WO2024106320A1 - Électrode à nanoparoi de carbone et son procédé de production - Google Patents

Électrode à nanoparoi de carbone et son procédé de production Download PDF

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WO2024106320A1
WO2024106320A1 PCT/JP2023/040507 JP2023040507W WO2024106320A1 WO 2024106320 A1 WO2024106320 A1 WO 2024106320A1 JP 2023040507 W JP2023040507 W JP 2023040507W WO 2024106320 A1 WO2024106320 A1 WO 2024106320A1
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carbon
substrate
electrode
carbon nanowall
nanowall
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Japanese (ja)
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正美 内藤
ビシュワカーマ リテシュクマー
儒成 朱
正義 梅野
康史 宮田
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名古屋市
シーズテクノ株式会社
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Priority to JP2024519417A priority Critical patent/JP7576785B2/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials

Definitions

  • the present invention relates to a carbon nanowall electrode in which carbon nanowalls are erected on a substrate and a method for manufacturing the same. It also relates to an all-solid-state secondary battery using the same and a method for manufacturing the same.
  • Carbon nanowalls are nanostructures in which multilayer graphene is erected on a substrate, and are expected to be used as electrodes in batteries, capacitors, biosensors, electrochemical sensors, and other devices (e.g., Non-Patent Documents 1 and 2).
  • Patent Document 1 describes a lithium ion secondary battery with a carbon nanochips electrode as the negative electrode.
  • the carbon nanochips electrode is defined as an electrode in which graphene sheets are grown from a substrate at an inclination in various directions.
  • This secondary battery uses Li1 - xCoO2 as the positive electrode active material and a solution in which LiPF6 is dissolved in a mixed solvent of ethylene carbonate and dimethyl carbonate as the electrolyte, and it has been found that the charge/discharge capacity per unit weight of carbon exceeds the theoretical capacity of graphite and that there is little deterioration due to repeated charge/discharge.
  • the above conventional carbon nanowall electrodes had problems such as peeling easily occurring between the copper substrate and the carbon nanowalls, and insufficient mechanical strength.
  • the graphene sheets grow at an angle in various directions from the substrate, so when used in an all-solid-state secondary battery using a solid electrolyte, the solid electrolyte can only come into contact with the outermost graphene sheet. This reduces the contact area between the solid electrolyte and the carbon nanochips, resulting in a problem of a small battery capacity per unit volume (or unit weight) of the negative electrode material.
  • the present invention has been made in consideration of the above-mentioned conventional situation, and aims to provide a carbon nanowall electrode that is less susceptible to peeling between the substrate and the carbon nanowalls, and that increases the battery capacity per unit volume (or unit weight) of the negative electrode material even when applied to an all-solid-state battery using a solid electrolyte.
  • the inventors conducted research on carbon nanowall electrodes. As a result, they found that if a graphene sheet is formed on a substrate using microwave plasma CVD, the graphene sheet grows almost vertically on the substrate. They also found that by using a material containing elements such as iron and nickel for the substrate, a carbide (i.e., a carbide, which is a compound of carbon and an electropositive element (hereinafter the same)) layer with excellent adhesion to the substrate is formed near the substrate surface. They further found that the formation of this carbide layer makes it difficult for the carbon nanowall to peel off from the substrate, resulting in a carbon nanowall electrode with high mechanical strength and excellent durability. They also found that if this carbon nanowall electrode is applied to an all-solid-state secondary battery using a solid electrolyte, the capacity per unit volume (or per unit weight) of the negative electrode material can be extremely large.
  • a carbide i.e., a carbide, which is a compound of carbon and an electropositive element (hereinafter the
  • the carbon nanowall electrode of the present invention is characterized in that carbon nanowalls are erected on a substrate, and that a carbide-based peak is present near the substrate surface in a narrow scan of C1s in an X-ray photoelectron spectroscopy (XPS) analysis.
  • XPS X-ray photoelectron spectroscopy
  • a peak based on carbide is present near the substrate surface in a narrow scan of C1s in X-ray photoelectron spectroscopy (XPS) analysis (in other words, a carbide layer is present near the substrate surface).
  • XPS X-ray photoelectron spectroscopy
  • the area of the peak based on carbide in C1s in X-ray photoelectron spectroscopy (XPS) analysis is 2% or more of the total peak area in the C1s spectrum.
  • the substrate material preferably contains at least one of the elements iron, nickel, chromium, cobalt, aluminum, silicon, tungsten, molybdenum, manganese, titanium, and tantalum. These elements react with carbon to easily form carbide.
  • the substrate may be a thin plate or foil made of pure iron, carbon steel, stainless steel, or an iron alloy.
  • the substrate may also be a material that doubles as a current collector, or may be a material that serves as a current collector with a coating layer containing these elements laminated on its surface.
  • Austenitic stainless steel, ferritic stainless steel, and martensitic stainless steel are particularly preferred, as they contain iron, chromium, and nickel, which easily form carbides, and are resistant to corrosion.
  • the average distance between adjacent carbon nanowalls is 1.2 ⁇ m or more.
  • the average distance between the carbon nanowalls is less than 1.2 ⁇ m, it becomes difficult for the solid electrolyte to fill the gaps between the carbon nanowalls, and the contact area between the carbon and lithium is reduced, resulting in a smaller charging capacity.
  • the carbon nanowall electrode of the present invention can be produced as follows. That is, the method for producing a carbon nanowall electrode of the present invention is characterized in that it includes a CVD step of forming carbon nanowalls on a substrate by performing a microwave plasma CVD method while supplying a mixed gas containing at least hydrogen and a hydrocarbon, and the temperature of a stage on which the substrate is placed is set to 400 to 600° C.
  • the mixed gas may contain a rare gas such as helium gas or argon gas in addition to hydrogen and a hydrocarbon.
  • This method for manufacturing carbon nanowall electrodes allows the formation of a carbon layer containing carbide on a substrate.
  • the carbide-containing carbon layer thus formed is thin and has good adhesion, preventing the carbon layer from peeling off or bending due to distortion caused by differences in the thermal expansion coefficients of the substrate and the carbon layer. If the temperature of the table on which the substrate is placed is set to less than 400°C, the front side of the substrate is heated relatively more strongly than the back side by the radiant heat from the plasma, and becomes higher in temperature than the table on which the substrate is placed. This causes a temperature difference in the thickness direction of the substrate, which can lead to problems such as the substrate bending or warping.
  • the all-solid-state secondary battery of the present invention is characterized in that the carbon nanowall electrode of the present invention is used as the negative electrode for the secondary battery.
  • the all-solid-state secondary battery of the present invention uses a carbon nanowall electrode in which graphene sheets are erected on a substrate, so that the solid electrolyte comes into contact with the graphene sheet surface of each carbon nanowall, thereby increasing the contact area. Furthermore, not only is lithium absorbed between the layers of the carbon nanowall by intercalation during the charging process, but lithium is also precipitated in several layers on the carbon nanowall surface. As a result, the battery capacity per unit volume or unit weight of the negative electrode material is significantly increased.
  • the method for producing an all-solid-state secondary battery of the present invention is characterized by comprising the steps of forming a solid electrolyte layer on the carbon nanowall electrode of the present invention by a physical vapor deposition method, and forming a positive electrode material layer on the solid electrolyte by a physical vapor deposition method.
  • each production step is performed in a vacuum device, so there is no risk of contamination with moisture or impurities from the atmosphere, and production can be automated.
  • the inventors have fabricated an all-solid-state lithium ion battery using the carbon nanowall electrode of the present invention and confirmed that it exhibits excellent battery characteristics.
  • This all-solid-state lithium ion battery has the advantages of being able to operate at a higher temperature and being safer without the risk of electrolyte leakage, compared to batteries using a liquid electrolyte.
  • the solid electrolyte may be LiPON, etc.
  • the positive electrode active material may be LiMnO, etc., which is a positive electrode active material that is commonly used in lithium ion batteries that use an electrolyte.
  • FIG. 2 is a schematic diagram showing the process of carbon nanowall growth on a substrate.
  • FIG. 2 is a schematic cross-sectional view of a microwave plasma CVD apparatus used in the examples.
  • 2A and 2B are scanning electron microscope photographs of the surface and cross section of the carbon nanowall electrode of Example 1.
  • 2 is a transmission electron microscope photograph of a cross section of a carbon nanowall in the carbon nanowall electrode of Example 1.
  • 1 shows the results of X-ray photoelectron spectroscopy (XPS) measurement of the carbon nanowall electrode and graphite of Example 1.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 1 shows a Raman spectrum of the carbon nanowall electrode of Example 1.
  • 11 shows scanning electron microscope photographs of the carbon nanowall electrode surfaces of Examples 5-4, 5-5, and 5-6.
  • 1 shows scanning electron microscope photographs of the surfaces of carbon nanowall electrodes in Examples 6-1, 6-2, and 6-3.
  • 1 is a scanning electron microscope photograph of the surface of the carbon nanowall electrode of Comparative Example 2.
  • 1 is a graph showing the change in weight of a substrate before and after plasma exposure.
  • 1 shows scanning electron microscope photographs and Raman spectrum graphs of the surfaces of the carbon nanowall electrodes produced in Examples 7-1 to 7-4.
  • 1 is a graph showing the results of XPS measurement of the carbon nanowall electrode prepared in Example 7-1.
  • 1 is a schematic cross-sectional view of a lithium-ion all-solid-state secondary battery. 1 is a graph showing charge/discharge characteristics of a lithium-ion all-solid-state secondary battery. 1 is a scanning electron microscope photograph of a cross section of a lithium-ion all-solid-state secondary battery.
  • the carbon nanowall electrode of the present invention has carbon nanowalls standing on a substrate.
  • Carbon nanowalls are relatively perfect crystals composed of nano-sized graphite crystallites, and are plate-shaped nanostructures in which several to about 100 graphene sheets are stacked.
  • the substrate may be made of a material containing at least one of the elements iron, nickel, chromium, cobalt, aluminum, silicon, tungsten, molybdenum, manganese, titanium, and tantalum. It may also be made of a metal substrate, such as copper, copper alloy, nickel, nickel alloy, iron, iron alloy, stainless steel, molybdenum, tungsten, or tantalum, which has been conventionally used as a current collector, and on whose surface a coating of at least one of the elements iron, nickel, chromium, cobalt, aluminum, silicon, tungsten, molybdenum, manganese, titanium, or tantalum is formed by a surface treatment method such as plating or vapor deposition.
  • a surface treatment method such as plating or vapor deposition.
  • Austenitic stainless steel and martensitic stainless steel containing iron, nickel and chromium, and ferritic stainless steel containing iron and chromium are particularly preferred as substrate materials due to their excellent corrosion resistance.
  • any type of stainless steel can be used, including austenitic (SUS304, SUS304-L, SUS302, SUS301, SUS310S, SUS321, SUS316, SUS316-L, etc.), ferritic (SUS430, SUS434, etc.), martensitic (SUS410S, SUS420J2, etc.), and precipitation hardened (SUS631, ASL-350, etc.) stainless steels specified in JIS G4305:2005 "Cold-rolled stainless steel sheets and strips.”
  • Semiconductor substrates such as Si, SiC, AlGaAs, and AlGaN can also be used.
  • the thickness of the substrate is preferably about 1 mm or less in order to reduce the weight of the electrode, and a foil material of about 5 ⁇ m to 100 ⁇ m that is conventionally used as a current collector is more preferable, and from a practical standpoint, a foil material of 5 ⁇ m to 20 ⁇ m is even more preferable.
  • the carbon nanowall electrode of the present invention it is required that a peak based on carbide is present near the substrate surface in a narrow scan of C1s in an X-ray photoelectron spectroscopy (XPS) analysis.
  • near the substrate surface means a range within 100 nm from the substrate surface.
  • carbide is generated near the substrate surface, which plays a role in increasing the adhesion between the substrate and the carbon nanowalls.
  • the area of the peak based on carbide is preferably 2% or more of the total peak area in the C1s spectrum, more preferably 3% or more, and most preferably 5% or more.
  • the average distance between adjacent carbon nanowalls is preferably 1.2 ⁇ m or more.
  • the average distance between the carbon nanowalls is less than 1.2 ⁇ m, it becomes difficult for the solid electrolyte to fill the narrow gaps between the carbon nanowalls, and the contact area between the carbon and lithium is reduced, resulting in a decrease in charging capacity.
  • a method for producing the carbon nanowall electrode of the present invention will be described.
  • a substrate containing at least one element selected from the group consisting of iron, nickel, chromium, cobalt, aluminum, silicon, tungsten, molybdenum, manganese, titanium, and tantalum is prepared, cut to a required size, and the surface is cleaned.
  • the cleaning method may be a method using a surfactant, an organic solvent, electrolytic cleaning in an alkaline solution, or plasma treatment.
  • the cleaned substrate is placed on the sample stage of the microwave plasma CVD apparatus, and the microwave plasma CVD method is performed.
  • the microwave plasma CVD method refers to a method in which a raw material gas is turned into plasma by microwave power to activate a chemical reaction, and chemical vapor deposition is performed.
  • the excitation method for generating microwave plasma examples include microwave surface wave plasma CVD method and ECR plasma CVD method in which microwaves and an ECR magnetic field are applied.
  • the supply gas in microwave plasma CVD can be a mixture of an inert gas such as argon, a hydrocarbon gas (methane, ethane, acetylene, etc.) that serves as a carbon source for carbon nanowalls, and hydrogen. It is estimated that the supply gas that flows into the chamber of the plasma CVD device becomes argon ions and carbonium ions, and these ions further react to turn into argon gas, hydrogen, and carbon nanowalls.
  • Figure 1 shows the growth process of carbon nanowalls on a substrate.
  • a solid-state lithium ion battery can be constructed by contacting the carbon nanowall electrode of the present invention with a solid electrolyte capable of transferring lithium ions, and further laminating a cathode material and a current collector that have been conventionally used in lithium ion batteries.
  • a solid electrolyte capable of transferring lithium ions lithium oxides (e.g., lithium phosphate oxynitride (LiPON), Li 3 PO 4 , LiBO 3 , etc.) can be used.
  • lithium oxides e.g., lithium manganate (LiMnO), lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), etc.
  • These solid electrolytes and cathode active materials are formed in a vacuum device using a physical vapor deposition method such as a sputtering method or a vapor deposition method.
  • a solid electrolyte is laminated on a carbon nanowall electrode by a sputtering method, a lithium oxide or the like can be used as a target electrode.
  • the output per target area in the sputtering method can be appropriately selected in consideration of the adhesion between the carbon nanowall and the solid electrolyte, but it is usually preferable to set it to about 0.2 to 5 W/cm 2 .
  • the structure of the negative electrode surface remains stable and hardly changes even after repeated charge and discharge.
  • the charging process not only is lithium absorbed between the carbon nanowalls by intercalation, but lithium is also precipitated over several layers on the surface of the carbon nanowalls. Therefore, not only the lithium absorbed between the layers but also the lithium precipitated on the surface of the carbon nanowalls contributes to the charge and discharge capacity, far exceeding the charge and discharge capacity theoretically calculated from the amount of lithium absorbed between the layers. This allows the battery to be significantly more compact and lightweight.
  • it is possible to operate at a high potential in the range of about 3.2 V to 4.2 V.
  • a solid electrolyte since a solid electrolyte is used, there is no need to worry about liquid leakage, and the operating temperature can be made higher.
  • Example 1 A 40 ⁇ m thick stainless steel foil made of SUS304 was prepared and cut to 50 mm x 50 mm to serve as a substrate.
  • SUS304 is a type of austenitic stainless steel. This substrate was placed on the susceptor 6 in the reactor 1 of the microwave surface wave plasma CVD device 200 shown in Figure 2, and microwave plasma CVD was performed under the following conditions. After that, nitrogen was introduced into the reactor 1 to return it to atmospheric pressure, and the substrate was removed, and this was used as a negative electrode for a lithium ion secondary battery.
  • Flow gas: CH4 : H2 :Ar 5:3:3 mixed gas.
  • Temperature of susceptor 6 500°C, process pressure: 10 Pa.
  • Plasma irradiation time 3 minutes, 8 minutes and 10 minutes, applied microwave power: 1 kW, Applied microwave frequency: 2.45 GHz, Distance from plasma excitation plate to substrate: 55 mm
  • the plasma CVD device 200 is provided with a reaction vessel 1 and a waveguide 2 disposed above the CVD reaction vessel 1.
  • a plasma excitation plate 3 made of quartz is provided between the CVD reaction vessel 1 and the waveguide 2, and a number of minute recesses 30 are formed on the plasma excitation plate 3 on the CVD reaction vessel 1 side. By concentrating an electric field in the recesses 30, the recesses 30 become the plasma generation starting points, making it easy to generate plasma at low power.
  • a slot antenna 4 is provided below the waveguide 2.
  • a microwave of 2.45 GHz is supplied to the waveguide 2 from a microwave generator (not shown), and electromagnetic waves are supplied to the inside of the CVD reaction vessel 1 and the plasma excitation plate 3 via the slot antenna 4.
  • a susceptor 6 for placing a substrate 5 thereon and a heating device 7 for heating the susceptor 6 are provided inside the CVD reaction vessel 1.
  • the supply amounts of the mixed gas are adjusted by mass flow controllers (not shown) for each gas component, and the gases are introduced into the CVD reaction vessel 1 through an inlet 11 provided on the upper side of the CVD reaction vessel 1.
  • An outlet 12 for discharging the gas is provided at the lower part of the side of the CVD reaction vessel 1.
  • the inside of the CVD reaction vessel 1 can be depressurized to about 10-3 torr by a vacuum pump (not shown).
  • the substrate 5 was ultrasonically cleaned in methanol, and then ultrasonically cleaned in acetone, and then dried and placed on the susceptor 6.
  • the heating device 7 was turned on, and the temperature of the susceptor 6 was controlled to a predetermined temperature.
  • the gas flow rates of methane, hydrogen, and argon were supplied to the inside of the CVD reaction vessel 1 while being controlled by the mass flow controller, and the inside of the CVD reaction vessel 1 was controlled to a predetermined pressure.
  • the microwave generator was driven to supply microwaves of 2.45 GHz to the waveguide 2, and plasma of the mixed gas was generated inside the CVD reaction vessel 1.
  • the plasma microwave surface wave plasma was generated above the substrate 5.
  • the microwave generator was stopped to drive, and the heating device 7 was turned off, and after a certain time, the inside of the CVD reaction vessel 1 was returned to atmospheric pressure, and the substrate 5 on whose surface the carbon nanowalls were formed was taken out, and this was used as the carbon nanowall electrode of Example 1.
  • Example 2 In Example 2, the same SUS304 substrate as in Example 1 was used, and the conditions for microwave plasma CVD were as follows: The other steps were the same as in Example 1, and therefore the description will be omitted.
  • Flow gas: Acetylene: Hydrogen: Argon 3:20:20 mixed gas, Temperature of susceptor 6: 500° C., process pressure: 7 Pa, Plasma exposure time: 5 minutes Applied microwave power: 1.5 kW, applied microwave frequency: 2.45 GHz, ⁇ Distance from plasma excitation plate to substrate: 50 mm
  • Example 3 In Example 3, an austenitic stainless steel (SUS316) foil having a thickness of 40 ⁇ m was used as the substrate. The other steps were the same as those in Example 2, and therefore the description thereof will be omitted.
  • SUS316 austenitic stainless steel
  • Example 4 A ferritic stainless steel (SUS430) foil having a thickness of 50 ⁇ m was used as the substrate in Example 4. The other steps were the same as those in Example 2, and therefore the description thereof will be omitted.
  • Comparative Example 1 A copper foil having a thickness of 40 ⁇ m was used as the substrate in Comparative Example 1. The other steps were the same as those in Example 1, and therefore the description thereof will be omitted.
  • Example 1 Observation by Transmission Electron Microscope
  • the carbon nanowalls were peeled off from the substrate 1, solidified with a hardener, and then thinned to enable cross-section observation using a microtome or the like to prepare a sample, and a transmission electron microscope photograph was taken (see FIG. 4).
  • the thickness of the carbon nanowall was about 4.5 nm, and that about 10 or so graphene sheets were overlapped. Similar carbon nanowalls were also observed in Examples 2, 3, and 4.
  • XPS X-ray photoelectron spectroscopy
  • the sample before etching had a peak similar to that of graphite, and it was found to be made of carbon nanowalls.
  • the surface of this sample was argon sputter etched, it was found that the peak due to carbon nanowalls in the C1s spectrum, which appeared at 284.4 eV, became smaller with the passage of etching time, and a peak due to carbide appeared at 283.2 eV.
  • the same results were obtained for Examples 2 and 3. This also showed that carbide was present near the very surface of the substrate.
  • Comparative Example 1 in which a copper foil was used as the substrate, no peaks due to carbide were observed in the C1s spectrum.
  • the Raman spectrum of the sample of Example 1 was measured using a microscopic laser Raman spectrometer (Renishaw InVia Raman microscope).
  • the laser light was an argon laser with a wavelength of 532 nm.
  • the measurement results are shown in FIG. 8. Peaks indicated by D, G, and 2D were observed near 1350 cm -1 , 1580 cm -1 , and 2682 cm -1 , respectively.
  • G is a peak derived from the graphite structure, and a small peak, G' peak, was observed on the shoulder of this peak. This G' peak indicates that the formed carbon nanowalls extend in a direction perpendicular to the substrate.
  • Example 6-1 to 6-3 and Comparative Examples 2 and 3 SUS304 was used as the substrate, the temperature of the susceptor 6 was varied (400° C. in Example 6-1, 500° C. in Example 6-2, 600° C. in Example 6-3, 200° C. in Comparative Example 2, and 700° C. in Comparative Example 3), and the plasma irradiation time in microwave plasma CVD was 10 minutes. The rest is the same as in Example 1, and the description will be omitted.
  • FIG. 12 shows a graph of the weight change of the substrate before and after plasma exposure.
  • Example 7-1 to 7-4 an aluminum plate having a thickness of 100 ⁇ m was used as the substrate, and the temperature of the table on which the substrate was placed and the plasma exposure time in microwave plasma CVD were set as conditions shown in Table 2. The rest of the conditions were the same as in Example 2, and therefore a description thereof will be omitted.
  • an all-solid-state lithium ion secondary battery was prepared by the following steps.
  • the negative electrode for lithium ion secondary battery of Example 1 was placed on a sample stage in a chamber of a magnetron sputtering device with the carbon nanowalls facing up, and a solid electrolyte was laminated by sputtering.
  • LiPON layer a lithium phosphate nitride ceramic (hereinafter referred to as LiPON layer), which is a solid electrolyte capable of lithium ion migration, was laminated on the carbon nanowalls, which are the negative electrode for lithium ion secondary battery of Example 1.
  • a positive electrode was laminated on the LiPON layer by sputtering.
  • the sputtering target was a sintered lithium manganese oxide (LiMnO)
  • the sputtering gas was Ar
  • the gas introduction rate was 60 sccm
  • the output per target area was 2 W/ cm2
  • the sputtering time was 6 hours.
  • LiMnO a positive electrode active material
  • gold was evaporated on the LiMnO in an evaporation device to obtain an all-solid-state lithium-ion secondary battery.
  • the structure of this battery is shown in Fig. 15.
  • this battery has a carbon nanowall 21 standing on a substrate 20 made of stainless steel SUS304, with a carbide-containing carbon layer 22 sandwiched between them, and further a LiPON layer 23, a LiMnO layer 24, and a gold evaporated layer 25 laminated in this order.
  • the substrate 20 is a negative electrode side current collector
  • the carbon nanowall 21 is a negative electrode active material
  • the LiPON layer 23 is a solid electrolyte in which lithium ions can move
  • the gold evaporated film 25 is a positive electrode side current collector.
  • the LiPON layer 23, which is a solid electrolyte is formed by leaving a certain amount of space between the walls of the carbon nanowalls so that it can come into contact with the walls of the carbon nanowalls.
  • a gold electrode is formed on the surface of the positive electrode to complete the all-solid-state battery structure.
  • This discharge capacity per unit weight is a value that greatly exceeds the theoretical discharge capacity of the carbon raw material of 372 mAh/g calculated from the amount of lithium that can be intercalated between the layers of the graphene sheet (one lithium atom per six carbon atoms). The reason for this is thought to be that not only the charge/discharge reaction involving graphene but also the lithium precipitated on the graphene surface is involved in the charge/discharge reaction.
  • the carbon nanowalls it is desirable to set the carbon nanowalls almost perpendicular to the substrate, but since it is also possible for the solid electrolyte film to be formed from an oblique direction, it is also possible to set the carbon nanowalls at an angle of about 45 degrees to the substrate, as shown in FIG. 17 .
  • the carbon nanowall electrode of the present invention can be made into a negative electrode active material consisting only of carbon nanowalls, which are carbon materials, without using any conventional binders or conductive additives. This simplifies the manufacturing process, and allows for a higher battery capacity than conventional graphite negative electrodes, making it possible to produce a small battery with a large capacity. Furthermore, when used as an electrode for a capacitor, the electrode has a larger surface area, resulting in a capacitor with a large capacity.

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Abstract

La présente invention vise une électrode à nanoparoi de carbone qui est peu susceptible de présenter une séparation entre le substrat et la nanoparoi de carbone et qui, même lorsqu'elle est utilisée dans une batterie à l'état solide utilisant un électrolyte solide, présente une grande capacité de batterie par unité de volume (ou par unité de poids) de matériau d'électrode négative. À cet effet, une nanoparoi de carbone 21 est disposée de façon à se tenir debout sur un substrat 20, et il y a un pic à base de carbure à proximité de la surface de substrat dans un balayage étroit de C1s selon une analyse de spectroscopie photoélectronique à rayons X (XPS).
PCT/JP2023/040507 2022-11-14 2023-11-10 Électrode à nanoparoi de carbone et son procédé de production WO2024106320A1 (fr)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2010009980A (ja) * 2008-06-27 2010-01-14 Yokohama City Univ リチウムイオン電池用負極材料及びそれを用いた急速充放電型リチウムイオン電池
JP2011103256A (ja) * 2009-11-11 2011-05-26 Toyota Motor Corp リチウム二次電池用負極およびその製造方法
WO2021201199A1 (fr) * 2020-04-01 2021-10-07 国立大学法人東海国立大学機構 Dispositif de stockage d'énergie et électrode pour dispositif de stockage d'énergie
JP2022187853A (ja) * 2021-06-08 2022-12-20 国立大学法人東海国立大学機構 カーボンナノウォール成長用金属基板とカーボンナノウォール付き金属基板とこれらの製造方法

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JP4751841B2 (ja) 2007-02-05 2011-08-17 財団法人高知県産業振興センター 電界放出型電極及び電子機器
JP6328870B2 (ja) 2011-11-11 2018-05-23 株式会社Ihi ナノ構造物の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010009980A (ja) * 2008-06-27 2010-01-14 Yokohama City Univ リチウムイオン電池用負極材料及びそれを用いた急速充放電型リチウムイオン電池
JP2011103256A (ja) * 2009-11-11 2011-05-26 Toyota Motor Corp リチウム二次電池用負極およびその製造方法
WO2021201199A1 (fr) * 2020-04-01 2021-10-07 国立大学法人東海国立大学機構 Dispositif de stockage d'énergie et électrode pour dispositif de stockage d'énergie
JP2022187853A (ja) * 2021-06-08 2022-12-20 国立大学法人東海国立大学機構 カーボンナノウォール成長用金属基板とカーボンナノウォール付き金属基板とこれらの製造方法

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