CN114890392B - Carbon-coated tin selenide composite glue-linked three-dimensional graphene and preparation method and application thereof - Google Patents
Carbon-coated tin selenide composite glue-linked three-dimensional graphene and preparation method and application thereof Download PDFInfo
- Publication number
- CN114890392B CN114890392B CN202210642447.3A CN202210642447A CN114890392B CN 114890392 B CN114890392 B CN 114890392B CN 202210642447 A CN202210642447 A CN 202210642447A CN 114890392 B CN114890392 B CN 114890392B
- Authority
- CN
- China
- Prior art keywords
- carbon
- mixed solution
- dimensional graphene
- hydrothermal
- tin selenide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- MFIWAIVSOUGHLI-UHFFFAOYSA-N selenium;tin Chemical compound [Sn]=[Se] MFIWAIVSOUGHLI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003292 glue Substances 0.000 title claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 22
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000084 colloidal system Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000007773 negative electrode material Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims description 71
- 238000003756 stirring Methods 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 33
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- 238000004108 freeze drying Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 238000011049 filling Methods 0.000 claims description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000009831 deintercalation Methods 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
- C01B32/192—Preparation by exfoliation starting from graphitic oxides
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses carbon-coated tin selenide composite gel-linked three-dimensional graphene and a preparation method and application thereof, belongs to the technical field of electrochemical energy storage, and solves the technical problem that when a carbon material is used as a negative electrode material of a potassium ion battery, the electrochemical performance of the potassium ion battery is poor due to volume expansion of the electrode material. According to the preparation method of the carbon-coated tin selenide composite colloid three-dimensional graphene, snSe nano particles are uniformly distributed on a carbon-coated colloid three-dimensional graphene sheet layer through a solvothermal combination heat treatment method, and a 3DGO three-dimensional colloid structure is synthesized to enable the SnSe to relieve the volume expansion problem in the potassium ion deintercalation process. When the prepared carbon-coated tin selenide composite colloidal three-dimensional graphene is used as a cathode material of a potassium ion battery, the carbon-coated tin selenide composite colloidal three-dimensional graphene has excellent electrochemical performance and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to carbon-coated tin selenide composite glue-linked three-dimensional graphene, and a preparation method and application thereof.
Background
The potassium has the characteristics of abundant reserves in the crust, wide sources and low price; meanwhile, in an electrochemical system, potassium has lower electrode potential and faster ion conductivity, and compared with alkali metal sodium of the same main group, potassium has lower reduction potential, so that the potassium ion battery can work at higher potential and is expected to become an ideal substitute of the lithium ion battery. Potassium ion batteries are therefore considered to be ideal energy storage systems for future replacement of lithium ion batteries.
The tin-based material has the characteristics of high conductivity, environmental friendliness and the like. The tin selenide alloy has the characteristics of high theoretical specific capacity, good safety performance, abundant reserves and the like, and the performance of the alkali metal ion battery of the current tin selenide-based anode material has great potential, but the stability of the charge-discharge structure of the alkali metal ion battery still needs to be further improved. Many researchers choose to compound the SnSe/r-GO electrode material with a certain carbon material to improve the problems, and the SnSe/r-GO electrode material is prepared by taking Sn and Se as raw materials by a high-energy ball milling method by using yang-air (yang) of Jilin university, has a reversible capacity of 590mAh g-1, has a reversible capacity of 260mAh g-1 under a current density of 10Ag-1, and shows excellent multiplying power performance. Research shows that the carbon material is used as the anode material of the potassium ion battery, K + Intercalation/deintercalation causes volumetric expansion of the electrode material, which may shorten the cycle life of PIBs, resulting in significant lack of electrochemical performance advantages of potassium ion batteries.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide carbon-coated tin selenide composite colloid three-dimensional graphene, and a preparation method and application thereof, which are used for solving the technical problem that when a carbon material is used as a negative electrode material of a potassium ion battery, the electrochemical performance of the potassium ion battery is poor due to the volume expansion of the electrode material.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of carbon-coated tin selenide composite colloidal-linked three-dimensional graphene, which comprises the following steps:
s1: mixing graphite powder, potassium permanganate and sulfuric acid, and performing hydrothermal reaction to obtain a mixture A; cooling the mixture A, mixing the mixture A with deionized water to obtain a mixed solution, adding hydrogen peroxide into the mixed solution until the mixed solution does not bubble any more, standing for layering, and regulating the pH value to be neutral to obtain graphene oxide slurry B; freeze-drying the graphene oxide slurry B to obtain graphene oxide C;
s2: mixing graphene oxide C with deionized water, and performing dispersion treatment to obtain a mixed solution D; carrying out hydrothermal reaction on the mixed solution D, cooling and freeze-drying to obtain cylindrical three-dimensional graphene F; mixing cylindrical three-dimensional graphene F with glycerol, adding stannous chloride dihydrate or potassium stannate, stirring, and adding a surfactant to obtain a mixed solution G;
s3: mixing selenium powder and a reducing solvent to obtain a mixed solution H; dropwise adding the obtained mixed solution H into the mixed solution G to obtain a mixed solution I; uniformly stirring the mixed solution I, performing hydrothermal reaction to obtain a reaction product, separating and collecting the reaction product to obtain powder, and drying the powder to obtain a product X; mixing and grinding the product X and 2-methylimidazole solid phase, and then carrying out homogeneous phase reaction to obtain black powder Z; and calcining the black powder Z to obtain the carbon-coated tin selenide composite colloidal three-dimensional graphene.
Further, in S1, the dosage ratio of the graphite powder, the potassium permanganate, the sulfuric acid and the deionized water is (0.1-1) g: (1-6) g: (10-50) mL: (100-200) mL; the temperature of the hydrothermal reaction is 50-150 ℃, and the time of the hydrothermal reaction is 1-5 h; the pH value is adjusted to be neutral, and hydrochloric acid and deionized water are adopted for cleaning.
Further, in S2, the dosage ratio of the graphene oxide C to the deionized water is (80-150) mg: (10-50) mL; the dispersion treatment mode is ultrasonic dispersion treatment, and the ultrasonic dispersion treatment time is 15-45 min; the reaction temperature of the mixed solution D for hydrothermal reaction is 120-240 ℃, and the hydrothermal reaction time is 8-16 h; the dosage ratio of the glycerol to the stannous chloride dihydrate or the potassium stannate to the surfactant is (20-85) mL: (0.0235-5.067) g: (0.057-0.57) g; the surfactant is a surfactant 6501 or a surfactant EDTA.
Further, in S3, the reducing solvent includes n-butylamine, hydrazine hydrate or sodium borohydride; the dosage ratio of the selenium powder to the reducing solvent is (0.0088-2.07) g: (2-10) mL.
Further, in S3, uniformly stirring the mixed solution I by adopting a magnetic stirrer, wherein the rotating speed of the magnetic stirrer is 300-500 r/min; the mixed solution I is put into a reaction vessel for hydrothermal reaction, the volume filling ratio of the mixed solution I in the reaction vessel is kept to be 50% -80%, the temperature of the hydrothermal reaction is 100-200 ℃, and the time of the hydrothermal reaction is 12-24 h.
In S3, the powder is dried by freeze drying for 10-15 hours.
Further, in S3, the mass ratio of the product X to the 2-methylimidazole solid is 3: (1-4); the temperature of the homogeneous reaction is 160-240 ℃; the calcination temperature is 600-800 ℃, and the calcination time is 4-8 h.
The invention also discloses the carbon-coated tin selenide composite crosslinked three-dimensional graphene prepared by the preparation method.
The invention also discloses application of the carbon-coated tin selenide composite glue-linked three-dimensional graphene, and the carbon-coated tin selenide composite glue-linked three-dimensional graphene is used as a negative electrode material of a potassium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of carbon-coated tin selenide composite colloid three-dimensional graphene, which is characterized in that SnSe nano particles are uniformly distributed on a carbon-coated colloid three-dimensional graphene sheet layer through a solvothermal combination heat treatment method to synthesize a SnSe/3D r-GO@C composite material, wherein a 3DGO three-dimensional colloid structure is adopted, so that the volume expansion problem of the SnSe is relieved in the potassium ion deintercalation process. The method for preparing the carbon-coated tin selenide composite colloidal three-dimensional graphene has the advantages of simple reaction condition requirements, easiness in operation, easiness in control of experimental process and substance morphology, capability of industrial production and good application prospect.
The invention also discloses the carbon-coated tin selenide composite colloid three-dimensional graphene prepared by the preparation method, and the nano SnSe structure grown on the carbon-coated tin selenide composite colloid three-dimensional graphene sheet is uniform and loose, and the carbon source coated outside can improve the capacity of the composite material as an electrode material, and the 3DGO three-dimensional colloid structure can relieve the volume expansion problem of the SnSe in the potassium ion deintercalation process.
The invention also discloses application of the carbon-coated tin selenide composite gel-like three-dimensional graphene as a negative electrode material of a potassium ion battery, because the radius of potassium ions is larger, the migration rate in a negative electrode material body phase is relatively slow, K ions are inserted to cause volume expansion, the cycle life of PIBs can be shortened, tin selenide is used as an alloy negative electrode material, the carbon-coated tin selenide composite gel-like three-dimensional graphene has excellent potassium storage performance, and because of a 3DGO three-dimensional gel-like structure, the problem of electrode volume expansion of SnSe in a potassium ion deintercalation process is relieved, and the coating of pyrolytic carbon further improves the specific capacity of the composite material as the potassium ion negative electrode material and the stability in a potassium ion deintercalation process. When the carbon-coated tin selenide composite gel-linked three-dimensional graphene is used as a negative electrode material of a potassium ion battery, excellent electrochemical performance is shown, and related experimental results prove that the first-ring charge-discharge specific capacity of the SnSe/3D r-GO@C composite electrode is 300mAh g -1 The reversible capacity of the electrode can still reach 250mAh g when the electrode circulates for 150 circles -1 The composite electrode is compared with other electrodesHas good cycle stability.
Drawings
FIG. 1 is an XRD pattern of carbon-coated tin selenide composite colloidal three-dimensional graphene prepared in example 1 of the invention;
fig. 2 is an SEM image of the carbon-coated tin selenide composite colloidal three-dimensional graphene prepared in example 1 of the present invention;
fig. 3 is an SEM image of the carbon-coated tin selenide composite colloidal three-dimensional graphene prepared in example 1 of the present invention;
fig. 4 is an electrochemical performance diagram of the carbon-coated tin selenide composite colloidal three-dimensional graphene prepared in example 1 of the present invention as a negative electrode material of a potassium ion battery.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise indicated, "comprising," "including," "having," or similar terms encompass the meanings of "consisting of … …" and "consisting essentially of … …," e.g., "a includes a" encompasses the meanings of "a includes a and the other and" a includes a only.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The following examples used various starting materials, unless otherwise indicated, were conventional commercial products, the specifications of which are conventional in the art. In the description of the present invention and the following examples, "%" means weight percent, and "parts" means parts by weight, and ratios means weight ratio, unless otherwise specified.
Example 1
A preparation method of carbon-coated tin selenide composite colloid three-dimensional graphene comprises the following steps:
s1: adding 0.1g of graphite powder, 1g of potassium permanganate and 10mL of concentrated sulfuric acid into a hydrothermal kettle, sealing the hydrothermal kettle, and then placing the kettle into a homogeneous reactor for hydrothermal reaction at 50 ℃ for 1h to obtain a mixture A; naturally cooling the hydrothermal kettle to room temperature, pouring the product A in the hydrothermal lining into 100mL of deionized water for mixing to obtain a mixed solution, stirring the mixed solution, adding hydrogen peroxide in the stirring process until the mixed solution does not bubble any more, standing for layering, and washing with hydrochloric acid and deionized water until the mixed solution is neutral to obtain graphene oxide slurry B; lyophilizing the graphene oxide slurry B to obtain graphene oxide C;
s2: mixing 80mg of graphene oxide C with 10mL of deionized water, and performing ultrasonic dispersion for 15min to obtain a mixed solution D; putting the mixed solution D into a polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 50%, performing hydrothermal reaction at 120 ℃ for 8 hours, cooling to room temperature, and performing freeze drying to obtain cylindrical three-dimensional graphene F; adding cylindrical three-dimensional graphene F into 20mL of glycerin, uniformly dispersing, adding 0.0235G of stannous chloride dihydrate, and continuously stirring while adding 0.057G of surfactant 6501 to obtain a solution G;
s3: adding 0.0088g selenium powder into 2mL reducing solvent n-butylamine, and stirring until the selenium powder is completely dissolved to obtain solution H; dropwise adding the solution H into the solution G to form a mixed solution I, and uniformly stirring at a rotating speed of 300r/min by using a magnetic stirrer; then pouring the uniformly mixed solution I into a 100mL polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 50%, carrying out hydrothermal reaction at 100 ℃ for 12 hours to obtain a reaction product, separating and collecting the reaction product to obtain powder, freeze-drying the powder for 10 hours to obtain a product X, carrying out solid-phase mixing and grinding on the product X and 2-methylimidazole according to the ratio of 3:1, and carrying out homogeneous reaction at 160 ℃ to obtain black powder Z; calcining black powder Z at 600 ℃ for 4 hours to obtain the SnSe/3Dr-GO@C compound.
Example 2
A preparation method of carbon-coated tin selenide composite colloid three-dimensional graphene comprises the following steps:
s1: adding 0.3g of graphite powder, 3g of potassium permanganate and 25mL of concentrated sulfuric acid into a hydrothermal kettle, sealing the hydrothermal kettle, and then placing the kettle into a homogeneous reactor for hydrothermal reaction at 120 ℃ for 3 hours to obtain a mixture A; naturally cooling the hydrothermal kettle to room temperature, pouring the product A in the hydrothermal lining into 180mL of deionized water for mixing to obtain a mixed solution, stirring the mixed solution, adding hydrogen peroxide in the stirring process until the mixed solution does not bubble any more, standing for layering, and washing with hydrochloric acid and deionized water until the mixed solution is neutral to obtain graphene oxide slurry B; lyophilizing the graphene oxide slurry B to obtain graphene oxide C;
s2: mixing 100mg of graphene oxide C with 40mL of deionized water, and performing ultrasonic dispersion for 30min to obtain a mixed solution D; putting the mixed solution D into a polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 70%, performing hydrothermal reaction for 15h at 220 ℃, cooling to room temperature, and performing freeze drying to obtain cylindrical three-dimensional graphene F; adding cylindrical three-dimensional graphene F into 50mL of glycerin, uniformly dispersing, adding 3.98G of potassium stannate, and continuously stirring while adding 0.35G of surfactant EDTA to obtain a solution G;
s3: adding 1.01g of selenium powder into 8mL of solvent hydrazine hydrate, and stirring until the selenium powder is completely dissolved to obtain solution H; dropwise adding the solution H into the solution G to form a mixed solution I, and uniformly stirring at the rotating speed of 450r/min by using a magnetic stirrer; then pouring the uniformly mixed solution I into a 100mL polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 60%, carrying out hydrothermal reaction at 160 ℃ for 8 hours to obtain a reaction product, separating and collecting the reaction product to obtain powder, freeze-drying the powder for 10 hours to obtain a product X, carrying out solid-phase mixing and grinding on the product X and 2-methylimidazole according to the mass ratio of 3:4, and carrying out homogeneous reaction at 160 ℃ to obtain black powder Z; calcining the black powder Z at 650 ℃ for 5 hours to obtain the SnSe/3Dr-GO@C compound.
Example 3
A preparation method of carbon-coated tin selenide composite colloid three-dimensional graphene comprises the following steps:
s1: adding 0.5g of graphite powder, 5g of potassium permanganate and 30mL of concentrated sulfuric acid into a hydrothermal kettle, sealing the hydrothermal kettle, and then placing the kettle into a homogeneous reactor for hydrothermal reaction at 110 ℃ for 3 hours to obtain a mixture A; naturally cooling the hydrothermal kettle to room temperature, pouring the product A in the hydrothermal lining into 180mL of deionized water for mixing to obtain a mixed solution, stirring the mixed solution, adding hydrogen peroxide in the stirring process until the mixed solution does not bubble any more, standing for layering, and washing with hydrochloric acid and deionized water until the mixed solution is neutral to obtain graphene oxide slurry B; lyophilizing the graphene oxide slurry B to obtain graphene oxide C;
s2: mixing 120mg of graphene oxide C with 40mL of deionized water, and performing ultrasonic dispersion for 30min to obtain a mixed solution D; putting the mixed solution D into a polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 70%, performing hydrothermal reaction at 200 ℃ for 15 hours, cooling to room temperature, and performing freeze drying to obtain cylindrical three-dimensional graphene F; adding cylindrical three-dimensional graphene F into 65mL of glycerin, uniformly dispersing, adding 4.34G of potassium stannate, and continuously stirring while adding 0.49G of surfactant EDTA to obtain a solution G;
s3: adding 0.89g of selenium powder into 7mL of reducing solvent n-butylamine, and stirring until the selenium powder is completely dissolved to obtain solution H; dropwise adding the solution H into the solution G to form a mixed solution I, and uniformly stirring at the rotating speed of 450r/min by using a magnetic stirrer; then pouring the uniformly mixed solution I into a 100mL polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 80%, carrying out hydrothermal reaction at 160 ℃ for 20 hours to obtain a reaction product, separating and collecting the reaction product to obtain powder, freeze-drying the powder for 13 hours to obtain a product X, carrying out solid-phase mixing and grinding on the product X and 2-methylimidazole according to the ratio of 3:2, and carrying out homogeneous reaction at 180 ℃ to obtain black powder Z; calcining black powder Z at 700 ℃ for 6 hours to obtain the SnSe/3Dr-GO@C compound.
Example 4
A preparation method of carbon-coated tin selenide composite colloid three-dimensional graphene comprises the following steps:
s1: adding 0.4g of graphite powder, 3.5g of potassium permanganate and 40mL of concentrated sulfuric acid into a hydrothermal kettle, sealing the hydrothermal kettle, and then placing the kettle into a homogeneous reactor for hydrothermal reaction for 4 hours at 145 ℃ to obtain a mixture A; naturally cooling the hydrothermal kettle to room temperature, pouring the product A in the hydrothermal lining into 175mL of deionized water for mixing to obtain a mixed solution, stirring the mixed solution, adding hydrogen peroxide in the stirring process until the mixed solution does not bubble any more, standing for layering, and washing with hydrochloric acid and deionized water until the mixed solution is neutral to obtain graphene oxide slurry B; lyophilizing the graphene oxide slurry B to obtain graphene oxide C;
s2: mixing 95mg of graphene oxide C with 40mL of deionized water, and performing ultrasonic dispersion for 40min to obtain a mixed solution D; putting the mixed solution D into a polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 70%, performing hydrothermal reaction at 160 ℃ for 12 hours, cooling to room temperature, and performing freeze drying to obtain cylindrical three-dimensional graphene F; adding cylindrical three-dimensional graphene F into 75mL of glycerin, uniformly dispersing, adding 2.089G of potassium stannate, and continuously stirring while adding 0.35G of surfactant 6501 to obtain solution G;
s3: adding 0.97g of selenium powder into 8mL of reducing solvent sodium borohydride, and stirring until the selenium powder is completely dissolved to obtain solution H; dropwise adding the solution H into the solution G to form a mixed solution I, and uniformly stirring at a rotating speed of 400r/min by using a magnetic stirrer; then pouring the uniformly mixed solution I into a 100mL polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 70%, carrying out hydrothermal reaction at 160 ℃ for 18 hours to obtain a reaction product, separating and collecting the reaction product to obtain powder, freeze-drying the powder for 12 hours to obtain a product X, carrying out solid-phase mixing and grinding on the product X and 2-methylimidazole according to the ratio of 3:3, and carrying out homogeneous reaction at 200 ℃ to obtain black powder Z; calcining black powder Z at 700 ℃ for 7 hours to obtain the SnSe/3Dr-GO@C compound.
Example 5
A preparation method of carbon-coated tin selenide composite colloid three-dimensional graphene comprises the following steps:
s1: adding 0.5g of graphite powder, 4.0g of potassium permanganate and 45mL of concentrated sulfuric acid into a hydrothermal kettle, sealing the hydrothermal kettle, and then placing the kettle into a homogeneous reactor for hydrothermal reaction at 140 ℃ for 4 hours to obtain a mixture A; naturally cooling the hydrothermal kettle to room temperature, pouring the product A in the hydrothermal lining into 180mL of deionized water for mixing to obtain a mixed solution, stirring the mixed solution, adding hydrogen peroxide in the stirring process until the mixed solution does not bubble any more, standing for layering, and washing with hydrochloric acid and deionized water until the mixed solution is neutral to obtain graphene oxide slurry B; lyophilizing the graphene oxide slurry B to obtain graphene oxide C;
s2: mixing 100mg of graphene oxide C with 45mL of deionized water, and performing ultrasonic dispersion for 40min to obtain a mixed solution D; putting the mixed solution D into a polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 70%, performing hydrothermal reaction at 180 ℃ for 15 hours, cooling to room temperature, and performing freeze drying to obtain cylindrical three-dimensional graphene F; adding cylindrical three-dimensional graphene F into 75mL of glycerin, dispersing uniformly, adding 3.067G of potassium stannate, and adding 0.46G of surfactant 6501 while continuously stirring to obtain a solution G;
s3: adding 1.05g of selenium powder into 8mL of reducing solvent sodium borohydride, and stirring until the selenium powder is completely dissolved to obtain solution H; dropwise adding the solution H into the solution G to form a mixed solution I, and uniformly stirring at the rotating speed of 450r/min by using a magnetic stirrer; then pouring the uniformly mixed solution I into a 100mL polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 60%, carrying out hydrothermal reaction at 180 ℃ for 18 hours to obtain a reaction product, separating and collecting the reaction product to obtain powder, freeze-drying the powder for 13 hours to obtain a product X, carrying out solid-phase mixing and grinding on the product X and 2-methylimidazole according to the mass ratio of 3:4, and carrying out homogeneous reaction at 220 ℃ to obtain black powder Z; and calcining the black powder Z at 750 ℃ for 7 hours to obtain the SnSe/3Dr-GO@C compound.
Example 6
A preparation method of carbon-coated tin selenide composite colloid three-dimensional graphene comprises the following steps:
s1: adding 1.0g of graphite powder, 6.0g of potassium permanganate and 50mL of concentrated sulfuric acid into a hydrothermal kettle, sealing the hydrothermal kettle, and then placing the kettle into a homogeneous reactor for hydrothermal reaction at 150 ℃ for 5 hours to obtain a mixture A; naturally cooling the hydrothermal kettle to room temperature, pouring the product A in the hydrothermal lining into 200mL of deionized water for mixing to obtain a mixed solution, stirring the mixed solution, adding hydrogen peroxide in the stirring process until the mixed solution does not bubble any more, standing for layering, and washing with hydrochloric acid and deionized water until the mixed solution is neutral to obtain graphene oxide slurry B; lyophilizing the graphene oxide slurry B to obtain graphene oxide C;
s2: mixing 150mg of graphene oxide C with 50mL of deionized water, and performing ultrasonic dispersion for 45min to obtain a mixed solution D; putting the mixed solution D into a polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 80%, performing hydrothermal reaction at 240 ℃ for 16 hours, cooling to room temperature, and performing freeze drying to obtain cylindrical three-dimensional graphene F; adding cylindrical three-dimensional graphene F into 85mL of glycerin, uniformly dispersing, adding 5.067G of potassium stannate, and continuously stirring while adding 0.57G of surfactant EDTA to obtain a solution G;
s3: adding 2.07g of selenium powder into 10mL of reducing solvent hydrazine hydrate, and stirring until the selenium powder is completely dissolved to obtain solution H; dropwise adding the solution H into the solution G to form a mixed solution I, and uniformly stirring at a rotating speed of 500r/min by using a magnetic stirrer; then pouring the uniformly mixed solution I into a 100mL polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 80%, carrying out hydrothermal reaction at 200 ℃ for 24 hours to obtain a reaction product, separating and collecting the reaction product to obtain powder, freeze-drying the powder for 15 hours to obtain a product X, carrying out solid-phase mixing and grinding on the product X and 2-methylimidazole according to the mass ratio of 3:4, and carrying out homogeneous reaction at 240 ℃ to obtain black powder Z; calcining black powder Z at 800 ℃ for 8 hours to obtain the SnSe/3Dr-GO@C compound.
Fig. 1 shows an XRD pattern of the carbon-coated tin selenide composite colloidal three-dimensional graphene prepared in example 1 of the present invention, and it can be seen from the figure that the corresponding standard card is SnSe 48-1224, and tin selenide nanoparticles enter the carbon-coated three-dimensional graphene. Fig. 2 shows an SEM map of the carbon-coated tin selenide composite colloidal three-dimensional graphene prepared in example 1 of the present invention, from which the morphology of the carbon-coated colloidal three-dimensional graphene can be seen. Fig. 3 is an SEM image of carbon-coated tin selenide composite colloidal three-dimensional graphene prepared in example 1 of the present invention, and it can be seen that SnSe nanoparticles are uniformly attached to a carbon-coated three-dimensional graphene sheet. FIG. 4 shows an electrochemical performance spectrum of the carbon-coated tin selenide composite colloidal three-dimensional graphene prepared in example 1 of the invention as a cathode material of a potassium ion battery, and can be seen that SnSe/3D r-GO@C composite electric powerThe first-circle charge-discharge specific capacity of the pole is 300mAh g -1 The reversible capacity of the electrode can still reach 250mAh g when the electrode circulates for 150 circles -1 The SnSe/3D r-GO@C composite electrode has good cycling stability compared with other electrodes.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (1)
1. The application of the carbon-coated tin selenide composite colloid three-dimensional graphene is characterized in that the carbon-coated tin selenide composite colloid three-dimensional graphene is used as a negative electrode material of a potassium ion battery;
the preparation method of the carbon-coated tin selenide composite glue-linked three-dimensional graphene comprises the following steps:
s1: adding 0.1g of graphite powder, 1g of potassium permanganate and 10mL of concentrated sulfuric acid into a hydrothermal kettle, sealing the hydrothermal kettle, and then placing the kettle into a homogeneous reactor for hydrothermal reaction at 50 ℃ for 1h to obtain a mixture A; naturally cooling the hydrothermal kettle to room temperature, pouring the product A in the hydrothermal lining into 100mL of deionized water for mixing to obtain a mixed solution, stirring the mixed solution, adding hydrogen peroxide in the stirring process until the mixed solution does not bubble any more, standing for layering, and washing with hydrochloric acid and deionized water until the mixed solution is neutral to obtain graphene oxide slurry B; lyophilizing the graphene oxide slurry B to obtain graphene oxide C;
s2: mixing 80mg of graphene oxide C with 10mL of deionized water, and performing ultrasonic dispersion for 15min to obtain a mixed solution D; putting the mixed solution D into a polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 50%, performing hydrothermal reaction at 120 ℃ for 8 hours, cooling to room temperature, and performing freeze drying to obtain cylindrical three-dimensional graphene F; adding cylindrical three-dimensional graphene F into 20mL of glycerin, uniformly dispersing, adding 0.0235G of stannous chloride dihydrate, and continuously stirring while adding 0.057G of surfactant 6501 to obtain a solution G;
s3: adding 0.0088g selenium powder into 2mL reducing solvent n-butylamine, and stirring until the selenium powder is completely dissolved to obtain solution H; dropwise adding the solution H into the solution G to form a mixed solution I, and uniformly stirring at a rotating speed of 300r/min by using a magnetic stirrer; then pouring the uniformly mixed solution I into a 100mL polytetrafluoroethylene lining high-pressure reaction kettle, keeping the volume filling ratio at 50%, carrying out hydrothermal reaction at 100 ℃ for 12 hours to obtain a reaction product, separating and collecting the reaction product to obtain powder, freeze-drying the powder for 10 hours to obtain a product X, carrying out solid-phase mixing and grinding on the product X and 2-methylimidazole according to the ratio of 3:1, and carrying out homogeneous reaction at 160 ℃ to obtain black powder Z; calcining black powder Z at 600 ℃ for 4 hours to obtain the SnSe/3Dr-GO@C compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210642447.3A CN114890392B (en) | 2022-06-08 | 2022-06-08 | Carbon-coated tin selenide composite glue-linked three-dimensional graphene and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210642447.3A CN114890392B (en) | 2022-06-08 | 2022-06-08 | Carbon-coated tin selenide composite glue-linked three-dimensional graphene and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114890392A CN114890392A (en) | 2022-08-12 |
| CN114890392B true CN114890392B (en) | 2024-01-30 |
Family
ID=82727496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210642447.3A Active CN114890392B (en) | 2022-06-08 | 2022-06-08 | Carbon-coated tin selenide composite glue-linked three-dimensional graphene and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114890392B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104617271A (en) * | 2015-01-29 | 2015-05-13 | 中南大学 | Stannic selenide/graphene oxide negative pole composite material for sodium ion battery and preparation method thereof |
| KR20160078820A (en) * | 2014-12-24 | 2016-07-05 | 주식회사 포스코 | Negative active material for sodium rechargeable battery and sodium rechargeable battery including the same |
| CN106207121A (en) * | 2016-08-11 | 2016-12-07 | 山西大学 | A kind of porous graphene load carbon coated iron oxide nano particle composite material and preparation method |
| CN109167047A (en) * | 2018-09-19 | 2019-01-08 | 哈尔滨工业大学 | Self-supporting three-dimensional grapheme/tin composite lithium ion battery cathode material preparation method |
| CN113097484A (en) * | 2021-04-01 | 2021-07-09 | 陕西科技大学 | Carbon-coated sandwich structure SnSe/r-GO @ C compound and preparation method and application thereof |
| CN113097486A (en) * | 2021-04-01 | 2021-07-09 | 陕西科技大学 | SnSe quantum dot/CFF compound and preparation method and application thereof |
-
2022
- 2022-06-08 CN CN202210642447.3A patent/CN114890392B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160078820A (en) * | 2014-12-24 | 2016-07-05 | 주식회사 포스코 | Negative active material for sodium rechargeable battery and sodium rechargeable battery including the same |
| CN104617271A (en) * | 2015-01-29 | 2015-05-13 | 中南大学 | Stannic selenide/graphene oxide negative pole composite material for sodium ion battery and preparation method thereof |
| CN106207121A (en) * | 2016-08-11 | 2016-12-07 | 山西大学 | A kind of porous graphene load carbon coated iron oxide nano particle composite material and preparation method |
| CN109167047A (en) * | 2018-09-19 | 2019-01-08 | 哈尔滨工业大学 | Self-supporting three-dimensional grapheme/tin composite lithium ion battery cathode material preparation method |
| CN113097484A (en) * | 2021-04-01 | 2021-07-09 | 陕西科技大学 | Carbon-coated sandwich structure SnSe/r-GO @ C compound and preparation method and application thereof |
| CN113097486A (en) * | 2021-04-01 | 2021-07-09 | 陕西科技大学 | SnSe quantum dot/CFF compound and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 锂/钠离子电池用锡基负极材料的制备及电化学性能研究;程娅伊;中国博士学位论文全文数据库 工程科技Ⅱ辑(第12期);第C042-104页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114890392A (en) | 2022-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112349899B (en) | Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN100544081C (en) | A kind of nano lithium titanate and with the preparation method of the compound of titanium dioxide | |
| CN112103493A (en) | Preparation method of lithium battery negative electrode material titanium-niobium composite oxide | |
| CN109301204B (en) | Preparation method of hollow sphere structure tin sulfide/tin oxide lithium ion battery anode material | |
| CN112186182B (en) | One-dimensional hollow carbon-coated iron selenide nanotube composite electrode material and preparation method thereof | |
| CN109920995B (en) | Silicon or oxide @ titanium oxide core-shell structure composite material and preparation method thereof | |
| CN108039464A (en) | A kind of self-supporting sodium ions to potassium ions battery material and preparation method and application | |
| CN109449411B (en) | Method for synthesizing tungsten disulfide @ C composite electrode material in limited domain | |
| CN112786865A (en) | MoS2Preparation method and application of quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material | |
| CN113659139A (en) | Vanadium sodium phosphate electrode material of vanadium-position copper-doped composite carbon nanotube and preparation method and application thereof | |
| CN111370699A (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN105845920B (en) | A kind of high circulation stability nanometer rods self assembly molybdenum trioxide material and preparation method thereof | |
| CN113991084A (en) | SnS-SnO2-GO @ C heterostructure composite material and preparation method and application thereof | |
| CN113097486A (en) | SnSe quantum dot/CFF compound and preparation method and application thereof | |
| CN111224084B (en) | Lithium iron phosphate/lithium silicate composite material and preparation method and application thereof | |
| CN110061206B (en) | SiO-based nano composite material, negative electrode and preparation method thereof | |
| CN116936771A (en) | Hollow spherical shell structure ferric sodium sulfate composite positive electrode material, preparation method and sodium ion battery | |
| CN114890392B (en) | Carbon-coated tin selenide composite glue-linked three-dimensional graphene and preparation method and application thereof | |
| CN114094062B (en) | Preparation method and application of high-performance lithium and sodium storage material for synthesizing tin dioxide nanoparticle composite graphene with assistance of oxalic acid | |
| CN115911331A (en) | Preparation method of low-nickel copper manganese-based sodium ion battery positive electrode material | |
| CN112794360B (en) | Preparation of nano SnO 2 Method for preparing/GC composite anode material | |
| CN113937257A (en) | Nitrogen and fluorine co-doped titanium dioxide/carbon microsphere material, preparation method thereof and application thereof in sodium ion battery | |
| CN111403725A (en) | Aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material and preparation method thereof | |
| CN113871587B (en) | Preparation method of silicon @ carbon nanotube @ carbon composite negative electrode material of lithium ion battery | |
| CN115490213B (en) | VSe derived from metal-organic frameworks 2 Material, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |