WO2019164225A1 - Procédé de fabrication de nanotubes de carbone dopés avec des hétéroatomes à partir de dioxyde de carbone - Google Patents

Procédé de fabrication de nanotubes de carbone dopés avec des hétéroatomes à partir de dioxyde de carbone Download PDF

Info

Publication number
WO2019164225A1
WO2019164225A1 PCT/KR2019/002005 KR2019002005W WO2019164225A1 WO 2019164225 A1 WO2019164225 A1 WO 2019164225A1 KR 2019002005 W KR2019002005 W KR 2019002005W WO 2019164225 A1 WO2019164225 A1 WO 2019164225A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon nanotubes
boron
metal catalyst
carbon dioxide
reducing agent
Prior art date
Application number
PCT/KR2019/002005
Other languages
English (en)
Korean (ko)
Inventor
이재우
김기민
이희천
Original Assignee
한국과학기술원
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from KR1020190016813A external-priority patent/KR102201998B1/ko
Application filed by 한국과학기술원 filed Critical 한국과학기술원
Publication of WO2019164225A1 publication Critical patent/WO2019164225A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • 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
    • C01B32/158—Carbon nanotubes
    • C01B32/16—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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/178—Opening; Filling

Definitions

  • the present invention relates to a method for producing carbon nanotubes doped with heterogeneous elements from carbon dioxide. More specifically, the present invention relates to a chemical vapor deposition method using a complex composed of a boron hydride reducing agent and a metal catalyst based on an exhaust gas containing carbon dioxide. It relates to a method for producing a carbon nanotube doped with a hetero element by vapor deposition (CVD).
  • CVD vapor deposition
  • Fossil fuels the main energy sources of civilization, now emit greenhouse gases such as carbon dioxide during combustion. Emissions of greenhouse gases cause side effects that are harmful to humankind, including global warming and the occurrence of abnormal climates.
  • Representative technologies to reduce carbon dioxide include capture, conversion, and storage technologies, which are collectively defined as carbon capture, utilization, and storage technologies, among which conversion technology has added value using carbon dioxide as a raw material. It is recently attracting attention because it can be synthesized.
  • carbon nanotubes have very high thermal conductivity and mechanical and electrical properties, and thus, they are highly valuable because they are new materials that can be used in various fields such as nanotechnology, electrical engineering, optical engineering, and materials engineering.
  • a method for synthesizing carbon nanotubes from carbon dioxide has been proposed by Motiei in 2001 (Motiei, M. et al., J. Am. Chem. Soc . 2001, 123 (35), 8624-8625.) Carbon dioxide molecules are very stable. Therefore, it is difficult to induce a reaction, making carbon dioxide a supercritical fluid. However, in this process, the reaction conditions reach 1,000 ° C. and 10,000 bar, which is very unsuitable for industrialization that needs to be scaled up. As such, carbon nanotubes can be produced from gaseous carbon dioxide under mild conditions rather than supercritical fluids requiring extreme reaction conditions.
  • the present inventors have made efforts to solve the above problems and to break down the stability of carbon dioxide gas molecules and convert them to carbon nanotubes under mild reaction conditions.
  • a complex composed of sodium borohydride and a transition metal or alkaline earth metal catalyst was introduced.
  • the use of carbon dioxide-based chemical vapor deposition which is based on hydrocarbon-based chemical vapor deposition, enables the stable carbon dioxide gas to be activated under mild conditions, and at the same time confirms the mass production of carbon nanotubes, thereby completing the present invention. .
  • the present invention comprises the steps of (a) heating a complex of a solidified boron hydride reducing agent and a metal catalyst in the atmosphere of an inert gas; And (b) supplying and activating a gas containing carbon dioxide to decompose carbon dioxide molecules into carbon atoms to synthesize boron-coated carbon nanotubes, thereby providing a method for producing boron-coated carbon nanotubes from carbon dioxide.
  • the present invention also provides a boron-coated carbon nanotube manufactured by the above method, having a multi-walled structure, and having a storage rate of 50% or more at 900 ° C. and oxidizing conditions.
  • the present invention also provides a catalyst composite for producing carbon nanotubes comprising a boron hydride reducing agent and a transition metal or alkaline metal catalyst.
  • the present invention also provides a method of preparing a composite of a boron hydride reducing agent and a metal catalyst by mixing (a-1) a boron hydride reducing agent dispersed in a first solvent and a metal catalyst precursor or metal nanoparticles dispersed in a second solvent; And (a-2) evaporating the solvent in the metal catalyst complex to solidify the complex of the boron hydride reducing agent and the metal catalyst.
  • the present invention also provides an electrode or a separator of a supercapacitor, a lithium ion battery or a lithium sulfur battery containing carbon nanotubes.
  • FIG. 1 is a schematic diagram schematically showing a manufacturing process for performing an embodiment of the present invention.
  • Figure 2 is a photograph showing an electron microscope image of the carbon nanotubes prepared by Example 1 of the present invention.
  • Example 3 is an electron micrograph and a graph showing that the carbon nanotubes prepared by Example 1 of the present invention had a boron coating.
  • Example 5 is a photograph showing a process preparation process for implementing Example 2 of the present invention.
  • Figure 6 is a graph confirming the electron microscope image and synthesis of carbon nanotubes prepared by Example 2 of the present invention.
  • Example 7 is a photograph showing a process preparation process for implementing Example 3 of the present invention.
  • Example 8 is a graph confirming the electron microscope image and synthesis of the carbon nanotubes prepared by Example 3 of the present invention.
  • Example 9 is an electron microscope image of a carbon nanotube prepared and a process preparation process for carrying out Example 4 of the present invention.
  • Example 10 is a graph illustrating a cyclic voltammetry curve of a supercapacitor electrode using carbon nanotubes prepared in Example 5 of the present invention.
  • FIG. 11 is a graph showing charge and discharge curves of supercapacitor electrodes using carbon nanotubes prepared in Example 5 of the present invention.
  • Example 12 is a graph showing a storage capacity of a supercapacitor electrode using carbon nanotubes prepared in Example 5 of the present invention.
  • FIG. 13 is a graph showing charge and discharge curves of a lithium ion battery electrode using carbon nanotubes prepared in Example 6 of the present invention.
  • Example 14 is a graph illustrating a cycle curve of a lithium ion battery electrode using carbon nanotubes prepared in Example 6 of the present invention.
  • FIG. 15 is a graph showing a charge / discharge curve of a lithium sulfur battery electrode using carbon nanotubes prepared in Example 7 of the present invention.
  • FIG. 16 is a graph illustrating a cycle curve of a lithium sulfur battery electrode using carbon nanotubes prepared in Example 7 of the present invention.
  • the present invention is to introduce a complex consisting of a sodium borohydride as a reducing agent and a transition metal or alkaline earth metal catalyst to activate a carbon dioxide-based chemical vapor deposition method according to the hydrocarbon-based chemical vapor deposition method to activate a stable carbon dioxide gas under mild conditions, At the same time, it was confirmed that carbon nanotubes can be mass produced.
  • the present invention comprises the steps of (a) heating the complex of the solidified boron hydride reducing agent and the metal catalyst under an atmosphere of inert gas; And (b) supplying and activating a gas containing carbon dioxide to decompose carbon dioxide molecules into carbon atoms to synthesize boron-coated carbon nanotubes. .
  • Carbon dioxide-based chemical vapor deposition method proposed by the present invention is shown in the schematic diagram of FIG.
  • the boron hydride reducing agent used in step (a) is sodium borohydride (NaBH 4 ), lithium borohydride (LiBH 4 ), potassium borohydride (KBH 4 ), magnesium borohydride (Mg (BH 4) 2 ), calcium borohydride (Ca (BH 4 ) 2 ) and strontium borohydride (Sr (BH 4 ) 2 ), preferably sodium borohydride, but is not limited thereto. no.
  • the complex of the solidified boron hydride reducing agent and the metal catalyst in the step (a) is (a-1) a metal catalyst precursor or metal nano dispersed in the boron hydride reducing agent and the second solvent dispersed in the first solvent Mixing the particles to prepare a complex of a boron hydride reducing agent and a metal catalyst; And (a-2) evaporating the solvent in the metal catalyst complex to solidify the complex of the boron hydride reducing agent and the metal catalyst.
  • the metal catalyst precursor is a transition metal or magnesium selected from the group consisting of nickel (Ni), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn) and copper (cu). It may be a chloride or nitrate of alkaline earth metal, and the metal nanoparticle may be a nanoparticle of alkaline earth metal such as magnesium or transition metal selected from the group consisting of nickel, iron, cobalt, manganese, zinc and copper. And, preferably, a transition metal of nickel, iron or cobalt is used, but is not limited thereto.
  • the first solvent and the second solvent of step (a-1) may be each independently selected from the group consisting of dihydric alcohol, trihydric alcohol and amide, preferably isopropyl alcohol or dimethylform
  • amide preferably isopropyl alcohol or dimethylform
  • step (a-1) may be performed by ultrasonication or stirrer, and the ultrasonication is effective for 30 minutes to 1 hour or more. It is effective to be accompanied by dispersion through sonication in the mixing process.
  • the metal catalyst precursor of step (a-1) is reduced from a salt form to a metal form by a boron hydride reducing agent.
  • the evaporation process is effective at atmospheric pressure and temperatures above 80 ° C.
  • the supply of the inert gas is started.
  • the inert gas may be used without limitation, if it is an inert gas commonly recognized in the scientific community, such as nitrogen and argon.
  • the step (a) is effective in the temperature range of 400 ⁇ 700 °C and the temperature increase rate of 1 ⁇ 10 °C min -1 , preferably 2 ⁇ 5 °C min-1.
  • the appropriate flow rate is preferably 200mlmin -1 or less.
  • the carbon dioxide gas molecules activated and destabilized by the boron hydride reducing agent in step (b) are decomposed into carbon atoms and grown into carbon nanotubes by a metal catalyst.
  • step (b) (c) may further comprise the step of purifying with hydrochloric acid, water or ethanol, and further, after the step (c) (d) drying the carbon nanotubes It may further comprise a step.
  • the step (d) is to remove the salts remaining in the carbon nanotube powder after the heat treatment and carbon dioxide conversion, at this time, hydrochloric acid, distilled water, ethanol is used sequentially.
  • the step (d) is preferably dried at a temperature of 150 °C or less.
  • carbon nanotubes coated with boron based on carbon dioxide may be obtained.
  • the synthesized carbon nanotubes can be utilized in fields requiring heat resistance as well as nano and electronic fields.
  • the present invention provides a boron-coated carbon nanotube, which is manufactured by the above method in another aspect, has a multi-walled structure, and exhibits a retention of 50% or more at 900 ° C. and oxidation conditions. It is about.
  • the present invention relates to a catalyst composite for producing carbon nanotubes comprising a boron hydride reducing agent and a transition metal or alkaline metal catalyst.
  • the present invention (a-1) to prepare a complex of a borohydride reducing agent and a metal catalyst by mixing a boron hydride reducing agent dispersed in a first solvent and a metal catalyst precursor or metal nanoparticles dispersed in a second solvent. Making; And (a-2) evaporating the solvent in the metal catalyst composite to solidify the complex of the boron hydride reducing agent and the metal catalyst.
  • the boron hydride reducing agent, the transition metal and alkaline earth metal catalyst, the first solvent and the second solvent can be used as mentioned above, and the conditions of the dispersing and mixing process can also be applied as mentioned above. .
  • charge and discharge curves and cycle curves of carbon nanotubes prepared using a carbon dioxide-based chemical vapor deposition method in which a complex composed of a sodium borohydride and a transition metal or alkaline earth metal catalyst according to the present invention were introduced It has been confirmed that it can be used as an electrode or separator of a supercapacitor, a lithium ion battery or a lithium sulfur battery with an excellent capacitance.
  • the present invention relates to an electrode or separator of a supercapacitor, a lithium ion battery, or a lithium sulfur battery including carbon nanotubes in another aspect.
  • the storage capacity of the electrode of the supercapacitor according to the present invention is excellent value of 300 F / g (current density: 0.1 A / g) to 70 F / g (current density: 204.8 A / g) in the voltage range of 0 ⁇ 2.7 V Can have
  • Electrode of the lithium ion battery according to the present invention is 300 ⁇ 900 mAh / g, preferably 300 ⁇ 700 mAh / g, more preferably 300 based on a voltage range of 0.01 V ⁇ 3.0 V and a current density of 1 A / g It can have a capacity of ⁇ 400 mAh / g.
  • the electrode of the lithium sulfur battery according to the present invention has a voltage range of 1.7 V to 2.8 V and a current density of 1 C (1672 mA / g) based on 300 to 1000 mAh / g, preferably 500 to 900 mAh / g, more Preferably it may have a capacity of 650 ⁇ 750 mAh / g.
  • the overall manufacturing process is as shown in FIG.
  • FIG. 2 An electron microscope image of the synthesized carbon nanotubes is shown in FIG. 2.
  • FIG. 1 and 2 of FIG. 2 are scanning electron microscope (SEM) images, and the carbon nanotubes manufactured have a form of carbon nanotube fibers (CNT fibers) in which several strands form a fiber phase.
  • Shows. 3 and 4 of the Figure 2 is a transmission electron microscope (TEM) image, showing that the individual carbon nanotubes made are multi-walled CNTs.
  • FIG. 3 shows that the surface of the prepared carbon nanotubes is coated with boron. Scanning is performed in a direction perpendicular to the axis of the carbon nanotubes through an electron energy loss spectroscopy (EELS) analysis technique installed in a Cs-corrected TEM (No. 1 in FIG. 3). If the signal obtained through scanning is integrated and shown in a graph, it can be seen that boron (represented by a red line) covers the surface of the carbon nanotube (represented by a black line) (No. 2 in FIG. 3). . In the image on the transmission electron microscope, the coating layer by boron was confirmed (No. 3 in FIG. 3).
  • EELS electron energy loss spectroscopy
  • the dashed line represents normal boron coating the sample prior to high temperature and oxidation conditions and the solid line represents boron oxidized after high temperature and oxidation conditions.
  • Raman analysis was performed to determine whether the structure of the carbon nanotubes was not destroyed, and the structure of the carbon nanotubes was not destroyed but was very well preserved (No. 3 in FIG. 4).
  • Black lines are samples after high temperature and oxidation treatment and red lines are samples after high temperature and oxidation treatment. The sharper the peaks, the more excellent the development of the structure of the carbon nanotubes. Since the peaks are very sharp even after high temperature and oxidation treatment, the carbon nanotube structure is well preserved.
  • the overall manufacturing process is as shown in FIG.
  • 6 is data showing that the synthesis of carbon nanotubes is successful.
  • 6 is a scanning electron microscope image, showing that the manufactured carbon nanotubes have a form of a CNT array showing a specific array as a toothbrush.
  • 6 is a transmission electron microscope image, showing that the individual carbon nanotubes made are multi-walled carbon nanotubes.
  • 6 is X-ray diffraction spectroscopy (XRD), and shows that the C (002) peak representing carbon nanotubes is well developed, proving that the synthesis of carbon nanotubes is successful.
  • XRD X-ray diffraction spectroscopy
  • the overall manufacturing process is as shown in FIG.
  • 8 is data showing that the synthesis of carbon nanotubes is successful.
  • 8 is a scanning electron microscope image, showing that the prepared carbon nanotubes have a form of carbon nanotube fibers in which several strands form a fiber phase.
  • Figure 2 of Figure 8 shows that the individual carbon nanotubes made are multi-walled carbon nanotubes.
  • 8 is X-ray diffraction spectroscopy (XRD), and shows that the C (002) peak representing carbon nanotubes is well developed, proving that the synthesis of carbon nanotubes is successful.
  • XRD X-ray diffraction spectroscopy
  • Example 1 was carried out in the same manner as in Example 1 except that the nickel metal nanoparticles that are not a precursor such as a salt is added immediately.
  • Carbon nanotubes synthesized according to the preparation method of Example 1 were used as an electrode material of a supercapacitor, and the specific process is as follows.
  • N-metyl-2-pyrrolidone solvent is taken with 0.2 g of carbon nanotubes and 0.067 g of binder polyvinylidene fluoride and 0.067 g of carbon black conductive material. Under stirring at 1000 rpm for 24 hours to form a mixed solution. The mixed solution in the form of a slurry was evenly applied to aluminum foil and then placed in an oven at 80 ° C. for 12 hours to evaporate the solvent.
  • a two-electrode symmetric system consisting of two electrodes made as described above was constructed and a 1 M tetraethylammonium tetrafluoroborate / acetonitrile solution (TEABF4 / AN) was used as an electrolyte.
  • TEABF4 / AN 1 M tetraethylammonium tetrafluoroborate / acetonitrile solution
  • a lithium metal punched into a case with a diameter of 10 mm was fixed in a case, 5 ⁇ l of electrolyte, a separator punched into 14 mm in diameter, 15 ⁇ l of electrolyte, and a working electrode punched into 10 mm in diameter, a gasket, Cells were assembled by stacking spacers and springs in order and covering them with caps. The cell assembly was all done in a glove box in an argon environment where water and oxygen were blocked, and the assembled cell was attached to a measuring device to observe the electrode performance.
  • Carbon nanotubes synthesized according to the preparation method of Example 1 were used as electrode materials for lithium ion batteries, and the specific process is as follows.
  • the electrode made as above is used as a working electrode, lithium metal is used as a standard electrode and a counter electrode, and 1 M lithium hexafluorophosphate solution in ethyl carbonate / diethyl carbonate ( Half cell experiments using EC / DEC), 50/50 (v / v)) as electrolyte.
  • a lithium metal punched into a case with a diameter of 10 mm was fixed in a case, a separator punched with 5 ⁇ L of electrolyte and a diameter of 14 mm, a working electrode punched with 10 ⁇ L of electrolyte and a diameter of 10 mm, a gasket, Cells are assembled by stacking spacers and springs in order and covering them with caps. The cell assembly is all done in a glove box in an argon environment where water and oxygen are blocked, and the assembled cell is attached to a measuring device to observe the electrode performance.
  • Carbon nanotubes synthesized according to the preparation method of Example 1 were used as electrode materials for lithium sulfur batteries, and the specific process thereof is as follows.
  • the electrode made as above is used as a working electrode, lithium metal is used as a standard electrode and a counter electrode, and 1 M trifluoromethane sulfonamide lithium salt (LiTFSi) in Using dimethoxymethane / 1,3-dioxolane (DME / DOL) 50/50 (v / v)) as an electrolyte, the half cells were assembled in the same manner as in Example 6 to observe the electrode performance.
  • LiTFSi trifluoromethane sulfonamide lithium salt
  • carbon nanotubes having high added value can be activated by removing carbon dioxide, which is the main culprit of global warming, by activating carbon dioxide gas that is stable under mild conditions and according to hydrocarbon-based chemical vapor deposition. Can be mass produced.
  • the carbon nanotubes synthesized through the present invention are coated with boron on the surface to maintain structural stability even under high temperature and oxidation conditions of about 900 ° C. or more. Therefore, it can be used not only in nano and electronic fields but also in fields requiring heat resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un procédé de fabrication de nanotubes de carbone dopés avec des hétéroatomes à partir de dioxyde de carbone. Plus spécifiquement, un complexe formé d'un réducteur d'hydrure de bore et d'un catalyseur métallique est introduit et un dépôt chimique en phase vapeur à base de dioxyde de carbone est employé, de telle sorte qu'un dioxyde de carbone stable peut être activé même dans des conditions douces, tandis que des nanotubes de carbone peuvent être produits simultanément en masse à partir de ceux-ci.
PCT/KR2019/002005 2018-02-20 2019-02-20 Procédé de fabrication de nanotubes de carbone dopés avec des hétéroatomes à partir de dioxyde de carbone WO2019164225A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20180019631 2018-02-20
KR10-2018-0019631 2018-02-20
KR1020190016813A KR102201998B1 (ko) 2018-02-20 2019-02-13 이산화탄소로부터 이종원소가 도핑된 탄소나노튜브의 제조방법
KR10-2019-0016813 2019-02-13

Publications (1)

Publication Number Publication Date
WO2019164225A1 true WO2019164225A1 (fr) 2019-08-29

Family

ID=67686983

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2019/002005 WO2019164225A1 (fr) 2018-02-20 2019-02-20 Procédé de fabrication de nanotubes de carbone dopés avec des hétéroatomes à partir de dioxyde de carbone

Country Status (1)

Country Link
WO (1) WO2019164225A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220214A (ja) * 2001-01-23 2002-08-09 National Institute Of Advanced Industrial & Technology カーボンナノチューブの製造方法
KR20040031714A (ko) * 2001-07-03 2004-04-13 패컬티스 유니버시테이레스 노트레-다메 드 라 파익스 촉매 지지체 및 그 상부에 생성된 탄소 나노튜브
KR101340009B1 (ko) * 2013-03-06 2013-12-11 한국과학기술원 이산화탄소로부터 탄소소재를 제조하는 방법
KR20150027580A (ko) * 2013-09-04 2015-03-12 한국과학기술원 이산화탄소로부터 금속이 도핑된 탄소소재를 제조하는 방법
KR20170120494A (ko) * 2016-04-21 2017-10-31 한국과학기술원 산화전이금속의 함침을 통한 이산화탄소로부터 붕소가 도핑된 탄소소재의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220214A (ja) * 2001-01-23 2002-08-09 National Institute Of Advanced Industrial & Technology カーボンナノチューブの製造方法
KR20040031714A (ko) * 2001-07-03 2004-04-13 패컬티스 유니버시테이레스 노트레-다메 드 라 파익스 촉매 지지체 및 그 상부에 생성된 탄소 나노튜브
KR101340009B1 (ko) * 2013-03-06 2013-12-11 한국과학기술원 이산화탄소로부터 탄소소재를 제조하는 방법
KR20150027580A (ko) * 2013-09-04 2015-03-12 한국과학기술원 이산화탄소로부터 금속이 도핑된 탄소소재를 제조하는 방법
KR20170120494A (ko) * 2016-04-21 2017-10-31 한국과학기술원 산화전이금속의 함침을 통한 이산화탄소로부터 붕소가 도핑된 탄소소재의 제조방법

Similar Documents

Publication Publication Date Title
Yang et al. Constructing SbOC bond to improve the alloying reaction reversibility of free-standing Sb2Se3 nanorods for potassium-ion batteries
Banerjee et al. Synthesis of CuO nanostructures from Cu-based metal organic framework (MOF-199) for application as anode for Li-ion batteries
Liu et al. Multifunctional CoO@ C metasequoia arrays for enhanced lithium storage
AU2010358633B2 (en) Sulfide solid electrolyte glass, lithium solid-state battery, and method for producing sulfide solid electrolyte glass
CN101492576B (zh) 一种碳纳米复合物颗粒及其制备方法与应用
WO2013005887A1 (fr) Matière active de cathode utilisant un cœur-écorce de silicone-carbone pour une batterie secondaire au lithium et procédé de fabrication de ladite matière
CN107293743A (zh) 一种含铁酸镍多孔纳米管的钠离子电池正极材料及其制备方法
CN112777571A (zh) 一种合成电池级硫化锂的方法
Zhu et al. Urchin-like hollow-structured cobalt oxides with excellent anode performance for lithium-ion batteries
Su et al. CuO nanowire arrays synthesized at room temperature as a high-performance anode material for Li/Na-ion batteries
Gao et al. Scalable synthesis of high-performance anode material SiOx/C for lithium-ion batteries by employing the Rochow reaction process
Zhang et al. Three-dimensional interconnected porous carbon nanoflakes with improved electron transfer and ion storage for lithium-ion batteries
Wang et al. Fabrication of high-performance lithium ion battery anode materials from polysilsesquioxane nanotubes
Wan et al. Lithium sulfide nanocrystals as cathode materials for advanced batteries
Niu et al. A bimetallic ZIFs-triggered hierarchical carbon structure for stabilized silicon anode
Tian et al. Silicon-carbon anode with high interfacial stability by a facile thermal reaction involving alkaline nitrogenous carbon source for lithium ion batteries
KR102235013B1 (ko) 이산화탄소로부터 이종원소가 도핑된 탄소나노튜브의 제조방법
Huang et al. V2O5 nanocrystals: Chemical solution synthesis, hydrogen thermal treatment and enhanced rate capability as cathode materials for lithium-ion batteries
WO2019164225A1 (fr) Procédé de fabrication de nanotubes de carbone dopés avec des hétéroatomes à partir de dioxyde de carbone
CN102950015B (zh) 一种具有高氧还原催化活性的硼碳氮纳米管的制备方法
Huang et al. Rational design of hierarchical carbon hybrid microassemblies via reductive-catalytic chemical vapor deposition
CN111945252B (zh) 一种基于静电纺丝制备中空锑基二元合金复合纳米纤维材料的方法及其储钾应用
WO2017018855A1 (fr) Plaque de graphène dopée d'un métal
Fu et al. NixSy/N, S-codoped carbon (NSC) hollow microspheres derived from a novel metal organic porous polymer for high performance lithium ion batteries
Dar et al. Self-assembled Co3O4 nanoplatelets into micro-spheres via a simple solvothermal route: Structural and electrochemical properties

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19756858

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19756858

Country of ref document: EP

Kind code of ref document: A1