WO2015068361A1 - Matériau au carbone amorphe contenant du silicium, son procédé de fabrication et batterie secondaire lithium-ion - Google Patents

Matériau au carbone amorphe contenant du silicium, son procédé de fabrication et batterie secondaire lithium-ion Download PDF

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WO2015068361A1
WO2015068361A1 PCT/JP2014/005479 JP2014005479W WO2015068361A1 WO 2015068361 A1 WO2015068361 A1 WO 2015068361A1 JP 2014005479 W JP2014005479 W JP 2014005479W WO 2015068361 A1 WO2015068361 A1 WO 2015068361A1
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silicon
amorphous carbon
carbon material
particles
containing amorphous
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PCT/JP2014/005479
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English (en)
Japanese (ja)
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洋平 八木下
裕一 梶浦
浩平 山口
片山　美和
亙 小田
健太 濱井
知広 本田
精二 岡崎
坂本　明男
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エム・ティー・カーボン株式会社
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Priority to KR1020167013610A priority Critical patent/KR20160081931A/ko
Priority to CN201480060555.3A priority patent/CN105706278B/zh
Publication of WO2015068361A1 publication Critical patent/WO2015068361A1/fr

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the technology disclosed in the present specification relates to a silicon-containing amorphous carbon material used for a negative electrode of a lithium ion secondary battery and a manufacturing method thereof.
  • Lithium ion secondary batteries are lighter and have higher capacity than conventional secondary batteries such as nickel cadmium batteries, nickel metal hydride batteries, and lead batteries, so portable electronic devices such as mobile phones and notebook computers Has been put to practical use as a power source for driving. It is also used as a power source for electric vehicles and hybrid vehicles.
  • the negative electrode silicon, tin, germanium alloyed with lithium, oxides thereof, and the like can be used. However, these materials expand in volume during charging to absorb lithium ions and release lithium ions. The volume shrinks during discharge. For this reason, there is a possibility that the negative electrode material may fall off and collapse from the electrode due to a volume change when the charge / discharge cycle is repeated.
  • Patent Document 1 describes an active material for a lithium ion secondary battery containing silicon oxide and a carbon material. Since this active material has voids inside, the volume change during charging and discharging is suppressed to a small level.
  • Patent Document 2 describes a technique for embedding lithium storage material particles in a carbon material and preventing electrode breakdown during charge / discharge by reducing the size of the lithium storage material particles. .
  • the active material for a lithium ion secondary battery described in Patent Document 1 is obtained by carbonizing a sprayed resin aqueous solution together with colloidal silica, it is close to a true sphere and has a sharp particle size distribution. . For this reason, when the electrode is produced, there are few particle indirect points, and it is necessary to devise such as mixing a large amount of conductive material. Further, according to the method described in Patent Document 1, it is considered impractical because there are many steps for producing an active material.
  • an object of the present invention is to provide a material for a negative electrode such as a lithium ion secondary battery in which volume change during charge and discharge is small and cycle characteristics can be improved practically.
  • a silicon-containing amorphous carbon material includes graphitizable amorphous carbon, and is represented by SiO x (0 ⁇ x ⁇ 2) in the graphitizable amorphous carbon. Silicon oxide particles are included.
  • silicon oxide particles include those in which the surface of silicon particles added as a raw material is oxidized by air.
  • This silicon-containing amorphous carbon material contains 1% by weight or more and less than 50% by weight of silicon. Moreover, mainly as an oxygen content rate derived from silicon oxide, this silicon-containing amorphous carbon material may contain oxygen exceeding 0 wt% and less than 40 wt%.
  • the silicon-containing amorphous carbon material according to an embodiment of the present invention may have a molar ratio (O / Si) of silicon content to oxygen content of 0.2 or more and less than 2.0.
  • a method for producing a silicon-containing amorphous carbon material comprises a step of mixing raw coke powder and silicon-containing particles to dry granulate, and the granulated particles are treated with an inert gas. And carbonizing in an atmosphere.
  • the addition amount of the silicon particles or the silicon oxide particles when the sum of the volumes of the raw coke and the silicon particles or the silicon oxide particles is 100% is 2% by volume or more and 90% by volume or less. It is preferable to make it.
  • the carbonization temperature in the carbonization step is preferably 800 ° C. or higher and 1200 ° C. or lower.
  • the silicon-containing amorphous carbon material According to the silicon-containing amorphous carbon material according to an embodiment of the present invention, it is possible to suppress the destruction of the negative electrode due to the volume change of the silicon oxide particles during charge and discharge, which can contribute to the improvement of cycle characteristics. .
  • FIG. 1 is a view showing a micrograph of a cross section of the amorphous carbon material according to Example 8.
  • FIG. 2 is a diagram illustrating an example of a lithium ion secondary battery including a negative electrode using a silicon-containing amorphous carbon material according to an embodiment of the present invention.
  • FIG. 3 is a view showing a micrograph of a cross section of the amorphous carbon material according to Example 10.
  • FIG. 4 is a view showing a micrograph of a cross section of the amorphous carbon material according to Example 12.
  • a silicon-containing amorphous carbon material for a negative electrode of a lithium ion secondary battery according to an embodiment of the present invention and a lithium ion secondary battery using the material will be described below.
  • FIG. 1 is a view showing a photomicrograph of a cross section of a silicon-containing amorphous carbon material according to an embodiment of the present invention.
  • the silicon-containing amorphous carbon material 1 includes amorphous carbon 4, and the amorphous carbon 4 is represented by SiO x (0 ⁇ x ⁇ 2). Silicon oxide particles are included. The silicon oxide particles in the amorphous carbon 4 are present in a dispersed state, for example. The amorphous carbon 4 is graphitizable carbon, so-called soft carbon.
  • Each silicon-containing amorphous carbon material 1 is composed of a plurality of carbon particles derived from raw materials.
  • the amorphous carbon 4 contains silicon oxide particles
  • a sufficiently high level of cycle characteristics is achieved while improving the initial discharge capacity. Can be maintained.
  • the silicon-containing amorphous carbon material 1 of the present embodiment if the molar ratio (O / Si) between the silicon content and the oxygen content is 0.2 or more and less than 2.0, the initial discharge capacity is improved. However, it is more preferable because the initial efficiency and the cycle characteristics above a certain level can be provided in a well-balanced manner. More preferably, the molar ratio (O / Si) of silicon content to oxygen content is 0.3 or more and 1.7 or less.
  • the silicon-containing amorphous carbon material 1 may contain oxygen of more than 0% by weight and less than 40% by weight.
  • the average particle diameter of the silicon-containing amorphous carbon material 1 is, for example, about 5 ⁇ m to 40 ⁇ m. When the average particle diameter exceeds 40 ⁇ m, the strength of the carbon material may be lowered, and it may be difficult to form an electrode with an appropriate film thickness when producing the negative electrode. Moreover, it is difficult to disperse silicon oxide particles in amorphous carbon particles with a carbon material having an average particle size of less than 5 ⁇ m.
  • the average particle diameter of the silicon-containing amorphous carbon material 1 is more preferably 10 ⁇ m or more and 30 ⁇ m or less.
  • the maximum particle size of the silicon-containing amorphous carbon material 1 is about 45 ⁇ m or less.
  • the silicon content in the silicon-containing amorphous carbon material 1 is 1% by weight or more and 50% by weight or less. This is because an effect of improving the capacity of the battery is obtained when the silicon content is 1% by weight or more, and granulation is easy if the silicon content is 50% by weight or less. In order to sufficiently obtain the effect of improving the capacity, the silicon content is preferably 5% by weight or more.
  • voids 20 are formed around the silicon oxide particles. This is due to the fact that silicon-containing particles are easily placed in the gap between carbon particles derived from the carbon raw material, and that voids are easily formed around the silicon-containing particles when volatile components escape from raw coke and the like. Conceivable. Due to the presence of the voids 20 around the silicon oxide, even when lithium ions are inserted into the silicon-containing amorphous carbon material 1 at the time of charging, the influence of the expansion of the volume of the silicon oxide particles is suppressed due to the presence of the voids.
  • the density (true density) of the silicon-containing amorphous carbon material 1 is preferably about 1.8 g / cm 3 or more and 2.2 g / cm 3 or less. When the density of the silicon-containing amorphous carbon material 1 is in an appropriate range, a sufficient energy density per volume can be secured when used for the negative electrode of a lithium ion secondary battery.
  • the circularity of the silicon-containing amorphous carbon material 1 of the present embodiment is preferably about 0.70 or more and 1.0 or less, and more preferably 0.80 or more and 0.98 or less. According to this configuration, the packing density and the electrode density can be increased. When the degree of circularity is less than 0.7, the effect of combining cannot be sufficiently exhibited, and the catching between the particles becomes large, and the packing density and the electrode density are lowered. The circularity does not exceed 1.0, and even if the material has a circularity of 1.0, the effect of the present invention can be obtained, but in order to improve the packing density and increase the number of contact points between particles. More preferably, the circularity is 0.98 or less.
  • the volume change at the time of charging / discharging can be suppressed to be smaller than that of the conventional carbon material. It can be used as a negative electrode material for a secondary battery.
  • a value obtained by dividing the equivalent area circumference obtained by multiplying the projected area equivalent diameter by the circumference ( ⁇ ) by the circumference of the projected particle is an index of unevenness.
  • the degree of unevenness is 0.9 or more and less than 1.0. This indicates that the outline of the particles is not drawn in a smooth arc, but has a so-called “potato” shape with many irregularities.
  • the amorphous carbon 4 contained in the silicon-containing amorphous carbon material 1 manufactured using raw coke contains about 700 ppm to 2500 ppm of transition metal.
  • Transition metals mainly include nickel and vanadium.
  • the amorphous carbon 4 may contain 250 ppm or more of vanadium.
  • the amorphous carbon 4 contains a transition metal, so that an effect of promoting the insertion or desorption of lithium can be obtained. Further, when the transition metal is doped into silicon oxide, The expansion or contraction of the silicon oxide particles can be alleviated.
  • the initial charge capacity and the initial discharge capacity can be reduced. It can be made larger than the case where it is constituted only by the above.
  • silicon oxide particles or silicon particles are used as will be described later.
  • the above-described silicon is mixed by mixing the materials at an appropriate blending ratio.
  • the contained amorphous carbon material 1 can be obtained.
  • the silicon-containing amorphous carbon material 1 since the voids 20 (see FIG. 1) are formed inside, the influence of volume expansion of the silicon oxide particles when lithium ions are inserted can be reduced. it can. For this reason, the collapse of the silicon-containing amorphous carbon material 1 can be suppressed, the negative electrode can be hardly broken, and the cycle characteristics of the lithium ion secondary battery can be improved.
  • the silicon-containing amorphous carbon material 1 of the present embodiment is capable of charging / discharging more quickly than graphite because the insertion and extraction of lithium ions are performed in the same direction in the amorphous carbon portion. . Moreover, it has a high capacity by containing silicon oxide. For this reason, the silicon-containing amorphous carbon material 1 of the present embodiment is particularly preferably used for a lithium ion secondary battery for an electric vehicle.
  • the silicon-containing amorphous carbon material 1 of the present embodiment can be used not only as a lithium ion secondary battery but also as a negative electrode material such as a lithium ion capacitor.
  • the silicon-containing amorphous carbon material 1 of the present embodiment can be produced using raw coke such as needle (needle-like) coke and mosaic (non-needle-like) coke as a material.
  • the raw coke is obtained by, for example, heating and heating the heavy oil to about 300 ° C. to 700 ° C. using a coking facility such as a delayed coker for thermal decomposition and polycondensation.
  • the optical isotropic structure is uniformly dispersed and the optical isotropic structure ratio is 75% or more, more preferably 85% or more, and the total transition metal content is Petroleum-based raw coke that is 700 ppm or more and 2500 ppm or less can be used. Since this raw coke contains a large amount of soot, transition metals and the like as impurities, it is considered that the efficiency of Li insertion / desorption is improved when it is used as a negative electrode material for a lithium ion secondary battery.
  • Petroleum-based raw coke is pulverized with a mechanical pulverizer such as a super rotor mill (Nisshin Engineering Co., Ltd.), a jet mill (Nihon Pneumatic Kogyo Co., Ltd.) or the like.
  • a mechanical pulverizer such as a super rotor mill (Nisshin Engineering Co., Ltd.), a jet mill (Nihon Pneumatic Kogyo Co., Ltd.) or the like.
  • the average particle size (D50) after pulverization is 1 ⁇ m or more and 15 ⁇ m or less, more preferably 3 ⁇ m or more and 10 ⁇ m or less.
  • the average particle size is based on measurement by a laser diffraction particle size distribution meter.
  • D50 is less than 1 ⁇ m, the necessary pulverization energy becomes enormous, so it is not realistic.
  • D50 is less than 3 ⁇ m, sufficient mechanical energy cannot be imparted to the particles when dry granulation is performed. Comes out.
  • D50 exceeds 15 ⁇ m, the number of particles having a suitable size as a negative electrode material for a lithium ion secondary battery is reduced after granulation.
  • the above pulverized product can be further classified.
  • the classifier include a precision air classifier such as a turbo classifier (manufactured by Nisshin Engineering Co., Ltd.), an elbow jet (manufactured by Nittetsu Mining Co., Ltd.), a class seal (manufactured by Seishin Enterprise Co., Ltd.), and the like.
  • silicon particles and / or silicon oxide particles as silicon raw materials are prepared.
  • the average particle diameter of the silicon raw material is not particularly limited, but by setting it to 1 ⁇ m or less, the expansion width of the silicon oxide particles during charging / discharging of the silicon-containing amorphous carbon material becomes small, so that the volume of the carbon layer changes. Can be suppressed.
  • silicon oxide particles having an average particle diameter of about 20 nm to 30 nm are used.
  • a silicon particle since a compounding ratio differs from the case where a silicon oxide particle is used, it mentions later.
  • the amount of silicon oxide particles added during granulation is not particularly limited, but the amount of silicon oxide particles added is 2 vol when the sum of the volume of raw coke and silicon oxide particles is 100%. % To 90% by volume is preferable. By making the addition amount of silicon oxide particles 2% by volume or more and 90% by volume or less, it becomes possible to obtain a silicon-containing carbon material whose capacity is improved by silicon.
  • the addition amount of silicon oxide particles is more preferably 10% by volume or more and 85% by volume or less, and further preferably 20% by volume or more and 80% by volume or less.
  • an apparatus capable of spheroidizing treatment that simultaneously applies stress such as shear, compression, and collision can be used, but the treatment apparatus is not limited to an apparatus using such a structure and principle. .
  • Examples of the apparatus used for this treatment include a ball-type kneader such as a rotary ball mill, a wheel-type kneader such as an edge runner, a hybridization system (manufactured by Nara Machinery Co., Ltd.), mechanofusion (manufactured by Hosokawa Micron), and nobilta. (Manufactured by Hosokawa Micron Corporation), COMPOSI (manufactured by Nippon Coke Industries Co., Ltd.) and the like.
  • an apparatus having a structure in which compaction stress or compression stress is applied to the powder in the gap between the blade of the rotating blade and the housing is preferably used. If the temperature applied to the powder during processing is controlled to be 60 ° C to 300 ° C, the volatile matter contained in the raw coke will generate appropriate tackiness, and the action of particles adhering to each other will work. Growth is promoted.
  • the circularity of raw coke used as a raw material is about 0.5 to 0.8
  • the circularity of the powder obtained after shape processing by compressive shear stress is greater than 0.70 and 1.0 or less.
  • the circularity of the powder is desirably 0.80 or more and 0.98 or less. Even if the circularity of the powder is 1.0, the effect of alleviating the influence of expansion and contraction of the silicon oxide particles can be obtained. However, particles processed to a circularity exceeding 0.98 are nearly spherical. There are fewer contacts between particles.
  • the range of the circularity of the particles is preferably 0.90 or more and 0.96 or less.
  • the total amount of silicon oxide particles may be mixed with raw coke, but if the amount of silicon oxide particles is large, it becomes difficult to granulate, so the raw coke and some silicon oxide particles are mixed and granulated.
  • silicon oxide particles may be added in a plurality of times (for example, three times or more). Further, silicon oxide particles and raw coke may be added after adding silicon oxide particles at the start of granulation, and only the raw coke is added at the end of granulation to coat the surface of silicon oxide particles with raw coke. May be. In this step, a part of silicon oxide may be replaced with single silicon.
  • dissimilar materials and raw coke by replacing part of raw coke used for granulation with carbon materials such as acetylene black, inorganic compounds such as transition metal compounds, and organic compounds. It is. As long as the granulation is not hindered, a part of raw coke to be added at the start of granulation or during granulation may be replaced with a different material, or only a different material may be added during the granulation. .
  • the amount of the different material added is not particularly limited as long as it does not interfere with granulation.
  • the average particle size of the dissimilar material is not particularly limited as long as it does not interfere with granulation, but is preferably 1 ⁇ 2 or less of the granulated particle size at the time of addition.
  • the granulated particles are carbonized.
  • the method of carbonization is not particularly limited.
  • the heat treatment is performed in an atmosphere of an inert gas such as nitrogen or argon with the maximum temperature of 800 ° C. or higher and 1200 ° C. or lower, and the holding time at the maximum temperature reached longer than 0 hours and shorter than 10 hours. The method of doing is mentioned.
  • the carbonization temperature is 800 ° C. or higher, the amount of low-molecular hydrocarbons and functional groups remaining in the coke can be reduced, so that an increase in irreversible capacity due to these impurities can be effectively suppressed.
  • a carbonization temperature of 1200 ° C. or lower is preferable because it is possible to suppress generation of insulating silicon carbide in the material.
  • the carbonization temperature is particularly preferably about 900 ° C. or higher and 1100 ° C. or lower. By setting the carbonization temperature to 900 ° C. or higher, an increase in irreversible capacity due to residual low-molecular hydrocarbons can be more effectively suppressed.
  • the holding time at the maximum arrival time may be longer than 10 hours, but it is not economical because the heat treatment is continued after the carbonization is completed.
  • the material used for the negative electrode of a lithium ion secondary battery can be manufactured easily compared with the method described in Patent Document 1.
  • the silicon particle tends to form an oxide film on the surface of the particle by handling in the air, and in order to prevent excessive oxidation of the silicon particle, an oxide film may be formed on the surface of the silicon particle in advance.
  • these silicon particles can also be used in the present invention.
  • dry granulation is performed by thoroughly mixing raw coke particles and silicon particles.
  • the amount of silicon particles added is, for example, 2% by volume or more and 90% by volume or less with respect to the amount of raw coke.
  • the amount of silicon particles added is preferably 5% by volume to 50% by volume, and more preferably 5% by volume to 35% by volume. preferable.
  • an apparatus capable of simultaneously applying stresses such as shear, compression, and collision can be used as in the above-described method.
  • the circularity of raw coke used as a raw material is about 0.5 to 0.8
  • the circularity of the powder obtained after shape processing by compressive shear stress is greater than 0.70 and 1.0 or less.
  • the circularity of the powder is desirably 0.80 or more and 0.98 or less. Even if the circularity of the powder is 1.0, the effect of alleviating the influence of expansion and contraction of the silicon particles can be obtained. However, in the case of particles processed to a circularity exceeding 0.98, it is close to a true sphere. , There will be fewer contacts between particles.
  • the range of the circularity of the particles is preferably 0.90 or more and 0.96 or less.
  • the total amount of silicon particles may be mixed with raw coke, but if the amount of silicon particles is large, granulation becomes difficult, so granulation was started by mixing raw coke and some silicon particles. Thereafter, the silicon particles may be added in a plurality of times (for example, three times or more). Further, silicon particles and raw coke may be added after adding silicon particles or the like at the start of granulation, or only the raw coke may be added at the end of granulation to coat the surface of silicon particles with raw coke. . In this step, part of silicon may be replaced with silicon oxide.
  • dissimilar materials and raw coke by replacing part of raw coke used for granulation with carbon materials such as acetylene black, inorganic compounds such as transition metal compounds, and organic compounds. It is. As long as the granulation is not hindered, a part of raw coke to be added at the start of granulation or during granulation may be replaced with a different material, or only a different material may be added during the granulation. .
  • the amount of the different material added is not particularly limited as long as it does not interfere with granulation.
  • the average particle size of the dissimilar material is not particularly limited as long as it does not interfere with granulation, but is preferably 1 ⁇ 2 or less of the granulated particle size at the time of addition.
  • the granulated particles are carbonized.
  • the method of carbonization is not particularly limited.
  • the heat treatment is performed in an atmosphere of an inert gas such as nitrogen or argon with the maximum temperature of 800 ° C. or higher and 1200 ° C. or lower, and the holding time at the maximum temperature reached longer than 0 hours and shorter than 10 hours. The method of doing is mentioned.
  • the carbonization temperature is 800 ° C. or higher, the amount of low-molecular hydrocarbons and functional groups remaining in the coke can be reduced, so that an increase in irreversible capacity due to these impurities can be effectively suppressed.
  • a carbonization temperature of 1200 ° C. or lower is preferable because it is possible to suppress generation of insulating silicon carbide in the material.
  • the carbonization temperature is about 900 ° C. or higher and 1100 ° C. or lower.
  • the carbonization temperature is about 900 ° C. or higher, an increase in irreversible capacity due to residual low-molecular hydrocarbons or the like can be suppressed.
  • the holding time at the maximum arrival time may be longer than 10 hours, but it is not economical because the heat treatment is continued after the carbonization is completed.
  • This carbonization treatment is considered to have the effect that the volatile components in the raw coke reduce the oxide film on the surface of the silicon particles.
  • a carbon material containing silicon particles having a small oxidation number is preferable as a negative electrode material because it exhibits a high capacity.
  • silicon particles having a small oxidation number have a larger expansion and contraction. According to the present invention, since the void formed by the gas of the volatile component generated during carbonization escapes to the outside, the expansion and contraction of the silicon particles is buffered, so that a high-capacity silicon-containing amorphous carbon material can be provided.
  • a gas release path is formed in the particles, and this release path is used when used as a negative electrode material for a lithium ion secondary battery. It becomes a route for lithium to diffuse.
  • the material used for the negative electrode of the lithium ion secondary battery can also be easily manufactured by the above method.
  • the size of the irregularities on the surface of the granulated particles can be adjusted. Specifically, in the granulation process, raw coke having a larger particle size than the raw coke particles added at the beginning of granulation, such as shortening the granulation time, lowering the pressure during granulation, etc. By adding particles, surface irregularities can be increased. On the contrary, the surface unevenness
  • FIG. 2 is a diagram illustrating an example of a lithium ion secondary battery including a negative electrode using the silicon-containing amorphous carbon material of the present embodiment.
  • a lithium ion secondary battery 10 includes a negative electrode 11, a negative electrode current collector 12, a positive electrode 13, a positive electrode current collector 14, and a negative electrode 11 and a positive electrode 13. And an exterior 16 made of an aluminum laminate film or the like.
  • the negative electrode 11 for example, a metal foil in which the above-described amorphous carbon-containing material 1 of the present embodiment is applied on both sides or one side is used.
  • the average particle diameter and circularity of the coated silicon-containing amorphous carbon material 1 are not substantially changed before and after the battery manufacturing process, and are 5 ⁇ m to 40 ⁇ m and 0.70 to 1.0, respectively. ing.
  • a conductive auxiliary such as acetylene black (AB) and a binder such as polyvinylidene fluoride (PVdF) is added, and N A paste kneaded using a solvent such as “methyl-2-pyrrolidone (NMP)” is applied onto a copper foil for current collection.
  • NMP methyl-2-pyrrolidone
  • the lithium ion secondary battery according to the present embodiment has the negative electrode coated with the above silicon-containing amorphous carbon material, it can be charged / discharged quickly, has a large capacity, and is charged / discharged. Even if it repeats, the negative electrode becomes difficult to collapse. Furthermore, the energy density is high, the irreversible capacity is kept small, and the cycle characteristics can be improved.
  • the counts of the polishing plates are # 500, # 1000, and # 2000 in this order.
  • mirror polishing is performed using alumina (trade name: Baikalox type 0.3CR, particle size 0.3 ⁇ m, manufacturing company: Baikowski). To do.
  • the polished sample was observed using a polarizing microscope (manufactured by Nikon Corporation) at a magnification of 500 times at observation angles of 0 degrees and 45 degrees, and each image was taken into a Keyence digital microscope VHX-2000.
  • the color of the optically anisotropic domain changes depending on the orientation of the crystallite. On the other hand, optical isotropic domains always show the same color. Using this property, a portion where the color does not change is extracted from the binarized image, and the area ratio of the optically isotropic portion is calculated. When binarization is performed, a portion having a threshold value of 0 to 34 and a portion having a threshold value of 239 to 255 are set as pure massenders. The black part was treated as a void. (B) Measurement of transition metal content in raw material The coke used as the raw material was quantitatively analyzed according to an emission spectroscopic analysis method using a Hitachi ratio beam spectrophotometer U-5100.
  • (G) Measurement of oxygen content of amorphous carbon material The oxygen content in the sample was quantitatively analyzed by an inert gas melting-infrared absorption method.
  • (H) Measurement of silicon content of amorphous carbon material A sample was incinerated at 1050 ° C., and the silicon content was calculated with the remaining amount as the silicon content. In addition, O / Si ratio is calculated
  • (I) Measurement of circularity and unevenness level A scanning electron microscope (S-4800, manufactured by Hitachi High-Tech Co., Ltd.) was used to disperse and fix the flat particles so that the particles do not stack and the flat surfaces are arranged parallel to the sheet.
  • Electrode sheet paste Preparation of electrode sheet paste: Add 1 part by weight of the sample to 0.044 parts by weight of acetylene black (AB), 0.066 part by weight of Kurewa Chemical KF polymer (polyvinylidene fluoride (PVdF)), After kneading with a Lee mixer, it was applied to Cu metal foil and dried. This sheet was rolled and punched to a predetermined size to produce an electrode for evaluation. Metal lithium was used for the counter electrode, and a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) in which 1 mol / l LiPF 6 was dissolved (1: 2 by volume) was used for the electrolyte. The following coin cells were assembled in a dry argon atmosphere with a dew point of ⁇ 80 ° C. or lower.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • coke A which is petroleum non-needle coke
  • coke B which is petroleum needle-like coke
  • Table 1 shows the isotropic texture ratio, transition metal content, and vanadium content of coke A and B.
  • Coke A had much higher transition metal content and vanadium content than coke B.
  • Table 3 shows the measurement results of the parameters of the carbon materials produced in these examples and comparative examples.
  • Example 1 Raw coke A was pulverized and classified so that D50 was 5.7 ⁇ m, and raw coke particles and silicon dioxide particles were mixed, and dry granulation was performed by the method described above.
  • the particle diameter of the silicon dioxide particles was 20 to 30 nm. When the sum of the volume of silicon dioxide particles and raw coke particles is 100%, the amount of silicon dioxide particles added is 50% by volume.
  • Raw coke particles and a part of silicon dioxide particles were put into COMPOSI CP15 type (manufactured by Nihon Coke Kogyo Co., Ltd.) to start spheroidization at low speed, and all silicon dioxide particles were put in several times. After the entire amount was charged, the treatment was performed for 120 minutes at a peripheral speed of 80 m / s to obtain granulated particles.
  • the granulated particles were carbonized at 1000 ° C. and the retention time (carbonization time) at the highest temperature reached 5 hours.
  • the amorphous carbon material according to Example 1 obtained in this way has a D50 of 13.5 ⁇ m, a BET of 1.5 m 2 / g, a circularity of 0.970, and a roughness value.
  • the true density was 2.02 g / cm 3 and the O / Si ratio (molar ratio) was 1.03.
  • Si content rate in the obtained carbon material was 15.0 wt%.
  • Example 2 Raw coke B was pulverized and classified so that D50 was 9.6 ⁇ m, and raw coke particles and silicon dioxide particles were mixed, and dry granulation and carbonization were performed by the above-described method. At this time, the amount of silicon dioxide particles added was 53% by volume. The entire amount of silicon dioxide particles was charged in several times. After the entire amount was added, granulation and carbonization were performed under the same conditions as in Example 1 except that the peripheral speed was 80 m / s and the treatment time was 120 minutes.
  • the amorphous carbon material according to Example 2 obtained in this way had a D50 of 24.9 ⁇ m, a BET of 8.1 m 2 / g, a circularity of 0.953, and a roughness value.
  • the true density was 2.10 g / cm 3 and the O / Si ratio (molar ratio) was 1.21.
  • Si content rate in the obtained carbon material was 14.5 wt%.
  • Example 3 Raw coke A was pulverized and classified so that D50 was 7.9 ⁇ m, and raw coke particles and silicon dioxide particles were mixed, and dry granulation and carbonization were performed by the above-described methods. At this time, the amount of silicon dioxide particles added was 53% by volume. The entire amount of silicon dioxide particles was charged in several times. After the entire amount was added, granulation and carbonization were performed under the same conditions as in Example 1 except that the peripheral speed was 70 m / s and the treatment time was 120 minutes.
  • the amorphous carbon material according to Example 3 obtained in this way has a D50 of 27.1 ⁇ m, a BET of 10.7 m 2 / g, a circularity of 0.901, and a roughness value.
  • the true density was 2.07 g / cm 3 and the O / Si ratio (molar ratio) was 1.29.
  • Si content rate in the obtained carbon material was 14.4 wt%.
  • Example 4 Raw coke A was pulverized and classified so that D50 was 7.9 ⁇ m, and raw coke particles and silicon dioxide particles were mixed, and dry granulation and carbonization were performed by the above-described methods. At this time, the amount of silicon dioxide particles added was 50% by volume. The entire amount of silicon dioxide particles was charged in several times. After the entire amount was added, granulation was performed under the same conditions as in Example 1 except that the peripheral speed was 70 m / s and the treatment time was 180 minutes.
  • the amorphous carbon material according to Example 4 obtained in this way had a D50 of 21.1 ⁇ m, a BET of 1.6 m 2 / g, a circularity of 0.947, and a roughness value.
  • the true density was 2.02 g / cm 3 and the O / Si ratio (molar ratio) was 1.31.
  • Si content rate in the obtained carbon material was 15.0 wt%.
  • the tap density was 1.2 g / cm 3 .
  • Example 5 Raw coke A was pulverized and classified so that D50 was 4.8 ⁇ m, and raw coke particles and silicon dioxide particles were mixed, and dry granulation and carbonization were performed by the above-described method. At this time, the amount of silicon dioxide particles added was 50% by volume. The entire amount of silicon dioxide particles was charged in several times. Granulation and carbonization were performed under the same conditions as in Example 1 except that the peripheral speed after charging the entire amount was 80 m / s and the treatment time was 210 minutes.
  • the amorphous carbon material according to Example 5 obtained in this way has a D50 of 9.6 ⁇ m, a BET of 2.5 m 2 / g, a circularity of 0.963, and a value of the degree of unevenness.
  • the true density was 2.04 g / cm 3 and the O / Si ratio (molar ratio) was 1.27.
  • Si content rate in the obtained carbon material was 15.1 wt%.
  • the tap density was 1.17 g / cm 3 .
  • Example 6 was an amorphous carbon material obtained by mixing the amorphous carbon material according to Example 4 and the amorphous carbon material according to Example 5 at a weight ratio of 7: 3.
  • the tap density of the obtained carbon material was 1.27 g / cm 3 .
  • Example 7 Raw coke A was pulverized and classified so that D50 was 5.8 ⁇ m, and raw coke particles and silicon dioxide particles were mixed, and dry granulation and carbonization were performed by the above-described methods. At this time, the addition amount of silicon dioxide particles was 61% by volume, and the entire amount of silicon dioxide particles was charged in several times. Granulation and carbonization were performed under the same conditions as in Example 1 except that the peripheral speed after charging the entire amount was 80 m / s and the treatment time was 120 minutes.
  • the amorphous carbon material according to Example 7 obtained in this way had a D50 of 12.1 ⁇ m, a BET of 5.0 m 2 / g, a circularity of 0.967, and a roughness value.
  • the true density was 2.09 g / cm 3 and the O / Si ratio (molar ratio) was 1.14.
  • Si content rate in the obtained carbon material was 20.0 wt%.
  • Example 8 Raw coke A was pulverized and classified so that D50 was 5.7 ⁇ m, and raw coke particles and silicon dioxide particles were mixed, and dry granulation and carbonization were performed by the above-described methods. At this time, the amount of silicon dioxide particles added was 80% by volume, and the silicon dioxide particles were charged in several portions. Granulation and carbonization were performed under the same conditions as in Example 1 except that the peripheral speed after charging the entire amount was 80 m / s and the treatment time was 60 minutes.
  • the amorphous carbon material according to Example 8 obtained in this way had a D50 of 13.6 ⁇ m, a BET of 27.2 m 2 / g, a circularity of 0.967, and a roughness value.
  • the true density was 2.19 g / cm 3 and the O / Si ratio (molar ratio) was 1.26.
  • Si content rate in the obtained carbon material was 35.0 wt%.
  • FIG. 1 which has already been described is a diagram showing a micrograph obtained by photographing the cross section of the amorphous carbon material according to the present embodiment by the above-described method. From the figure, it can be seen that the amorphous carbon material according to this example has a high degree of circularity and a void 20 formed inside.
  • Example 9 Coke A was pulverized and classified so that D50 was 4.8 ⁇ m, mixed with silicon particles crushed so as to have a particle diameter of 400 nm, and dry granulation and carbonization were performed by the above-described methods. At this time, in Example 9, the addition amount of silicon particles was 7% by volume, and in Example 10, the addition amount of silicon particles was 28% by volume. All the silicon particles were charged in several times. Example 1 except that the peripheral speed was set to 80 m / s and the processing time was set to 420 minutes in Example 9, and the peripheral speed was set to 80 m / s and the processing time was set to 390 minutes in Example 10 after the entire amount of silicon particles was charged. Granulation and carbonization were performed under the same conditions as in Example 1.
  • the amorphous carbon material according to Example 9 obtained in this way has a D50 of 8.8 ⁇ m, a BET of 1.8 m 2 / g, a circularity of 0.966, and a value of the degree of unevenness.
  • the true density was 1.80 g / cm 3 and the O / Si ratio (molar ratio) was 1.18.
  • Si content rate in the obtained carbon material was 3.0 wt%.
  • D50 of the amorphous carbon material which concerns on Example 10 is 8.8 micrometers
  • BET is 9.5 m ⁇ 2 > / g
  • Circularity is 0.963
  • corrugation degree is 0.982. there were.
  • the true density was 1.94 g / cm 3 and the O / Si ratio (molar ratio) was 1.17.
  • Si content rate in the obtained carbon material was 11.7 wt%.
  • FIG. 3 is a view showing a photomicrograph obtained by photographing the cross section of the amorphous carbon material according to this example by the above-described method. From the figure, it can be seen that the amorphous carbon material according to the present embodiment includes the silicon oxide particles 5 with the voids 20 formed therein.
  • Example 11 Raw coke B was pulverized and classified so that D50 was 9.6 ⁇ m, and raw coke particles and silicon dioxide particles were mixed, and dry granulation and carbonization were performed by the above-described method. At this time, the amount of silicon dioxide particles added was 53% by volume. The entire amount of silicon dioxide particles was charged in several times. After the entire amount was added, granulation and carbonization were performed under the same conditions as in Example 1 except that the peripheral speed was 80 m / s and the treatment time was 105 minutes.
  • the amorphous carbon material according to Example 11 obtained in this way had a D50 of 24.8 ⁇ m, a BET of 8.8 m 2 / g, a circularity of 0.921, and a roughness value. Was 0.961.
  • the true density was 2.10 g / cm 3 and the O / Si ratio (molar ratio) was 1.22.
  • Si content rate in the obtained carbon material was 10.0 wt%.
  • Example 12 Raw coke A was pulverized and classified so that D50 was 5.7 ⁇ m, and raw coke particles and silicon dioxide particles were mixed, and dry granulation and carbonization were performed by the above-described methods. At this time, the amount of silicon dioxide particles added was 80% by volume. The entire amount of silicon dioxide particles was charged in several times. Granulation and carbonization were carried out under the same conditions as in Example 1 except that the peripheral speed after charging the entire amount was 80 m / s, the treatment time was 60 minutes, and the carbonization temperature was 1200 ° C.
  • the amorphous carbon material according to Example 12 obtained in this way had a D50 of 14.0 ⁇ m, a BET of 32.5 m 2 / g, a circularity of 0.965, and a degree of roughness value. Was 0.979.
  • the true density was 2.18 g / cm 3 and the O / Si ratio (molar ratio) was 1.59. Si content rate in the obtained carbon material was 35.2 wt%.
  • FIG. 4 is a view showing a micrograph of a cross section of the amorphous carbon material according to Example 12 taken by the above-described method. From the figure, it can be seen that the amorphous carbon material according to this example has a high degree of circularity and a void 20 formed inside.
  • the amorphous carbon material according to Comparative Example 1 thus obtained has a D50 of 14.6 ⁇ m, a BET of 0.3 m 2 / g, a circularity of 0.963, and a value of the degree of unevenness.
  • the true density was 1.76 g / cm 3 and the O / Si ratio (molar ratio) was 1.44.
  • Graphite having a D50 of 8.5 ⁇ m was mixed with silicon dioxide particles, and dry granulation and carbonization were performed by the method described above. At this time, the amount of silicon dioxide particles added was 63% by volume. The entire amount of silicon dioxide particles was charged in several times. After the entire amount was added, granulation and carbonization were performed under the same conditions as in Example 1 except that the peripheral speed was 70 m / s and the treatment time was 120 minutes.
  • the carbon material which concerns on the comparative example 2 obtained was not fully compounded, and a part of silicon dioxide particle was not adhering to graphite.
  • the BET was 33.2 m 2 / g, the circularity was 0.812, and the unevenness value was 0.899.
  • the true density was 2.31 g / cm 3 and the O / Si ratio (molar ratio) was 1.96.
  • Si content rate in the obtained carbon material was 14.8 wt%.
  • Coke A was pulverized and classified so that D50 was 4.8 ⁇ m, and raw coke particles and silicon dioxide particles were mixed by hand. The amount of silicon particles added to the coke particles was 50% by volume. The granulation process was not performed, and the carbonization process was performed at 1000 ° C. for 5 hours.
  • the amorphous carbon material according to Comparative Example 3 obtained in this way had a BET of 39.1 m 2 / g, a circularity of 0.745, and an irregularity value of 0.856.
  • the true density was 2.14 g / cm 3 and the O / Si ratio (molar ratio) was 1.88.
  • the initial charge capacity and the initial discharge capacity were measured, and the initial efficiency was calculated. Moreover, the ratio of the discharge capacity after 10 cycles of charge / discharge with respect to the initial discharge capacity was defined as the cycle maintenance ratio.
  • Comparative Example 3 an attempt was made to produce an electrode in the same manner as in Examples 1 to 12 and Comparative Examples 1 and 2. However, since the active material layer was peeled from the copper foil, acetylene black was used with respect to 1 part by weight of the sample. The composition was changed so that 0.047 parts by weight and 0.116 parts by weight of PVdF were added.
  • the carbon materials according to Examples 1 to 10 and 12 all had an initial discharge capacity sufficiently exceeding 300 mAh, and the cycle retention rate was 80% or more, and carbon containing silicon oxide. As a material, it was able to be made high enough.
  • the carbon material according to Example 1 and the carbon material according to Comparative Example 1 both use raw coke as a raw material, and thus the obtained carbon material contains graphitizable amorphous carbon. .
  • the initial efficiency is slightly lowered as compared with the carbon material according to Comparative Example 1, the initial discharge capacity is greatly increased, and the deterioration of the cycle characteristics is suppressed to a small level. It was confirmed that
  • the O / Si ratio was 0.2 or more and less than 2.0, and the silicon content was more than 1% by weight and 50% by weight. It was as follows.
  • the true density is 1.8 g / cm 3 or more and 2.2 g / cm 3 or less in all cases, which is larger than the case where no silicon raw material is used (Comparative Example 1), and when graphite is used as a carbon raw material (Comparative Example). It was smaller than 2).
  • Example 6 in which the carbon material according to Example 4 and the carbon material according to Example 5 were mixed at a weight ratio of 7: 3, silicon oxide was compounded into easily graphitized amorphous carbon by granulation. By mixing and using two types of particles having different particle sizes, it is possible to improve the tap density without impairing the effect of improving the cycle characteristics of the present invention, and to obtain a carbon material that can increase the electrode density. It was.
  • the transition metal contents of the amorphous carbon materials according to Examples 1 to 12 were all 700 ppm or more and 2500 ppm or less, but the transition metal contents contained in the carbon materials according to Comparative Examples 1 to 3 There was no significant difference between them.
  • the silicon-containing amorphous carbon material according to an example of the present embodiment is useful as a negative electrode material of a lithium ion secondary battery or a lithium ion capacitor used in an electric vehicle, a power storage system such as solar power generation and wind power generation, for example. It is.

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Abstract

La présente invention porte sur un matériau au carbone amorphe contenant du silicium en tant que matériau d'anode d'une batterie secondaire lithium-ion ou analogue dont l'amélioration de caractéristiques de cycle est pratiquement possible sans un changement de volume lors d'une charge/décharge. Le matériau au carbone amorphe contenant du silicium (1) comporte du carbone amorphe facilement graphitisé (4) ; des particules d'oxyde de silicium comprenant du SiOx (0 < x < 2) sont contenues dans le carbone amorphe facilement graphitisé ; et un espace est formé à la périphérie des particules d'oxyde de silicium. Le contenu de silicium dans le matériau au carbone amorphe contenant du silicium (1) est de 1-50 % en poids inclus.
PCT/JP2014/005479 2013-11-05 2014-10-29 Matériau au carbone amorphe contenant du silicium, son procédé de fabrication et batterie secondaire lithium-ion WO2015068361A1 (fr)

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