CN113044840B - Active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material and preparation method and application thereof - Google Patents
Active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113044840B CN113044840B CN202110255160.0A CN202110255160A CN113044840B CN 113044840 B CN113044840 B CN 113044840B CN 202110255160 A CN202110255160 A CN 202110255160A CN 113044840 B CN113044840 B CN 113044840B
- Authority
- CN
- China
- Prior art keywords
- composite material
- nitrogen double
- active carbon
- sheet array
- array composite
- 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 145
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 108
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000002135 nanosheet Substances 0.000 title claims abstract description 49
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 48
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000011733 molybdenum Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 59
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 25
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 24
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 16
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 abstract description 8
- 229940010552 ammonium molybdate Drugs 0.000 abstract description 8
- 235000018660 ammonium molybdate Nutrition 0.000 abstract description 8
- 239000011609 ammonium molybdate Substances 0.000 abstract description 8
- 229910052786 argon Inorganic materials 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000002064 nanoplatelet Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 241000630627 Diodella Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XACAZEWCMFHVBX-UHFFFAOYSA-N [C].[Mo] Chemical class [C].[Mo] XACAZEWCMFHVBX-UHFFFAOYSA-N 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/372—Coating; Grafting; Microencapsulation
-
- 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
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
-
- 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
- H01M4/58—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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 an active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite materialA preparation method and application thereof, belonging to the technical field of preparation of anode materials of potassium ion batteries. The method firstly uses the functionalized activated carbon, 2, 3-pyridine dicarboxylic acid and CoCl 2 ·6H 2 O, urea and ammonium molybdate are uniformly mixed, a precursor is prepared by heating treatment, and then carbonized at high temperature in an argon environment to prepare the active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material. The active carbon loaded molybdenum and nitrogen double-doped carbon nano sheet array composite material prepared by the method has high purity, can be used as a negative electrode material of a potassium ion battery, has good cyclic stability and high discharge specific capacity, and can be widely used as the negative electrode material of the potassium ion battery.
Description
Technical Field
The invention belongs to the technical field of preparation of a negative electrode material of a potassium ion battery, relates to an active carbon-loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material, a preparation method thereof and application thereof, and in particular relates to an active carbon-loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material, a preparation method thereof and application thereof as a negative electrode of a potassium ion battery.
Background
Potassium ion batteries are considered to be the most promising alternatives to lithium ion batteries as a sustainable energy storage device due to the potassium-rich and low cost of the crust. [ Wu, x.; chen, y; xing, Z.; lam, c.w.k.; pang, s—s; zhang, w.; ju, z.adv.energy mate.2019, 9,1900343.]The crustal deposition amount of potassium (1.5 wt%) was 882.4 times that of lithium (0.0017 wt%). [ Zheng, j.; yang, y; fan, x.; ji, g.; ji, x; wang, h.; hou, s.; zachariah, m.r.; wang, c.energy.environ.sci.2019, 12,615.]At the same time K + The redox potential of/K is closer to Li + The redox potential of/Li (-2.93V vs E compared to-3.04V vs E, standard hydrogen electrode (E, SHE)), indicates that the potassium ion cell has a wider voltage range and higher energy density. [ Kubota, k.; dahbi, m.; hosaka, t.; kumakura, s.; komaba, s.chem. Rec.2018,18,459.]The potassium ion battery also has K + vs Li + The advantage of weaker Lewis acidity results in a smaller stokes radius for solvated ions, and higher transport number and mobility in the electrolyte, which provides an opportunity for designing large current cells. [Kubota,K.;Dahbi,M.;Hosaka,T.;Kumakura,S.;Komaba,S.Chem.Rec.2018,18,459.]However, the main challenge of potassium ion batteries is K + Is larger than Li + />Thus, K is + The insertion/de-insertion of (c) will cause the electrode material to expand in volume, resulting in low capacity, poor cycling stability, and poor rate performance.
To overcome the barrier to potassization and potassium removal, a good alternative is to control the expansion of carbon lattice spacing by doping N, S, O and P, and generally exhibit higher cycle reversibility than undoped carbon. The three-dimensional S and N co-doped carbon nanofiber aerogel electrode is 2A g -1 168mA h g with high reversible capacity -1 。[Lv,C.;Xu,W.;Liu,H.;Zhang,L.;Chen,S.;Yang,X.;Xu,X.;Yang,D.Small 2019,15,1900816.]The composite carbon rich in S (12.9 at%) and rich in N (9.9 at%) is used as the anode material of the potassium ion battery, and the anode material is 1A g -1 When it reaches 234mA h g -1 Is a function of the capacity of the battery. [ Tao, l.; yang, y; wang, h.; zheng, y; hao, h.; song, w.; shi, j.; huang, m.; mitlin, d.energy Storage mate.2020, 27,212.]The double-doped carbon with the synergistic effect has stronger reversibility.
In recent years, double doped carbon has good electrochemical properties including N, O doped hard carbon, P, N doped carbon, and S, O doped porous hard carbon microspheres. The co-doped carbon materials of metals and non-metals not only increase lattice spacing, but also have higher capacities than potassium-doped materials. Molybdenum-carbon composites have higher theoretical capacity, good conductivity, stable metallic properties and thermal stability, and have been successfully used to enhance Li and Na storage. However, the use of in situ carbonized nitrogen-rich phthalocyanine to synthesize Mo and N co-doped carbon nanocomposites as anode for potassium ion batteries has been reported.
Disclosure of Invention
The invention aims to provide a preparation method of an active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material similar to a silver ear structure and application of the active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material as a negative electrode material of a potassium ion battery, and the preparation method has the characteristics of no pollution, simple process, short time, low energy consumption, good stability, high yield and the like, and can meet the requirement of mass production; the active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material prepared by the method has the characteristics of high specific capacity, stable cycle performance and the like in the preparation of the potassium ion battery 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 an active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material, which comprises the following steps:
1) 2, 3-Pyridinedicarboxylic acid, coCl 2 ·6H 2 Mixing O, urea, molybdic acid and functionalized activated carbon uniformly to prepare a mixture;
2) Heating the mixture from room temperature to 100-200 ℃, performing heat preservation treatment for 10-60 min, then heating to 200-300 ℃, performing heat preservation treatment for 1-3 h, and cooling to room temperature;
3) Heating the product treated in the step 2) to 500-700 ℃ from room temperature under argon atmosphere, preserving heat for 10-60 min, then heating to 700-1000 ℃, preserving heat for 1-4 h, and cooling to room temperature;
4) And (3) cleaning and drying the product treated in the step (3) to obtain the active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material.
Preferably, in step 1), 2, 3-pyridinedicarboxylic acid, coCl 2 ·6H 2 The mass ratio of O, urea, molybdic acid and the functionalized activated carbon is (1-2): (0.75-1.5): (1.5-3): (0.1-0.25): (0.5-1).
Preferably, the activated carbon after the functionalization treatment is prepared by placing the activated carbon in HNO with the concentration of 2 to 8mol/L 3 Heating in water bath at 40-80 deg.c for 10-40 hr to obtain the product.
Preferably, the step 2) is carried out in a muffle furnace, the temperature of the mixture is raised to 100-200 ℃ from room temperature at a temperature raising speed of 5-15 ℃/min, the heat preservation treatment is carried out for 10-60 min, and the mixture is heated to 200-300 ℃ at a temperature raising speed of 5-15 ℃/min.
Preferably, the step 3) is carried out in a tube furnace, the product treated in the step 2) is heated to 500-700 ℃ from room temperature at a heating rate of 5-15 ℃/min, and the temperature is kept for 10-60 minutes; then heating to 700-1000 ℃ at a heating rate of 5-15 ℃/min.
The invention also discloses the active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material prepared by the preparation method.
The invention also discloses application of the active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material in preparation of a potassium ion battery anode material.
The invention also discloses a potassium ion battery anode material which is prepared from the active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material, and the cycle performance of the potassium ion battery anode material under the current density of 50mA/g is as follows: the first circle reaches 457.5mAh/g, and the product is stabilized at 383.1mAh/g after 100 circles of circulation; at a high current density of 5A/g, the high capacity was 144.4mAh/g, and the loss rate per cycle was 0.49% per mill.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the active carbon supported molybdenum and nitrogen double-doped carbon nano-sheet array composite material has novel design thought, and the functionalized active carbon, 2, 3-pyridine dicarboxylic acid and CoCl are firstly treated 2 ·6H 2 O, urea and ammonium molybdate are uniformly mixed, a precursor is prepared by heating treatment, and then high-temperature carbonization is carried out under an argon environment, so that the active carbon supported molybdenum and nitrogen double-doped carbon nano-sheet array composite material is prepared, the active carbon is used as a carrier, the molybdenum and nitrogen double-doped carbon nano-sheet is grown on the surface and the mesopore of the active carbon in situ, and the active carbon supported molybdenum and nitrogen double-doped carbon nano-sheet array composite material is generated.
Further, the activated carbon used in the invention is prepared by adopting 2 to 8mol/L HNO 3 The activated carbon is functionalized by water bath heating treatment, and the operation condition can lead the surface of the activated carbon to generate carboxyl functional groups, and the carboxyl functional groups are compounded with the nitrogen-rich phthalocyanine to provide C-O-Co chemical bonds.
The active carbon loaded molybdenum and nitrogen double-doped carbon nano sheet array composite material prepared by the invention has high purity, can be used as a negative electrode material of a potassium ion battery, has good cycle stability (the cycle performance under the current density of 50mA/g is that the first circle reaches 457.5mAh/g, the cycle performance is that the active carbon is stabilized at 383.1mAh/g after 100 circles are circulated), has high discharge specific capacity (the high capacity is 144.4mAh/g under the high current density of 5A/g), and can be widely used as the negative electrode material of the potassium ion battery.
Drawings
FIG. 1 is an XRD pattern of an active carbon supported molybdenum and nitrogen double-doped carbon nano-sheet array composite material prepared by the invention;
FIG. 2 is an electron microscope photograph of the active carbon supported molybdenum and nitrogen double-doped carbon nano-sheet array composite material prepared by the invention; a and b are SEM images with different magnifications of the prepared active carbon loaded molybdenum and nitrogen double-doped carbon nano sheet array composite material; c. d is a TEM image with different magnification factors of the prepared active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material;
FIG. 3 is a graph showing the rate performance of the active carbon supported molybdenum and nitrogen double-doped carbon nano-sheet array composite material prepared by the invention in potassium ion batteries with different current densities.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the attached drawing figures:
example 1
The preparation method of the active carbon loaded molybdenum and nitrogen double-doped carbon nano sheet array composite material comprises the following steps:
1) Taking 0.1g of functionalized activated carbon (HNO of 2 mol/L) 3 In solution, heated in a 40℃water bath for 10 hours), 1.2g of 2, 3-pyridinedicarboxylic acid, 0.55g of CoCl 2 ·6H 2 Uniformly mixing 1.8g of O, 1.1 g of urea and 0.1g of ammonium molybdate; the method comprises the steps of carrying out a first treatment on the surface of the
2) Placing the mixture in a muffle furnace, heating the mixture to 100 ℃ from room temperature at a heating rate of 5 ℃/min, and preserving heat for 20 minutes; then heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature;
3) Placing the product treated in the step 2) into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under the argon environment, and preserving heat for 10 minutes; then heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, and cooling to room temperature;
4) And (3) cleaning and drying the product in the step (3) to synthesize the active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material.
Example 2
The preparation method of the active carbon loaded molybdenum and nitrogen double-doped carbon nano sheet array composite material comprises the following steps:
1) Taking 0.2g of functionalized activated carbon (4 mol/L HNO) 3 In solution, heated in a water bath at 20℃for 10 hours), 1.4g of 2, 3-pyridinedicarboxylic acid, 0.85g of CoCl 2 ·6H 2 Uniformly mixing 2.0g of urea and 0.15g of ammonium molybdate; the method comprises the steps of carrying out a first treatment on the surface of the
2) Placing the mixture in a muffle furnace, heating the mixture to 140 ℃ from room temperature at a heating rate of 10 ℃/min, and preserving the temperature for 30 minutes; then heating to 250 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and cooling to room temperature;
3) Placing the product treated in the step 2) into a tube furnace, heating to 600 ℃ at a heating rate of 10 ℃/min under the argon environment, and preserving heat for 10 minutes; then heating to 780 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature;
4) And (3) cleaning and drying the product in the step (3) to synthesize the active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material.
Example 3
The preparation method of the active carbon loaded molybdenum and nitrogen double-doped carbon nano sheet array composite material comprises the following steps:
1) Taking 0.15g of functionalized activated carbon (HNO of 6 mol/L) 3 In solution, heated in a water bath at 60℃for 15 hours), 1.8g of 2, 3-pyridinedicarboxylic acid, 1.5g of CoCl 2 ·6H 2 Uniformly mixing 2.0g of urea and 0.1g of ammonium molybdate; the method comprises the steps of carrying out a first treatment on the surface of the
2) Placing the mixture in a muffle furnace, heating the mixture to 180 ℃ from room temperature at a heating rate of 5 ℃/min, and preserving heat for 20 minutes; then heating to 350 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, and cooling to room temperature;
3) Placing the product treated in the step 2) into a tube furnace, heating to 650 ℃ at a heating rate of 5 ℃/min under the argon environment, and preserving heat for 30 minutes; then heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 3 hours, and cooling to room temperature;
4) And (3) cleaning and drying the product in the step (3) to synthesize the active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material.
Example 4
The preparation method of the active carbon loaded molybdenum and nitrogen double-doped carbon nano sheet array composite material comprises the following steps:
1) Taking 0.5g of functionalized activated carbon (3 mol/L HNO) 3 In solution, heated in a water bath at 80℃for 10 hours), 1.5g of 2, 3-pyridinedicarboxylic acid, 0.75g of CoCl 2 ·6H 2 Mixing 3g of urea and 0.25g of ammonium molybdate uniformly; the method comprises the steps of carrying out a first treatment on the surface of the
2) Placing the mixture in a muffle furnace, heating the mixture to 180 ℃ from room temperature at a heating rate of 15 ℃/min, and preserving the temperature for 60 minutes; then heating to 270 ℃ at a heating rate of 15 ℃/min, preserving heat for 1.5h, and cooling to room temperature;
3) Placing the product treated in the step 2) into a tube furnace, heating to 700 ℃ at a heating rate of 15 ℃/min under the argon environment, and preserving heat for 60 minutes; then heating to 900 ℃ at a heating rate of 15 ℃/min, preserving heat for 4 hours, and cooling to room temperature;
4) And (3) cleaning and drying the product in the step (3) to synthesize the active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material.
Example 5
The preparation method of the active carbon loaded molybdenum and nitrogen double-doped carbon nano sheet array composite material comprises the following steps:
1) Taking 1g of functionalized activated carbon (8 mol/L HNO) 3 In solution, heated in a water bath at 80℃for 40 hours), 2g of 2, 3-pyridinedicarboxylic acid, 1.5g of CoCl 2 ·6H 2 Uniformly mixing 2.5g of O, 2.2 g of urea and 0.2g of ammonium molybdate; the method comprises the steps of carrying out a first treatment on the surface of the
2) Placing the mixture in a muffle furnace, heating the mixture to 160 ℃ from room temperature at a heating rate of 5 ℃/min, and preserving heat for 40 minutes; then heating to 300 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature;
3) Placing the product treated in the step 2) into a tube furnace, heating to 650 ℃ at a heating rate of 5 ℃/min under the argon environment, and preserving heat for 30 minutes; then heating to 875 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and cooling to room temperature;
4) And (3) cleaning and drying the product in the step (3) to synthesize the active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material.
Referring to FIG. 1, the active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material Mo prepared by the invention 2 The X-ray diffraction (XRD) pattern of C-MoC/AC-N showed a peak at 25.2℃corresponding to the (002) plane of carbon, indicating that the carbon material had high crystallinity. According to the calculation of 2dsin θ=nλ, the (002) peak is shifted to the left by 0.7 ° compared to AC-F at 25.9 °, and the interlayer spacing due to N doping is increasedIt facilitates the insertion and insertion of K ions, which corresponds to TEM images. Mo (Mo) 2 The C-MoC/AC-N composite material shows obvious diffraction, which corresponds to Mo respectively 2 C (PDF#35-0787) and MoC (PDF#89-4305). The two peaks at 37.9 ° and 39.4 ° correspond to (002) and Mo 2 The (101) plane of C, and the two peaks at 39.2 ° and 42.6 ° correspond to the (103) and (104) planes of MoC, respectively. The precursor CoTAP/AC-F was formed by the superposition of diffraction peaks of AC-F and CoTAP at the (002) plane of (26.2) and shifted 0.3 to the right, indicating a reduction in the interlayer spacing of the carbon material. These four typical diffraction peaks at 13.35 °,16.48 °,26.07 °, and 43.04 ° are characteristic peaks of CoTAP.
Referring to FIG. 2, FIG. 2a shows Mo 2 Low-magnification SEM micrograph of C-MoC/AC-N composite showing uniform Mo immobilized on AC-F 2 C-MoC/G-N nano-sheets. FIG. 2 b shows the nanoplatelets interlaced to form a uniform array over AC-F, with higher magnification micrographs highlighting Mo 2 The size of the C-MoC/G-N nanoplatelets is about 5nm. Panel c in FIG. 2 shows a beautiful filamentous nanoplatelet wrapped around AC-F. The nanoplatelets are very thin, giving a graphene-like structure. The nano sheets are mutually staggered to present a 3D network structure. The nanoplatelets are about 5nm, which is consistent with SEM micrographs. Higher magnification images show the presence of amorphous carbon, short range ordered carbon and MoxC flakes. FIG. 2d shows Mo 2 The C-layer spacing was about 0.229nm, which corresponds to XRD PDF#35-0787.Mo (Mo) 2 The carbon lattices at the bottom of C are visible, demonstrating that they adhere in flakes to the graphite nanoplatelets.
Referring to FIG. 3, mo 2 The rate performance of the C-MoC/AC-N and AC-F electrodes was evaluated by the potassization and potassium removal processes. At current densities of 0.05, 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0A g -1 Under the condition of (2), mo 2 Reversible capacities of the C-MoC/AC-N electrodes were 440.8, 356.4, 275.7, 206.8, 175.2, 146.9 and 122.3mA h g, respectively -1 . Its capacity at each current density is much greater than that of the AC-F electrode. After 70 cycles at different current densities, the current density was 0.05A g -1 When the capacity is restored to 354.5mA h g -1 。
In conclusion, the method has novel design thought, and the functionalized activated carbon, 2, 3-pyridine dicarboxylic acid and CoCl 2 ·6H 2 O, urea and ammonium molybdate are uniformly mixed, a precursor is prepared in a muffle furnace, then the precursor is put in a tubular furnace, high-temperature carbonization is carried out in an argon environment, the active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material is prepared, active carbon is used as a carrier, and molybdenum and nitrogen double-doped carbon nano-sheets are grown on the surface and the middle hole of the active carbon in situ, so that the active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material is generated. The method is environment-friendly, short in production period, low in energy consumption, easy in raw material acquisition and beneficial to large-scale production. The active carbon loaded molybdenum and nitrogen double-doped carbon nano sheet array composite material prepared by the method has high purity and can be used as a negative electrode material of a potassium ion battery in the range of 0.05A g -1 The capacity at current density was 457.5mA h g -1 At 5A g -1 The capacity at large current is 144.4mA h g -1 And each cycle capacity loss rate is 0.49 per mill, so that the composite material can be widely used as a negative electrode material of a potassium ion battery.
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 (6)
1. The preparation method of the active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material is characterized by comprising the following steps of:
1) 2, 3-Pyridinedicarboxylic acid, coCl 2 •6H 2 Mixing O, urea, molybdic acid and functionalized activated carbon uniformly to prepare a mixture; the activated carbon after the functionalization treatment is prepared by placing the activated carbon in HNO with the concentration of 2-8 mol/L 3 Heating the solution in a water bath at 40-80 ℃ for 10-40 hours to obtain the water-based paint;
2) Heating the mixture to 100-200 ℃ from room temperature, performing heat preservation treatment for 10-60 min, heating to 200-300 ℃, performing heat preservation treatment for 1-3 h, and cooling to room temperature;
3) Heating the product treated in the step 2) to 500-700 ℃ from room temperature under argon atmosphere, carrying out heat preservation treatment for 10-60 min, then heating to 700-1000 ℃, carrying out heat preservation for 1-4 h, and cooling to room temperature;
4) And (3) cleaning and drying the product treated in the step (3) to obtain the active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material.
2. The method for preparing the active carbon supported molybdenum and nitrogen double-doped carbon nano-sheet array composite material according to claim 1, wherein in the step 1), 2, 3-dipicolinic acid and CoCl are adopted 2 •6H 2 The mass ratio of O, urea, molybdic acid and the functionalized activated carbon is (1-2): (0.75-1.5): (1.5 to 3): (0.1 to 0.25): (0.5-1).
3. The method for preparing the active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material according to claim 1, wherein the step 2) is carried out in a muffle furnace, the temperature of the mixture is raised to 100-200 ℃ at a temperature raising speed of 5-15 ℃/min from room temperature, the heat is preserved for 10-60 min, and the mixture is heated to 200-300 ℃ at a temperature raising speed of 5-15 ℃/min.
4. The method for preparing the active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material according to claim 1, wherein the step 3) is carried out in a tube furnace, the product treated in the step 2) is heated to 500-700 ℃ from room temperature at a heating rate of 5-15 ℃/min, and the temperature is kept for 10-60 minutes; and then heating to 700-1000 ℃ at a heating rate of 5-15 ℃/min.
5. The application of the active carbon supported molybdenum and nitrogen double-doped carbon nano-sheet array composite material prepared by the preparation method of any one of claims 1-4 in preparation of a potassium ion battery anode material.
6. The negative electrode material of the potassium ion battery is characterized in that the negative electrode material of the potassium ion battery is prepared from the active carbon supported molybdenum and nitrogen double-doped carbon nano sheet array composite material prepared by the preparation method of any one of claims 1-4, and the cycle performance of the negative electrode material of the potassium ion battery under the current density of 50mA/g is as follows: the first circle reaches 457.5mAh/g, and the product is stabilized at 383.1mAh/g after 100 circles of circulation; at a high current density of 5A/g, the high capacity was 144.4mAh/g, and the loss rate per cycle was 0.49% per mill.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110255160.0A CN113044840B (en) | 2021-03-09 | 2021-03-09 | Active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110255160.0A CN113044840B (en) | 2021-03-09 | 2021-03-09 | Active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113044840A CN113044840A (en) | 2021-06-29 |
CN113044840B true CN113044840B (en) | 2023-11-21 |
Family
ID=76510876
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110255160.0A Active CN113044840B (en) | 2021-03-09 | 2021-03-09 | Active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113044840B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113745508A (en) * | 2021-09-03 | 2021-12-03 | 陕西科技大学 | Tremella-like MoS2Functionalized activated carbon sodium ion battery cathode material and preparation method thereof |
CN114300663B (en) * | 2021-12-28 | 2023-07-14 | 广州天赐高新材料股份有限公司 | Potassium ion secondary battery anode material and preparation method thereof, anode sheet and potassium ion secondary battery |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1712522A1 (en) * | 2005-04-14 | 2006-10-18 | Robert Prof. Dr. Schlögl | Nanosized carbon material-activated carbon composite |
CN105110317A (en) * | 2015-08-27 | 2015-12-02 | 中南大学 | Preparation method and application of ultrathin-sheet porous carbon |
WO2016027042A1 (en) * | 2014-08-21 | 2016-02-25 | The University Of Liverpool | Two-dimensional carbon nitride material and method of preparation |
CN106158403A (en) * | 2016-07-15 | 2016-11-23 | 中山大学 | Metal-complexing supermolecule grid and Two-dimensional Carbon composite and preparation method and application |
CN106179444A (en) * | 2016-06-29 | 2016-12-07 | 陶雪芬 | A kind of preparation method of activated carbon supported carbon doping graphite phase carbon nitride |
CN107045945A (en) * | 2017-05-04 | 2017-08-15 | 重庆石墨烯研究院有限公司 | A kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array and preparation method thereof |
CN207009293U (en) * | 2017-05-04 | 2018-02-13 | 重庆石墨烯研究院有限公司 | A kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array |
CN108923030A (en) * | 2018-06-29 | 2018-11-30 | 大连理工大学 | A kind of cobalt nitride/porous carbon sheet/carbon cloth self-supporting lithium sulfur battery anode material preparation method |
CN109037664A (en) * | 2018-07-05 | 2018-12-18 | 华南理工大学 | A kind of carbon-coated Mo of N doping2The preparation method of C/C functional composite material and its application in lithium-sulfur cell |
WO2019034396A1 (en) * | 2017-08-15 | 2019-02-21 | Paul Scherrer Institut | Non-noble metal oxygen reduction catalyst prepared using non-porous porosity precursors |
CN110212204A (en) * | 2019-04-22 | 2019-09-06 | 浙江大学 | A kind of efficient carbon nanosheet support type fuel cell positive electrode and its preparation method and application |
CN110575839A (en) * | 2019-09-05 | 2019-12-17 | 北京纳米能源与***研究所 | M2C/carbon nanosheet composite material and preparation method and application thereof |
CN110649245A (en) * | 2019-09-30 | 2020-01-03 | 陕西科技大学 | Active carbon loaded nano-scale N-doped cobalt phthalocyanine composite material and in-situ solid phase preparation method and application thereof |
CN110660982A (en) * | 2019-09-30 | 2020-01-07 | 陕西科技大学 | Activated carbon supported N-phthalocyanine-rich nanocomposite and in-situ solid phase preparation method and application thereof |
CN110931795A (en) * | 2019-12-04 | 2020-03-27 | 南京工业大学 | Flexible self-supporting composite electrode and preparation method and application thereof |
CN111146015A (en) * | 2020-01-13 | 2020-05-12 | 上海大学 | Nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite material electrode, application and preparation method thereof |
CN111710860A (en) * | 2020-06-29 | 2020-09-25 | 山东大学 | Nitrogen-phosphorus co-doped carbon composite material modified by cobalt-molybdenum phosphide particles and preparation method and application thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100048380A1 (en) * | 2008-08-21 | 2010-02-25 | Board Of Trustees Of Michigan State University | Novel catalyst for oxygen reduction reaction in fuel cells |
KR101851317B1 (en) * | 2011-07-26 | 2018-05-31 | 삼성전자주식회사 | porous carbonaceous composite material, cathode and lithium air battery comprsing the material, and preparation method thereof |
KR101902926B1 (en) * | 2012-01-18 | 2018-10-02 | 삼성전자주식회사 | Porous carbonaceous composite material, cathode and lithium air battery comprising the composite material, and method of preparing the composite material |
KR101739295B1 (en) * | 2012-11-26 | 2017-05-24 | 삼성에스디아이 주식회사 | Composite anode active material, anode and lithium battery containing the same, and preparation method thereof |
US20170170459A1 (en) * | 2015-12-15 | 2017-06-15 | Purdue Research Foundation | Method of making electrodes containing carbon sheets decorated with nanosized metal particles and electrodes made therefrom |
-
2021
- 2021-03-09 CN CN202110255160.0A patent/CN113044840B/en active Active
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1712522A1 (en) * | 2005-04-14 | 2006-10-18 | Robert Prof. Dr. Schlögl | Nanosized carbon material-activated carbon composite |
WO2016027042A1 (en) * | 2014-08-21 | 2016-02-25 | The University Of Liverpool | Two-dimensional carbon nitride material and method of preparation |
CN105110317A (en) * | 2015-08-27 | 2015-12-02 | 中南大学 | Preparation method and application of ultrathin-sheet porous carbon |
CN106179444A (en) * | 2016-06-29 | 2016-12-07 | 陶雪芬 | A kind of preparation method of activated carbon supported carbon doping graphite phase carbon nitride |
CN106158403A (en) * | 2016-07-15 | 2016-11-23 | 中山大学 | Metal-complexing supermolecule grid and Two-dimensional Carbon composite and preparation method and application |
CN107045945A (en) * | 2017-05-04 | 2017-08-15 | 重庆石墨烯研究院有限公司 | A kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array and preparation method thereof |
CN207009293U (en) * | 2017-05-04 | 2018-02-13 | 重庆石墨烯研究院有限公司 | A kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array |
WO2019034396A1 (en) * | 2017-08-15 | 2019-02-21 | Paul Scherrer Institut | Non-noble metal oxygen reduction catalyst prepared using non-porous porosity precursors |
CN108923030A (en) * | 2018-06-29 | 2018-11-30 | 大连理工大学 | A kind of cobalt nitride/porous carbon sheet/carbon cloth self-supporting lithium sulfur battery anode material preparation method |
CN109037664A (en) * | 2018-07-05 | 2018-12-18 | 华南理工大学 | A kind of carbon-coated Mo of N doping2The preparation method of C/C functional composite material and its application in lithium-sulfur cell |
CN110212204A (en) * | 2019-04-22 | 2019-09-06 | 浙江大学 | A kind of efficient carbon nanosheet support type fuel cell positive electrode and its preparation method and application |
CN110575839A (en) * | 2019-09-05 | 2019-12-17 | 北京纳米能源与***研究所 | M2C/carbon nanosheet composite material and preparation method and application thereof |
CN110649245A (en) * | 2019-09-30 | 2020-01-03 | 陕西科技大学 | Active carbon loaded nano-scale N-doped cobalt phthalocyanine composite material and in-situ solid phase preparation method and application thereof |
CN110660982A (en) * | 2019-09-30 | 2020-01-07 | 陕西科技大学 | Activated carbon supported N-phthalocyanine-rich nanocomposite and in-situ solid phase preparation method and application thereof |
CN110931795A (en) * | 2019-12-04 | 2020-03-27 | 南京工业大学 | Flexible self-supporting composite electrode and preparation method and application thereof |
CN111146015A (en) * | 2020-01-13 | 2020-05-12 | 上海大学 | Nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite material electrode, application and preparation method thereof |
CN111710860A (en) * | 2020-06-29 | 2020-09-25 | 山东大学 | Nitrogen-phosphorus co-doped carbon composite material modified by cobalt-molybdenum phosphide particles and preparation method and application thereof |
Non-Patent Citations (6)
Title |
---|
Darshna Potphode.Carbon Nanosheets Decorated Activated Carbon Derived from Borassus Flabellifer Fruit Skin for High Performance Supercapacitors.Journal of The Electrochemical Society.2020,第140508页. * |
Dongming Xu,等.Flexible Quasi-Solid-State Sodium-Ion Capacitors Developed Using 2D Metal–Organic-Framework Array as Reactor.Adv. Energy Mater..2018,第1702769页. * |
Jixin Zhu,等.A General Salt-Templating Method To Fabricate Vertically Aligned Graphitic Carbon Nanosheets and Their Metal Carbide Hybrids for Superior Lithium Ion Batteries and Water Splitting.JACS.2015,第5480−5485页. * |
Yan Luo,等.Self-supported flexible supercapacitor based on carbon fibers covalently combined with monoaminophthalocyanine.Chemical Engineering Journal.2019,第123535页. * |
二维碳质材料的制备和应用;汤艳萍;徐庆;唐睿智;张帆;;新型炭材料(03);全文 * |
刘玉荣.介孔碳材料的合成及应用.国防工业出版社,2012,第193页. * |
Also Published As
Publication number | Publication date |
---|---|
CN113044840A (en) | 2021-06-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Hu et al. | Ti 2 Nb 2x O 4+ 5x anode materials for lithium-ion batteries: a comprehensive review | |
Wang et al. | PVD amorphous carbon coated 3D NiCo2O4 on carbon cloth as flexible electrode for both sodium and lithium storage | |
Zhao et al. | Hierarchical vine-tree-like carbon nanotube architectures: in situ CVD self-assembly and their use as robust scaffolds for lithium-sulfur batteries | |
Wang et al. | Synthesis of LiFePO4@ carbon nanotube core–shell nanowires with a high-energy efficient method for superior lithium ion battery cathodes | |
US11634332B2 (en) | Selenium-doped MXene composite nano-material, and preparation method and use thereof | |
JP2019530190A (en) | Composite, its preparation method and use in lithium ion secondary battery | |
Zhao et al. | High-performance Li-ion batteries and supercapacitors based on prospective 1-D nanomaterials | |
Wang et al. | Ternary Sn–Ti–O based nanostructures as anodes for lithium ion batteries | |
Cheng et al. | Heterostructure enhanced sodium storage performance for SnS 2 in hierarchical SnS 2/Co 3 S 4 nanosheet array composite | |
Jiang et al. | A novel CoO hierarchical morphologies on carbon nanofiber for improved reversibility as binder-free anodes in lithium/sodium ion batteries | |
Zhang et al. | Self-assembled Co3O4 nanostructure with controllable morphology towards high performance anode for lithium ion batteries | |
CN109524649B (en) | Sodium-ion battery positive electrode material with coating structure and preparation method and application thereof | |
CN113044840B (en) | Active carbon loaded molybdenum and nitrogen double-doped carbon nano-sheet array composite material and preparation method and application thereof | |
CN106784693B (en) | Preparation method of nitrogen-rich nano lithium titanate electrode material with uniform carbon coating layer on surface | |
CN108492996A (en) | A kind of preparation method of fluorine, nitrogen co-doped class graphene film layer material | |
Yang et al. | Self-assembled FeF3 nanocrystals clusters confined in carbon nanocages for high-performance Li-ion battery cathode | |
Peng et al. | Facile synthesis of mesoporous Co3O4–carbon nanowires array nanocomposite for the enhanced lithium storage | |
Wang et al. | Realization of superior electrochemical performances for ZnMoO4 anode material through the construction strategy of 3D flower-like single crystalline | |
Fang et al. | Establishment of PPy-derived carbon encapsulated LiMn2O4 film electrode and its performance for efficient Li+ electrosorption | |
Zhou et al. | Mn3O4 nanoparticles on activated carbonitride by soft chemical method for symmetric coin cell supercapacitors | |
Choi et al. | Processing and characterization of titanium dioxide grown on titanium foam for potential use as Li-ion electrode | |
Yang et al. | Rational construction of multidimensional oxygen-deficient Co3O4 nanosheet/nanowire arrays as high-performance electrodes for aqueous Zn-ion batteries and asymmetric supercapacitors | |
Lan et al. | Nano-MnS@ N doped lignite derived carbon composites as superior anode material for sodium-ion batteries | |
Wang et al. | Coordination-assisted fabrication of N-doped carbon nanofibers/ultrasmall Co3O4 nanoparticles for enhanced lithium storage | |
CN109192938B (en) | Flexible material and 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 |