WO2022109960A1 - Agrégat de nanotubes de carbone tridimensionnels et méthode de préparation associée et application associée - Google Patents

Agrégat de nanotubes de carbone tridimensionnels et méthode de préparation associée et application associée Download PDF

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Publication number
WO2022109960A1
WO2022109960A1 PCT/CN2020/131966 CN2020131966W WO2022109960A1 WO 2022109960 A1 WO2022109960 A1 WO 2022109960A1 CN 2020131966 W CN2020131966 W CN 2020131966W WO 2022109960 A1 WO2022109960 A1 WO 2022109960A1
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Prior art keywords
precursor
carbon nanotube
jungle
dimensional carbon
sintering container
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PCT/CN2020/131966
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English (en)
Chinese (zh)
Inventor
杨瑞枝
郑祥俊
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苏州大学
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Priority to PCT/CN2020/131966 priority Critical patent/WO2022109960A1/fr
Publication of WO2022109960A1 publication Critical patent/WO2022109960A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material

Definitions

  • the invention relates to a novel preparation method of a three-dimensional carbon nanotube jungle and its application in the technical field of electrocatalysis, which can be used as an electrocatalyst for zinc-air batteries.
  • Zinc-air batteries are considered as promising next-generation energy storage sources due to their high theoretical energy density, environmental friendliness, high safety, and low cost.
  • ORR oxygen reduction reaction
  • OER oxygen evolution reaction
  • both ORR and OER involve slow kinetic processes of multiple electron transfer reactions, there is an urgent need to develop stable and efficient bifunctional oxygen catalysts for rechargeable ZABs.
  • platinum-based materials are currently commercialized as ORR catalysts and iridium/ruthenium-based materials as OER catalysts, these noble metal catalysts only exhibit a single catalytic activity, and their high cost and poor stability greatly limit their potential applications.
  • Application of charging ZAB Therefore, there is an urgent need to explore efficient and low-cost reversible bifunctional oxygen electrocatalysts.
  • transition metal alloy nanoparticles encapsulated in nitrogen-doped carbon nanotubes (N-CNTs) can effectively improve the active sites of electrocatalysts.
  • the strong bonding between TMA-NPs and N-CNTs can effectively improve the electronic structure of the carbon framework, thereby lowering the adsorption energy barrier of oxygen and its intermediates on the catalyst, which is favorable for the bonding between them.
  • the invention discloses a three-dimensional carbon nanotube jungle (FeNi@NCNT-CP) electrocatalyst inlaid with FeNi alloy, which has low preparation cost and uniform diameter of the grown CNT, which is suitable for zinc-air battery electrode catalysis.
  • the present invention adopts the following technical scheme: three-dimensional carbon nanotube jungle, the preparation method is as follows: nitrogen precursor, iron precursor, nickel precursor and water are mixed and then frozen to obtain precursor mixture powder; and then the precursor mixture powder is put into Inside the small sintering container, the small sintering container is inverted on the large sintering container, and cotton cloth is placed on the large sintering container and outside the small sintering container, and then calcined in nitrogen to obtain a three-dimensional carbon nanotube jungle.
  • the creativity of the present invention lies in changing the calcination method of the existing metal hybrid carbon nanotubes, and beyond imagination, FeNi@NCNT-CP electrocatalyst can be obtained.
  • the network structure shows relatively strong carbon peaks and weak metal peaks.
  • This hierarchical three-dimensional porous network structure provides abundant three-phase reaction interfaces and material transport channels for the electrochemical process, which is conducive to the adsorption and reaction of oxygen. .
  • the nitrogen precursor, the iron precursor and the nickel precursor are all water-soluble compounds, for example, the nitrogen precursor is urea, the iron precursor is ferric nitrate nonahydrate, and the nickel precursor is nickel nitrate hexahydrate; the obtained three-dimensional carbon In the nanotube jungle, the top of the CNT is wrapped with the catalyst metal particles necessary for its growth, which is a core-shell structure, and its outer layer is 3-4 layers of highly graphitized layered carbon with a layer spacing of 0.35 nm corresponds to the C(002) crystal plane, while the inner metal part shows lattice fringes with good resolution with a lattice spacing of 0.209 nm, which corresponds to the (111) crystal plane of FeNi alloy.
  • the nitrogen precursor is urea
  • the iron precursor is ferric nitrate nonahydrate
  • the nickel precursor is nickel nitrate hexahydrate
  • the obtained three-dimensional carbon In the nanotube jungle the top of the CNT is wrapped with the catalyst metal particles necessary for its growth,
  • the mixed powder obtained by freeze-drying in the present invention can keep all components well It is as uniformly dispersed as in the aqueous solution, and iron and nickel are not easily oxidized, which solves the problem that the precursors of iron and nickel cannot be heated and dried due to their strong reducing properties.
  • the XRD pattern of FeNi@NCNT-CP shows weak carbon diffraction peaks at 2 ⁇ 26°, corresponding to the C(002) crystal plane; at 2 ⁇ 43.5°, 50.8° and There are strong metal diffraction peaks at 74.6°, corresponding to the (111), (200) and (220) crystal planes of FeNi alloy, respectively; this confirms the existence of carbon and the formation of FeNi alloy, and compared with FeNi@
  • the outer layer CNTs of NCNT and FeNi@NCNT-CP have a higher degree of graphitization, while the metal in the inner layer is more finely and uniformly wrapped inside the CNTs.
  • the invention discloses the application of the above-mentioned three-dimensional carbon nanotube jungle as a battery electrocatalyst and the application in the preparation of the battery; it can be used as an oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalyst in the preparation of a zinc-air battery (ZAB). application in.
  • ORR oxygen reduction reaction
  • OER oxygen evolution reaction
  • the electrocatalyst of the present invention separates the C, N and metal precursor mixture from the carbon nanotube (CNT) growth substrate by designing an inverted corundum boat pattern, and controls the rapid heating rate so that the precursor mixture can be rapidly decomposed
  • the 3D carbon nanotube jungle (FeNi@NCNT-CP) composites studded with FeNi alloys were prepared by this simple one-step pyrolysis method, and exhibited excellent ORR and OER electrical properties. catalytic performance.
  • the advantages of the CNT-based bifunctional oxygen electrocatalyst disclosed in the present invention are: unique preparation method, novel material structure, close separation of precursor material and growth substrate, and porous growth substrate.
  • the diameter of the CNT and the particle size of the embedded metal particles are fine, uniform and evenly dispersed, with a large specific surface area and abundant micro/nano-hole channels, which are conducive to exposing more active sites and material transport. It exhibited minimal overpotential and excellent stability during ORR and OER, and was successfully applied to ZAB as a cathode catalyst showing good cycling stability and small potential polarization.
  • the present invention improves the existing pyrolysis method, separates and places the precursor mixture (urea, hexahydrate ferric nitrate, hexahydrate nickel nitrate) and the CNT growth substrate (cotton cloth) by inverting large and small corundum boats, and proposes a novel , and controllably synthesized FeNi alloy-embedded homogeneous carbon nanotube jungle (FeNi@NCNT-CP) composites with a three-dimensional network structure, which exhibited efficient catalytic performance and excellent stability in ORR and OER. And can be successfully applied to rechargeable ZAB as a cathode catalyst.
  • the preparation process is novel and simple, the source of raw materials is abundant, and the cost is low, showing broad application prospects.
  • Figure 3 (a) X-ray diffraction patterns of FeNi@NCNT-CP and FeNi@NCNT and PDF card of Fe 0.64 Ni 0.36 , (b) N adsorption and desorption isotherms of FeNi@ NCNT -CP and FeNi@NCNT, ( c) and the corresponding pore size distribution.
  • Preparation of precursor mixture 3 g urea (CO(NH 2 ) 2 ), 0.105 g ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O), 0.075 g nickel nitrate hexahydrate (Ni(NO 3 ) 2 6H 2 O) and 20 mL of ultrapure water were added to the beaker, and the beaker was dissolved under normal stirring at room temperature; then the beaker was transferred to a refrigerator at -18 °C for 12 h, and then freeze-dried at -50 °C in a freeze dryer. After 24 h, the precursor mixture powder containing C, N, Fe, and Ni was obtained.
  • Figure 3a is the X-ray diffraction (XRD) patterns of FeNi@NCNT-CP and FeNi@NCNT.
  • XRD X-ray diffraction
  • Preparation of precursor mixture 3 g urea (CO(NH 2 ) 2 ), 0.105 g ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O), 0.075 g nickel nitrate hexahydrate (Ni(NO 3 ) 2 6H 2 O) and 20 mL of ultrapure water were added to the beaker, and the beaker was dissolved under normal stirring at room temperature; then the beaker was transferred to a refrigerator at -18 °C for 12 h, and then freeze-dried at -50 °C in a freeze dryer. After 24 h, the precursor mixture powder containing C, N, Fe, and Ni was obtained.
  • Preparation of precursor mixture 3 g urea (CO(NH 2 ) 2 ), 0.105 g ferric nitrate nonahydrate (Fe(NO 3 ) 3 9H 2 O), 0.075 g nickel nitrate hexahydrate (Ni(NO 3 ) 2 6H 2 O) and 20 mL of ultrapure water were added to the beaker, and the beaker was dissolved under normal stirring at room temperature; then the beaker was transferred to a refrigerator at -18 °C for 12 h, and then freeze-dried at -50 °C in a freeze dryer. After 24 h, the precursor mixture powder containing C, N, Fe, and Ni was obtained.
  • the combination of the above-mentioned inverted corundum boat with cotton cloth was transferred to the middle of the tube furnace, and calcined at 10 °C/min in a nitrogen atmosphere to the design temperature for 1 h, and then naturally cooled to room temperature to obtain three-dimensional carbon.
  • Nanotube jungle FeNi@NCNT-CP the design temperatures are 600°C, 700°C, 900°C, and 1000°C, respectively.

Abstract

La présente invention appartient au domaine technique de l'électrocatalyse, et concerne spécifiquement un agrégat de nanotubes de carbone (CNT) tridimensionnels et sa méthode de préparation et son application, qui peut être utilisé en tant qu'électrocatalyseur de réaction de réduction d'oxygène (ORR) et de réaction d'évolution d'oxygène (OER) dans une batterie zinc-air (ZAB). Un précurseur d'azote, un précurseur de fer et un précurseur de nickel sont mélangés avec de l'eau puis congelés pour obtenir une poudre de mélange précurseur ; la poudre de mélange précurseur est placée dans un petit récipient de frittage, puis le petit récipient de frittage est inversé sur un grand récipient de frittage, et le tissu de coton est placé sur le grand récipient de frittage et sur l'extérieur du petit récipient de frittage, puis la calcination est effectuée dans de l'azote pour obtenir un agrégat de nanotubes de carbone tridimensionnels. La présente invention concerne une nouvelle manière de préparer des CNT tridimensionnels hautement efficaces et contrôlables au moyen d'une méthode de chromatographie en phase gazeuse pyrolytique en une étape.
PCT/CN2020/131966 2020-11-26 2020-11-26 Agrégat de nanotubes de carbone tridimensionnels et méthode de préparation associée et application associée WO2022109960A1 (fr)

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CN115224293A (zh) * 2022-08-17 2022-10-21 郑州大学 一种orr和oer双功能催化剂及其制备方法和应用
CN115224293B (zh) * 2022-08-17 2024-01-16 郑州大学 一种orr和oer双功能催化剂及其制备方法和应用

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