WO2018056204A1 - Agrégats de particules de si et leur procédé de production - Google Patents

Agrégats de particules de si et leur procédé de production Download PDF

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WO2018056204A1
WO2018056204A1 PCT/JP2017/033436 JP2017033436W WO2018056204A1 WO 2018056204 A1 WO2018056204 A1 WO 2018056204A1 JP 2017033436 W JP2017033436 W JP 2017033436W WO 2018056204 A1 WO2018056204 A1 WO 2018056204A1
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powder
particle
flow
gas
particles
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PCT/JP2017/033436
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English (en)
Japanese (ja)
Inventor
宏隆 曽根
尚 杉江
佑介 杉山
裕輔 山本
合田　信弘
井上　敏樹
隆行 渡邉
田中　学
拓也 影山
周平 吉田
大輔 岡元
建太郎 山野
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株式会社豊田自動織機
国立大学法人九州大学
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Priority to JP2018541040A priority Critical patent/JP6743159B2/ja
Publication of WO2018056204A1 publication Critical patent/WO2018056204A1/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
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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

Definitions

  • the present invention relates to a novel Si particle, a method for producing the same, and a non-aqueous electrolyte secondary battery using the novel Si particle.
  • Si is used in various applications such as solar cell materials, secondary battery active material, and photoreceptor materials.
  • Patent Document 1 International Publication No. 2014/080608 synthesizes a layered silicon compound mainly composed of layered polysilane obtained by reacting CaSi 2 with an acid to remove Ca, A silicon material in which a layered silicon compound is heated at 300 ° C. or higher to release hydrogen and a lithium ion secondary battery including the silicon material as an active material is described.
  • the negative electrode active material expands and contracts with the insertion and extraction of lithium (Li) during charge and discharge.
  • Li lithium
  • the negative electrode active material expands and contracts, a load is applied to the binder that holds the negative electrode active material on the current collector.
  • the adhesion between the negative electrode active material and the current collector may be reduced, or the conductive path in the electrode may be destroyed.
  • the resistance of the electrode increases and the capacity of the battery may be reduced.
  • the negative electrode active material may be distorted due to repeated expansion and contraction, and may be refined and detached from the electrode.
  • the expansion and contraction of the negative electrode active material also affects the deterioration of the cycle characteristics of the battery.
  • the formation of fine particles of the silicon-based material has been studied.
  • gas atomization method in which gas is blown to molten Si flowing down from a nozzle to form fine droplets of molten Si, or molten Si is put into a dish-shaped disk that rotates at high speed, and centrifugal force is applied.
  • a rotating disk method that scatters droplets is known.
  • Patent Document 2 Japanese Patent Laid-Open No. 2005-320195 discloses a method for producing Si particles having a particle diameter of 10 ⁇ m to 50 ⁇ m by a rotating disk method.
  • Patent Document 2 discloses that a dispersion containing Si particles having a particle diameter of 10 ⁇ m to 50 ⁇ m manufactured by the rotating disk method is manufactured, and the operation is performed by pressing the dispersion and passing it through a small-diameter nozzle. It is disclosed to obtain nanometer-sized Si particles with a reduced diameter.
  • the present inventor puts raw material Si powder into the plasma, turns the raw material Si powder into a gas or liquid state, cools the outside of the plasma, and uses the extreme temperature difference between the inside and outside of the plasma to produce the product. It recalled that it was rapidly cooled to obtain Si particles.
  • the inventor has conducted intensive studies and introduced raw material Si powder into the plasma as an introduction flow, and a cooling gas that opposes the passage flow after the introduction flow has passed through the plasma. It was confirmed that a new form of Si particle combination was obtained by cooling with a flow. Further, it was confirmed that a carbon-containing film can be formed on the Si particle bonded body by bringing a carbon source gas into contact with Si during cooling.
  • a special carbon-containing film can be formed under conditions where the plasma output is 5 kW or more and less than 15 kW, or by specifying the supply position of the carbon source gas in the cooling gas.
  • this inventor manufactures the negative electrode which comprises Si particle
  • the Si particle bonded body of the present invention has Si particles and fibrous Si bonded to the Si particles, and the particle size of the Si particles is larger than the fiber diameter of the fibrous Si. .
  • FIG. 1 It is a schematic diagram of the Si particle combination of the present invention. It is a schematic diagram of a plasma generator.
  • 2 is a result of observation of a cross section of a powder of Example 1 by a scanning electron microscope (hereinafter, appropriately referred to as a cross section SEM). It is a cross-sectional SEM observation result in the magnification of 10 times of FIG. It is a cross-sectional SEM observation result in the magnification of 100 times of FIG. It is an observation result of the transmission electron microscope (hereinafter referred to as TEM as appropriate) of the powder of Example 1.
  • 3 is a particle size distribution diagram of Si particles of the powder of Example 1.
  • FIG. 10 is an observation result by electron energy loss spectroscopy (hereinafter referred to as EELS (Electron Energy-Loss Spectroscopy) as appropriate) of the fibrous Si 20 in FIG. It is a schematic diagram which shows the observation result of FIG.
  • XPS X-ray Photoelectron Spectroscopy
  • FIG. 5 shows the results of pyrolysis gas chromatography (Pyrolysis Gas Chromatography, hereinafter referred to as “Py-GC” as appropriate) of the coating films of the powder of Example 4, the powder of Reference Example 1, and the powder of Reference Example 2.
  • FIG. 4 is an XRD chart of measurement results of powders of Examples 1 to 4 and Example 6 by a powder X-ray diffraction method (hereinafter referred to as XRD as appropriate). It is a charging / discharging curve of the lithium ion secondary battery of Example A and Comparative Example A. It is a charging / discharging curve of the lithium ion secondary battery of Example B, Example C, and Example D. It is a graph which shows the relationship between the cycle number of the lithium ion secondary battery of Example B, Example C, and Example D, and a capacity
  • the numerical range “x to y” described in this specification includes the lower limit x and the upper limit y.
  • the numerical range can be configured by arbitrarily combining these upper limit value and lower limit value and the numerical values listed in the examples.
  • numerical values arbitrarily selected from the numerical value range can be used as upper and lower numerical values.
  • the Si particle bonded body of the present invention has Si particles and fibrous Si bonded to the Si particles, and the particle size of the Si particles is larger than the fiber diameter of the fibrous Si.
  • the form of the Si particle combination includes a combination of one Si particle and one fibrous Si bonded to the Si particle, a combination of one Si particle and two or more fibrous Si bonded to the Si particle, two Si particles, A combination of one fibrous Si bonded to both of them and a combination of a plurality of Si particles and a plurality of fibrous Si are included.
  • the fibrous Si is preferably bonded to a plurality of Si particles.
  • the Si particle bonded body is preferably a combination in which a plurality of Si particles and a plurality of fibrous Si are bonded.
  • the surface area of the Si particle bonded body is much larger than the surface area of the Si particle.
  • the particle diameter of the Si particles is preferably 10 nm or more and 1500 nm or less, more preferably 20 nm or more and 1200 nm or less, and further preferably 30 nm or more and 1000 nm or less.
  • the particle size of the Si particles here means the major axis of the observed Si particle image when the Si particle combination is observed with an electron microscope such as a scanning electron microscope or a transmission electron microscope.
  • the average particle diameter of the Si particles in the Si particle bonded body having a plurality of Si particles, or the aggregate or aggregate of the Si particle bonded bodies is preferably 10 nm to 300 nm, and preferably 20 nm to 200 nm. More preferably, it is 50 nm or more and 150 nm or less.
  • the average particle size of the means D 50 or the arithmetic mean value of the particle size of the Si particles.
  • D 50 is a particle size corresponding to an integrated value of volume distribution in the particle size distribution measurement by laser diffraction method of 50%. That is, the D 50, means the median size measured by volume.
  • the arithmetic average value can be obtained, for example, from the measurement result of the particle size of 200 Si particles.
  • the shape of the Si particles is not particularly limited, and examples thereof include a spherical shape, an elliptical spherical shape, and a droplet shape.
  • the fiber diameter of fibrous Si is preferably 4 nm or more and 25 nm or less, more preferably 5 nm or more and 20 nm or less, and further preferably 6 nm or more and 18 nm or less.
  • the fiber diameter of fibrous Si means the fiber diameter of the observed fibrous Si image when the Si particle combination is observed with an electron microscope such as a scanning electron microscope or a transmission electron microscope.
  • the fiber length of the fibrous Si is preferably 10 nm or more and 20 ⁇ m or less, more preferably 15 nm or more and 5 ⁇ m or less, and further preferably 20 nm or more and 2 ⁇ m or less.
  • the fiber length of fibrous Si means the fiber length of the observed fibrous Si image when the Si particle combination is observed with an electron microscope such as a scanning electron microscope or a transmission electron microscope.
  • the shape of the fibrous Si is not particularly limited as long as the fiber has a fiber length longer than the fiber diameter. Fibrous Si is bonded to Si particles at the end in the fiber length direction.
  • the particle diameter of Si particles is larger than the fiber diameter of fibrous Si.
  • the particle size of the Si particles is preferably 2 to 300 times the fiber diameter, more preferably 4 to 100 times, and even more preferably 6 to 20 times.
  • a plurality of Si particle aggregates may aggregate to form aggregates.
  • the size of the aggregate in the longitudinal direction is preferably 1 ⁇ m or more and 150 ⁇ m or less, more preferably 3 ⁇ m or more and 100 ⁇ m or less, and further preferably 5 ⁇ m or more and 50 ⁇ m or less.
  • the size of the aggregate in the longitudinal direction means the length in the longitudinal direction of the observed aggregate image when the aggregate is observed with an electron microscope such as a scanning electron microscope or a transmission electron microscope.
  • the Si particle bonded body includes voids due to its form.
  • a Si particle bonded body having a combination in which a plurality of Si particles and a plurality of fibrous Si are bonded includes a large number of voids.
  • the Si particle combination is used as a negative electrode active material for a non-aqueous electrolyte secondary battery, even if Si expands and contracts during charge and discharge, the voids serve as a buffering factor, so the overall size of the Si particle combination is Expect little change.
  • FIG. 1 shows a schematic diagram of a bonded Si particle of the present invention.
  • each fibrous Si 20 is bonded to a plurality of Si particles 10 to form one Si particle bonded body 40. Further, the Si particle bonded body 40 shown in FIG. In FIG. 1, a plurality of fibrous Si 20 bonded to a plurality of Si particles 10 forms a network structure.
  • Si contained in the Si particle bonded body has Si crystal.
  • both the Si particles and the fibrous Si preferably contain Si crystals.
  • the coated Si particle bonded body of the present invention is characterized by having the above Si particle bonded body and a carbon-containing film disposed on the surface of the Si particle bonded body.
  • the Si particle combination is as described above.
  • the surface of the Si particle bonded body refers to the surface of the Si particles, the surface of the fibrous Si, and the surface of the bonded portion between the Si particles and the fibrous Si.
  • the carbon-containing coating is preferably disposed on the entire surface of the Si particle bonded body.
  • the thickness of the carbon-containing film is not particularly limited.
  • the thickness of the carbon-containing coating is preferably 1 nm or more and 20 nm or less, more preferably 1 nm or more and 10 nm or less, and further preferably 1 nm or more and 5 nm or less.
  • the thickness of the carbon-containing coating here refers to the thickness when observed with an electron microscope such as a scanning electron microscope or a transmission electron microscope.
  • the carbon-containing film has at least carbon.
  • the carbon-containing film may further contain hydrogen and oxygen. Since Si has low conductivity, it is presumed that conductivity can be improved by having a carbon-containing film.
  • the coated Si particle combination of the present invention is used as a negative electrode active material of a battery, it is expected that battery characteristics can be improved.
  • the carbon-containing film preferably contains amorphous carbon.
  • the coated Si particle combination of the present invention having a carbon-containing coating containing amorphous carbon is used as the negative electrode active material of a battery, the carbon-containing coating is bonded to Si particles even if Si expands or contracts during charge and discharge. Expected to be difficult to peel off from the surface of the body and expected to improve battery characteristics.
  • the carbon-containing film is preferably a film containing C, H, and O elements.
  • XPS X-ray photoelectron spectroscopy
  • the peak tops found in the range of 1420 cm ⁇ 1 to 1480 cm ⁇ 1 are derived from CH 2 or CH 3 .
  • the carbon-containing film has an ester skeleton when the carbon-containing film has the above peak in the high resolution spectrum of the C1s orbit by XPS.
  • Films containing C, H, and O elements should detect terpene fragments in pyrolysis gas chromatograph mass spectrometry (hereinafter referred to as pyrolysis GC-MS as appropriate) at pyrolysis temperatures up to 270 ° C. Is preferred.
  • pyrolysis GC-MS pyrolysis gas chromatograph mass spectrometry
  • the Si particle bonded body of the present invention since the film is formed on the surface of the Si particle bonded body, the Si particle bonded body is hardly oxidized even in an oxygen-containing atmosphere.
  • the oxygen content of the coated Si particle conjugate of the present invention is preferably 10% or less, more preferably 8% or less, and even more preferably 6% or less.
  • the method for producing a Si particle bonded body of the present invention includes a step of introducing raw material Si powder into a plasma having a plasma output of 5 kW or more and less than 15 kW by an introduction flow, and a flow after the introduction flow has passed through the plasma. And a cooling step of cooling with a cooling gas flow facing the passing flow.
  • the method for producing a coated Si particle assembly of the present invention includes a step of introducing raw material Si powder into a plasma having a plasma output of 5 kW or more and less than 15 kW by an introduction flow, and after the introduction flow has passed through the plasma.
  • the D 50 of the raw material Si powder is not particularly limited, but is preferably 1 ⁇ m to 100 ⁇ m, more preferably 1 ⁇ m to 40 ⁇ m, and even more preferably 2 ⁇ m to 10 ⁇ m.
  • the raw material Si powder of D 50 is too small, the less likely to move the raw material Si powder due to static electricity or the like, the raw material Si powder of D 50 is too large, to have hardly a possibility that uniformly moves the raw material Si powder, In addition, it may be difficult to vaporize or make the entire amount of the raw material Si powder introduced into the liquid state in the plasma.
  • D 50 can be measured by particle size distribution measurement method.
  • D 50 is a particle diameter corresponding to an integrated value of volume distribution in particle size distribution measurement by laser diffraction method corresponding to 50%. That is, the D 50, means the median size measured by volume.
  • the manufacturing method of the Si particle combination and the coated Si particle combination of the present invention is carried out using a plasma generator.
  • the plasma may be generated by arc discharge, multiphase arc discharge, high frequency electromagnetic induction, microwave heating discharge, or the like.
  • the frequency may be, for example, in the range of 0.5 MHz to 400 MHz, preferably in the range of 1 MHz to 80 MHz.
  • the plasma output is 5 kW or more and less than 15 kW, and more preferably 5 kW or more and 10 kW or less. If the plasma output is 5 kW or more and less than 15 kW, SiC is hardly generated when a gas containing a carbon source gas is used as the cooling gas.
  • the pressure in the plasma generator may be set as appropriate, for example, the range of 10 kPa to atmospheric pressure can be exemplified.
  • the average particle diameter of the Si particles can be changed by changing the plasma output or the pressure in the plasma generator.
  • the average particle size of the Si particles can be reduced by bringing the pressure in the plasma generator close to atmospheric pressure.
  • the introduction flow is generated by the flow of gas toward the plasma.
  • a gas that can be used under the plasma is preferably used as the main flow.
  • the gas constituting the introduction flow that is, the introduction gas, a rare gas such as helium or argon or hydrogen is preferable.
  • an introduction gas flow rate 20 L / min. ⁇ 120 L / min. Can be illustrated.
  • the introduced gas it is introduced into the coil separately from the carrier gas carrying the raw Si powder and the carrier gas. It is preferable to employ an inner gas to be used and a process gas for bringing the plasma generation site into an inert atmosphere.
  • the carrier gas flow rate is 1 L / min. ⁇ 10L / min. Can be illustrated.
  • the flow rate of the carrier gas is 1 L / min. ⁇ 5L / min. Is preferred.
  • the flow rate of the inner gas is 1 L / min. ⁇ 10L / min. Can be illustrated.
  • the flow rate of the inner gas is 1 L / min. ⁇ 5L / min. Is preferred.
  • the flow rate of the process gas is 15 L / min. To 100 L / min. Can be illustrated.
  • As the flow rate of the process gas 30 L / min. To 100 L / min. Is preferred.
  • the introduction flow rate is the sum of the carrier gas flow rate, the inner gas flow rate, and the process gas flow rate.
  • the temperature in the plasma becomes higher than when only argon is used as the process gas.
  • the temperature in the plasma when only argon is used as the process gas is about 10,000 ° C.
  • a mixed gas of argon and helium when using as a process gas, the temperature in the plasma is about 15,000 ° C.
  • the feed rate of the raw material Si powder is 50 mg / min. -1000 mg / min. Is preferable, and 50 mg / min. ⁇ 500 mg / min. Is more preferable. If the supply speed of the raw material Si powder becomes too fast, a lot of Si powder is vaporized. There are cases where the thermal energy of the plasma is deprived by the vaporization of many Si powders and the temperature in the plasma is too low.
  • the flow after the introduction flow passes through the plasma is cooled by the opposing cooling gas flow. Since the inside of the plasma is in a high temperature state and the ambient temperature outside the plasma is room temperature, the passing flow is rapidly cooled simply by going out of the plasma from the plasma. Further, the ambient temperature outside the plasma can be further lowered by cooling the entire plasma generator with cooling water or the like.
  • the cooling gas flow facing the through flow toward the through flow the cooling gas flow and the through flow are in good contact with each other, and the through flow is uniformly cooled. Further, the cooling gas flow facing the passing flow is injected toward the passing flow, so that Si in the passing flow rides on the cooling gas flow and convects.
  • the temperature in the plasma is about 8,000 ° C. to 20,000 ° C.
  • Si nuclei are generated at about 2,000 ° C. to 2,300 ° C., and it is considered that many particles are generated around the nuclei. It is considered that the particles grow as a result of the other particles agglomerating with the generated particles as the through flow is cooled.
  • Si in the passing flow rides on the cooling gas flow and convects, Si having different degrees of cooling, that is, Si having different particle diameters, come into contact with each other during convection.
  • the Si particle bonded body of the present invention is presumed to be formed by bonding Si having different particle diameters during convection. Although the reason for the fibrous Si in the Si particle bonded body of the present invention is unknown, it is considered that Si particles having small particle diameters are connected to form fibrous Si.
  • the cooling gas is preferably a rare gas such as helium or argon.
  • the temperature of the cooling gas may be room temperature or lower than room temperature.
  • the flow rate of the cooling gas may be a flow rate smaller than the introduction flow, for example, 0.1 L / min. ⁇ 30 L / min. This can be illustrated as an example.
  • the flow rate of the cooling gas is 0.2 L / min. 25 L / min. Or less, preferably 0.3 L / min. 20 L / min. The following is more preferable.
  • cooling is performed with a cooling gas flow containing a carbon source gas, and Si in the passing flow is brought into contact with the carbon source gas to form a carbon-containing coating on Si.
  • the cooling gas flow containing the carbon source gas is injected toward the passing flow, it is preferable that the carbon source gas is not mixed into the plasma. If the carbon source gas is mixed in the plasma, Si and C may react to generate SiC as an impurity. When SiC is generated, Si is consumed, and the amount of Si particles may be reduced.
  • the carbon source gas is injected toward the passing flow so that the reaction field becomes an atmosphere of 1700 K (about 1427 ° C.) or less.
  • the temperature atmosphere of the reaction field can be adjusted by adjusting the plasma output and the injection position of the carbon source gas.
  • Examples of the carbon source gas include alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, and octane, alkynes such as acetylene, methylacetylene, butyne, pentyne, hexyne, heptine, and octyne, ethylene, Alkenes such as propylene, butene, pentene, hexene, heptene, octene, ethers such as dimethyl ether, ethyl methyl ether, diethyl ether, ethyl propyl ether, dipropyl ether, propyl butyl ether, dibutyl ether, ethylene glycol, propylene glycol, glycerin Glycols such as methyl formate, ethyl formate, ethyl acetate, methyl acetate,
  • a carbon source gas When producing a coated Si particle combination, only a carbon source gas may be used as a cooling gas, or a carbon source gas and a rare gas may be used in combination.
  • the flow rate of the carbon source gas is, for example, 0.1 L / min. ⁇ 10L / min. Within the range of 0.1 L / min. 5 L / min. Or less, preferably 0.1 L / min. 3 L / min. The following is more preferable.
  • the coating structure can be adjusted by adjusting the number of moles of carbon source gas supplied per unit time relative to the number of moles of raw material Si powder supplied per unit time. .
  • the production of SiC can be suppressed by setting C / Si, which is the ratio of the number of moles of carbon source gas supplied per unit time to the number of moles of raw material Si powder supplied per unit time, to 1.5 or less. . If C / Si is 0.5 or more, a carbon-containing coating can be easily produced on the surface of the Si particle combination. When C / Si is too large, SiC is likely to be generated, and when C / Si is too small, it becomes difficult to form a carbon-containing coating on the surface of the Si particle combination.
  • the carbon particle-containing Si particle bonded body formed in the cooling step is maintained in an oxygen-containing atmosphere, and oxygen is introduced into the carbon-containing coated film.
  • the cooling step when the temperature of the reaction field is low or the reaction time is short, all of the H contained in the carbon source gas is not dissociated and CH in the radical state exists on the surface of the Si particle bonded body. Is guessed. Therefore, when the carbon-containing film having CH in the radical state is placed in an oxygen-containing atmosphere after the cooling step, oxygen is bonded to the CH in the radical state, and oxygen is easily introduced into the carbon-containing film. Further, it is considered that the surface of the Si particle bonded body is stabilized by contact of oxygen and radical state CH. That is, it can be said that the oxygen introduction step is a stabilization step of the coated Si particle combination.
  • a raw material Si powder is introduced into a plasma by an introduction flow, and a passing flow after the introduction flow passes through the plasma is opposed to the passing flow. Cooling with a cooling gas stream containing a carbon source gas, and contacting Si in the passing stream with the carbon source gas to form a carbon-containing film on the Si, wherein the cooling gas stream is carbon
  • the supply position of the carbon source gas includes the source gas and the rare gas, and is characterized in that the supply position of the carbon source gas is downstream with respect to the passage direction of the passing flow.
  • the opening for supplying the rare gas and the opening for supplying the carbon source gas are separated, and the position of the opening for supplying the carbon source gas is changed to the position of the rare gas. What is necessary is just to set to the position which is downstream with respect to the passage direction of a passage flow rather than the position of the opening part to supply.
  • the distance between the opening of the carbon source gas supply pipe and the opening in the plasma generator is 50 mm or more than the distance between the opening of the rare gas supply pipe and the opening in the plasma generator. It is preferable to enlarge it.
  • the plasma output, the feed rate of the raw material Si powder, the flow rate of the carbon source gas, and the supply position of the carbon source gas are appropriately adjusted.
  • the supply rate of the raw material Si powder, the flow rate of the carbon source gas, and the supply position of the carbon source gas may be adjusted in accordance with the magnitude of the plasma output. If the plasma output is increased, the feed rate of the raw material Si powder can be increased without greatly reducing the temperature in the plasma.
  • the supply position of the carbon source gas may be further downstream than the supply position of the rare gas with respect to the passing direction of the passing flow. By making the supply position of the carbon source gas further downstream with respect to the passing direction of the passing flow, the generation of SiC as an impurity can be suppressed even if the supply speed of the raw material Si powder is increased.
  • the plasma output is preferably 3 kW to 300 kW, more preferably 5 kW to 100 kW, and even more preferably 5 kW to 20 kW.
  • the supply rate of the raw material Si powder per plasma output is 0.01 g / min. / KW to 1 g / min. / KW is preferred, and 0.01 g / min. / KW to 0.5 g / min. / KW is more preferable, 0.01 g / min. / KW to 0.1 g / min. / KW is more preferable.
  • the Si particle bonded body or coated Si particle bonded body of the present invention can be used as a negative electrode active material for a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery.
  • the negative electrode active material containing the Si particle combination or the coated Si particle combination of the present invention is referred to as the negative electrode active material of the present invention.
  • the following invention can be grasped as the second negative electrode active material of the present invention derived from the negative electrode active material of the present invention.
  • the second negative electrode active material of the present invention has Si particles and a carbon-containing film that is disposed on the surface of the Si particles and contains C, H, and O.
  • the carbon-containing film has a pyrolysis gas chromatograph mass. The analysis is characterized in that fragments of terpenes are detected.
  • the Si particles may be of any shape as long as they are manufactured using the plasma generator.
  • the negative electrode active material of the present invention For other matters related to the second negative electrode active material of the present invention, the description of the negative electrode active material of the present invention is incorporated.
  • the negative electrode including the negative electrode active material or the second negative electrode active material of the present invention is referred to as the negative electrode of the present invention
  • the nonaqueous electrolyte secondary battery including the negative electrode of the present invention is referred to as the nonaqueous electrolyte secondary battery of the present invention.
  • the non-aqueous electrolyte secondary battery of the present invention will be described using a lithium ion secondary battery as an example.
  • the negative electrode in the lithium ion secondary battery of the present invention has a current collector and a negative electrode active material layer bound to the surface of the current collector.
  • the negative electrode active material of the present invention or the second negative electrode active material of the present invention is used as the negative electrode active material.
  • the negative electrode active material layer in the lithium ion secondary battery of the present invention includes other known negative electrode active materials, binders, conductive assistants, Other additives may be included.
  • Examples of other known negative electrode active materials include carbon-based materials capable of inserting and extracting lithium, elements capable of being alloyed with lithium, compounds having elements capable of being alloyed with lithium, and polymer materials. it can. As other known negative electrode active materials, carbon-based materials are preferable.
  • the carbon-based material examples include non-graphitizable carbon, graphite, coke, graphite, glassy carbon, organic polymer compound fired body, carbon fiber, activated carbon, or carbon black.
  • the organic polymer compound fired body refers to a material obtained by firing and carbonizing a polymer material such as phenols and furans at an appropriate temperature.
  • elements that can be alloyed with lithium include Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si. , Ge, Sn, Pb, Sb, and Bi.
  • compounds having elements that can be alloyed with lithium include ZnLiAl, AlSb, SiB 4 , SiB 6 , Mg 2 Si, Mg 2 Sn, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2, CrSi 2, Cu 5 Si, FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3 N 4, Si 2 N 2 O, SiO v (0 ⁇ v ⁇ 2), SnO w (0 ⁇ w ⁇ 2), SnSiO 3 , LiSiO 2 or LiSnO.
  • polymer material examples include polyacetylene and polypyrrole.
  • the amount of the negative electrode active material when the total amount of the negative electrode active material layer is 100% by mass is preferably in the range of 60% by mass to 99% by mass, more preferably in the range of 65% by mass to 98% by mass, A range of 70% by mass to 97% by mass is particularly preferable.
  • the binder serves to bind the negative electrode active material and the conductive auxiliary agent to the surface of the current collector.
  • Binders include fluorine-containing resins such as polyvinylidene fluoride, polytetrafluoroethylene, and fluororubber, thermoplastic resins such as polypropylene and polyethylene, imide resins such as polyimide and polyamideimide, alkoxysilyl group-containing resins, and styrene butadiene. Rubber can be exemplified. Moreover, you may employ
  • hydrophilic group of the polymer having a hydrophilic group examples include a carboxyl group, a sulfo group, a silanol group, an amino group, a hydroxyl group, and a phosphate group.
  • Specific examples of the polymer having a hydrophilic group include a polymer containing a carboxyl group in a molecule such as polyacrylic acid, carboxymethylcellulose, and polymethacrylic acid, or a polymer containing a sulfo group such as poly (p-styrenesulfonic acid). It is done.
  • a crosslinked polymer obtained by crosslinking a carboxyl group-containing polymer such as polyacrylic acid or polymethacrylic acid with a polyamine such as diamine disclosed in International Publication No. 2016/063882 may be used as a binder.
  • Diamines used in the crosslinked polymer include alkylene diamines such as ethylene diamine, propylene diamine, and hexamethylene diamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, isophorone diamine, bis (4-aminocyclohexyl) methane, and the like.
  • the blending amount of the binder is not particularly limited. However, when the blending amount of the binder in the negative electrode active material layer is given, it is preferably in the range of 0.5% by mass to 10% by mass, and 1% by mass to 7% by mass. Is more preferable, and the range of 2% by mass to 5% by mass is particularly preferable. If the blending amount of the binder is too small, the moldability of the negative electrode active material layer may be lowered. Moreover, when there are too many compounding quantities of a binder, since the quantity of the negative electrode active material in a negative electrode active material layer reduces relatively, it is unpreferable.
  • the conductive auxiliary agent may be any chemically inert electronic high conductor, such as carbon black, graphite, vapor grown carbon fiber (Vapor Grown Carbon Fiber), and various metal particles.
  • carbon black examples include acetylene black, ketjen black (registered trademark), furnace black, and channel black.
  • These conductive assistants can be added to the negative electrode active material layer alone or in combination of two or more.
  • the shape of the conductive auxiliary agent is not particularly limited, but it is preferable that the average particle size of the conductive auxiliary agent is small in view of its role.
  • a preferable average particle size of the conductive assistant is 10 ⁇ m or less, and a more preferable average particle size is in the range of 0.01 ⁇ m to 1 ⁇ m.
  • the blending amount of the conductive assistant is not particularly limited, but if the blending amount of the conductive assistant in the negative electrode active material layer is given, it is preferably in the range of 0.5% by mass to 10% by mass, and 1% by mass to 7% by mass. Is preferably within the range of 2% by mass to 5% by mass.
  • additives can be used as additives such as a dispersant other than the conductive auxiliary agent and the binder.
  • a current collector refers to a chemically inert electronic high conductor that keeps a current flowing through an electrode during discharge or charging of a lithium ion secondary battery.
  • the current collector at least one selected from silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, and stainless steel, etc. Metal materials can be exemplified.
  • the current collector may be covered with a known protective layer. What collected the surface of the electrical power collector by the well-known method may be used as an electrical power collector.
  • the current collector can take the form of a foil, a sheet, a film, a linear shape, a rod shape, a mesh, or the like. Therefore, for example, a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector.
  • a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector.
  • the thickness is preferably in the range of 1 ⁇ m to 100 ⁇ m.
  • a negative electrode active material may be applied to the surface of the current collector.
  • an active material, a solvent, and if necessary, a binder and a conductive additive are mixed to form a slurry, and the slurry is applied to the surface of the current collector and then dried.
  • the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water.
  • the dried product may be compressed.
  • Examples of one aspect of the lithium ion secondary battery of the present invention include those equipped with the negative electrode, positive electrode, electrolytic solution, and separator of the present invention.
  • the positive electrode has a current collector and a positive electrode active material layer bound on the current collector.
  • the positive electrode active material layer includes a positive electrode active material and a binder, and may further include a conductive additive and other additives.
  • a positive electrode active material, a conductive support agent, and a binder are not particularly limited.
  • the positive electrode active material a material capable of occluding and releasing charge carriers such as Li may be used.
  • a solid solution composed of a spinel such as LiMn 2 O 4 and Li 2 Mn 2 O 4 and a mixture of a spinel and a layered compound, LiMPO 4 , LiMVO 4, or Li 2 MSiO 4 (M in the formula) are selected from at least one of Co, Ni, Mn, and Fe).
  • tavorite compound (the M a transition metal) LiMPO 4 F, such as LiFePO 4 F represented by, Limbo 3 such LiFeBO 3 (M is a transition metal) include borate-based compound represented by be able to.
  • any metal oxide used as the positive electrode active material may have the above composition formula as a basic composition, and a metal element contained in the basic composition may be substituted with another metal element.
  • a positive electrode active material that does not contain lithium ions contributing to charge / discharge, for example, sulfur alone (S), a compound in which sulfur and carbon are combined, a metal sulfide such as TiS 2 , V 2 O, etc. 5 , oxides such as MnO 2 , polyaniline and anthraquinone, compounds containing these aromatics in the chemical structure, conjugated materials such as conjugated diacetic acid organic materials, and other known materials can also be used.
  • a compound having a stable radical such as nitroxide, nitronyl nitroxide, galvinoxyl, phenoxyl, etc. may be adopted as the positive electrode active material.
  • a positive electrode active material that does not contain lithium it is necessary to add ions to the positive electrode and / or the negative electrode in advance by a known method.
  • a metal or a compound containing the ion may be used.
  • the current collector used for the positive electrode is not limited as long as it is generally used for the positive electrode of a lithium ion secondary battery, such as aluminum, nickel, and stainless steel. .
  • the electrolytic solution contains a non-aqueous solvent and an electrolyte dissolved in the non-aqueous solvent.
  • cyclic esters examples include ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone, and gamma valerolactone.
  • chain esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, ethyl methyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester.
  • ethers examples include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane.
  • non-aqueous solvent a compound in which a part or all of hydrogen in the chemical structure of the above specific solvent is substituted with fluorine may be employed.
  • Examples of the electrolyte include lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , and LiN (CF 3 SO 2 ) 2 .
  • a lithium salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 in a nonaqueous solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate, and diethyl carbonate.
  • a solution dissolved at a concentration of about / L can be exemplified.
  • the separator separates the positive electrode and the negative electrode and allows lithium ions to pass while preventing a short circuit due to contact between the two electrodes.
  • natural resins such as polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramid (Aromatic polymer), polyester, polyacrylonitrile, etc., polysaccharides such as cellulose, amylose, fibroin, keratin, lignin, suberin, etc. Examples thereof include porous bodies, nonwoven fabrics, and woven fabrics using one or more electrically insulating materials such as polymers and ceramics.
  • the separator may have a multilayer structure.
  • the method for producing a lithium ion secondary battery of the present invention includes a step of disposing the negative electrode of the present invention. Specifically, it is as follows.
  • a separator is sandwiched between the positive electrode and the negative electrode as necessary to form an electrode body.
  • the electrode body may be any of a stacked type in which a positive electrode, a separator and a negative electrode are stacked, or a wound type in which a positive electrode, a separator and a negative electrode are sandwiched.
  • an electrolytic solution is added to the electrode body to form a lithium ion secondary battery. It is good to do.
  • the lithium ion secondary battery of this invention should just be charged / discharged in the voltage range suitable for the kind of active material contained in an electrode.
  • the shape of the lithium ion secondary battery of the present invention is not particularly limited, and various shapes such as a cylindrical shape, a square shape, a coin shape, and a laminate shape can be adopted.
  • the lithium ion secondary battery of the present invention may be mounted on a vehicle.
  • the vehicle may be a vehicle that uses electric energy from the secondary battery for all or part of its power source, and may be, for example, an electric vehicle, a hybrid vehicle, or the like.
  • a lithium ion secondary battery is mounted on a vehicle, a plurality of lithium ion secondary batteries may be connected in series to form an assembled battery.
  • devices equipped with lithium ion secondary batteries include various home appliances driven by batteries such as personal computers and portable communication devices, office devices, and industrial devices in addition to vehicles.
  • the lithium ion secondary battery of the present invention includes wind power generation, solar power generation, hydroelectric power generation and other power system power storage devices and power smoothing devices, power supplies for ships and / or auxiliary power supply sources, aircraft, Power supply for spacecraft and / or auxiliary equipment, auxiliary power supply for vehicles that do not use electricity as a power source, power supply for mobile home robots, power supply for system backup, power supply for uninterruptible power supply, You may use for the electrical storage apparatus which stores temporarily the electric power required for charge in the charging station for electric vehicles.
  • Example 1 The powder of Example 1 was manufactured using the plasma generator shown in FIG.
  • the raw material powder is supplied from the powder supplier 1, and the raw material powder is introduced into the plasma generator 11 through the carrier gas path 6.
  • the carrier gas is introduced into the plasma generator 11 through the carrier gas path 6, the process gas is introduced into the plasma generator 11 through the process gas path 7, and the inner gas is introduced into the plasma generator 11 through the inner gas path 8.
  • the Power is supplied by the power supply device 2, and plasma is generated in the plasma generator 11.
  • the cooling gas carried through the cooling gas path 9 is injected in a direction opposite to the passing flow after passing through the plasma.
  • the distance between the opening of the cooling gas supply pipe 91 and the opening of the plasma generator 11 was 200 mm.
  • Each gas is exhausted out of the apparatus through an exhaust section 3 provided with a filter 4.
  • the product falls by its own weight and is stored in the lower part of the internal chamber 5.
  • the white arrow represents the cooling water.
  • Si powder having a D 50 of 3 ⁇ m (manufactured by Kojundo Chemical Laboratory Co., Ltd., product number SIE23PB) was prepared.
  • the raw material Si powder was placed in a powder feeder.
  • argon gas as a process gas was added at 60 L / min. At 5 L / min. As an inner gas.
  • Methane gas as a cooling gas at 0.32 L / min. Supplied with.
  • the flow rate of methane gas was measured using a float type flow meter attached to the supply pipe. At this time, power was supplied from the power supply device, and a magnetic field with a frequency of 4 MHz was applied to the coil to generate plasma with an output of 10 kW.
  • the pressure in the plasma generator was atmospheric pressure.
  • the powder feeder is operated, and the raw material Si powder is 400 mg / min. Was introduced into the plasma together with the carrier gas at a rate of The powder released along with the flow after passing through the plasma was collected and held in an oxygen atmosphere for 1 hour. The obtained powder was used as the powder of Example 1.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, is 1.0.
  • Example 1 The powder cross section of Example 1 was observed by SEM. Cross-sectional SEM observation results are shown in FIG. 3, FIG. 4, and FIG. FIG. 4 shows the result of 10 ⁇ magnification of FIG. 3, and FIG. 5 shows the result of 100 ⁇ magnification of FIG. In FIG. 3, FIG. 4, and FIG. 5, a coated Si particle combination having the form of an aggregate was observed. In FIG. 4, it was clearly observed that the Si particles were dispersed in the aggregate.
  • the size in the longitudinal direction of the aggregate of the powder Si particle aggregate of Example 1 was measured. As a result of measuring 100 aggregates of the Si particle aggregate, the size in the longitudinal direction of the entire Si particle aggregate of the powder of Example 1 was 20 ⁇ m or more and 150 ⁇ m or less.
  • Example 1 was observed with a TEM.
  • the TEM observation result of the powder of Example 1 is shown in FIG.
  • Si particles 10 and fibrous Si20 were observed.
  • a plurality of fibrous Si was bonded to the Si particles 10 and that the fibrous Si 20 was bonded to a plurality of Si particles.
  • the fiber diameter of fibrous Si is about 10 nm, and the particle diameter of Si particle is about 100 nm.
  • the particle size of the Si particles of the powder of Example 1 was measured. 200 major axes of each Si particle of the powder of Example 1 were measured. The particle size of the Si particles in the powder of Example 1 was not less than 30 nm and less than 1000 nm. A particle size distribution diagram of the Si particles of the powder of Example 1 was created using the measured numerical values. A particle size distribution diagram is shown in FIG. The D 50 of the Si particles of the powder of Example 1 was 70 nm.
  • the fiber diameter of fibrous Si was measured. 100 fiber diameters of each fibrous Si of the powder of Example 1 were measured. The fiber diameter of fibrous Si was 8 nm or more and 15 nm or less. The arithmetic average value of the fiber diameter of fibrous Si of the powder of Example 1 calculated from the measured value was 10 nm.
  • the fiber length of fibrous Si was measured. 100 fiber lengths of each fibrous Si of the powder of Example 1 were measured. The fiber length of the fibrous Si was 30 nm or more and 1 ⁇ m or less.
  • the surface of the powder Si particle combination of Example 1 was observed with a transmission electron microscope-energy dispersive X-ray spectroscopy (hereinafter referred to as TEM-EDS).
  • TEM-EDS transmission electron microscope-energy dispersive X-ray spectroscopy
  • Si was measured in the Si particles 10
  • Si was measured in the central portion of the bonding portion 50. That is, it was observed that the fibrous Si and the Si particles 10 were integrated in the joint portion 50.
  • the coating was observed on both the Si particles, the fibrous Si, and the bonding portion, it is presumed that the coating has an effect of reinforcing the structure of the Si particle bonded body.
  • C and O were measured on the film 60.
  • the following can be considered as a mechanism in which C and O are contained in the film 60.
  • the powder after passing through the plasma was held for 1 hour in an oxygen atmosphere. It is presumed that CH in a radical state exists on the surface of the powder after passing through the plasma. Therefore, when a film having CH in a radical state is placed in an oxygen-containing atmosphere, oxygen is bonded to CH in the radical state, and oxygen is easily introduced into the film. As a result, it is presumed that C and O are contained in the coating 60 on the surface of the powder.
  • FIG. 11 A schematic diagram of the TEM observation result of the powder of Example 1 is shown in FIG.
  • TEM-EELS transmission electron microscope-electron energy loss spectroscopy
  • Example 2 Argon gas was used as a cooling gas at 20 L / min.
  • the powder of Example 2 was produced in the same manner as the powder of Example 1 except that methane gas was not supplied.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 0.
  • Example 3 As a cooling gas, methane gas is 0.16 L / min. Thus, the powder of Example 3 was produced in the same manner as the powder of Example 1 except that it was supplied.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 0.5.
  • Example 4 As a cooling gas, methane gas is 0.48 L / min. Thus, the powder of Example 4 was produced in the same manner as the powder of Example 1 except that it was supplied.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 1.5.
  • Example 5 Methane gas is used as the cooling gas at 0.576 L / min.
  • a powder of Example 5 was produced in the same manner as the powder of Example 1 except that the powder was supplied in Step 1.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 1.8.
  • Example 6 As a cooling gas, methane gas is 0.64 L / min.
  • a powder of Example 6 was produced in the same manner as the powder of Example 1 except that the powder was supplied in Step 6.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 2.0.
  • Example 7 The distance between the opening of the cooling gas supply pipe and the opening in the plasma generator is 150 mm, and methane gas is used as the cooling gas at 0.56 L / min. At a raw material Si powder of 700 mg / min. The powder of Example 7 was produced in the same manner as the powder of Example 1, except that the speed was changed. C / Si, which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 1.
  • Comparative Example 1 A powder of Comparative Example 1 was obtained in the same manner as the powder of Example 1 except that the plasma output was 15 kW.
  • Comparative Example 2 A powder of Comparative Example 2 was obtained in the same manner as the powder of Example 1 except that the plasma output was 20 kW.
  • FIG. 14 shows the Raman spectra of the powder coating of Example 1, the powder coating of Comparative Example 1, and the powder coating of Comparative Example 2.
  • the horizontal axis represents the wave number (cm ⁇ 1 )
  • the vertical axis represents the scattering intensity.
  • the measurement conditions were a wavelength of 532 nm, a measurement range of 450 cm ⁇ 1 -1700 cm ⁇ 1 , a measurement time of 30 seconds, and an integration count of 50 times.
  • the G band is a peak due to graphite
  • the D band is a peak due to carbon atoms having dangling bonds such as amorphous carbon. From this, it was confirmed that the powder coating of Example 1, the powder coating of Comparative Example 1, and the powder coating of Comparative Example 2 contained graphite and amorphous carbon.
  • the Raman spectra of the powder of Example 1 further, 1230 cm -1 ⁇ 1270 cm -1, a peak was observed in the range of 1420cm -1 ⁇ 1480cm -1. These peaks were not observed in the Raman spectra of the powder of Comparative Example 1 and the powder of Comparative Example 2.
  • the peaks in the range of 1230 cm ⁇ 1 to 1270 cm ⁇ 1 are peaks derived from Si—CH 2 and / or Si—CH 3, and the peaks in the range of 1420 cm ⁇ 1 to 1480 cm ⁇ 1 are CH 2 and / or CH 3. It is a peak derived from. From this, unlike the powder coating of Comparative Example 1 and the powder coating of Comparative Example 2, the element H remains in the powder coating of Example 1, and the structure is derived from CH 2 and / or CH 3. It was confirmed that
  • the following may be considered as a mechanism in which the coating in the powder of Example 1 has a structure derived from CH 2 and / or CH 3 .
  • the powder of Example 1 was produced with a plasma output of 10 kW, and was cooled by a cooling gas containing a carbon source gas during production. In the hydrocarbon gas contained in the carbon source gas, dissociation of H proceeds by thermal plasma.
  • the dissociation energy of C—H bond is about 480 kJ / mol. For example, in order to dissociate all H from CH 4 , energy of about 1600 kJ / mol is required.
  • the plasma output at the time of production was 15 kW and 20 kW, which was higher energy than at the time of production of the powder of Example 1, so CH 4 was decomposed to C alone, and the coating film was It is presumed that there was no structure derived from CH 2 and / or CH 3 .
  • FIG. 15 shows the XPS measurement results of the coating films of the powder of Example 1, the powder of Example 3, and the powder of Example 4.
  • the horizontal axis represents the binding energy (eV)
  • the vertical axis represents the strength (au).
  • FIG. 15 shows a side-by-side description of the high-resolution spectrum of the C1s orbit of each sample. As shown in FIG. 15, peaks were observed at 287 eV to 290 eV in the high resolution spectrum of the C1s orbit of each sample.
  • the peak observed at 287 eV to 290 eV is presumed to be a peak derived from R—COO—R ′. Therefore, it is considered that the structure of C and O included in the coating includes O ⁇ C—O. Therefore, it is estimated that the film has an ester skeleton.
  • the peak seen at 287 eV to 290 eV increases toward the high energy side as the C / Si ratio increases. A shift was observed.
  • the coating film of the powder of Example 4, the coating film of the powder of Reference Example 1 shown below, and the coating film of the powder of Reference Example 2 were measured by pyrolysis gas chromatography.
  • the heating conditions in the measurement were 25 ° C. to 270 ° C., and the heating rate was 10 ° C./min. It was.
  • Substances adsorbed by pyrolysis gas chromatography in the temperature range of 25 ° C. to 270 ° C. were analyzed.
  • FIG. 16 shows the measurement results of the powder coating of Example 4, the powder coating of Reference Example 1, and the powder coating of Reference Example 2.
  • the powder of Reference Example 1 and the powder of Reference Example 2 are the following Si-based powders with a carbon coating.
  • the silicon material coated with carbon was used as the powder of Reference Example 1.
  • the furnace core tube of the reactor was disposed in the horizontal direction, and the rotational speed of the core tube was 1 rpm.
  • a baffle plate is disposed on the inner peripheral wall of the core tube, and the contents accumulated on the baffle plate with the rotation of the core tube are configured to fall from the baffle plate at a predetermined height. The contents are stirred during the reaction.
  • the average thickness of the powder coating of Reference Example 1 was 15 nm.
  • Si powder coated with carbon was produced by performing thermal CVD with a rotary kiln using Si powder having a D 50 of 3 ⁇ m manufactured by Kojundo Chemical Laboratory Co., Ltd. in the same manner as the powder of Reference Example 1 above.
  • the Si powder coated with carbon was used as the powder of Reference Example 2.
  • the average thickness of the powder coating of Reference Example 2 was 15 nm.
  • the powder coating of Reference Example 1 and the powder coating of Reference Example 2 were thin films formed by products obtained by thermally decomposing propane gas by a thermal CVD method in a rotary kiln type reactor. From this, it can be said that the powder coating of Example 4 is a coating different from the coating manufactured in the rotary kiln type reactor.
  • Example 7 (Coating analysis 4) Analysis of the powder of Example 7 confirmed that a number of SiC crystals were present on the surface of the Si particles. Due to the presence of SiC crystals, the powder coating of Example 7 is estimated to have a smaller surface area of Si particles than the powder coating of Example 1. In the powder production conditions of Example 1 and Example 7, Example 7 was closer to the cooling gas jet outlet than in Example 1 in the plasma generator, and the carbon source gas and Si particles were in contact with each other. It is inferred that SiC was easily generated in the powder of Example 7 at a high temperature. In addition, when a large amount of SiC is present, it is assumed that oxygen is difficult to be introduced into the coating film in the oxygen introduction process during production. Therefore, it can be inferred that the powder film of Example 7 has a smaller amount of oxygen introduced into the film than the powder film of Example 1, and the ester skeleton contained in the film.
  • the powder of Example 2 is composed of a Si particle bonded body having no carbon-containing coating.
  • the powder of Example 3, the powder of Example 4, and the powder of Example 6 are made of a Si particle combination having a carbon-containing coating. From the results of the oxygen content, it was found that the powder in which the carbon-containing film was formed had a lower oxygen content in the whole powder than the powder in which the carbon-containing film was not formed. Therefore, it can be said that the oxidation of the whole powder is suppressed by the presence of the carbon-containing coating. Moreover, it was confirmed that the one with a higher C / Si ratio has a lower oxygen content in the whole powder. From this, it is presumed that the carbon-containing coating uniformly coats the entire Si particle combination when the C / Si ratio is high.
  • a 20 ⁇ m thick copper foil was prepared as a current collector.
  • the composition for negative electrode active material layers was placed on the surface of the copper foil, and the composition for negative electrode active material layers was applied to form a film using a doctor blade.
  • the copper foil coated with the negative electrode active material layer composition was dried to remove N-methyl-2-pyrrolidone by volatilization, and the negative electrode of Example A in which the negative electrode active material layer was formed on the copper foil surface was produced. did.
  • the mixture of polyacrylic acid and 4,4'-diaminodiphenylmethane used as the binder is a crosslinked polymer in which the dehydration reaction proceeds by drying and the polyacrylic acid is crosslinked with 4,4'-diaminodiphenylmethane. To change.
  • a lithium ion secondary battery (half cell) was produced using the negative electrode of Example A produced in the above procedure as a working electrode.
  • the counter electrode was a metal lithium foil.
  • a working electrode and a counter electrode, and a separator (Hoechst Celanese glass filter and Celgard “Celgard 2400”) interposed between the two electrodes were disposed to form an electrode body.
  • This electrode body was accommodated in a battery case (CR2032-type coin battery member, manufactured by Hosen Co., Ltd.).
  • Comparative Example A A negative electrode of Comparative Example A and a lithium ion secondary battery of Comparative Example A were produced in the same manner as in Example A, except that the powder of Reference Example 1 was used instead of the powder of Example 4.
  • the negative electrode of Example B was prepared in the same manner as the negative electrode of Example A, except that this mixture was dispersed in an appropriate amount of N-methyl-2-pyrrolidone to produce a slurry-like composition for negative electrode active material layer.
  • Manufactured And the lithium ion secondary battery of Example B was manufactured like the lithium ion secondary battery of Example A except having used the negative electrode of Example B.
  • Example D A lithium ion secondary battery of Example D was produced in the same manner as Example B except that the powder of Example 7 was used instead of the powder of Example 4.
  • the discharge capacity of the lithium ion secondary battery of Example A was larger than the discharge capacity of the lithium ion secondary battery of Comparative Example A. Since the Si particle combination contained in the powder of Example 4 used for the negative electrode of Example A has fibrous Si, the surface area is larger than that of the powder of Reference Example 1 used for the negative electrode of Comparative Example A. It is estimated that the discharge capacity of the lithium ion secondary battery has increased.
  • the initial efficiency was calculated from each charge capacity and discharge capacity.
  • the initial efficiency was calculated from the following formula.
  • Initial efficiency (%) (charge capacity / discharge capacity) ⁇ 100
  • the initial efficiency of the lithium ion secondary battery of Example A was 82.3%, and the initial efficiency of the lithium ion secondary battery of Comparative Example A was 78.7%. From this, it was confirmed that the lithium ion secondary battery of Example A using the Si particle combination had higher initial efficiency than the lithium ion secondary battery of Comparative Example A using the powder of Reference Example 1. It was done.
  • the discharge curve of the lithium ion secondary battery of Comparative Example A shows 0 mAh / g ⁇ It was observed that the potential was higher than the discharge curve of the lithium ion secondary battery of Example A at around 300 mAh / g. This potential is presumed to be due to the decomposition current of the electrolyte. In the discharge curve of the lithium ion secondary battery of Example A, the high potential portion was not observed. Therefore, it is considered that the decomposition of the electrolytic solution was suppressed in the lithium ion secondary battery of Example A.
  • the coating of the negative electrode active material has an ester skeleton, thereby suppressing the decomposition of the electrolytic solution.
  • the coating having an ester skeleton is presumed to be similar in structure to the organic solvent used in the electrolytic solution and have a reduction potential window similar to that of the organic solvent used in the electrolytic solution. Therefore, it is presumed that decomposition of the electrolytic solution is suppressed by the presence of the coating film having an ester skeleton on the surface of the negative electrode active material. From FIG. 18, it was confirmed that the lithium ion secondary battery including the negative electrode including the negative electrode active material or the second negative electrode active material of the present invention is excellent in battery capacity and initial efficiency.
  • the powder of Example 4 used in the lithium ion secondary battery of Example B and the powder of Example 3 used in the lithium ion secondary battery of Example C In comparison with the powder of Example 7 used in the lithium ion secondary battery of Example D, in the powder of Example 4, an Si particle composite having a combination of a plurality of Si particles and a plurality of fibrous Si Many were observed. In the powder of Example 3 and the powder of Example 7, many Si particle combinations having a combination of one Si particle and one fibrous Si were observed. From this, it is surmised that in the Si particle combination having a combination of a plurality of Si particles and a plurality of fibrous Si, the irreversible capacity is reduced and the initial efficiency is increased in the lithium ion secondary battery.
  • the discharge curve of the lithium ion secondary battery of Example D shows 0 mAh on the X axis. It was found that the potential was higher than the discharge curves of the lithium ion secondary batteries of Examples B and C in the vicinity of / g to 300 mAh / g. This potential is presumed to be due to the decomposition current of the electrolyte. In the discharge curves of the lithium ion secondary batteries of Example B and Example C, the high potential portion was not observed. Therefore, in the lithium ion secondary batteries of Example B and Example C, the decomposition of the electrolyte was suppressed. It is thought that.
  • the proportion of the powder coating of Example 7 having an ester skeleton is considered to be smaller than the proportion of the coating of the powder coating of Example 4 and Example 3. Therefore, it is presumed that the effect of suppressing the decomposition of the electrolytic solution is increased when the powder film has more ester skeletons.
  • Example B From FIG. 20, it was confirmed that the lithium ion secondary batteries of Example B, Example C, and Example D had a capacity retention rate of 80% or more even in the 20th cycle and were excellent in capacity retention rate. .
  • the lithium ion secondary battery of Example B had a capacity retention rate of 90% or more even at the 20th cycle, and was confirmed to be particularly excellent.
  • the powder of Example 4 used for the lithium ion secondary battery of Example B many Si particle combinations having a combination of a plurality of Si particles and a plurality of fibrous Si were observed.
  • the Si particle combination having a combination of a plurality of Si particles and a plurality of fibrous Si includes a large number of voids, even if Si expands and contracts during charge and discharge, the voids serve as a buffering factor, and the Si particles It is speculated that the variation in the overall size of the conjugate was particularly small. Therefore, it is considered that the capacity retention rate of the lithium ion secondary battery of Example B was particularly high. From FIG. 20, it was confirmed that the lithium ion secondary battery of the present invention is excellent in capacity retention rate.
  • Example 8 The powder of Example 8 was produced using an apparatus obtained by improving a part of the plasma generator shown in FIG.
  • the cooling gas supply pipes 91 in FIG. 2 are a plurality of supply pipes, a part is a rare gas supply pipe, and the other part is a carbon source gas supply pipe.
  • the distance between the opening of the rare gas supply pipe and the opening of the plasma generator 11 was 150 mm.
  • the distance between the opening of the carbon source gas supply pipe and the opening of the plasma generator 11 was 200 mm.
  • argon gas as a process gas was added at 60 L / min. At 5 L / min. As an inner gas. At a flow rate of 3 L / min. Supplied with.
  • argon gas was supplied at 20 L / min. Supplied with. From the carbon source gas supply pipe, 0.096 L / min. Of methane gas is used as the carbon source gas. Supplied with.
  • the flow rate of methane gas was measured using a flow meter using a thermal flow sensor (manufactured by Cofrock, small mass flow controller Model EX250S series). At this time, power was supplied from the power supply device, and a magnetic field with a frequency of 4 MHz was applied to the coil to generate plasma with an output of 10 kW.
  • the pressure in the plasma generator was atmospheric pressure. After the plasma was stabilized, the powder feeder was operated, and the raw material Si powder was added at 400 mg / min.
  • Example 8 which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 0.3.
  • Example 9 Methane gas is used as the carbon source gas at 0.22 L / min.
  • the powder of Example 9 was produced in the same manner as the powder of Example 8 except that the powder was supplied.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 0.69.
  • Example 10 Methane gas as the carbon source gas is 0.33 L / min.
  • the powder of Example 10 was produced in the same manner as the powder of Example 8 except that it was supplied.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 1.03.
  • Example 11 Methane gas is used as a carbon source gas at 0.8 L / min.
  • the powder of Example 11 was produced in the same manner as the powder of Example 8 except that the powder was supplied in step VII.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 2.5.
  • Example 12 Methane gas is used as the carbon source gas at 0.96 L / min.
  • a powder of Example 12 was produced in the same manner as the powder of Example 8 except that the powder was supplied in step VII.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 3.0.
  • Example 13 Methane gas is used as a carbon source gas at 1.24 L / min.
  • the powder of Example 13 was produced in the same manner as the powder of Example 8 except that the powder was supplied in step VII.
  • C / Si which is the ratio of the number of moles of carbon source gas supplied per unit time to the number of moles of raw material Si powder supplied per unit time, was 3.87.
  • Example 14 The raw material Si powder was 100 mg / min. The methane gas was introduced into the plasma together with the carrier gas at a rate of 0.08 L / min. A powder of Example 14 was produced in the same manner as the powder of Example 8, except that the powder was supplied in step VII.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 1.0.
  • Example 15 The raw material Si powder was 700 mg / min. The methane gas was introduced into the plasma together with the carrier gas at a rate of 0.56 L / min. The powder of Example 15 was produced in the same manner as the powder of Example 14, except that the powder was supplied in step S2. C / Si, which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 1.0.
  • Example 16 The plasma output was 15 kW, the distance between the opening of the carbon source gas supply pipe and the opening in the plasma generator was 350 mm, and methane gas as the carbon source gas was 0.32 L / min.
  • a powder of Example 16 was produced in the same manner as the powder of Example 8, except that the powder was supplied in (4).
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 1.0.
  • Example 17 A powder of Example 17 was produced in the same manner as the powder of Example 16, except that the plasma output was 20 kW.
  • C / Si which is the ratio of the number of moles of carbon source gas fed per unit time to the number of moles of raw material Si powder fed per unit time, was 1.0.
  • the mechanism having a structure derived from CH 2 and / or CH 3 is as follows. Conceivable. In the production of the powders of Comparative Examples 1 and 2, the distance between the opening of the cooling gas supply pipe and the opening in the plasma generator was 200 mm, whereas in the production of the powders of Examples 16 and 17, The distance between the opening of the rare gas supply pipe and the opening in the plasma generator was 150 mm, and the distance between the opening of the carbon source gas supply pipe and the opening in the plasma generator was 350 mm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne de nouveaux agrégats de particules de Si et leur procédé de production. Ces agrégats de particules de Si sont caractérisés en ce qu'ils comportent des particules de Si et des Si fibreux liées aux particules de Si, et sont en outre caractérisés en ce que la taille de grain des particules de Si est supérieure au diamètre de fibre du Si fibreux.
PCT/JP2017/033436 2016-09-23 2017-09-15 Agrégats de particules de si et leur procédé de production WO2018056204A1 (fr)

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JP2021141040A (ja) * 2020-03-02 2021-09-16 力哲科技股▲ふん▼有限公司 電池材料及びその製造方法
CN114944466A (zh) * 2021-02-16 2022-08-26 泰星能源解决方案有限公司 电极活性物质复合材料的湿润造粒体及其制造方法和制造装置、电极板的制造方法

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CN114944466A (zh) * 2021-02-16 2022-08-26 泰星能源解决方案有限公司 电极活性物质复合材料的湿润造粒体及其制造方法和制造装置、电极板的制造方法

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