified graphite skeleton according to comparative example 4 of the present invention;
FIG. 18 is a scanning electron micrograph of a material prepared according to comparative example 4 of the present invention after 30 cycles of deposition.
Detailed Description
In order to further illustrate the present invention, the following will describe in detail the preparation method of a nano-metal modified graphite skeleton material and the three-dimensional graphite skeleton pole piece provided by the present invention with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1) Firstly, preparing 0.01M silver nitrate solution; weighing silver nitrate (AgNO)3) 424.675mg of solid is dissolved in 20mL of deionized water, and the mixture is stirred for 5min at room temperature, so that silver nitrate is fully dissolved in the water; transferring the obtained silver nitrate solution into a 250mL volumetric flask, adding deionized water into a beaker for washing, transferring the washed solution into the 250mL volumetric flask, repeating the process for three times, and finally performing constant volume for later use.
2) Weighing 800mg of spherical graphite CMB and 100mg of polyvinylpyrrolidone, placing the spherical graphite CMB and the polyvinylpyrrolidone in a 250mL wide-mouth bottle, adding 75mL of 0.01M silver nitrate solution, stirring at room temperature for 0.5 hour, adding water to 200mL, and stirring for 2 hours to fully disperse the silver nitrate on the surface of the graphite; the solution was sonicated for 30 minutes as shown in figure 1.
3) Spray drying: the sonicated solution was placed on a magnetic stirrer and stirred while feeding the solution into a spray drying apparatus using a peristaltic pump at 25rpm with a spray drying inlet temperature of 220 ℃ and an outlet temperature of 110 ℃.
4) Annealing the obtained solid, heating to 500 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, preserving the heat at 500 ℃ for 2 hours, and naturally cooling.
Nano silver modification is carried out on spherical graphite, then a nano silver modified three-dimensional graphite framework is prepared to be used as an electrode, and a counter electrode lithium sheet is assembled into a half-cell to carry out electrochemical cycle test of coulomb efficiency at 1mA cm-2Current density of 2mAh cm-2The battery with the nano-silver modified three-dimensional graphite framework as the electrode can stably circulate for more than 90 circles (600 hours) and keep the average coulombic efficiency at about 95 percent; in contrast, a pure three-dimensional graphite skeleton can only cycle around 40 cycles. Therefore, the nano-silver modified three-dimensional graphite framework material can promote the metal lithium to be uniformly deposited/dissolved on the surface of the electrode, improve the stability of a deposition interface, and greatly improve the cycle efficiency and cycle life of the metal lithium on the surface of the electrode.
Example 2
The difference from example 1 was that a 150ml of 0.01M silver nitrate solution was used and the product obtained was designated CMB @ Ag-150.
FIG. 6 is a scanning electron micrograph of CMB @ Ag-150 prepared in example 2 of the present invention;
example 3
The difference from example 1 was that 200mL of 0.01M silver nitrate solution was used and the resulting product was designated CMB @ Ag-200.
FIG. 7 is a scanning electron micrograph of CMB @ Ag-200 prepared in example 3 of the present invention;
example 4
1) Firstly, preparing 0.01M zinc nitrate solution; weighing zinc nitrate hexahydrate (ZnNO)3·6H2O) 743.725mg of solid, dissolved in 20mL of deionized water, and stirred at room temperature for 5min to fully dissolve the zinc nitrate in the water; transferring the obtained zinc nitrate solution into a 250mL volumetric flask, adding deionized water into a beaker for washing, transferring the washed solution into the 250mL volumetric flask, repeating the process for three times, and finally performing constant volume for later use;
2) weighing 800mg of spherical graphite CMB; 100mg of polyvinylpyrrolidone is placed in a 250mL wide-mouth bottle, 75mL of 0.01M zinc nitrate solution is added, stirring is carried out at room temperature for 0.5 hour, water is added to 200mL, and stirring is carried out for 2 hours, so that the zinc nitrate is fully dispersed on the surface of the graphite; sonicating the solution for 30 minutes;
3) spray drying: placing the ultrasonic solution on a magnetic stirrer for stirring, and simultaneously feeding the solution into a spray drying device by using a peristaltic pump, wherein the rotating speed of the peristaltic pump is 25 revolutions per minute, the inlet temperature of spray drying is 220 ℃, and the outlet temperature of spray drying is 110 ℃;
4) and annealing the obtained solid, heating to 400 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, keeping the temperature at 400 ℃ for 2 hours, and naturally cooling to obtain the nano-zinc modified graphite framework material.
Fig. 8 and 9 are a scanning electron microscope image and an XRD image of the nano-zinc modified graphite skeleton material prepared in example 4 of the present invention, respectively.
Example 5
1) Firstly, preparing 0.01M magnesium nitrate solution; magnesium nitrate hexahydrate (MgNO) is weighed3·6H2O) 641.003mg of solid, dissolved in 20mL of deionized water, and stirred at room temperature for 5min to fully dissolve the magnesium nitrate in the water; transferring the obtained magnesium nitrate solution into a 250mL volumetric flask, adding deionized water into a beaker for washing, transferring the washed solution into the 250mL volumetric flask, repeating the process for three times, and finally performing constant volume for later use;
2) weighing 800mg of spherical graphite CMB; 100mg of polyvinylpyrrolidone is placed in a 250mL wide-mouth bottle, 75mL of 0.01M magnesium nitrate solution is added, stirring is carried out for 0.5 hour at room temperature, water is added to 200mL, and stirring is carried out for 2 hours, so that the magnesium nitrate is fully dispersed on the surface of graphite; sonicating the solution for 30 minutes;
3) spray drying: placing the ultrasonic solution on a magnetic stirrer for stirring, and simultaneously feeding the solution into a spray drying device by using a peristaltic pump, wherein the rotating speed of the peristaltic pump is 25 revolutions per minute, the inlet temperature of spray drying is 220 ℃, and the outlet temperature of spray drying is 110 ℃;
4) and annealing the obtained solid, heating to 400 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, keeping the temperature at 400 ℃ for 2 hours, and naturally cooling to obtain the nano magnesium modified graphite framework material.
Fig. 10 is an SEM image of the nano-magnesium modified graphite skeleton material prepared in example 5 of the present invention.
Comparative example 1
1) Firstly, preparing 0.01M silver nitrate solution; weighing silver nitrate (AgNO)3) 424.675mg of solid is dissolved in 20mL of deionized water, and the mixture is stirred for 5min at room temperature, so that silver nitrate is fully dissolved in the water; transferring the obtained silver nitrate solution into a 250mL volumetric flask, adding deionized water into a beaker for washing, transferring the washed solution into the 250mL volumetric flask, repeating the process for three times, and finally performing constant volume for later use.
2) Taking 50mL (4.3mg/L) of graphene solution; 100mg of polyvinylpyrrolidone is placed in a 250mL wide-mouth bottle, 75mL of 0.01M silver nitrate solution is added, the mixture is stirred for 0.5 hour at room temperature, water is added to 200mL, and the mixture is stirred for 2 hours, so that the silver nitrate is fully dispersed on the surface of the graphite; sonicating the solution for 30 minutes;
3) spray drying: the sonicated solution was placed on a magnetic stirrer and stirred while feeding the solution into a spray drying apparatus using a peristaltic pump at 25rpm with a spray drying inlet temperature of 220 ℃ and an outlet temperature of 110 ℃. Annealing the obtained solid, heating to 500 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, preserving the heat at 500 ℃ for 2 hours, and naturally cooling to obtain the nano-silver modified graphene framework material;
4) carrying out nano-silver modification on graphene, then preparing a nano-silver modified three-dimensional graphene framework as an electrode, assembling the nano-silver modified three-dimensional graphene framework and a counter electrode lithium sheet into a half-cell, and carrying out electrochemical cycle test on coulomb efficiency at 1mA cm-2Current density of 2mAh cm-2Is circulated at capacity of (a).
Fig. 11 is a scanning electron microscope image of the nano-silver modified graphene framework material prepared in comparative example 1 of the present invention;
fig. 12 is an electrochemical cycle test chart of coulombic efficiency of a half-cell assembled by a nano-silver modified three-dimensional graphene framework as an electrode and a counter electrode lithium plate, which is prepared in comparative example 1 of the present invention.
Comparative example 2
1) Firstly, preparing 0.01M silver nitrate solution; weighing silver nitrate (AgNO)3) 424.675mg of solid is dissolved in 20mL of deionized water, and the mixture is stirred for 5min at room temperature, so that silver nitrate is fully dissolved in the water; transferring the obtained silver nitrate solution into a 250mL volumetric flask, adding deionized water into a beaker for washing, transferring the washed solution into the 250mL volumetric flask, repeating the process for three times, and finally performing constant volume for later use;
2) weighing 800mg of spherical graphite CMB; 100mg of polyvinylpyrrolidone, placing the polyvinylpyrrolidone in a 250mL wide-mouth bottle, adding 25mL of 0.01M silver nitrate solution, stirring at room temperature for 0.5 hour, adding water to 200mL, and stirring for 2 hours to fully disperse the silver nitrate on the surface of the graphite; the solution was sonicated for 30 minutes.
3) Spray drying: placing the ultrasonic solution on a magnetic stirrer for stirring, and simultaneously feeding the solution into a spray drying device by using a peristaltic pump, wherein the rotating speed of the peristaltic pump is 25 revolutions per minute, the inlet temperature of spray drying is 220 ℃, and the outlet temperature is 110 ℃;
4) annealing the obtained solid, heating to 500 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, preserving the heat at 500 ℃ for 2 hours, naturally cooling, and adding 25mL of AgNO3The prepared nano-silver modified graphite framework material is named as CMB @ Ag-25;
5) nano silver modification is carried out on spherical graphite, then a nano silver modified three-dimensional graphite framework is prepared to be used as an electrode, and a counter electrode lithium sheet is assembled into a half-cell to carry out electrochemical cycle test of coulomb efficiency at 1mA cm-2Current density of 2mAh cm-2Is circulated at capacity of (a).
FIG. 13 is a scanning electron micrograph of CMB @ Ag-25 prepared in comparative example 2 of the present invention;
fig. 14 is an electrochemical cycle test chart of coulombic efficiency of a half-cell assembled by a nano-silver modified three-dimensional graphite skeleton prepared in examples 2 to 3 and comparative example 2 of the present invention as an electrode and a counter electrode lithium plate.
Comparative example 3
On the basis of example 1, the annealing temperatures were set to 450 ℃ and 550 ℃, respectively.
FIG. 15 is an SEM image of a nano-silver particle-modified graphite skeleton material prepared in comparative example 3 of the present invention at an annealing temperature of 450 ℃;
fig. 16 is an SEM image of the nano silver particle-modified graphite skeleton material of comparative example 3 of the present invention prepared at an annealing temperature of 550 ℃.
Comparative example 4
Based on example 1, no PVP was added.
FIG. 17 is a scanning electron micrograph of a nano-silver modified graphite skeleton according to comparative example 4 of the present invention; it can be seen that the silver particles on the graphite surface are not uniform in size and distribution without adding PVP.
FIG. 18 is a scanning electron micrograph of a comparative example 4 material of the present invention prepared after 30 cycles of deposition; it can be seen that after 30 cycles, the lithium metal deposition on the surface of the material is relatively uniform, but still with lithium dendrites present.
From the above embodiments, the present invention provides a preparation method of a graphite framework material modified by nano-silver, which includes the following steps: mixing graphite, metal salt, polyvinylpyrrolidone and water, fully stirring and then carrying out ultrasonic treatment to obtain a mixed solution; the mass ratio of the graphite substance to the metal salt substance to the polyvinylpyrrolidone is (33.5-134) mol:1mol, (3-15) mg; spray drying the mixed solution to obtain solid powder; and annealing the solid powder in argon at 495-505 ℃, cooling and grinding to obtain the nano metal modified graphite framework material. According to the invention, the proportion of graphite, metal salt and PVP is controlled, the graphite is modified, the graphite modified by metal nano particles with uniform distribution and consistent particle size is obtained, and the obtained three-dimensional graphite skeleton pole piece has rich gaps through coating, and can accommodate the volume expansion of metal lithium. According to the invention, graphite is used as a deposition substrate, lithium is preferentially inserted into the graphite layers and then deposited on the graphite surface, and the graphite can store a part of lithium, so that a part of problems caused by lithium metal deposition are avoided, and the three-dimensional structure of the graphite pole piece is more stable.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of a metal nanoparticle modified graphite three-dimensional framework material comprises the following steps:
mixing graphite, metal salt, polyvinylpyrrolidone and water, fully stirring and then carrying out ultrasonic treatment to obtain a mixed solution; the mass ratio of the graphite substance to the metal salt substance to the polyvinylpyrrolidone is (33.5-134) mol:1mol, (3-15) mg;
spray drying the mixed solution to obtain solid powder;
and annealing the solid powder in argon at 495-505 ℃, cooling and grinding to obtain the nano metal modified graphite framework material.
2. The method according to claim 1, wherein the metal salt is one or more selected from the group consisting of silver salts, zinc salts, gold salts, tin salts, and magnesium salts.
3. The method of claim 1, wherein the graphite is selected from spherical graphite and flake graphite.
4. The preparation method according to claim 1, wherein the time for sufficient stirring is 2-4 h; the ultrasonic time is 0.5-1 h.
5. The method according to claim 1, wherein the spray-drying has an inlet temperature of 200 to 220 ℃ and an outlet temperature of 100 to 110 ℃.
6. The method according to claim 1, wherein the annealing is carried out at 495 to 505 ℃ for 110 to 130 min.
7. The graphite three-dimensional framework pole piece is characterized by comprising a nano metal modified graphite framework material, conductive carbon black, sodium carboxymethylcellulose and styrene butadiene rubber in a mass ratio of 90: 3.5-4.5: 2.5-3.5.
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