WO2012043666A1 - 非水電解液二次電池負極用炭素材及びその製造方法、これを用いた非水系二次電池用負極並びに非水電解液二次電池 - Google Patents
非水電解液二次電池負極用炭素材及びその製造方法、これを用いた非水系二次電池用負極並びに非水電解液二次電池 Download PDFInfo
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- 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
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
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- C01P2006/12—Surface area
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- 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
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to a carbon material for a negative electrode of a non-aqueous electrolyte secondary battery and a method for producing the same.
- the present invention also relates to a negative electrode for a non-aqueous secondary battery containing the carbon material, and a non-aqueous electrolyte secondary battery including the negative electrode.
- amorphous carbon material is also used because it is relatively stable with respect to some electrolyte solutions. Furthermore, a carbon material is also used in which amorphous carbon is coated or adhered on the surface of the graphitic carbon particles to have the characteristics of graphite and amorphous carbon.
- Patent Document 2 a carbon material having a multi-layer structure in which amorphous carbon is coated or adhered on the surface of graphitic carbon particles, the amount of CO up to 800 ° C. measured by a temperature rising pyrolysis mass spectrometer (TPD-MS). It is disclosed that a battery having excellent rapid charge / discharge characteristics can be obtained by using, as an electrode, a carbon material having an A of 0.8 ⁇ 10 ⁇ 6 mol / g or more and 30 ⁇ 10 ⁇ 6 mol / g or less.
- Patent Document 1 increases the rapid charge / discharge performance because the particles of the electrode carbon material are spherical, and further, by covering the amorphous carbon, the irreversible capacity is increased.
- negative electrode materials that have both rapid charge / discharge characteristics and high cycle characteristics for high performance devices in recent years. Absent.
- Patent Document 2 a mixture of raw material graphite and an organic substance is baked in an oxidizing gas with a controlled oxygen concentration, so that the temperature rise desorption amount of the composite carbon material is in a certain range.
- Materials have been proposed.
- the raw material graphite flaky graphite or scaly graphite having a flaky particle shape is used.
- an oxygen functional group is introduced by firing in a gas containing oxygen, and in order to bring all the raw material particles that are powder into uniform contact with the oxygen-containing gas, It is necessary to pack the raw material powder thinly or to use a rotary-type baking apparatus, resulting in a problem that the production efficiency is not good, resulting in an expensive production process.
- the present inventors have solved the above-mentioned problems and are intended for notebook computers, mobile communication devices, portable cameras, portable game machines, etc., which are expected to have higher performance than conventional ones, and further, electric tools.
- the present invention also proposes a negative electrode material for a non-aqueous electrolyte secondary battery that has high capacity, rapid charge / discharge characteristics, and high cycle characteristics, and is suitable for applications such as electric vehicles.
- the present invention is as follows. 1. A carbon material for a negative electrode of a nonaqueous electrolyte secondary battery, characterized by satisfying the following (1) and (2). (1) The aspect ratio of the carbon material is 10 or less. (2) The amount of CO desorbed up to 1000 ° C. by a pyrolysis mass spectrometer (TPD-MS) of the carbon material is 2 ⁇ mol / g or more and 15 ⁇ mol / g or less. 2. 2. The carbon material for a negative electrode of a non-aqueous electrolyte secondary battery according to item 1 above, wherein the surface spacing (d002) of the 002 surface by an X-ray wide angle diffraction method is 0.337 nm or less. 3. 3.
- FIG. 1 is an electron micrograph of the negative electrode carbon material obtained in Example 1.
- FIG. 2 is an electron micrograph of the negative electrode carbon material obtained in Comparative Example 1.
- FIG. 3 is an electron micrograph of the negative electrode carbon material obtained in Comparative Example 4.
- 4 is an electron micrograph of the negative electrode carbon material obtained in Comparative Example 5.
- FIG. 5 is an electron micrograph of the negative electrode carbon material obtained in Comparative Example 6.
- 6 is an electron micrograph of the negative electrode carbon material obtained in Comparative Example 7.
- FIG. 1 is an electron micrograph of the negative electrode carbon material obtained in Example 1.
- FIG. 2 is an electron micrograph of the negative electrode carbon material obtained in Comparative Example 1.
- FIG. 3 is an electron micrograph of the negative electrode carbon material obtained in Comparative Example 4.
- 4 is an electron micrograph of the negative electrode carbon material obtained in Comparative Example 5.
- FIG. 5 is an electron micrograph of the negative electrode carbon material obtained in Comparative Example 6.
- 6 is an electron micrograph of the negative electrode carbon material obtained in Comparative Example 7.
- the carbon material for a non-aqueous electrolyte secondary battery negative electrode (also referred to as a carbon material in the present specification) according to the present invention satisfies the following (1) and (2).
- the aspect ratio of the carbon material is 10 or less.
- the amount of CO desorbed up to 1000 ° C. by a temperature rising pyrolysis mass spectrometer (TPD-MS) of the carbon material is 2 ⁇ mol / g or more and 15 ⁇ mol / g or less.
- the interplanar spacing (d002) of the 002 plane according to the X-ray wide angle diffraction method of the carbon material for a nonaqueous electrolyte secondary battery negative electrode is usually 0.337 nm or less. If the d002 value is too large, it indicates that the crystallinity is low, and the initial irreversible capacity may increase. On the other hand, since the theoretical value of the interplanar spacing of the 002 plane of graphite is 0.335 nm, it is usually preferably 0.335 nm or more. Lc is usually preferably 90 nm or more, and more preferably 95 nm or more.
- the inter-surface distance (d002) of the 002 surface by the X-ray wide angle diffraction method is measured by the method described later in the examples.
- the tap density of the carbon material for a non-aqueous electrolyte secondary battery negative electrode is usually preferably 0.8 g / cm 3 or more, and more preferably 0.85 g / cm 3 or more. Moreover, it is usually preferably 1.5 g / cm 3 or less.
- the tap density is measured by the method described later in the examples. If the tap density is too small, the carbon material for the negative electrode of the non-aqueous electrolyte secondary battery tends not to have sufficient spherical particles, and the continuous voids in the electrode are not secured sufficiently, and the electrolyte retained in the voids. When the mobility of Li ions in the liquid is reduced, the rapid charge / discharge characteristics tend to deteriorate.
- the aspect ratio of the carbon material for a non-aqueous electrolyte secondary battery negative electrode is usually 10 or less, preferably 7 or less, more preferably 5 or less, and still more preferably 3 or less. Moreover, since the aspect ratio 1 is theoretically the minimum value, it is usually preferably 1 or more.
- An aspect ratio that is too large means that the shape of the particles is not spherical, but is close to a flake shape or a scale shape. When an electrode is used, the particles tend to be aligned in a direction parallel to the current collector. Sufficient continuous voids in the thickness direction are not ensured, and the mobility of Li ions in the thickness direction is reduced, so that the rapid charge / discharge characteristics tend to deteriorate.
- the aspect ratio in the present invention is measured as follows. A binder is added to the electrode carbon material to form a slurry, which is coated on a metal foil and further dried to form a coated electrode. Next, the coated electrode is cut in a direction perpendicular to the coated surface, and the cut surface is photographed with an electron microscope. For 50 particles in an arbitrarily selected region, the longest diameter of the cross section of each particle is a ( ⁇ m). ), A / b is determined with the shortest diameter being b ( ⁇ m), and the average value of 50 particles of a / b is defined as the aspect ratio. *
- (D) Desorbed CO amount up to 1000 ° C by temperature rising pyrolysis mass spectrometer (TPD-MS) Up to 1000 ° C by temperature rising pyrolysis mass spectrometer (TPD-MS) of carbon material for negative electrode of non-aqueous electrolyte secondary battery
- the amount of desorbed CO is 2 ⁇ mol / g or more, preferably 2.3 ⁇ mol / g or more, more preferably 3.4 ⁇ mol / g or more, and still more preferably 5.1 ⁇ mol / g or more. Moreover, it is preferably 15 ⁇ mol / g or less, more preferably 10 ⁇ mol / g or less.
- the amount of desorbed CO is too small, the amount of oxygen functional groups imparted to the particles is small, and as a result, the affinity with the electrolytic solution tends to be low, and rapid chargeability and cycle characteristics tend to be low. Also, if the amount of desorbed CO is too large, the mechanical treatment is too strong and the amount of oxygen functional groups increases, and at the same time, the pulverization and particle size reduction of the particles proceeds and the specific surface area also increases. There is a tendency to increase irreversible capacity.
- Controlling the amount of desorbed CO up to 1000 ° C. by a temperature rising pyrolysis mass spectrometer (TPD-MS) within the above range means that an oxygen functional group is added to the surface of the multilayer carbon material.
- the presence of the oxygen functional group increases the affinity with the electrolyte that is a polar solvent, and when the carbon material is used as an electrode, the permeability and liquid retention of the electrolyte are increased, and rapid charge / discharge characteristics It becomes the negative electrode material for nonaqueous electrification secondary batteries which has cycling characteristics.
- a Raman R value is the peak intensity ratio in the vicinity of 1360 cm -1 to the peak intensity near 1580 cm -1 in the argon ion laser Raman spectrum of the Raman R value nonaqueous electrolyte secondary battery negative electrode carbon material is usually 0.25 As mentioned above, Preferably it is 0.3 or more. Usually, it is preferably 0.5 or less, and preferably 0.4 or less. The Raman R value is measured by the method described later in the examples.
- the Raman R value is too small, the rapid charge / discharge characteristics tend to deteriorate. Further, when the Raman R value of the carbon material is too large, it indicates that the amount of amorphous carbon covering the graphite particles is large, and the influence of the irreversible capacity of the amorphous carbon amount is large. As a result, the battery capacity tends to decrease.
- the specific surface area by the BET method of the carbon material for a negative electrode of a non-aqueous electrolyte secondary battery is usually preferably 0.5 m 2 / g or more, more preferably 1 m 2 / g or more, Preferably it is 1.5 m ⁇ 2 > / g or more, Most preferably, it is 3 m ⁇ 2 > / g or more. Moreover, it is preferable that it is usually 8 m ⁇ 2 > / g or less, More preferably, it is 7 m ⁇ 2 > / g or less, More preferably, it is 6 m ⁇ 2 > / g or less.
- the specific surface area by BET method is measured by the method of the Example mentioned later.
- the average particle diameter (d50) of the carbon material for a non-aqueous electrolyte secondary battery negative electrode is usually preferably 2 ⁇ m or more, more preferably 4 ⁇ m or more, further preferably 6 ⁇ m or more, and usually 50 ⁇ m. It is preferable that it is below, More preferably, it is 40 micrometers or less, More preferably, it is 35 micrometers or less. An average particle diameter is measured by the method of the Example mentioned later.
- the average particle size is too small, it tends to be difficult to prevent an increase in irreversible capacity due to an increase in specific surface area. Moreover, when too large, there exists a tendency for it to become difficult to prevent the rapid charge / discharge property fall by the contact area of electrolyte solution and the particle
- the average circularity is 1 in a flow type particle analyzer capable of photographing several thousand particles dispersed in a liquid one by one using a CCD camera and calculating an average shape parameter thereof. Measured by the method of Examples described later, targeting particles in the range of 5-40 ⁇ m.
- the average circularity is a ratio in which the circumference of a circle equivalent to the particle area is the numerator and the circumference of the photographed particle projection image is the denominator. The closer the particle image is to a perfect circle, the closer it is to 1 and the particle image is elongated or bumpy. The smaller the value, the smaller the value.
- the number-based fine powder amount of 3 ⁇ m or less obtained by a flow-type particle analyzer of the carbon material for a nonaqueous electrolyte secondary battery negative electrode is usually preferably 13% or more, more preferably. Is 15% or more, preferably 80% or less, more preferably 75% or less, still more preferably 70% or less, and particularly preferably 65% or less.
- Fine powder is generated by mechanical treatment, but the fine powder has a small particle size, so that the contact area with the electrolytic solution increases, so that the electrolytic solution is easily held. As a result, it is possible to prevent the electrolytic solution from draining during charge and discharge, and the rate characteristics and cycle characteristics tend to be good. However, since the fine powder has a small particle size, the amount of surface precipitation is large. Therefore, when there is too much fine powder, there exists a tendency which brings about the increase in an irreversible capacity
- O / C value Peak area of O1s spectrum with respect to C atom concentration determined based on peak area of C1s spectrum in X-ray photoelectron spectroscopy (XPS) analysis of carbon material for negative electrode of nonaqueous electrolyte secondary battery
- the lower limit of O / C which is the value of the O atom concentration determined based on the above, is usually preferably 1.3% or more, more preferably 1.4% or more, still more preferably 1.5% or more, particularly Preferably it is 1.6% or more.
- the upper limit is usually preferably 10% or less, more preferably 8% or less, still more preferably 6% or less, and particularly preferably 5%.
- the carbon material for a non-aqueous electrolyte secondary battery negative electrode has an aspect ratio of 10 or less, and the amount of CO desorbed up to 1000 ° C. by a thermal decomposition mass spectrometer (TPD-MS) of the carbon material is 2 ⁇ mol / g.
- TPD-MS thermal decomposition mass spectrometer
- the surface spacing (d002) of the 002 plane by X-ray wide angle diffraction method is 0.337 nm or less
- the tap density is 0.8 g / cm 3 or more
- the raw material before the mechanical treatment is appropriately distinguished from the carbon material, and the material subjected to the mechanical treatment is appropriately distinguished from the carbon material.
- the interplanar spacing (d002) of the 002 plane by the X-ray wide angle diffraction method of the carbon material is usually 0.337 nm or less. Moreover, it is preferable that it is 0.335 nm or more normally. Lc is usually preferably 90 nm or more, and more preferably 95 nm or more.
- the interplanar spacing (d002) of the 002 surface by the X-ray wide angle diffraction method of the carbon material is measured by the method described later in the examples. If the d002 value is too large, the crystallinity may decrease and the initial irreversible capacity may increase.
- the tap density of the carbon material is usually 0.8 g / cm 3 or more, preferably 0.85 g / cm 3 or more.
- the tap density is measured by the method described later in the examples. If the tap density of the carbon material is too small, the carbon material tends not to have sufficient spherical particles, and even when it is used as a carbon material for a negative electrode of a non-aqueous electrolyte secondary battery, it continues in the electrode. Sufficient voids are not secured, and the mobility of Li ions in the electrolyte held in the voids tends to decrease, so that the rapid charge / discharge characteristics tend to deteriorate.
- the Raman R value of the carbon material is usually 0.2 to 0.5.
- the Raman R value of the carbon material is measured by the method described later in the examples. When the Raman R value of the carbon material is too small, the rapid charge / discharge characteristics tend to deteriorate.
- the surface spacing (d002) of the 002 surface by the X-ray wide angle diffraction method is 0.337 nm or less, and the tap density is 0.8 g / cm 3 or more.
- Raman R value is the peak intensity ratio in the vicinity of 1360 cm -1 to the peak intensity near 1580 cm -1 in the argon ion laser Raman spectrum is 0.2-0.5, amorphous covering the its surface graphite particles
- a mechanical treatment is applied to a multilayer structure carbon material containing carbonaceous material. The production method of the multi-layer structure carbon material will be specifically described below.
- Graphite particles used as a raw material for the multi-layer structure carbon material include, for example, scale, scale-like, plate-like or block-like naturally-produced graphite, and petroleum coke, coal pitch coke, coal needle coke, or mesophase pitch.
- the mechanical energy treatment is, for example, using a device having a rotor with a plurality of blades installed inside the casing, and rotating the rotor at a high speed, thereby allowing the natural graphite or artificial graphite introduced into the interior to be
- the mechanical action such as impact compression, friction and shear force is repeatedly applied.
- the flat graphite particles are bent, entrained or rounded while being rounded, and at the same time fine cracks and defects on the particle surface.
- spheroidized graphite particles in which structural defects and the like are formed can be produced.
- Raman R value is the peak intensity ratio in the vicinity of 1360 cm -1 to the peak intensity near 1580 cm -1 in the argon ion laser Raman spectrum of the graphite particles is preferably usually 0.2 or more. Moreover, it is preferable that it is 0.5 or less normally, More preferably, it is 0.4 or less. The Raman R value is measured by the method described later in the examples.
- the Raman R value of the graphite particles When the Raman R value of the graphite particles is too small, the rapid charge / discharge characteristics tend to deteriorate. In addition, when the Raman R value of the graphite particles is too large, it indicates that the amount of amorphous carbon covering the graphite particles is large, and the influence of the irreversible capacity of the amorphous carbon amount is affected. As a result, the battery capacity tends to decrease.
- the interplanar spacing (d002) of the 002 planes by graphite X-ray wide angle diffraction method is usually preferably 0.337 nm or less.
- the theoretical value of the interplanar spacing of the 002 plane of graphite is 0.335 nm and is usually 0.335 nm or more.
- Lc is usually preferably 90 nm or more, and more preferably 95 nm or more.
- the inter-surface distance (d002) of the 002 surface by the X-ray wide angle diffraction method is measured by the method described later in the examples.
- the crystallinity may decrease and the initial irreversible capacity may increase.
- the fact that the surface spacing (d002) of the 002 plane is too large indicates that the graphite particles are not a material having sufficient crystallinity, and the capacity tends to decrease due to an increase in irreversible capacity.
- Lc being too small means that the crystallinity is low, and there is a tendency that the capacity decreases due to the increase in the irreversible capacity.
- the aspect ratio of the graphite particles is usually preferably 10 or less, more preferably 7 or less, still more preferably 5 or less, and particularly preferably 3 or less. Moreover, since the aspect ratio 1 is theoretically the minimum value, it is usually preferably 1 or more.
- the aspect ratio of graphite particles is too large, the shape of the particles is not spherical, but close to a flake shape or a scale shape.
- the particles tend to line up in parallel with the current collector.
- a sufficient continuous gap in the thickness direction of the electrode is not secured, and the mobility of Li ions in the thickness direction is lowered, so that rapid charge / discharge characteristics tend to be deteriorated.
- the aspect ratio of the scale-like carbon material is larger than 10.
- the tap density of the graphite particles is preferably 0.8 g / cm 3 or more, and more preferably 0.85 g / cm 3 or more.
- the tap density of the graphite particles is measured by the method described later in the examples. If the tap density is too small, the graphite particles that are the raw material of the carbon material for the non-aqueous electrolyte secondary battery negative electrode tend not to have sufficient spherical particles, and the carbon material for the non-aqueous electrolyte secondary battery negative electrode and In such a case, there is a tendency that the continuous gaps in the electrode are not sufficiently secured, and the mobility of Li ions in the electrolyte held in the gaps is lowered, so that the rapid charge / discharge characteristics tend to deteriorate. is there.
- the fact that the tap density of the graphite particles is 0.8 g / cm 3 or more can also be defined as graphite particles that are spheroidized by applying mechanical energy treatment. Is possible.
- a multilayer carbon material can be produced by using the above-mentioned graphite particles as a raw material and coating the surfaces of the graphite particles with amorphous carbon.
- the graphite particles are mixed with petroleum-based or coal-based tar or pitch, or a resin such as polyvinyl alcohol, polyacrylonitrile, phenol resin, or cellulose, if necessary using a solvent or the like, and non-oxidized.
- An amorphous carbon-coated graphite fired at 500 ° C. or higher, preferably 700 ° C. or higher, more preferably 800 ° C. or higher, usually 2500 ° C. or lower, preferably 2000 ° C. or lower, more preferably 1500 ° C. or lower. Preferably there is.
- pulverization and classification may be performed after firing.
- the coverage of the amorphous carbon coating the graphite particles is usually preferably 0.1% or more, more preferably 0.2% or more, and further preferably 0.4% or more. It is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. The coverage is measured by the method described later in the examples.
- the carbon material of the present invention is manufactured by subjecting the carbon material to mechanical treatment.
- the carbon material of the present invention is obtained by subjecting the multilayer structure carbon material manufactured by the above-described manufacturing method to mechanical treatment. Manufacturing is efficient in order to exhibit the effects of the present invention.
- organic medium examples include N-methylpyrrolidone and dimethylformamide.
- the positive electrode for a lithium secondary battery is formed by forming a positive electrode active material layer containing the above-described lithium transition metal compound powder for a lithium secondary battery positive electrode material and a binder on a current collector.
- a liquid medium for forming a slurry it is possible to dissolve or disperse a lithium transition metal compound powder as a positive electrode material, a binder, and a conductive material and a thickener used as necessary. If it is a solvent, there is no restriction
- a dispersant is added together with the thickener, and a slurry such as SBR is slurried.
- these solvents may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
- the content ratio of the lithium transition metal-based compound powder as the positive electrode material in the positive electrode active material layer is usually preferably 10% by mass or more and 99.9% by mass or less. If the proportion of the lithium transition metal compound powder in the positive electrode active material layer is too large, the strength of the positive electrode tends to be insufficient, and if it is too small, the capacity may be insufficient. *
- the thickness of the positive electrode active material layer is usually preferably about 10 to 200 ⁇ m.
- the electrode density after pressing the positive electrode is usually preferably 2.2 g / cm 3 or more and 4.2 g / cm 3 or less.
- the positive electrode active material layer obtained by coating and drying is preferably consolidated by a roller press or the like in order to increase the packing density of the positive electrode active material.
- a positive electrode for a lithium secondary battery can be prepared.
- Nonaqueous electrolyte examples include known non-aqueous electrolytes, polymer solid electrolytes, gel electrolytes, and inorganic solid electrolytes. Among these, non-aqueous electrolytes are preferable.
- the non-aqueous electrolyte solution is configured by dissolving a solute (electrolyte) in a non-aqueous solvent.
- the electrolyte is preferably a lithium salt.
- the non-aqueous solvent contained in the non-aqueous electrolyte solution is not particularly limited as long as it is a solvent that does not adversely affect the battery characteristics when used as a battery.
- a high dielectric constant solvent such as cyclic carbonate or cyclic carboxylic acid ester in combination with a low viscosity solvent such as chain carbonate or linear carboxylic acid ester.
- an auxiliary may be appropriately added to the non-aqueous electrolyte depending on the purpose.
- an auxiliary agent that has the effect of improving the battery life in order to form a film on the negative electrode surface
- unsaturated cyclic carbonates such as vinylene carbonate, vinyl ethylene carbonate and ethynyl ethylene carbonate, and fluorine atoms such as fluoroethylene carbonate are used.
- fluorinated unsaturated cyclic carbonates such as 4-fluorovinylene carbonate.
- the amount of these auxiliaries is not particularly limited, and is arbitrary as long as the effects of the present invention are not significantly impaired.
- a separator is interposed between the positive electrode and the negative electrode in order to prevent a short circuit.
- the nonaqueous electrolytic solution of the present invention is usually used by impregnating the separator.
- the material and shape of the separator are not particularly limited, and known ones can be arbitrarily adopted as long as the effects of the present invention are not significantly impaired.
- a resin, glass fiber, inorganic material or the like formed of a material that is stable with respect to the non-aqueous electrolyte solution of the present invention is used, and a porous sheet or a nonwoven fabric-like material having excellent liquid retention properties is used. Is preferred.
- the porosity of the separator is arbitrary, but is usually preferably 20% or more, more preferably 35% or more, and further preferably 45% or more. Moreover, 90% or less is preferable normally, 85% or less is more preferable, and 75% or less is further more preferable. If the porosity is too smaller than the above range, the membrane resistance tends to increase and the rate characteristics tend to deteriorate. Moreover, when larger than the said range, it exists in the tendency for the mechanical strength of a separator to fall and for insulation to fall.
- the average pore diameter of the separator is also arbitrary, but is usually preferably 0.5 ⁇ m or less, more preferably 0.2 ⁇ m or less, and usually 0.05 ⁇ m or more. If the average pore diameter exceeds the above range, a short circuit tends to occur. On the other hand, below the above range, the film resistance may increase and the rate characteristics may deteriorate.
- the Gurley value of the separator of the present invention is low, it can be used for various purposes.
- a low Gurley value means that lithium ions can be easily transferred and is preferable because of excellent battery performance.
- the Gurley value of the separator is arbitrary, but is preferably 10 to 1000 seconds / 100 ml, more preferably 15 to 800 seconds / 100 ml, and still more preferably 20 to 500 seconds / 100 ml. If the Gurley value is 1000 seconds / 100 ml or less, the electrical resistance is substantially low, which is preferable as a separator.
- the battery capacity decreases. Also, if the above range is exceeded, the void space is small, the battery expands, and the member expands or the vapor pressure of the electrolyte liquid component increases and the internal pressure rises. In some cases, the gas release valve that lowers various characteristics such as storage at high temperature and the like, or releases the internal pressure to the outside is activated.
- the material of the outer case is not particularly limited as long as it is a substance that is stable with respect to the non-aqueous electrolyte used.
- nickel-plated steel plates, metals such as stainless steel, aluminum, aluminum alloys, and magnesium alloys, or laminated films (laminate films) of a resin and an aluminum foil are included.
- a metal of aluminum or an aluminum alloy or a laminate film is preferable.
- the metal is welded together by laser welding, resistance welding, or ultrasonic welding to form a sealed sealed structure, or a caulking structure using the above metals via a resin gasket. Things.
- Examples of the outer case using the laminate film include a case where a resin-sealed structure is formed by heat-sealing resin layers.
- a resin different from the resin used for the laminate film may be interposed between the resin layers.
- a resin layer is heat-sealed through a current collecting terminal to form a sealed structure, a metal and a resin are joined, so that a resin having a polar group or a modified group having a polar group introduced as an intervening resin is used.
- Resins are preferably used.
- Protection elements such as PTC (Positive Temperature Coefficient), thermal fuse, thermistor, which increases resistance when abnormal heat is generated or excessive current flows, shuts off current flowing through the circuit due to sudden increase in battery internal pressure or internal temperature during abnormal heat generation
- a valve current cutoff valve or the like can be used. It is preferable to select a protective element that does not operate under normal use at a high current, and it is more preferable that the protective element is designed so as not to cause abnormal heat generation or thermal runaway even without the protective element.
- the shape of the exterior body is also arbitrary, and may be any of, for example, a cylindrical shape, a square shape, a laminate shape, a coin shape, or a large size.
- Particle size Laser diffraction particle size distribution obtained by adding about 20 mg of carbon powder to about 1 ml of 2% (volume) aqueous solution of polyoxyethylene (20) sorbitan monolaurate and dispersing it in about 200 ml of ion-exchanged water A volume-based particle size distribution was measured using a meter (Horiba, Ltd., LA-920), and an average particle diameter (median diameter), a d10 particle diameter of 10% integration part, and a d90 particle diameter of 90% integration part were obtained. The measurement conditions are ultrasonic dispersion for 1 minute, ultrasonic intensity 2, circulation speed 2, and relative refractive index 1.50.
- the amount of CO (carbon monoxide) generated was quantified with a mass spectrometer and expressed as the amount of CO generated ( ⁇ mol) per gram of carbon material.
- Average circularity A flow type particle image analyzer (FPIA-2000 manufactured by Toa Medical Electronics Co., Ltd.) was used to measure the particle size distribution by the equivalent circle diameter and calculate the circularity. Ion exchange water was used as a dispersion medium, and polyoxyethylene (20) monolaurate was used as a surfactant.
- the equivalent circle diameter is the diameter of a circle (equivalent circle) having the same projected area as the photographed particle image, and the circularity is the circumference of the equivalent particle as a molecule and the circumference of the photographed particle projection image.
- the ratio is the denominator.
- the average circularity of the measured particles in the range of 1.5 to 40 ⁇ m was averaged.
- BET specific surface area Measured using AMS-8000 manufactured by Okura Riken Co., Ltd. After pre-drying at 250 ° C. and flowing nitrogen gas for 30 minutes, the BET one-point method by nitrogen gas adsorption was used for measurement.
- True density Measured using a pycnometer and a 0.1% aqueous solution of a surfactant as a medium.
- X-ray diffraction Carbon powder is mixed with about 15% X-ray standard high-purity silicon powder, and CuK ⁇ ray monochromatized with a graphite monochromator is used as a radiation source. Wide angle by reflection diffractometer method The X-ray diffraction curve was measured, and the interplanar spacing (d002) and crystallite size (Lc) were determined using the Gakushin method.
- O / C value (%) O atom concentration obtained based on the peak area of the O1s spectrum in the X-ray photoelectron spectroscopy (XPS) analysis ⁇ 100 / C obtained based on the peak area of the C1s spectrum in the XPS analysis Atomic concentration
- X-ray photoelectron spectroscopy is measured using an X-ray photoelectron spectrometer, the object to be measured is placed on a sample stage so that the surface is flat, and K ⁇ rays of aluminum are used as an X-ray source.
- the spectra of C1s (280 to 300 eV) and O1s (525 to 545 eV) are measured.
- the obtained C1s peak top is corrected to be 284.3 eV, the peak areas of the C1s and O1s spectra are obtained, and the device sensitivity coefficient is multiplied to calculate the surface atomic concentrations of C and O, respectively.
- K is the mass (kg) of spherical graphitic carbon subjected to mixing with tar pitch
- T is the mass (kg) of tar pitch that is a coating raw material subjected to mixing with spherical graphitic carbon
- D is Of the mixture of K and T, the amount of the mixture actually subjected to firing, N, indicates the mass of the coated spherical graphite carbon material after firing.
- the obtained spheroidized graphitic carbon has a 002 plane spacing (d002) of 0.336 nm by X-ray wide angle diffraction method, Lc of 100 nm or more, a tap density of 1.01 g / cm 3 , and an aspect ratio of 1.9.
- Raman R value is 0.24, which is the peak intensity ratio in the vicinity of 1360 cm -1 to the peak intensity near 1580 cm -1 in the argon ion laser Raman spectrum, the average particle diameter 16.1Myuemu, BET method specific surface area of 7.0 m 2 / g
- the true density was 2.26 g / cm 3 and the average circularity was 0.93.
- this spheroidized graphitic carbon 100 parts by weight of this spheroidized graphitic carbon and 33 parts by weight of petroleum-derived tar were mixed with a mixer, then fired to 1300 ° C. in a non-oxidizing atmosphere, and then cooled to room temperature.
- this fired product is mechanically treated by rotating the rotor at a peripheral speed of 100 m / sec using an apparatus having a rotor in which a plurality of blades are installed inside the casing, to obtain a carbon material for an electrode. It was.
- Table 1 shows the properties of this carbon material for electrodes.
- the electron micrograph of the carbon material for electrodes obtained in Example 1 is shown in FIG.
- a coin-type battery for a charge / discharge test was fabricated by stacking the negative electrode and a lithium metal having a thickness of 0.5 mm through a separator impregnated with an electrolytic solution.
- a battery for a charge / discharge test was fabricated by stacking the above negative electrode and positive electrode through a separator impregnated with an electrolytic solution.
- Comparative Example 1 The fired product was processed in the same manner as in Example 1 except that a mechanical treatment was performed by rotating the rotor at a peripheral speed of 48 m / sec using an apparatus having a rotor with a plurality of blades installed inside the casing. A carbon material for an electrode was obtained. The results are shown in Table 1.
- FIG. 2 shows an electron micrograph of the electrode carbon material obtained in Comparative Example 1.
- Example 2 The same procedure as in Example 1 was performed except that 25 parts by weight of petroleum-derived tar mixed with 100 parts by weight of spheroidized graphitic carbon was used, and that the mechanical treatment was performed at a rotor peripheral speed of 83 m / second. .
- the results are shown in Table 1.
- Comparative Example 2 A carbon material for an electrode was obtained in the same manner as in Example 2 except that the mechanical treatment was performed by rotating the rotor at a peripheral speed of 48 m / sec. The results are shown in Table 1.
- Example 3 It implemented like Example 2 except having made the calcination temperature in non-oxidizing atmosphere into 1000 degreeC. The results are shown in Table 1.
- Comparative Example 3 A carbon material for an electrode was obtained in the same manner as in Example 3 except that the rotor was rotated at a peripheral speed of 48 m / sec. The results are shown in Table 1.
- Example 4 70% of the carbon material for an electrode obtained in Example 2 has an 002 plane spacing (d002) of 0.336 nm, a tap density of 0.90 g / cm 3 by an X-ray wide angle diffraction method, and 1580 cm in an argon ion laser Raman spectrum.
- Raman R value 0.25 is the peak intensity ratio in the vicinity of 1360 cm -1 to the peak intensity in the vicinity of -1
- average particle size (d50) is the graphite particles is 20 [mu] m 30%
- the electrolyte absorption time, initial battery characteristics, rapid discharge characteristics, rapid charge characteristics, and cycle characteristics were measured in the same manner as in Example 2. The results are shown in Table 1.
- Comparative Example 5 The same operation as in Comparative Example 4 was performed except that the mechanical treatment time was 30 minutes.
- Table 1 shows the properties of the obtained carbon material for an electrode. Using this carbon material for electrodes, a slurry was prepared in the same manner as in Example 1, and coating was attempted on the copper foil by the doctor blade method. However, streaks or uncoated parts were generated. Therefore, the electrode was not used for battery evaluation.
- FIG. 4 shows an electron micrograph of the electrode carbon material obtained in Comparative Example 5.
- FIG. 5 shows an electron micrograph of the electrode carbon material obtained in Comparative Example 6.
- Comparative Example 7 The 002 plane spacing (d002) by X-ray wide angle diffraction method is 0.336 nm, Lc is 100 nm or more, tap density is 0.43 g / cm 3 , and 1360 cm ⁇ with respect to the peak intensity near 1580 cm ⁇ 1 in the argon ion laser Raman spectrum.
- the Raman R value as a peak intensity ratio near 1 is 0.09, the average particle diameter is 23.9 ⁇ m, the true density is 2.26 g / cm 3 , and 100 parts by weight of scaly graphite particles having an aspect ratio of 17 and petroleum-derived tar 33 The parts by weight were mixed in a mixer, then fired to 1300 ° C.
- Example 1 was used except that this fired product was mechanically processed by rotating the rotor at a peripheral speed of 83 m / sec using an apparatus having a rotor with a plurality of blades installed inside the casing. It carried out like. The results are shown in Table 1.
- FIG. 6 shows an electron micrograph of the electrode carbon material obtained in Comparative Example 7.
- the non-aqueous electrolyte secondary battery using the carbon material for a non-aqueous electrolyte secondary battery negative electrode of the present invention as an electrode exhibited excellent rapid charge / discharge characteristics and high cycle characteristics.
- the non-aqueous electrolyte secondary battery using the carbon material for a negative electrode of the non-aqueous electrolyte secondary battery of the present invention as an electrode exhibits excellent characteristics having both rapid charge / discharge characteristics and high cycle characteristics.
- the time for absorbing the electrolyte is increased, and the process of immersing the electrolyte in the electrode in the battery can is shortened, so that the manufacturing cost of the battery can be reduced.
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Abstract
Description
1.下記(1)及び(2)を満たすことを特徴とする非水電解液二次電池負極用炭素材。
(1)炭素材のアスペクト比が10以下である。
(2)炭素材の温熱分解質量分析計(TPD-MS)による1000℃までの脱離CO量が2μmol/g以上15μmol/g以下である。
2.炭素材のX線広角回折法による002面の面間隔(d002)が0.337nm以下である前項1に記載の非水電解液二次電池負極用炭素材。
3.比表面積が0.5~8m2/gである前項1または2に記載の非水電解液二次電池負極用炭素材。
4.フロー式粒子解析計で求められる平均円形度が0.9以上である前項1~3のいずれか1項に記載の非水電解液二次電池負極用炭素材。
5.集電体と、該集電体上に形成された活物質層とを含み、該活物質層が、前項1~4のいずれか1項に記載の非水電解液二次電池用炭素材を含有する、非水系二次電池用負極。
6.リチウムイオンを吸蔵・放出可能な正極及び負極、並びに電解質を含むリチウムイオン二次電池であって、該負極が前項5に記載の非水系二次電池用負極であるリチウムイオン二次電池。
7.X線広角回折法による002面の面間隔(d002)が0.337nm以下、タップ密度が0.8g/cm3以上、及びアルゴンイオンレーザーラマンスペクトルにおける1580cm-1付近のピーク強度に対する1360cm-1付近のピーク強度比であるラマンR値が0.2~0.5である炭素材料に機械的処理を施すことを特徴とする非水電解液二次電池負極用炭素材の製造方法。
8.機械的処理が、ケーシング内部に複数のブレードを設置したローターを有する装置を用い、且つ該ローターの周速度を50m/秒~300m/秒にて処理を施すことである前項7に記載の非水電解液二次電池負極用炭素材の製造方法。
9.炭素材料が、黒鉛質粒子とその表面を被覆する非晶質炭素とを含む複層構造炭素材料である前項7または8に記載の非水電解液二次電池負極用炭素材の製造方法。
(1)炭素材のアスペクト比が10以下である。
(2)炭素材の昇温熱分解質量分析計(TPD-MS)による1000℃までの脱離CO量が2μmol/g以上15μmol/g以下である。
本発明の炭素材は、天然黒鉛、人造黒鉛および非晶質被覆黒鉛から選ばれる材料を用いることが好ましい。これらの炭素材は二種以上を任意の組成及び組み合わせで併用して、炭素材として好適に使用することができ、一種又は二種以上を、他の一種又は二種以上の炭素材と混合し、炭素材として用いてもよい。また、これらの中でも上述した材料が複層構造となっている炭素材(以下、複層構造炭素材ともいう)がより好ましい。
以下に、本発明の非水電解液二次電池負極用炭素材の代表的な物性を記載する。
非水電解液二次電池負極用炭素材のX線広角回折法による002面の面間隔(d002)は通常0.337nm以下である。d002値が大きすぎるということは結晶性が低いことを示し、初期不可逆容量が増加する場合がある。一方黒鉛の002面の面間隔の理論値は0.335nmであるため、通常0.335nm以上であることが好ましい。またLcは通常90nm以上であることが好ましく、95nm以上であることがより好ましい。X線広角回折法による002面の面間隔(d002)は実施例で後述する方法により測定する。
非水電解液二次電池負極用炭素材のタップ密度は、通常0.8g/cm3以上であることが好ましく、0.85g/cm3以上であることがより好ましい。また、通常1.5g/cm3以下であることが好ましい。タップ密度は実施例で後述する方法により測定する。タップ密度が小さすぎると、非水電解液二次電池負極用炭素材が充分な球形粒子となっていない傾向にあり、電極内での連続した空隙が充分確保されず、空隙に保持された電解液内のLiイオンの移動性が落ちることで、急速充放電特性が低下してしまう傾向がある。
非水電解液二次電池負極用炭素材のアスペクト比は、通常10以下であり、好ましくは7以下、より好ましくは5以下、更に好ましくは3以下である。また、アスペクト比1が理論上最小値となるので、通常1以上であることが好ましい。アスペクト比が大きすぎるということは、粒子の形状が球状ではなく、薄片形状、鱗片形状に近くなるということで、電極とした場合に、粒子が集電対と平行方向に並ぶ傾向となり、電極の厚み方向への連続した空隙が充分確保されず、厚み方向へのLiイオンの移動性が落ちることで、急速充放電特性が低下してしまう傾向がある。
非水電解液二次電池負極用炭素材の昇温熱分解質量分析計(TPD-MS)による1000℃までの脱離CO量は2μmol/g以上、好ましくは2.3μmol/g以上、より好ましくは3.4μmol/g以上、更に好ましくは5.1μmol/g以上である。また、好ましくは15μmol/g以下、より好ましくは10μmol/g以下である。
非水電解液二次電池負極用炭素材のアルゴンイオンレーザーラマンスペクトルにおける1580cm-1付近のピーク強度に対する1360cm-1付近のピーク強度比であるラマンR値は通常0.25以上、好ましくは0.3以上であることが好ましい。また通常、0.5以下であることが好ましく、好ましくは0.4以下である。ラマンR値は実施例で後述する方法により測定する。
非水電解液二次電池負極用炭素材のBET法による比表面積は通常0.5m2/g以上であることが好ましく、より好ましくは1m2/g以上、さらに好ましくは1.5m2/g以上、特に好ましくは3m2/g以上である。また、通常8m2/g以下であることが好ましく、より好ましくは7m2/g以下、さらに好ましくは6m2/g以下である。BET法による比表面積は後述する実施例の方法により測定する。
非水電解液二次電池負極用炭素材の平均粒径(d50)は通常2μm以上であることが好ましく、より好ましくは4μm以上、さらに好ましくは6μm以上であり、通常50μm以下であることが好ましく、より好ましくは40μm以下、さらに好ましくは35μm以下である。平均粒径は、後述する実施例の方法により測定する。
非水電解液二次電池負極用炭素材の平均円形度は通常0.88以上、好ましくは0.89以上、より好ましくは0.9以上、更に好ましくは0.93以上である。平均円形度の最大値は理論上1となるため、通常1以下である。また、より好ましい態様として黒鉛質粒子とその表面を被覆する非晶質炭素とを含む複層構造炭素材が挙げられるが、その場合、被覆前の黒鉛質粒子は、球形化黒鉛質粒子であることが好ましい。被覆前の黒鉛質粒子の平均円形度を通常0.88以上、好ましくは0.89以上、より好ましくは0.9以上、更に好ましくは0.93以上とすることにより、高容量で、急速放電特性を併せ持った炭素材を得ることができる。
非水電解液二次電池負極用炭素材のフロー式粒子解析計で求められる3μm以下の個数基準微粉量が通常13%以上であることが好ましく、より好ましくは15%以上であり、通常80%以下であることが好ましく、より好ましく75%以下、さらに好ましくは70%以下、特に好ましくは65%以下である。
非水電解液二次電池負極用炭素材のX線光電子分光法(XPS)分析におけるC1sのスペクトルのピーク面積に基づいて求めたC原子濃度に対するO1sのスペクトルのピーク面積に基づいて求めたO原子濃度の値であるO/Cの下限が、通常1.3%以上であることが好ましく、より好ましくは1.4%以上、さらに好ましくは1.5%以上、特に好ましくは1.6%以上である。上限は通常10%以下であることが好ましく、より好ましくは8%以下、さらに好ましくは6%以下、特に好ましくは5%である。
非水電解液二次電池負極用炭素材として、炭素材のアスペクト比が10以下であり、炭素材の温熱分解質量分析計(TPD-MS)による1000℃までの脱離CO量が2μmol/g以上15μmol/g以下であることを具備していれば、どのような製法で作製しても特に制限はない。
本発明の非水電解液二次電池負極用炭素材(以下、負極材料ともいう)を用いて負極を作製するには、負極材料に結着樹脂を配合したものを水性若しくは、有機系媒体でスラリーとし、必要によりこれに増粘材を加えて集電体に塗布し、乾燥すればよい。結着樹脂としては、非水電解液に対して安定で、かつ非水溶性のものを用いるのが好ましい。
本発明の非水電解液二次電池、特にリチウムイオン二次電池の基本的構成は、従来公知のリチウムイオン二次電池と同様であり、本発明の非水電解液二次電池負極用炭素材を適用した負極以外の部材として、通常、リチウムイオンを吸蔵・放出可能な正極及び電解質等を備える。
正極は、正極活物質及びバインダを含有する正極活物質層を、集電体上に形成したものである。
以下に正極に使用される正極活物質(リチウム遷移金属系化合物)について述べる。
リチウム遷移金属系化合物とは、Liイオンを脱離、挿入することが可能な構造を有する化合物であり、例えば、硫化物、リン酸塩化合物またはリチウム遷移金属複合酸化物などが挙げられる。
また、リチウム含有遷移金属化合物は、例えば、下記組成式(A)または(B)で示されるリチウム遷移金属系化合物であることが挙げられる。
Li1+xMO2 …(A)
ただし、xは通常0以上、0.5以下である。Mは、Ni及びMn、または、Ni、Mn及びCoから構成される元素であり、Mn/Niモル比は通常0.1以上、5以下である。Ni/Mモル比は通常0以上、0.5以下である。Co/Mモル比は通常0以上、0.5以下であることが好ましい。なお、xで表されるLiのリッチ分は、遷移金属サイトMに置換している場合もある。
αLi2MO3・(1-α)LiM’O2・・・(A’)
Li[LiaMbMn2-b-a]O4+δ・・・(B)
ただし、Mは、Ni、Cr、Fe、Co、Cu、Zr、AlおよびMgから選ばれる遷移金属のうちの少なくとも1種から構成される元素である。
リチウム二次電池用正極は、上述のリチウム二次電池正極材料用リチウム遷移金属系化合物粉体及び結着剤を含有する正極活物質層を集電体上に形成してなるものである。
非水電解質としては、例えば、公知の非水系電解液、高分子固体電解質、ゲル状電解質および無機固体電解質等が挙げられるが、中でも非水系電解液が好ましい。非水系電解液は、非水系溶媒に溶質(電解質)を溶解させて構成される。
非水系電解液に用いられる電解質には制限はなく、電解質として用いられる公知のものを任意に採用して含有させることができる。本発明の非水系電解液を非水系電解液二次電池に用いる場合には、電解質はリチウム塩が好ましい。
非水系電解液が含有する非水系溶媒は、電池として使用した際に、電池特性に対して悪影響を及ぼさない溶媒であれば特に制限されないが、通常使用される非水系溶媒としては、例えば、ジメチルカーボネート、エチルメチルカーボネートおよびジエチルカーボネート等の鎖状カーボネート、エチレンカーボネート、プロピレンカーボネートおよびブチレンカーボネート等の環状カーボネート、酢酸メチル、酢酸エチル、プロピオン酸メチルおよびプロピオン酸エチル等の鎖状カルボン酸エステル、γ-ブチロラクトン等の環状カルボン酸エステル、ジメトキシエタンおよびジエトキシエタン等の鎖状エーテル、テトラヒドロフラン、2-メチルテトラヒドロフランおよびテトラヒドロピラン等の環状エーテル、アセトニトリル、プロピオニトリル、ベンゾニトリル、ブチロニトリルおよびバレロニトリル等のニトリル、リン酸トリメチルおよびリン酸トリエチル等のリン酸エステル、並びにエチレンサルファイト、1,3-プロパンスルトン、メタンスルホン酸メチル、スルホランおよびジメチルスルホン等の含硫黄化合物等が挙げられる。これら化合物は、水素原子が一部ハロゲン原子で置換されていてもよい。
非水系電解液には、上述の電解質、非水系溶媒以外に、目的に応じて適宜助剤を配合してもよい。負極表面に皮膜を形成するため、電池の寿命を向上させる効果を有する助剤としては、例えば、ビニレンカーボネート、ビニルエチレンカーボネートおよびエチニルエチレンカーボネート等の不飽和環状カーボネート、フルオロエチレンカーボネート等のフッ素原子を有する環状カーボネート並びに4-フルオロビニレンカーボネート等のフッ素化不飽和環状カーボネート等が挙げられる。
正極と負極との間には、短絡を防止するために、通常はセパレータを介在させる。この場合、本発明の非水系電解液は、通常はこのセパレータに含浸させて用いる。
・電極群
電極群は、上記の正極板と負極板とを上記のセパレータを介してなる積層構造のもの、及び上記の正極板と負極板とを上記のセパレータを介して渦巻き状に捲回した構造のもののいずれでもよい。電極群の体積が電池内容積に占める割合(以下、電極群占有率と称する)は、通常40%以上が好ましく、50%以上がより好ましく、また、通常90%以下が好ましく、80%以下がより好ましい。
外装ケースの材質は用いられる非水系電解液に対して安定な物質であれば特に制限されない。具体的には、例えば、ニッケルめっき鋼板、ステンレス、アルミニウム若しくはアルミニウム合金、マグネシウム合金等の金属類、又は、樹脂とアルミ箔との積層フィルム(ラミネートフィルム)が挙げられる。これらの中でも、軽量化の観点から、アルミニウム若しくはアルミニウム合金の金属、またはラミネートフィルムが好ましい。
保護素子として、異常発熱や過大電流が流れた時に抵抗が増大するPTC(Positive Temperature Coefficient)、温度ヒューズ、サーミスター、異常発熱時に電池内部圧力や内部温度の急激な上昇により回路に流れる電流を遮断する弁(電流遮断弁)等を使用することができる。上記保護素子は高電流の通常使用で作動しない条件のものを選択することが好ましく、保護素子がなくても異常発熱や熱暴走に至らない設計にすることがより好ましい。
本発明の非水系電解液二次電池は、通常、上記の非水系電解液、負極、正極、セパレータ等を外装体内に収納して構成される。この外装体は、特に制限されず、本発明の効果を著しく損なわない限り、公知のものを任意に採用することができる。具体的に、外装体の材質は任意であるが、通常は、例えば、ニッケルメッキを施した鉄、ステンレス、アルミウム若しくはその合金、ニッケルまたはチタン等が用いられる。
電極用炭素材100重量部に、カルボキシメチルセルロースの1%水溶液100重量部、及びをスチレンブタジエンゴムの50%水分散液2重量部を加えて混練し、スラリーとした。銅箔上にこのスラリーをドクターブレード法で目付け12mg/cm2に塗布し、110℃で乾燥して塗布電極とした。次いでこの塗布電極を塗布面と直角方向に切断し、その切断面を電子顕微鏡で写真撮影し、任意選んだ領域内の50個の粒子について、それぞれの粒子の断面の最長径をa(μm)、最短径をb(μm)としてa/bを求め、a/bの50個の粒子の平均値をアスペクト比とした。
被覆率(質量%)=100-(K×D)/[(K+T)×N]×100
この式において、Kはタールピッチとの混合に供した球形黒鉛質炭素の質量(kg)、Tは球形黒鉛質炭素との混合に供した被覆原料であるタールピッチの質量(kg)、DはKとTの混合物のうち実際に焼成に供した混合物量、Nは焼成後の被覆球形黒鉛質炭素材の質量をしめす。
天然に産出する黒鉛で、X線広角回折法による002面の面間隔(d002)が0.336nmでLcが100nm以上、タップ密度が0.46g/cm3、アルゴンイオンレーザーラマンスペクトルにおける1580cm-1付近のピーク強度に対する1360cm-1付近のピーク強度比であるラマンR値が0.13、平均粒径28.7μm、真密度2.26g/cm3にある鱗片状黒鉛粒子を、(株)奈良機械製作所製社製ハイブリダイゼーションシステムを用いて、ローターの周速度40m/秒、10分の条件で20kg/hrの処理速度で鱗片状黒鉛粒子を連続的に処理することで、黒鉛粒子表面にダメージを与えながら球形化処理を行い、その後更に分級処理により微粉及び粗粉の除去を行った。
上記の電極用炭素材100重量部に、カルボキシメチルセルロースの1%水溶液100重量部、及びをスチレンブタジエンゴムの50%水分散液2重量部を加えて混練し、スラリーとした。銅箔上にこのスラリーをドクターブレード法で目付け12mg/cm2に塗布した。110℃で乾燥したのちロールプレスにより密度が1.63g/ccとなるように圧密化した。これを12.5mmφに切り出し、150℃で乾燥して浸液性評価用電極とした。この浸液性評価用電極に、エチレンカーボネート:ジメチルカーボネート:エチルメチルカーボネート=3:3:4(質量比)混合液に、LiPF6を1.2モル/リットルとなるように溶解させた電解液1μLを滴下し、該電解液が該電極に吸収され該電極表面から完全に電解液がなくなる時間を測定し電解液浸液性の指標とした。電解液吸収時間が短いほど電解液浸液性が大きい。
上記の電極用炭素材100重量部に、カルボキシメチルセルロースの1%水溶液100重量部、及びをスチレンブタジエンゴムの50%水分散液2重量部を加えて混練し、スラリーとした。銅箔上にこのスラリーをドクターブレード法で目付け12mg/cm2に塗布した。110℃で乾燥したのちロールプレスにより密度が1.63g/ccとなるように圧密化した。これを12.5mmφに切り出し、190℃で減圧乾燥して負極とした。
上記の電極用炭素材100重量部に、カルボキシメチルセルロースの1%水溶液100重量部、及びをスチレンブタジエンゴムの50%水分散液2重量部を加えて混練し、スラリーとした。銅箔上にこのスラリーをドクターブレード法で目付け12mg/cm2に塗布した。110℃で乾燥したのちロールプレスにより密度が1.63g/ccとなるように圧密化した。これを32mm×42mm角に切り出し、190℃で減圧乾燥して負極とした。
それぞれ充電は、0.2C(5hrで充電)で4.2Vまで充電し更に4.2Vで2hr充電したのち(0.2C-CCCV)、0.2C(5hrで放電)、1C(1hrで放電),2C(0.5hrで放電)、3C(0.33hrで放電)、4C(0.25hrで放電)で3.0Vまでの放電試験を実施し、0.2C(5hrで放電)の放電容量に対する各レートでの放電容量を%で表した結果を表1に記した。
0.2C(5hrで充電)で4.2Vまで充電し更に4.2Vで2hr充電(0.2C-CCCV)、及び0.2C(5hrで充電)、1C(1hrで充電)、2C(0.5hrで充電)、3C(0.33hrで充電)、4C(0.25hrで充電)での4.2Vまでの充電試験を実施し、0.2C(5hrで充電)で4.2Vまで充電し更に4.2Vで2hr充電(0.2C-CCCV)した時の充電容量に対する各充電試験での充電容量を%で表した結果を表1に記した。なお、それぞれの充電の後、0.2Cで3.0Vまでの放電を行っている。
上記電池で、1Cで4.2Vまで充電、0.5(2hrでの放電)Cで3・0Vまでの放電を繰り返し、1サイクル目の放電容量に対する500サイクル目の放電容量を500サイクル維持率として%で表し、表1に記した。
焼成物を、ケーシング内部に複数のブレードを設置したローターを有する装置を用い、そのローターを48m/秒の周速度で回転させることにより機械的処理を施した以外は実施例1と同様に行い、電極用炭素材を得た。結果を表1に記す。また、図2に比較例1で得られた電極用炭素材の電子顕微鏡写真を示す。
球形化黒鉛質炭素100重量部に混合する石油由来のタールを25重量部としたこと、ローターの周速度を83m/秒にして機械的処理を施した以外は、実施例1と同様に実施した。結果を表1に記す。
ローターを48m/秒の周速度で回転させることにより機械的処理を施した以外は実施例2と同様に行い、電極用炭素材を得た。結果を表1に記す。
非酸化性雰囲気での焼成温度を1000℃とすること以外は、実施例2と同様に実施した。結果を表1に記す。
ローターを48m/秒の周速度で回転させることにより機械的処理を施した以外は実施例3と同様に行い、電極用炭素材を得た。結果を表1に記す。
実施例2で得られた電極用炭素材料70%に、X線広角回折法による002面の面間隔(d002)が0.336nm、タップ密度0.90g/cm3、アルゴンイオンレーザーラマンスペクトルにおける1580cm-1付近のピーク強度に対する1360cm-1付近のピーク強度比であるラマンR値0.25、BET比表面積が4.9m2/g、平均粒径(d50)が20μmである黒鉛粒子を30%混合して、実施例2と同様の方法で、電解液吸収時間、初期電池特性、急速放電特性、急速充電特性、サイクル特性を測定した。結果を表1に示す。
焼成物を、内径60mmφ、内高65mmの容器に、外形40mmφ、高さ55mmのロッドを入れた振動ボールミル用容器に25g投入し、3分間機械的処理を施した以外は、実施例1と同様に実施した。結果を表1に記す。また、図3に比較例4で得られた電極用炭素材の電子顕微鏡写真を示す。
機械的処理をした時間を30分間とした以外は、比較例4と同様実施した。得られた電極用炭素材の性状を表1に記す。この電極用炭素材料を用いて実施例1と同様の方法で、スラリーを作製し、銅箔上にドクターブレード法で塗布を試みたが、スジを引いたり、未塗工部が生じてしまうなどで、電池評価に供する電極とはならなかった。また、図4に比較例5で得られた電極用炭素材の電子顕微鏡写真を示す。
X線広角回折法による002面の面間隔(d002)が0.336nmでLcが100nm以上、タップ密度が0.43g/cm3、アルゴンイオンレーザーラマンスペクトルにおける1580cm-1付近のピーク強度に対する1360cm-1付近のピーク強度比であるラマンR値が0.09、平均粒径23.9μm、真密度2.26g/cm3、アスペクト比15である鱗片状黒鉛粒子100重量部と石油由来のタール33重量部を混合機で混合し、次いで500ppmの酸素を含んだ窒素ガス流通雰囲気下で1300℃まで焼成し、その後室温まで冷却した。次に、この焼成物を、ケーシング内部に複数のブレードを設置したローターを有する装置を用い、そのローターを48m/秒の周速度で回転させることにより粉砕処理を施した以外は、実施例1と同様に実施した。結果を表1に記す。また、図5に比較例6で得られた電極用炭素材の電子顕微鏡写真を示す。
X線広角回折法による002面の面間隔(d002)が0.336nmでLcが100nm以上、タップ密度が0.43g/cm3、アルゴンイオンレーザーラマンスペクトルにおける1580cm-1付近のピーク強度に対する1360cm-1付近のピーク強度比であるラマンR値が0.09、平均粒径23.9μm、真密度2.26g/cm3、アスペクト比17である鱗片状黒鉛粒子100重量部と石油由来のタール33重量部を混合機で混合し、次いで非酸化性雰囲気で1300℃まで焼成し、その後室温まで冷却した。次に、この焼成物を、ケーシング内部に複数のブレードを設置したローターを有する装置を用い、そのローターを83m/秒の周速度で回転させることにより機械的処理を施した以外は、実施例1と同様に実施した。結果を表1に記す。また、図6に比較例7で得られた電極用炭素材の電子顕微鏡写真を示す。
Claims (9)
- 下記(1)及び(2)を満たすことを特徴とする非水電解液二次電池負極用炭素材。
(1)炭素材のアスペクト比が10以下である。
(2)炭素材の温熱分解質量分析計(TPD-MS)による1000℃までの脱離CO量が2μmol/g以上15μmol/g以下である。 - 炭素材のX線広角回折法による002面の面間隔(d002)が0.337nm以下である請求項1に記載の非水電解液二次電池負極用炭素材。
- 比表面積が0.5~8m2/gである請求項1または2に記載の非水電解液二次電池負極用炭素材。
- フロー式粒子解析計で求められる平均円形度が0.9以上である請求項1~3のいずれか1項に記載の非水電解液二次電池用炭素材。
- 集電体と、該集電体上に形成された活物質層とを含み、該活物質層が、請求項1~4のいずれか1項に記載の非水電解液二次電池用炭素材を含有する、非水系二次電池用負極。
- リチウムイオンを吸蔵・放出可能な正極及び負極、並びに電解質を含むリチウムイオン二次電池であって、該負極が請求項5に記載の非水系二次電池用負極であるリチウムイオン二次電池。
- X線広角回折法による002面の面間隔(d002)が0.337nm以下、タップ密度が0.8g/cm3以上、及びアルゴンイオンレーザーラマンスペクトルにおける1580cm-1付近のピーク強度に対する1360cm-1付近のピーク強度比であるラマンR値が0.2~0.5である炭素材料に機械的処理を施すことを特徴とする非水電解液二次電池負極用炭素材の製造方法。
- 機械的処理が、ケーシング内部に複数のブレードを設置したローターを有する装置を用い、且つ該ローターの周速度を50m/秒~300m/秒にて処理を施すことである請求項7に記載の非水電解液二次電池負極用炭素材の製造方法。
- 炭素材料が、黒鉛質粒子とその表面を被覆する非晶質炭素とを含む複層構造炭素材料である請求項7または8に記載の非水電解液二次電池負極用炭素材の製造方法。
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US9240587B2 (en) | 2016-01-19 |
US20130224598A1 (en) | 2013-08-29 |
EP2624345A1 (en) | 2013-08-07 |
JP5799710B2 (ja) | 2015-10-28 |
JP2012094505A (ja) | 2012-05-17 |
CN103140969B (zh) | 2016-03-23 |
EP2624345A4 (en) | 2015-10-07 |
KR101863386B1 (ko) | 2018-05-31 |
EP2624345B1 (en) | 2020-10-21 |
EP3758115A1 (en) | 2020-12-30 |
KR20130113439A (ko) | 2013-10-15 |
CN103140969A (zh) | 2013-06-05 |
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