Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/134—Electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • 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
• • 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
  • H01M4/386—Silicon or alloys based on silicon
• • 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
  • H01M4/387—Tin or alloys based on tin
• • 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
  • H01M4/42—Alloys based on zinc
• • 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
  • H01M4/46—Alloys based on magnesium or aluminium
  • H01M4/463—Aluminium based
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C19/00—Alloys based on nickel or cobalt
  • C22C19/03—Alloys based on nickel or cobalt based on nickel
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C9/00—Alloys based on copper
• • 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
  • H01M2004/021—Physical characteristics, e.g. porosity, surface area
• • 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
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
  • H01M4/625—Carbon or graphite
• • 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 silicon-containing particle, a negative-electrode material for use in a non-aqueous electrolyte secondary battery using the same, and a non-aqueous electrolyte secondary battery.
• Silicon is the most promising material to reduce a battery size and increase a battery capacity since it exhibits a theoretical capacity of 4,200 mAh/g, which is much higher than a theoretical capacity of 372 mAh/g of carbonaceous materials that are currently used in commercial batteries.
• Patent document 1 discloses a lithium-ion secondary battery using a silicon single crystal as a support for a negative-electrode active material.
• Patent document 0.2 discloses a lithium-ion secondary battery using a lithium alloy comprising Li x Si (where x is a value of 0 to 5) of single crystal silicon, polycrystalline silicon, or amorphous silicon.
• Li x Si of amorphous silicon is preferred, and pulverized crystalline silicon coated with amorphous silicon obtained by plasma decomposition of monosilane is exemplified.
• Patent documents 3 to 5 disclose methods of depositing an amorphous silicon thin film on an electrode current collector by a vapor deposition method to use the film as a negative electrode.
• Patent document 6 discloses a method of controlling a growth direction to inhibit a decrease in cycle characteristics due to volume expansion during vapor phase growth of silicon directly on the current collector. This method achieves improvement in cycle characteristics, but limits its production rate of an electrode, thereby increasing cost. In addition, it is difficult to increase the thickness of the silicon thin film, and copper that forms the negative-electrode current collector is diffused into the silicon.
• Patent Document 1 Japanese Patent No. 2964732
• Patent Document 2 Japanese Patent No. 3079343
• Patent Document 3 Japanese Patent No. 3702223
• Patent Document 4 Japanese Patent No. 3702224
• Patent Document 5 Japanese Patent No. 4183488
• Patent Document 6 Japanese Unexamined Patent publication (Kokai) No. 2006-338996
• Patent Document 7 Japanese Unexamined Patent publication (Kokai) No. 2000-173596
• Patent Document 8 Japanese Patent No. 3291260
• Patent Document 9 Japanese Unexamined Patent publication (Kokai) No. 2005-317309
• Patent Document 10 Japanese Unexamined Patent publication (Kokai) No. 2003-109590
• Patent Document 11 Japanese Unexamined Patent publication (Kokai) No. 2004-185991
• Patent Document 12 Japanese Unexamined Patent publication (Kokai) No. 2004-303593
• the present invention was accomplished in view of the above-described problems. It is an object of the present invention to provide silicon-containing particles for use as a negative-electrode active material of a non-aqueous electrolyte secondary battery that enable manufacture of a non-aqueous electrolyte secondary battery having an excellent cycle characteristics and a higher capacity compared with graphite types.
• silicon-containing particles having the above crystal grain size and true density as a negative-electrode active material of a non-aqueous electrolyte secondary battery allows for its negative electrode having a high electron conductivity, a comparatively small volume expansion, and an excellent cycle characteristics, although the battery capacity per unit weight of the active material is in the range from 900 to 3000 mAh/g, which is lower than the theoretical capacity (4,200 mAh/g) per unit weight of an active material composed of silicon alone.
• These silicon-containing particles enable good cycle characteristics even when being mixed with a graphite-type negative-electrode material.
• the silicon-containing particle preferably has a powder particle size (referred to as a “particle size” below) ranging from 1 ⁇ m to 20 ⁇ m when this size is expressed by a volume median diameter D 50 (i.e., a particle size or a median diameter when a cumulative volume is 50%) by a measurement method of particle size distribution based on a laser diffraction scattering.
• a powder particle size referred to as a “particle size” below
• D 50 i.e., a particle size or a median diameter when a cumulative volume is 50%
• Increasing the particle size of the silicon-containing particle to 1 ⁇ m or more in terms of the volume median diameter D 50 can lower the risk of reduction in charge/discharge capacities per volume due to a decrease in bulk density.
• Decreasing the particle size of the silicon-containing particle to 20 ⁇ m or less in terms of the volume median diameter D 50 can lower the risk of a short circuit due to the silicon-containing particle penetrating a negative-electrode film to the minimum, and significantly reduce the possibility that the negative-electrode material is detached from a current collector contacting a negative electrode without making it difficult to form the electrode. This facilitates the formation of the electrode.
• a quotient of a volume median diameter D 50 of a particle size of the silicon-containing particle divided by the crystal grain size preferably ranges from 1 to 5000.
• the silicon-containing particle having the above relationship between the volume median diameter D 50 of its particle size and its crystal grain size can achieve inhibition of volume expansion due to the micronization of the silicon-containing particle.
• the silicon-containing particle preferably contains one or more elements selected from the group consisting of boron, aluminum, phosphorus, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, germanium, tin, antimony, indium, tantalum, tungsten, and gallium.
• the silicon-containing particle containing one or more elements selected from this group can reduce its volume resistivity and hence enables the formation of a negative electrode of a non-aqueous electrolyte secondary battery that has excellent electron conductivity.
• the above silicon-containing particle can be used for a negative-electrode material of a non-aqueous electrolyte secondary battery as the negative-electrode active material of the non-aqueous electrolyte secondary battery.
• the silicon-containing particle for the negative-electrode material as the negative-electrode active material allows a non-aqueous electrolyte secondary battery having a high capacity and a long lifetime to be provided at low cost.
• the negative-electrode material of a non-aqueous electrolyte secondary battery may contain graphite as a conductive agent.
• This negative-electrode material of a non-aqueous electrolyte secondary battery containing graphite as a conductive agent can maintain its conductivity.
• the non-aqueous electrolyte secondary battery preferably has a negative-electrode molded body made of the above negative-electrode material of the non-aqueous electrolyte secondary battery; a positive-electrode molded body; a separator configured to separate the negative-electrode molded body from the positive-electrode molded body; and a non-aqueous electrolyte.
• This non-aqueous electrolyte secondary battery having the negative-electrode molded body made of the above negative-electrode material can achieve a high capacity and a long lifetime.
• the non-aqueous electrolyte of the non-aqueous electrolyte secondary battery preferably contains lithium ions.
• the negative-electrode molded body made of the above negative-electrode material of the non-aqueous electrolyte secondary battery is used suitably for a lithium ion secondary battery having the non-aqueous electrolyte containing lithium ions.
• silicon-containing particles of the present invention as a negative-electrode active material allows for a non-aqueous electrolyte secondary battery having a high capacity and a long lifetime.
• the present inventors have diligently considered silicon active material that has a battery capacity per unit mass excessing a theoretical capacity of 372 mAh/g provided by carbonaceous materials and maintains its cycle stability, and a method of manufacturing this material at low cost.
• the inventors have
• Such silicon-containing particles inhibit their volume variation upon charging/discharging and hence a stress at their crystal grain boundary when being used as a negative-electrode active material of a secondary battery using a non-aqueous electrolyte, thereby maintaining a high initial efficiency and a high battery capacity that are attributable to silicon.
• a non-aqueous electrolyte secondary battery that inhibits the separation of the silicon particles from the graphite material and has an excellent cycle characteristics can thereby be obtained.
• An X-ray diffraction apparatus that may be used herein is D8 ADVANCE made by Bruker Corp.
• the X-ray source is a Cu-K ⁇ ray.
• the measurement is taken at the range from 10° to 90° under conditions of an output of 40 kv/40 mA, a slit width of 0.3°, a step width of 0.0164°, and a measurement time of one second per step.
• the measured data is compared after a smoothing process is performed by removing a K ⁇ 2 ray at an intensity ratio of 0.5. When the range from 10° to 60° is fully observed by this measurement, three sharp signals with large intensities can be observed.
• These signals are a 28.4° diffraction line attributable to Si (111) of a diamond structure, a 47.2° diffraction line attributable to Si (220), and a 56.0° diffraction line attributable to Si (311).
• the silicon-containing particle of the present invention is selected according to a crystal grain size calculated by analysis based on the Scherrer method from the full width at half maximum of the 28.4° diffraction line attributable to Si (111).
• the silicon-containing particle of the present invention preferably has a size of 300 nm or less, and more preferably a size of 200 nm or less.
• the silicon-containing particle of the present invention also has the true density of more than 2.320 g/cm 3 and less than 3.500 g/cm 3 . This value is measured by a dry densitometer.
• the measurement conditions of the dry densitometer are, for example, as follows:
• An example of the dry densitometer that may be used is accupyc ii 1340 made by SHIMADZU CORPORATION.
• a purge gas to be used is a helium gas. The measurement is made in a sample holder that maintains a temperature of 23° C. after the purge is repeated 200 times.
• the above true density of the silicon-containing particle can also be achieved, for example, by adding elements other than silicon.
• the additional elements include one or more elements selected from the group consisting of boron, aluminum, phosphorus, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, germanium, tin, antimony, indium, tantalum, tungsten, and gallium.
• these elements are added as necessary, and its amount may be about 50 mass % or less, preferably 0.001 to 30 mass %, more preferably 0.01 to 10 mass %.
• 0.01 mass % or more of the additional elements can reliably reduce the volume resistivity; 10 mass % or less of the additional elements makes it difficult to cause the segregation of the additional elements and can reliably prevent an increase in volume expansion.
• the silicon-containing particle of the present invention used as a negative-electrode active material of a non-aqueous electrolyte secondary battery preferably has a particle size ranging from 1 ⁇ m to 20 ⁇ m when this size is expressed by the volume median diameter D 50 (i.e., a particle size or a median diameter when a cumulative volume is 50%) by a measurement method of particle size distribution based on a laser diffraction scattering.
• D 50 volume median diameter
• D 50 is 20 ⁇ m or less, the risk of a short circuit due to the particle penetrating a negative-electrode film can be lowered to the minimum, and the possibility of detachment from a current collector can be significantly reduced without making it difficult to form the electrode.
• the quotient of the volume median diameter D 50 divided by the crystal grain size preferably ranges from 1 to 5000, more preferably from 3 to 1000, further preferably from 50 to 500, because the silicon-containing particle having a particle size of 20 ⁇ m or less, particularly 10 ⁇ m or less, further 1 ⁇ m or less inhibits its volume expansion due to its micronization.
• This type of silicon-containing particle has an amorphous grain boundary and a crystal grain boundary and relieves a stress in the amorphous grain boundary and the crystal grain boundary, thereby refraining from collapsing during charging/discharging cycles.
• Use of such silicon-containing particles as a negative electrode material of a non-aqueous electrolyte secondary battery thereby allows this negative electrode material to endure the stress due to its volume expansion upon charging/discharging.
• This non-aqueous electrolyte secondary battery with the negative electrode material using these silicon-containing particles exhibits battery characteristics of a high capacity and a long lifetime.
• the following description includes, by way of example, the detail of a method of manufacturing the silicon-containing particles for use as a negative-electrode active material of a non-aqueous electrolyte secondary battery of the present invention, and a negative-electrode material, a negative electrode, and a non-aqueous electrolyte secondary battery that use these obtained particles as the negative-electrode active material of the non-aqueous electrolyte secondary battery.
• the invention is not limited thereto.
• silicon can be deposited on a substrate by a vapor deposition method, for example, under reduced pressure.
• silicon alloy is preferably deposited by a vapor deposition method using a raw material of silicon and one or more elements selected from the group consisting of boron, aluminum, phosphorus, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, germanium, tin, antimony, indium, tantalum, tungsten, and gallium.
• This silicon to be used as the raw material is classified depending on the crystallinity into single crystal silicon, polycrystalline silicon and amorphous silicon, or depending on the purity into chemical grade silicon and metallurgical grade silicon, which are called metallic silicon, and may be selected from these. Among these, an inexpensive material is preferably used.
• the method of vapor depositing silicon may be performed by vacuum deposition or sputtering.
• the vacuum deposition is preferable because it is efficient due to a higher deposition rate.
• the vacuum deposition is selected, depending on a deposition material or substrate on which silicon is to be deposited, from various methods: a resistance heating method; an electron beam heating method; a dielectric heating method and so on; a laser heating method.
• the electron beam heating method is advantageous because of a high thermal efficiency.
• a silicon-containing alloy precipitated by vapor phase deposition such as the vacuum deposition enables its crystal grain size to be controlled optionally between an amorphous state and a polycrystalline state regardless of metal species to be added. Therefore, this is a useful method.
• Melt extraction is particularly advantageous when metal having a low melting point is used, or when a material composed so as to have a eutectic point of a silicon mixture is used.
• Preferable experimental conditions are as follows: a raw material is charged into a carbon crucible and melted by high frequency induction heating; this melting is performed in a melting apparatus under an inert gas atmosphere to inhibit the generation of an oxide.
• the silicon-containing particles for use as a negative-electrode active material of a non-aqueous electrolyte secondary battery of the present invention can be manufactured with a desired particle grain size by the melt extraction or the vacuum deposition. It is also possible to use the melt extraction or the vacuum deposition properly depending on metal species to be added.
• a silicon lump or a silicon alloy lump manufactured in the above manner is pulverized and classified by a conventional method that is described below such that the size of the resultant particles becomes a desired size.
• Examples of pulverizer to be used include a ball mill and a media agitating mill, which move grinding media such as balls or beads and pulverize an object by using impact forces, friction forces or compression forces generated by the kinetic energy; a roller mill, which pulverizes an object by using compression forces generated by rollers; a jet mill, which causes an object to collide against an inner wall or against part of the broken object at a high speed and pulverizes the object by impact forces generated by the collision; a hammer mill, pin mill and disc mill, which pulverize an object by using impact forces generated by rotation of a rotor with hammers, blades or pins attached thereto; a colloid mill using shear forces; and a wet, high pressure, counter-impingement dispersing machine “Ultimizer”.
• a ball mill and a media agitating mill which move grinding media such as balls or beads and pulverize an object by using impact forces, friction forces or compression forces generated by the kinetic energy
• Either wet or dry pulverizing may be employed.
• the pulverizing is followed by dry, wet or sieve classifying in order to make particle size distribution uniform.
• the dry classifying mainly uses a gas stream and is performed by successive or simultaneous processes of dispersion, separation (separation between fine and coarse particles), collection (separation between solid and gas), and discharge.
• a pretreatment such as adjustment of water content, dispersiveness, humidity, or other conditions may be performed, or the moisture content or oxygen concentration of the gas stream to be used may be adjusted. Performing either this pretreatment or this adjustment allows the prevention of reduction in classifying efficiency due to interference between particles, particle shape, turbulence of the gas stream, velocity distribution, electrostatic charges, or other causes.
• An integrated type of dry pulverizer and classifier can conduct pulverizing and classifying operations at once to achieve desired particle size distribution.
• each of these particles may be coated with a carbon film to further improve their conductivity; this carbon film is formed by performing an aging process of a heat treatment at temperatures ranging from 200° C. to 1200° C. (preferably 600° C. to 1000° C.) under normal pressure or reduced pressure and under an inert gas atmosphere, and thermal chemical vapor deposition with a hydrocarbon compound gas and/or vapor supplied.
• the silicon-containing particles pulverized so as to have a prescribed size may also be coated with a metallic oxide such as aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, or a mixture thereof.
• a metallic oxide such as aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, or a mixture thereof.
• these silicon-containing particles exhibit a high battery capacity of 900 to 3000 mAh/g, a high coulombic efficiency, and an excellent cycle characteristics even when being mixed with graphite material.
• the mass ratio of the silicon-containing particles in the negative-electrode material of the present invention to the entire negative-electrode material may be 3 to 97 mass %.
• the mass ratio of a binder in the negative-electrode material to the entire negative-electrode material may be 1 to 20 mass %, more preferably 3 to 10 mass %.
• the type of the graphite material is not particularly limited.
• Specific examples of this graphite material that can be used include natural graphite, synthetic graphite, powder of various cokes, meso-phase carbon, vapor phase grown carbon fiber, pitch base carbon fiber, PAN base carbon fiber, and various sintered resin.
• the mass ratio of the added graphite material to the entire negative-electrode material is 2 to 96 mass %. Even when this ratio is 60 to 95 mass %, the battery capacity is higher than the capacity of a conventional graphite material.
• a negative electrode can be produced as follows.
• the negative-electrode material composed of the above negative-electrode active material, the graphite material, the binder, and other additives are mixed in a solvent, such as water or N-methylpyrrolidone, suitable for dissolution and dispersion of the binder, so that a paste mixture is formed.
• This mixture is applied to the current collector so as to form a sheet thereof.
• a material such as copper foil or nickel foil that is commonly used for a negative electrode collector may be used for this current collector without limit of its thickness and a surface treatment.
• the method for forming the mixture sheet is not particularly limited, but may be a known method.
• a negative electrode including this type of negative-electrode material is mainly composed of a negative-electrode active material that is made of the silicon-containing particles for use as a negative-electrode active material of a non-aqueous electrolyte secondary battery of the present invention having a greatly smaller volume variation upon charging and discharging compared with one made of conventional silicon-containing particles.
• the variation in thickness of the negative electrode after charging is less than three times (especially 2.5 times) as large as before charging.
• a negative electrode molded body using the negative electrode thus obtained can be used to produce a non-aqueous electrolyte secondary battery, and particularly a lithium-ion secondary battery.
• Such a non-aqueous electrolyte secondary battery is characterized by using this negative electrode molded body.
• Other materials such as a positive electrode (a positive electrode molded body), a separator, an electrolytic solution, and a non-aqueous electrolyte and the battery shape are not particularly limited.
• Examples of a positive-electrode active material include oxides and sulfides that can occlude and release lithium ions, alone or in combination.
• lithium complex oxide based on Li p MetO 2 is preferably used to increase an energy density.
• Met is preferably at least one of cobalt, nickel, iron and manganese, and p is normally a value in the range of 0.05 ⁇ p ⁇ 1.10.
• lithium complex oxide examples include LiCoO 2 , LiNiO 2 , LiFeO 2 , and Li q Ni r Co 1-r O 2 that have a layered structure (where 0 ⁇ q ⁇ 1 and 0.7 ⁇ r ⁇ 1 in general, but q and r vary depending on charged/discharged states of a battery), LiMn 2 O 4 having a spinel structure, and rhombic LiMnO 2 .
• Exemplary positive-electrode active material for high voltage operation is a substitutional spinel manganese compound such as LiMet s Mn 1-s O 4 (0 ⁇ s ⁇ 1), where Met is titanium, chromium, iron, cobalt, nickel, copper, zinc or the like.
• the lithium complex oxide can be prepared, for example, by mixing a pulverized carbonate, nitrate, oxide or hydroxide of lithium with a pulverized carbonate, nitrate, oxide or hydroxide of a transition metal in accordance with the desired composition, and firing the mixture at temperatures ranging from 600° C. to 1,000° C. under an oxygen atmosphere.
• Organic materials may also be used as the positive-electrode active material.
• these materials include polyacetylene, polypyrrole, polyparaphenylene, polyaniline, polythiophene, polyacene, and polysulfide compound.
• the positive-electrode active material is mixed with the same conductive agent and binder as used for the negative-electrode material. This mixture is applied to the current collector.
• a positive-electrode molded body can be formed by a known method.
• the separator disposed between the positive and negative electrodes is not particularly limited, provided it stabilizes against an electrolyte solution and holds the electrolyte solution effectively.
• Typical examples of the separator include a porous sheet or nonwoven fabric of: polyolefins such as polyethylene and polypropylene; copolymers thereof; and aramid resins. These may be used alone or as a laminate of multiple layers. Ceramics such as metal oxides may be deposited on a surface thereof. Porous glass and ceramics may also be used.
• the solvent used for a non-aqueous electrolyte secondary battery in the present invention is not particularly limited, provided it can be used as a non-aqueous electrolyte solution.
• Typical examples of the solvent include aprotic high-dielectric-constant solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, and ⁇ -butyrolactone; and aprotic low-viscosity solvents such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, dipropyl carbonate, diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,3-dioxolan, sulfolane, methylsulfolane, acetonitrile, propionitrile, anisole, acetic acid esters, e.g., methyl acetate and propionic acid esters.
• These solvents are preferably used as a mixture of an aprotic high-dielectric-constant solvent and an aprotic low-viscosity solvent in a proper ratio.
• ionic liquid containing imidazolium, ammonium and pyridinium cations may be, but not particularly limited to, BF 4 ⁇ , PF 6 ⁇ and (CF 3 SO 2 ) 2 N ⁇ .
• the ionic liquid may be used as a mixture with the above non-aqueous electrolyte solvent.
• the electrolyte may contain a silicone gel, silicone polyether gel, acrylic gel, silicone acrylic gel, acrylonitrile gel, poly(vinylidene fluoride), or other material, as a polymeric material.
• the polymerization may be brought before or after liquid insertion. These materials may be used alone or in combination.
• Exemplary electrolyte salt include light metal salt.
• Examples of the light metal salt include salts of alkali metals such as lithium, sodium and potassium, salts of alkaline earth metals such as magnesium and calcium, and aluminum salts.
• Exemplary lithium salts include LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, C 4 F 9 SO 3 Li, CF 3 CO 2 Li, (CF 3 CO 2 ) 2 NLi, C 6 F 5 SO 3 Li, C 8 F 17 SO 3 Li, (C 2 F 5 SO 2 ) 2 NLi, (C 4 F 9 SO 2 ) (CF 3 SO 2 )NLi, (FSO 2 C 6 F 4 ) (CF 3 SO 2 )NLi, (CF 3 ) 2 CHOSO 2 ) 2 NLi, (CF 3 SO 2 ) 3 CLi, (3,5-(CF 3 ) 2 C 6 F 3 ) 4 BLi, Li
• the concentration of the electrolyte salt in the non-aqueous electrolyte solution preferably ranges from 0.5 to 2.0 mol/L.
• the conductivity of the electrolyte is preferably 0.01 S/cm or more at a temperature of 25° C. This conductivity may be adjusted by the type and concentration of the electrolyte salt.
• non-aqueous electrolytic solution may contain various additives as necessary.
• additives to improve cycle life such as vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate and 4-vinylethylene carbonate
• additives to prevent overcharge such as biphenyl, alkylbiphenyl, cyclohexylbenzene, t-butylbenzene, diphenyl ether, and benzofuran
• additives to remove acid and water such as various carbonate compounds, carboxylic acid anhydrides, nitrogen-containing compounds and sulfur-containing compounds.
• the shape of the non-aqueous electrolyte secondary battery is not particularly limited and may be freely selected.
• Typical batteries has a coin shape in which the electrodes and the separator that are punched out into a coin shape are stacked, or a square or cylindrical shape in which the electrode sheets and the separator are spirally coiled.
• the volume resistivity was measured with a volume resistivity measuring instrument with four probes (MCP-PD51 made by Mitsubishi Chemical Corporation) and the value when a load of 12 kN was applied was represented.
• the median diameter D 50 at a cumulative volume of 50% was measured by a wet method with a particle size distribution measuring instrument using laser diffractometry (MT3300EX II made by NIKKISO Co., Ltd.).
• Elementary analysis was performed by the absolute calibration method with ICPAES (Agilent 730 made by Agilent Technologies Corporation).
• a multipoint copper crucible having a 5-mm-thickness carbon hearth liber was installed in the interior of a vacuum chamber with exhaust equipment including an oil diffusion pump, a mechanical booster pump, and an oil-sealed rotary vacuum pump. Metallic silicon lumps and additional elements were introduced into the crucible. The pressure of its chamber was decreased so as to reach 2 ⁇ 10 ⁇ 4 Pa after 2 hours.
• example 1 used Ge as the additional elements, example 2 Al, example 3 Co, example 4 Ti, and example 5 Co and Ge.
• the output of an electron gun of a rectilinear electron beam type installed in the chamber was gradually increased to complete melting. Then, a vapor deposition process was performed under conditions of an output of 10 kW and a power density of 1.2 kW/cm 2 for two hours. During the vapor deposition process, the temperature of a stainless steel substrate for use in vapor deposition was adjusted to 600° C. Opening the chamber, a silicon deposition lump was obtained.
• the produced silicon deposition lump was pulverized and classified with a roll crusher mill and a jet mill, so that silicon-containing particles were obtained.
• the obtained silicon-containing particles were subjected to a heat treatment for three hours with a rotary kiln having an alumina furnace tube whose temperature was held at 400° C. under an argon air flow.
• silicon-containing particles was obtained in the same manner as example 1 except for using Mn, Co, and Ge as additional elements.
• Table 1 summarizes the composition, the median diameter D 50 at a cumulative volume of 50%, the crystal grain size, the true density, and the volume resistivity upon applying a load of 12 kN of the silicon-containing particles in examples 1 to 5 and comparative examples 1 to 4.
• the silicon-containing particles in examples 1 to 5 had a crystal grain size of 300 nm or less and a true density of more than 2.320 g/cm 3 and less than 3.500 g/cm 3 .
• the comparison of the volume resistivity revealed that the silicon-containing particles for use as a negative-electrode active material of a non-aqueous electrolyte secondary battery in examples 1 to 5, which were doped with other elements, had a lower volume resistivity and more excellent conductivity compared with comparative examples 1 and 2 that prepared the silicon-containing particles from the silicon for use in semiconductors, as a single substance.
• the battery characteristics attributable to the silicon-containing particles in examples 1 to 5 and comparative examples 1 to 4 were evaluated to check their usefulness as the negative-electrode active material.
• a mixture was made from 15 mass % of the silicon-containing particles as the negative-electrode active materials in each of examples 1 to 5 and comparative examples 1 to 4, 79.5 mass % of synthetic graphite having a median diameter D 50 of 10 ⁇ m as a conductive agent, and 1.5 mass % of carboxymethyl cellulose (CMC) powder.
• This mixture was further mixed with acetylene black (17.5% solids) dispersed in water at an amount of 2.5 mass % in terms of solids and styrene-butadiene rubber, SBR (40% solids), dispersed in water at an amount of 1.5 mass % in terms of solids.
• SBR styrene-butadiene rubber
• This slurry was applied to a 12- ⁇ m-thickness copper foil with a 150 ⁇ m doctor blade, pre-dried, and pressed by a roller press at 60° C. into an electrode form.
• This electrode form was dried at 160° C. for two hours and punched out into a 2 cm 2 of negative electrode molded body.
• lithium-ion secondary batteries for evaluation were manufactured by using the obtained negative-electrode molded body, a lithium foil as a counter electrode, a non-aqueous electrolyte solution obtained by dissolving a non-aqueous electrolyte of lithium bis(trifluoromethanesulfonyl)imide in a 1/1 (by volume) mixture of ethylene carbonate and diethyl carbonate at a concentration of 1 mol/L, and a separator of a polyethylene microporous film having a thickness of 30 ⁇ m.
• the manufactured lithium-ion secondary batteries were aged a night at room temperature. Two of the lithium-ion secondary batteries were then disassembled to measure the thickness of the negative electrodes and calculate electrode density on the basis of initial weight in a state where the swelling of electrodes by the electrolyte occurred. It is to be noted that it was calculated without taking into account an increase amount of lithium due to charge and the electrolyte.
• the other two lithium ion secondary batteries were charged with a constant current of 0.15 c until the voltage of the test cell reached 0 V. After the voltage reached 0 V, the charging was continued while the current was decreased so as to keep the voltage of the test cell 0 V. When the current was decreased to less than 0.02 c, the charging was terminated to calculate the charge capacity. It is to be noted that the symbol “c” means a current value with which the theoretical capacity of a negative electrode is charged in 1 hour.
• the lithium ion secondary batteries for evaluation were disassembled to measure the thickness of the negative electrodes.
• the electrode density was calculated from the measured thickness in the same manner as above and the charge capacity per volume upon charging was calculated. Table 2 shows the result.
• Negative-electrode molded bodies were prepared by using the negative-electrode active materials in examples 1 to 5 and comparative examples 1 and 4 to evaluate their cycle characteristics.
• Positive-electrode molded bodies were made by using a positive-electrode material: a positive-electrode active material of LiCoO 2 ; and a current collector of an aluminum foil single layer sheet (trade name: Pioxcel C-100 made by Pionics Co., Ltd.).
• lithium-ion secondary batteries in coin form were manufactured by using a non-aqueous electrolyte solution obtained by dissolving a non-aqueous electrolyte of lithium hexafluorophosphate in a 1/1 (by volume) mixture of ethylene carbonate and diethyl carbonate at a concentration of 1 mol/L, and a separator of a polyethylene macroporous film having a thickness of 30 ⁇ m.
• the manufactured lithium-ion secondary batteries were left at room temperature two nights. With the secondary battery charge/discharge tester (Nagano K.K.), the lithium ion secondary batteries were charged with a constant current of 1.2 mA (0.25 c on the positive electrode basis) until the voltage of the test cell reached 4.2 V. After the voltage reached 4.2 V, the charging was continued while the current was decreased so as to keep the voltage of the test cell 4.2 V. When the current was decreased to less than 0.3 mA, the charging was terminated. The batteries were then discharged at a constant current of 0.6 mA. The discharging was terminated when the cell voltage reached 3.3 V to calculate the discharge capacity.
• the secondary battery charge/discharge tester Nagano K.K.
• Table 2 shows the ratio (capacity maintenance rate) of the discharge capacity after 100 cycles or 300 cycles to the initial discharge capacity (i.e. the discharge capacity after 100 cycles or 300 cycles/the initial discharge capacity).
• Table 2 shows that examples 1 to 5 formed negative electrodes having higher charge capacities than the charge capacity per weight (372 mAh/g) of graphite. Table 2 also shows that the volume expansion rates of examples 1 to 5 were lower than those in comparative examples 1 to 3 and the capacity maintenance rates in the cycles of examples 1 to 5 were better than those of the negative-electrode material in comparative examples 1 to 3 that used silicon as a single substance and the negative-electrode material in comparative example 4 that used the silicon alloy having a true density of more than 3.500 g/cm 3 .

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Battery Electrode And Active Subsutance (AREA)

Applications Claiming Priority (3)

Related Parent Applications (1)

Related Child Applications (1)

Publications (1)

Family

ID=51490908

Family Applications (2)

Family Applications After (1)

Country Status (6)

Cited By (3)

Families Citing this family (7)

Citations (1)

Family Cites Families (20)

• 2013
  • 2013-03-05 JP JP2013042840A patent/JP6006662B2/ja active Active
• 2014
  • 2014-01-07 US US14/769,146 patent/US20150380726A1/en not_active Abandoned
  • 2014-01-07 KR KR1020157023901A patent/KR102107481B1/ko active IP Right Grant
  • 2014-01-07 CN CN201480012160.6A patent/CN105027334B/zh active Active
  • 2014-01-07 WO PCT/JP2014/000016 patent/WO2014136368A1/ja active Application Filing
  • 2014-01-07 EP EP14760542.2A patent/EP2966712B1/en active Active
• 2017
  • 2017-07-06 US US15/642,901 patent/US9837658B2/en active Active

Patent Citations (1)

Also Published As

Similar Documents

Legal Events