WO2016136803A1 - Matériau actif pour électrode négative de batterie secondaire au lithium-ion, électrode négative de batterie secondaire l'utilisant, et batterie secondaire - Google Patents

Matériau actif pour électrode négative de batterie secondaire au lithium-ion, électrode négative de batterie secondaire l'utilisant, et batterie secondaire Download PDF

Info

Publication number
WO2016136803A1
WO2016136803A1 PCT/JP2016/055416 JP2016055416W WO2016136803A1 WO 2016136803 A1 WO2016136803 A1 WO 2016136803A1 JP 2016055416 W JP2016055416 W JP 2016055416W WO 2016136803 A1 WO2016136803 A1 WO 2016136803A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
active material
secondary battery
electrode active
ion secondary
Prior art date
Application number
PCT/JP2016/055416
Other languages
English (en)
Japanese (ja)
Inventor
和徳 小関
和樹 田川
Original Assignee
新日鉄住金化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 新日鉄住金化学株式会社 filed Critical 新日鉄住金化学株式会社
Publication of WO2016136803A1 publication Critical patent/WO2016136803A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • 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 an active material for a negative electrode of a lithium ion secondary battery capable of obtaining a lithium ion secondary battery having high energy density and high efficiency and excellent metal lithium precipitation resistance, a lithium ion secondary battery negative electrode using the same, and
  • the present invention relates to a lithium ion secondary battery.
  • the lithium ion secondary battery obtained by the present invention can be applied to a wide range of uses such as a vehicle for hybrid vehicles and plug-in hybrid vehicles, and a stationary storage battery such as solar power generation and wind power generation.
  • lithium ion secondary batteries utilize the excellent features such as high operating potential, large battery capacity, long cycle life, and low environmental pollution. It is widely used in place of batteries and nickel metal hydride batteries.
  • Lithium-ion secondary batteries are mainly used for power sources for small portable electronic devices such as laptop computers and smartphones.
  • electric vehicles, motors, and gasoline engines have been used to address energy and environmental issues.
  • It is also widely used as a power source for hybrid electric vehicles and plug-in hybrid electric vehicles.
  • generators whose output fluctuates, such as solar power generation and wind power generation, to reduce fluctuation absorption or to control output to be constant, or to reduce fluctuations and peaks on the demand side
  • generators whose output fluctuates, such as solar power generation and wind power generation, to reduce fluctuation absorption or to control output to be constant, or to reduce fluctuations and peaks on the demand side
  • the use as a stationary storage battery for the purpose of shifting has attracted attention, and it is expected that the required characteristics will become higher with the increasing demand in various applications related to these energy environmental problems.
  • Examples of the negative electrode active material constituting the negative electrode of the lithium ion secondary battery include carbon materials such as graphite, lithium titanate, silicon, and tin. Carbon materials are generally used from the viewpoint of safety and life. It has been. Among carbon materials, graphite material is an excellent material with high energy density, so it is not only used as a power source for small portable electronic devices but also as a power source for stationary electric batteries and plug-in hybrid electric vehicles, as a stationary storage battery. As a negative electrode active material for lithium-ion secondary batteries, research and development are progressing.
  • Non-Patent Document 1 in order to guarantee the performance in a low temperature environment, as shown in Non-Patent Document 1, by using non-graphitizable carbon (hard carbon) or graphitizable carbon (soft carbon), the output characteristics at low temperature and It has been proposed to obtain a battery with high resistance to metallic lithium deposition.
  • hard carbon or soft carbon alone has a problem that energy density and efficiency are greatly reduced as compared with graphite.
  • Patent Document 1 it has been proposed to suppress precipitation of metallic lithium by using lithium titanate having a different reaction starting voltage in addition to graphite as a negative electrode active material.
  • a negative electrode active material having a low battery voltage such as lithium titanate significantly reduces the voltage of the entire battery, resulting in a problem that the amount of electricity (Wh) per cell is reduced.
  • Patent Document 2 proposes using graphite and amorphous carbon as a negative electrode active material to improve output characteristics at low temperatures.
  • safety at low temperatures that is, lithium metal on the negative electrode is proposed.
  • No consideration is given to precipitation resistance.
  • lithium iron phosphate is used for the positive electrode, there is a problem that the voltage of the whole battery is lowered.
  • Patent Document 3 proposes improving the resistance to metal lithium deposition by using graphite and amorphous carbon as a negative electrode active material and forming a film containing sulfur and nitrogen on the negative electrode surface.
  • this method has a problem that the composition of the electrolytic solution is limited and the initial efficiency is lowered due to the reaction at the time of film formation.
  • JP 2010-20912 A Japanese Patent No. 5,504,853 Japanese Patent No. 5167713
  • the present invention is not only high in energy density and efficiency as a secondary battery, regardless of positive electrode type and electrolyte composition, but also, for example, instantaneous DC resistance (DCR) at low temperatures and plug-in hybrids required for hybrid vehicles.
  • An object of the present invention is to provide a lithium ion secondary battery that is excellent in the charge capacity maintenance rate required for automobiles, and that is also safe at low temperatures, that is, excellent in lithium metal deposition resistance.
  • the present inventors have mixed a specific graphite particle and a specific low crystalline carbon particle, thereby achieving high energy density and efficiency as a lithium ion secondary battery. It has been found that the direct current resistance (DCR) at the moment of charging can be lowered even in a low temperature environment below the freezing point, and the metal lithium deposition resistance can be greatly improved, while having an excellent charge capacity maintenance rate. It came to do.
  • DCR direct current resistance
  • the present invention is a negative electrode active material used for a negative electrode of a lithium ion secondary battery, and a low crystalline carbon particle having an (002) plane interlayer distance (d002) of 0.340 nm or more measured by an X-ray diffractometer And graphite particles are mixed in a mass ratio of 40:60 to 10:90, and a direct current resistance during charging at a charge rate of 60% at 23 ° C. of a lithium ion secondary battery using the negative electrode active material as a negative electrode ( DCR 23 ° C. ) and DC resistance ratio (DCR ⁇ 20 ° C./DCR 23 ° C. ) of DC resistance (DCR ⁇ 20 ° C. ) during charging at ⁇ 20 ° C.
  • 60% charge rate is 6.0 or less.
  • It is a negative electrode active material for a lithium ion secondary battery.
  • low-crystalline carbon particles having an elliptical equivalent length-to-short ratio average of 0.20 to 0.31 of the particle cross section observed by a scanning electron microscope (SEM), and an elliptical equivalent length-to-short ratio average of the particle cross section of 0.37.
  • the negative electrode active material for a lithium ion secondary battery is obtained by mixing the above graphite particles at a mass ratio of 40:60 to 5:95.
  • the present invention is a negative electrode using the negative electrode active material, and a lithium ion secondary battery using the negative electrode.
  • the graphite particles are spheroidized natural graphite particles obtained by spheroidizing a plurality of scaly natural graphites.
  • the negative electrode active material for a lithium ion secondary battery is preferably a material in which the low crystalline carbon particles are made from coal or petroleum raw coke, and in particular, calcined by calcining the raw coke at 800 to 1500 ° C.
  • One or more selected from coke, or raw coke or calcined coke fired at 900 to 1500 ° C. can be used.
  • Another embodiment of the present invention is a negative electrode for a lithium ion secondary battery in which a negative electrode active material layer formed by mixing the negative electrode active material for a lithium ion secondary battery and a binder is formed on a current collector. .
  • the arithmetic average roughness (Ra) of the surface of the negative electrode active material layer is more preferably 6.5 ⁇ m or less.
  • the other aspect of this invention is a lithium ion secondary battery using the said negative electrode.
  • a negative electrode formed by forming a negative electrode active material layer formed by mixing the negative electrode active material for a lithium ion secondary battery and a binder is opposed to the positive electrode through a separator, and the initial capacity of the negative electrode Lithium ion secondary configured so that the initial capacity ratio (N / P) of N (mAh / cm 2 ) and the initial capacity P (mAh / cm 2 ) of the positive electrode is 1.0 to 1.5 It is a battery.
  • the energy density and efficiency of a lithium ion secondary battery can be increased, the direct current resistance (DCR) during instantaneous charging required for a hybrid vehicle can be lowered at low temperatures, and the plug It is possible to provide a lithium ion secondary battery that is excellent in charge capacity maintenance rate required for an in-hybrid vehicle and that is excellent in safety at low temperatures, that is, excellent in lithium metal deposition resistance. That is, according to the present invention, while having a high energy density and efficiency, and an excellent charge capacity maintenance rate, the direct current resistance (DCR) at the time of charging is low even in a low temperature environment below the freezing point, and the metal lithium deposition resistance is also high. Therefore, a lithium ion secondary battery excellent in safety can be obtained even when used in an environment below freezing point.
  • the graphite particles (A) used in the present invention are preferably graphite having a true specific gravity of 2.23 g / cm 3 or more and high crystallinity.
  • the true specific gravity indicates the development of the crystal structure of the carbon material. Generally, the more the crystal structure is developed, the higher the capacitance density per weight. Therefore, it is preferable true specific gravity of 2.23 g / cm 3 or more, preferably to 2.23 ⁇ 2.24g / cm 3.
  • the upper limit of 2.24 g / cm 3 is the theoretical true specific gravity of graphite. Spherical, flaky, fibrous, and irregularly shaped particles can be appropriately selected and used.
  • the spherical shape is preferred, and the elliptical equivalent length ratio of the particle cross section observed with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • graphite particles having an average of 0.37 or more, preferably 0.37 to 1.00 are used.
  • the graphite particles that give the true specific gravity include artificial graphite and natural graphite, but natural graphite is more preferable from the viewpoint of low cost and ease of electrode production.
  • the graphite particles preferably have few impurities, and are used after being subjected to various purification treatments as necessary.
  • Examples of natural graphite include scaly graphite, scaly graphite, and soil graphite.
  • the production area of scaly graphite is mainly Sri Lanka, the production area of scaly graphite is mainly Madagascar, China, Brazil, Ukraine, Canada, etc., and the main production area of soil graphite is the Korean Peninsula, China, Mexico, etc. is there.
  • soil graphite generally has a small particle size and low purity.
  • scaly graphite and scaly graphite have advantages such as a high degree of graphitization and a low amount of impurities, and therefore can be preferably used in the present invention. More specifically, it is spheroidized natural graphite obtained by subjecting highly purified scale-like natural graphite to spheroidization treatment.
  • the spheroidized graphite particles preferably have an average ellipse equivalent length ratio of 0.37 or more when the cross-sectional shape of the particles is observed with a scanning microscope (SEM), and such spheroidized natural graphite is obtained.
  • Examples of the method include a method of mixing scaly graphite in the presence of a binder of a graphite raw material, a method of applying mechanical external force to scaly graphite, and a method of using the above two methods in combination.
  • a method of granulating by applying a mechanical external force without using a binder component is particularly preferable.
  • a counter jet mill AFG manufactured by Hosokawa Micron Corporation, registered trademark
  • a current jet manufactured by Nissin Engineering Co., Ltd., registered trademark
  • an ACM pulverizer manufactured by Hosokawa Micron Corporation, A pulverizer such as a registered trademark
  • a pin mill a hybridization system (registered trademark, manufactured by Nara Machinery Co., Ltd.), a mechano hybrid (registered trademark, manufactured by Nippon Coke Industries, Ltd.), and the like can be used.
  • artificial graphite for example, coal tar pitch, coal heavy oil, atmospheric residue, petroleum heavy oil, aromatic hydrocarbon, nitrogen-containing cyclic compound, sulfur-containing cyclic compound, polyphenylene, polyvinyl chloride, polyvinyl
  • organic substances such as alcohol, polyacrylonitrile, polyvinyl butyral, natural polymer, polyphenylene sulfide, polyphenylene oxide, furfuryl alcohol resin, phenol-formaldehyde resin, and imide resin.
  • the firing temperature at the time of graphitization for obtaining artificial graphite can be in the range of 2500 ° C. or more and 3200 ° C. or less, and a silicon-containing compound or a boron-containing compound can be used as a graphitization catalyst at the time of firing. it can.
  • a shape control process such as granulation, a process of modifying and coating the surface with different organic and inorganic components, or a process of forming different metal components uniformly or dispersed on the surface are added. May be.
  • the graphite particles preferably have a BET specific surface area of 2.0 to 6.0 m 2 / g. This BET specific surface area is determined by the shape of the graphite particles and the properties of the surface coat layer. When the BET specific surface area is smaller than 2.0 m 2 / g, the charge / discharge rate of lithium ions is slowed. When the BET specific surface area is larger than 6.0 m 2 / g, the tap density is not increased and the electrode density is not sufficiently increased. Since the BET specific surface area affects the speed of surface reaction when lithium ions enter and exit the carbon structure, it is important to control the BET specific surface area to an appropriate value.
  • the graphite particles have been subjected to a specific surface area reduction treatment by spheroidizing treatment, and in addition to the spheroidizing treatment, the specific surface area is adjusted to an appropriate numerical value by pitch or CVD treatment. You may control.
  • the graphite particles preferably have a D50 of 5 to 20 ⁇ m.
  • D50 of the graphite particles is less than 5 ⁇ m, the BET specific surface area is excessively increased and the initial efficiency of the obtained secondary battery is lowered.
  • D50 exceeds 20 ⁇ m it becomes difficult to obtain an electrode having a uniform and smooth surface property at the time of electrode preparation due to the presence of coarse powder.
  • the smoothness of the electrode surface is lowered, there is a concern that the separator side may be damaged and coarse particles may be powdered off.
  • the low crystalline carbon particles (B) used in the present invention have an (002) plane interlayer distance (d002) of 0.340 nm or more as measured with an X-ray diffractometer and are observed with a scanning electron microscope (SEM).
  • the elliptical equivalent major axis / minor axis ratio of the particle cross section is 0.20 to 0.31.
  • the true specific gravity is 2.00 to 2.16 g / cm 3
  • the interlayer distance (d002) 0.340 to 0.350 nm
  • the ellipse equivalent length / short ratio average is 0.21 to 0.25.
  • the BET specific surface area is 1 to 10 m 2 / g and the average particle diameter D50 is 5 to 20 ⁇ m.
  • the low crystalline carbon particles (B) having such characteristics include coal-based raw coke, petroleum-based raw coke, coal-based calcined coke, or petroleum-based calcined coke, alone or mixed, Is preferably obtained by firing them as necessary.
  • Coal-based and petroleum-based include those obtained from a mixture of coal-based and petroleum-based oils.
  • the efficiency and discharge capacity of the lithium ion secondary battery can be made excellent, and as a result, side reactions during charging and discharging can be suppressed. it can.
  • the average elliptical length / short ratio ratio of the low crystalline carbon particles exceeds 0.31, irregularities on the surface of the active material layer of the formed negative electrode are increased, and current concentration is likely to be induced from the convex portions to easily induce precipitation of metallic lithium. End up.
  • the ellipse length / short ratio average is less than 0.20, the number of particles having an active material length exceeding the electrode thickness increases, which may hinder the diffusion of the electrolytic solution, or when the particles are not oriented in the electrode. Large protrusions, which may cause breakage of the separator and short circuit with the positive electrode.
  • a method for obtaining suitable low crystalline carbon particles will be described in detail.
  • heavy oil such as petroleum-based or coal-based is used, for example, using a coking facility such as a delayed coker, and the maximum temperature reached 400 ° C. to 700 ° C.
  • Coal-based raw coke is obtained by carrying out the thermal decomposition and polycondensation reaction for about 24 hours at a certain temperature. Note that coal-based and petroleum-based are collectively referred to as coal-based.
  • the heavy oil used here may be a petroleum heavy oil or a coal heavy oil, but the coal heavy oil is richer in aromatic properties and sulfur (S). Since heavy impurities such as vanadium (V) and iron (Fe) are small and the volatile content is small, heavy coal oil is preferable.
  • the obtained coal-based raw coke is pulverized to a predetermined size, for example, 5 ⁇ m to 15 ⁇ m as necessary.
  • An industrially used pulverizer can be used for the pulverization.
  • the coal-based raw coke is calcined at a maximum temperature of 800 ° C. to 1500 ° C. in a low oxygen atmosphere to produce coal-based calcined coke.
  • the calcination temperature is preferably in the range of 900 ° C to 1500 ° C, more preferably 1000 ° C to 1400 ° C.
  • the calcination treatment removes moisture and volatile components from the raw coke and converts hydrocarbons remaining as polymer components into coke to promote crystal growth.
  • equipment such as reed hammer furnace, shuttle furnace, tunnel furnace, rotary kiln, roller hearth kiln or microwave capable of mass heat treatment can be used, but it is particularly limited to these is not.
  • These heat treatment facilities may be either a continuous type or a batch type.
  • the obtained coal-based calcined coke lump is pulverized to a predetermined size, for example, 5 to 15 ⁇ m, using a pulverizer such as an atomizer used industrially in the same manner as described above.
  • the pulverized coke powder is preferably sized to a predetermined particle size by cutting fine powder by classification or removing coarse powder with a sieve or the like.
  • the low crystalline carbon particles (B) used in the present invention may be calcined coke such as the above-mentioned coal-based, but either raw coke such as the above-mentioned coal-based, or calcined coke such as coal-based alone, Or it is preferable that it is the baking coke obtained by baking by mixing both.
  • the calcining treatment is carried out for raw coke and calcined coke to further adjust the crystal state, and to control the surface and improve the surface.
  • Coke can produce anisotropy in particle fracture properties depending on its crystalline state, so by adjusting the crystalline state by firing, it is possible to obtain low crystalline carbon particles with the desired elliptical length-short ratio average It becomes.
  • a phosphorus compound or boron compound may be added to prepare the crystallization of the carbon material, or a plurality of firing treatments may be performed. Also, in the firing process, one or more steps such as a shape control step such as granulation, a step of modifying and coating the surface with different organic and inorganic components, or a step of forming different metal components uniformly or dispersed on the surface It may be added.
  • the baking treatment of raw coke or calcined coke is preferably performed at 900 ° C. or higher and 1500 ° C. or lower at the highest temperature reached.
  • the temperature is preferably 950 ° C to 1450 ° C, more preferably 1000 to 1400 ° C.
  • the holding time at the highest temperature of the baking treatment is not particularly limited, but is preferably 30 minutes or more, and the baking atmosphere is preferably an inert gas atmosphere such as argon or nitrogen.
  • the same treatment as the calcination treatment can be performed, and in this case, only the calcination treatment may be performed.
  • the low crystalline carbon particles preferably have a BET specific surface area of 1.0 to 10.0 m 2 / g. More preferably, it is 2.0 to 10.0 m 2 / g.
  • This BET specific surface area is determined by the shape at the time of pulverization due to the crystal state of the carbon material and the particle size distribution after pulverization. Since the BET specific surface area affects the rate of surface reaction when lithium ions enter and exit the carbon structure, the charge / discharge rate of lithium ions and the electrode density are improved by making the BET specific surface area within the above range. be able to.
  • the low crystalline carbon particles preferably have an ash content of 0.1% or less in the low crystalline carbon particles.
  • the battery is charged or discharged or left in the presence of ash, that is, impurities, particularly metal particles or metal compound particles, in the battery material.
  • metal ions are eluted into the electrolyte, and the eluted metal ions are deposited on the negative electrode and grow in a dendrite shape, causing a short circuit between the positive and negative electrodes, resulting in a voltage drop. For this reason, it is preferable to control ash to an appropriate value.
  • the negative electrode active material for a lithium ion secondary battery of the present invention comprises a mixture containing graphite particles (A) and low crystalline carbon particles (B), and the mixture as a whole has a BET specific surface area of 3 to 6 m 2 / g.
  • the average particle diameter D50 is preferably in the range of 5 to 15 ⁇ m.
  • the negative electrode active material for a lithium ion secondary battery of the present invention is a mixture of graphite particles (A) and low crystalline carbon particles (B), but the average particle diameter as a mixture of the particles (A) and (B).
  • D50 is in the above range, the dispersibility when slurried is good, and in particular, the effect of improving input / output characteristics at low temperatures can be sufficiently obtained.
  • the (002) plane interlayer distance (d002) calculated from any one of the diffraction peaks is in the range of 0.340 to 0.350 nm. If the interlayer distance (d002) is in the above range, it is advantageous in terms of quick chargeability. The reason why a plurality of diffraction peaks appear indicates that there are a plurality of carbon crystal structures. If the interlayer distance (d002) calculated from at least one of the diffraction peaks satisfies this range, it can be rapidly charged as a negative electrode active material. Is secured.
  • the mixture as a whole has a tap density of 0.5 g / cc or more, preferably 0.5 to 1.2 g / cc.
  • the tap density affects the contact between particles at the time of electrode production and also affects the deformation of the particles due to the press pressure. If the range is as described above, ensuring the conductive path and battery performance is good. be able to. Therefore, in order to increase the packing density before pressing, it is preferable to set the tap density as an index to 0.5 g / cc.
  • the ratio of fine particles having an average particle diameter D10 of a mixture of graphite particles (A) and low crystalline carbon particles (B) of less than 1 ⁇ m is increased, or the ratio of coarse particles in the vicinity of D90
  • the surface area of the powder may increase, and the uniformity and performance of the electrode may be disturbed due to the influence of coarse particles, leading to a decrease in battery performance. It is not necessary to exceed 1.2 g / cc.
  • the tap density of the powder can be measured using a Tap Denser KYT-400 (manufactured by Seishin Enterprise Co., Ltd.) with a cylinder volume of 100 cc, a tapping distance of 38 mm, and a tap count of 300.
  • a Tap Denser KYT-400 manufactured by Seishin Enterprise Co., Ltd.
  • the blending amount of the graphite particles (A) and the low crystalline carbon particles (B) is preferably in the range of 95 to 60% by mass of the graphite particles (A) and 5 to 40% by mass of the low crystalline carbon particles (B). . That is, the mass ratio of (A) :( B) is 60:40 to 95: 5, preferably 80:20 to 95: 5.
  • the blending amount of (B) is too small, the effect of blending the low crystalline carbon particles becomes insufficient, the direct current resistance (DCR) at the time of charging cannot be lowered sufficiently, and when it is excessive, the negative electrode active material The electric capacity density per weight will decrease.
  • the negative electrode active material according to the present invention when used, the negative electrode mixed with the binder to form the negative electrode active material layer on the current collector is compared with the case where a negative electrode active material made of a conventional carbon material is used.
  • the instantaneous DC resistance at low temperatures can be reduced.
  • the negative electrode active material according to the present invention includes a necessary amount of low crystalline carbon having a wide carbon interlayer distance, so that lithium ions can be smoothly inserted and desorbed. It is not affected by the type of positive electrode or the composition of the electrolyte when the battery is constructed. Therefore, the lithium ion secondary battery using the negative electrode active material of the present invention as a negative electrode has a direct current resistance (DCR 23 ° C.
  • the DC resistance ratio (DCR ⁇ 20 ° C./DCR 23 ° C. ) to the resistance (DCR ⁇ 20 ° C. ) can be 6.0 or less.
  • the direct current resistance ratio (DCR ⁇ 20 ° C./DCR 23 ° C. ) during charging exceeds 6.0, lithium ions are not smoothly inserted between the carbon crystal layers of the negative electrode active material.
  • Metal lithium is deposited on the electrode. The deposited metallic lithium breaks through the separator and causes a micro short circuit with the positive electrode, and heat is generated by the current concentrated in the short circuit part.
  • the method for measuring the direct current resistance ratio (DCR ⁇ 20 ° C./DCR 23 ° C. ) during charging depends on the conditions described later. Usually, the DC resistance ratio increases (DCR ⁇ 20 ° C./DCR 23 ° C. ) because the DC resistance increases as the temperature decreases.
  • This invention is also a negative electrode for lithium ion secondary batteries using the said negative electrode active material for lithium ion secondary batteries, and a negative electrode is for said lithium ion secondary batteries on a collector (generally copper foil).
  • a negative electrode active material layer formed by mixing a negative electrode active material and a binder is formed.
  • a water-soluble binder such as fluorine resin powder such as polyvinylidene fluoride or polyimide (PI) resin, styrene butadiene rubber, carboxymethyl cellulose is generally used.
  • fluorine resin powder such as polyvinylidene fluoride or polyimide (PI) resin, styrene butadiene rubber, carboxymethyl cellulose is generally used.
  • the negative electrode active material layer is formed on the current collector by preparing a slurry using the above-described negative electrode active material and binder using a solvent, and applying and drying the slurry on a current collector (generally a copper foil). Then, it can carry out by pressing on arbitrary conditions.
  • the solvent used is not particularly limited, and N-methylpyrrolidone (NMP), dimethylformamide, water, alcohol, or the like is used.
  • the negative electrode active material and the binder are kneaded at a mass ratio of 93: 7 to 99: 2 (negative electrode active material: binder), and this slurry is applied onto a copper foil having a predetermined thickness.
  • the solvent is dried under a drying condition of ⁇ 150 ° C., and then pressed at a linear pressure of 100 to 600 kg / cm to form a negative electrode.
  • the volume density is 1.20 to 1.45 g / cm.
  • An electrode in the range of 3 is obtained.
  • the surface roughness (Ra: arithmetic average roughness) of the active material layer of the negative electrode is preferably 6.5 ⁇ m or less, and more preferably 6.0 ⁇ m or less.
  • the surface roughness (Ra) is an arithmetic average roughness and is defined in JIS B 0601-2001.
  • a current collector obtained by slurrying a positive electrode active material, a binder, a conductive material and the like with an organic solvent or water, as in a normal secondary battery. It is used after being applied to and dried to form a sheet.
  • the positive electrode active material contains a transition metal and lithium and is preferably a material containing one kind of transition metal and lithium. Examples thereof include a lithium transition metal composite oxide and a lithium-containing transition metal phosphate compound. These may be used in combination.
  • the transition metal of the lithium transition metal composite oxide vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper and the like are preferable.
  • lithium transition metal composite oxide examples include lithium cobalt composite oxide such as LiCoO 2 , lithium nickel composite oxide such as LiNiO 2 , and lithium manganese composite oxide such as LiMnO 2 , LiMn 2 O 4 , and Li 2 MnO 3.
  • lithium cobalt composite oxide such as LiCoO 2
  • lithium nickel composite oxide such as LiNiO 2
  • lithium manganese composite oxide such as LiMnO 2 , LiMn 2 O 4 , and Li 2 MnO 3.
  • Some of the transition metal atoms that are the main components of these lithium transition metal composite oxides are aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, magnesium, gallium, zirconium, etc. The thing substituted with the metal etc. are mentioned.
  • substituted ones include, for example, LiNi 0.5 Mn 0.5 O 2 , LiNi 0.80 Co 0.17 Al 0.03 O 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiMn 1.8 Al 0.2 O 4 , LiMn 1.5 Ni 0.5 O 4 or the like.
  • transition metal of the lithium-containing transition metal phosphate compound vanadium, titanium, manganese, iron, cobalt, nickel and the like are preferable.
  • iron phosphates such as LiFePO 4 , LiCoPO 4 and the like.
  • Cobalt phosphates some of the transition metal atoms that are the main components of these lithium transition metal phosphate compounds are aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, magnesium, gallium, zirconium And those substituted with other metals such as niobium.
  • the binder for the positive electrode and the solvent for forming the slurry may be the same as those used for the negative electrode.
  • the amount of the binder used for the positive electrode is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and most preferably 0.02 to 8 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • the amount of the solvent used for the positive electrode is preferably 30 to 300 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • Examples of the conductive material for the positive electrode include graphite fine particles, carbon black such as acetylene black and ketjen black, amorphous carbon fine particles such as needle coke, and carbon nanofibers, but are not limited thereto.
  • the amount of the conductive material used for the positive electrode is preferably 0.01 to 20 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • As the current collector for the positive electrode aluminum, stainless steel, nickel-plated steel or the like is usually used.
  • the lithium ion secondary battery (E) of the present invention can be obtained by using the negative electrode and the positive electrode thus manufactured.
  • the lithium ion secondary battery of this invention is arrange
  • the initial capacity ratio (N / P) of the initial capacity N (mAh / cm 2 ) of the negative electrode and the initial capacity P (mAh / cm 2 ) of the positive electrode is preferably 1.0 to 1.5, preferably 1.0 to 1 .2 is most preferred.
  • a lithium ion secondary battery is equipped with a larger number of negative electrodes for receiving lithium than positive electrodes having lithium. That is, a negative electrode having a larger amount of negative electrode active material than that of the positive electrode is used. This is a measure for preventing lithium metal from being deposited on the electrode because the negative electrode cannot accept lithium ions during low-temperature charging.
  • N / P exceeds 1.5 and the negative electrode is mounted too much, the thickness of the negative electrode increases, and the output and input characteristics of the electrode itself deteriorate, or the negative electrode is excessively mounted. There is a problem that the cost increases due to the decrease in the volume capacity density.
  • the amount of excessive loading of the negative electrode is too small, the negative electrode may be less than the positive electrode as the effective capacity when it deteriorates in various environments, and metal lithium may be deposited on the negative electrode during charging. It is desirable that / P is 1.2 or more.
  • the negative electrode active material for the lithium ion secondary battery by using the negative electrode active material for the lithium ion secondary battery, the output and input characteristics of the negative electrode itself are improved. Therefore, the initial capacity ratio of the negative electrode to the positive electrode is a minimum of 1.0 to 1.5.
  • a lithium ion secondary battery can be configured with a limit amount of negative electrode mounted.
  • electrolyte solution containing an electrolyte and a non-aqueous electrolyte solution.
  • electrolyte conventionally known electrolytes can be used.
  • the group consisting of LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 , LiC (CF 3 SO 2 ) 3 , LiCF 3 SO 3 derivatives and LiC (CF 3 SO 2 ) 3 derivatives is preferable to use at least one selected from the group consisting of excellent electrical characteristics.
  • non-aqueous electrolyte examples include propylene carbonate, ethylene carbonate, butylene carbonate, chloroethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,1-dimethoxyethane, 1,2-dimethoxyethane, 1, 2-diethoxyethane, ⁇ -butyrolactan, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, anisole, diethyl ether, sulfolane, methylsulfolane, acetonitrile, chloronitrile, propio Nitrile, trimethyl borate, tetramethyl silicate, nitromethane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, trimethyl orthoformate, nitrobenzene Benzoyl chloride, benzoyl bromide, te
  • a separation membrane (separator) between the positive electrode and the negative electrode.
  • a separation membrane a commonly used polymer microporous film is used without any particular limitation. it can.
  • the film include polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polyacrylamide, polytetrafluoroethylene, polysulfone, polyethersulfone, polycarbonate, polyamide, polyimide, polyethylene oxide and polypropylene oxide.
  • the microporosity method includes a phase separation method in which a polymer compound and a solvent solution are formed into a film while microphase separation is performed, and the solvent is extracted and removed to make it porous.
  • the film is extruded and then heat treated, the crystals are arranged in one direction, and a “stretching method” or the like is performed by forming a gap between the crystals by stretching, and is appropriately selected depending on the film used.
  • the shape of the lithium ion secondary battery of the present invention is not particularly limited, and can be various shapes such as a coin shape, a cylindrical shape, and a square shape.
  • lithium ion secondary batteries were produced according to the following production procedure.
  • Examples 1 to 4 and Comparative Examples 1 to 3 As the graphite particles (A), spheroidized natural graphite having an elliptical equivalent length-average ratio of 0.38 in the particle cross section is used, and the coal-based raw coke is pulverized as the low crystalline carbon particles (B). Using the low crystalline carbon particles (B) obtained by firing in a nitrogen gas atmosphere at the temperature of Table 1 at ° C., the compounding ratio (mass ratio) shown in Table 1 is used, and the negative electrode active material (C1 To 6) were prepared.
  • the low-carbon carbon particles (B) obtained by calcination and pulverization of coal-based raw coke as it is without pulverization are blended at the blending ratio shown in Table 1, and the negative electrode An active material (C7) was prepared.
  • the low crystalline carbon particles (B) those having the properties described in Table 1 are used, and the properties of the graphite particles (A) are a true specific gravity of 2.23 m 3 / g and an average particle diameter (D50). 17.4 ⁇ m, BET specific surface area of 4.0 m 2 / g.
  • graphite particles (A) are repeatedly supplied to a pin mill manufactured by Lecce, which is set at a rotor rotational speed of 20000 rpm at a rate of 200 g / min. Thus, spherical processing is performed to obtain the above-described ellipse equivalent length / short ratio average value (0.38).
  • each of the negative electrode active materials C1 to C7 94.5 parts by mass of each of the negative electrode active materials C1 to C7, 1.0 part by weight of acetylene black as a conductive material, 2.0 parts by mass of styrene butadiene rubber as a binder, and 1.5 parts by mass of carboxymethyl cellulose as a thickener
  • the mixture was mixed and dispersed in 50 parts by mass of water to form a slurry.
  • This slurry was applied to a copper negative electrode current collector, dried, and press molded to form a negative electrode active material layer. Thereafter, the negative electrode was cut into a predetermined size to produce a negative electrode.
  • LiPF 6 was dissolved at a concentration of 1 mol / L in a mixed solvent consisting of 30% by volume of ethylene carbonate, 40% by volume of ethyl methyl carbonate, and 30% by volume of dimethyl carbonate to prepare an electrolyte solution.
  • the obtained negative electrode and positive electrode were held in an aluminum pack with a 25 ⁇ m-thick polypropylene microporous film (separation membrane) sandwiched between them. Thereafter, the non-aqueous electrolyte adjusted as described above was poured into the aluminum pack, the pack was sealed and sealed, and the lithium ion secondary batteries of Examples 1 to 4 and Comparative Examples 1 to 3 shown in Table 2 were obtained. Produced.
  • the true specific gravity was measured by a liquid phase replacement method (also known as a pycnometer method). Specifically, the powder of the negative electrode active material is put into a pycnometer, a solvent liquid such as distilled water is added, and the air and the solvent liquid on the powder surface are replaced by a method such as vacuum degassing to obtain an accurate powder weight and volume. The true specific gravity value was calculated.
  • the ellipse-equivalent length / short ratio average was obtained by preparing a cross section of the electrode by the CP (Cross-section Polisher) method and observing it at a magnification of 500 times using a scanning electron microscope (FE-SEM, manufactured by S4700 Hitachi High-Tech). The number of observed particles was 300 or more. The measurement of the ellipse-equivalent length-to-short ratio of the particles was analyzed using image analysis software (WinRooF: manufactured by Mitani Corporation), and the average value was calculated. In addition, even after electrode formation, (A) graphite particles and (B) low crystalline carbon particles can be specified, and the ellipse equivalent length / short ratio average of each particle can be measured.
  • the arithmetic average roughness (Ra) of the electrode surface (the surface of the negative electrode active material layer) was observed at a magnification of 500 times using a scanning electron microscope (FE-SEM S4700 manufactured by Hitachi High-Tech).
  • the line analysis range on the electrode surface was 500 ⁇ m or more.
  • the average height of the electrodes was analyzed using image analysis software (WinRooF: manufactured by Mitani Corporation), and the arithmetic average roughness was calculated.
  • the BET specific surface area was calculated according to the BET method by measuring the nitrogen adsorption by a multipoint method using BELSORP-mini II (manufactured by Nippon Bell Co., Ltd.) after vacuum drying the particles at 200 ° C. for 3 hours.
  • the average particle diameter (D50) was measured using an apparatus LA-920 (manufactured by HORIBA), and the dispersion medium was water + activator. As a reference for the abundance ratio of particles, the particle diameter was measured on a volume basis by the laser diffraction / scattering method, and the cumulative 50% particle diameter was defined as the average particle diameter (D50).
  • the interlayer distance (d002) of (002) plane is Rigaku's X-ray diffractometer model RINT-TTRIII, X-ray tube: CuK ⁇ , tube current: 300 mA, tube voltage: 50 kV, and high-purity silicon as the standard material Measured by the Gakushin method.
  • the counter electrode was made of lithium metal, charged from 1.5 V to 0 V at a constant current of a current density of 30 mA / cm 2 , and then charged at a constant voltage for 90 minutes. Next, after resting for 30 minutes, the battery was discharged from 0 V to 1.5 V at a constant current of 30 mA / cm 2 , and the discharge capacity per active material weight at that time was determined.
  • the initial capacity ratio N / P is a value obtained by measuring the charge capacity independently for each of the positive electrode and the negative electrode, and dividing the negative electrode charge capacity N (mAh) by the positive electrode charge capacity P (mAh).
  • the charge capacity P (mAh) of the positive electrode and the charge capacity N (mAh) of the negative electrode can be calculated as follows, for example. First, the charge capacity p (mAh / g) of the positive electrode active material and the charge capacity n (mAh / g) of the negative electrode active material are measured.
  • the charge capacity p (mAh / g) of the positive electrode active material is the charge capacity per weight of the active material when the counter electrode is made of lithium metal and charged from 2.5 V to 4.2 V at a constant current of 30 mA / cm 2. .
  • the charge capacity n (mAh / g) of the negative electrode active material is the weight of the active material when the counter electrode is lithium metal, charged from 1.5 V to 0 V at a constant current of 30 mA / cm 2 and a constant voltage charge for 90 minutes. Per charge capacity.
  • Capacity ratio N / P n (mAh / g) / p (mAh / g)
  • the ash content was measured according to JIS M8812: 2006 J coals and cokes-industrial analysis method.
  • DCR direct current resistance
  • the efficiency was lower than that of Comparative Example 1 using a negative electrode active material composed of graphite particles alone. Further, in Comparative Example 3, since the interlayer distance of the low crystalline carbon particles blended with the graphite particles is considerably smaller than 0.340 nm, the direct current resistance ratio (DCR ⁇ 20 ° C./DCR 23 ° C. ) during charging is 6.0 or more. As a result, metallic lithium was deposited on the negative electrode. On the other hand, in Examples 1 to 4, the direct current resistance ratio (DCR ⁇ 20 ° C./DCR 23 ° C.
  • the present invention provides an active material for a negative electrode of a lithium ion secondary battery that has high energy density and efficiency and is excellent in safety at a low temperature, a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery using the same.
  • Can be used in the automotive field such as hybrid vehicles and plug-in hybrid vehicles, as well as energy environment problems such as stationary storage batteries for peak shift purposes such as combined use with generators with variable output such as solar power generation and wind power generation. It can be used for various related purposes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne une batterie secondaire au lithium-ion qui présente non seulement une densité d'énergie et une efficacité élevées en tant que batterie secondaire, quel que soit le type d'électrode positive ou la composition de solution électrolytique, mais présente également une excellente résistance en courant continu (DCR) instantanée à basses températures qui est demandée par les véhicules hybrides, un excellent taux de maintien de capacité de charge qui est demandé par les véhicules hybrides rechargeables, et une excellente sécurité à basses températures. L'invention concerne un matériau actif d'électrode négative pour une batterie secondaire au lithium-ion dans lequel : des particules de carbone faiblement cristallines dont la distance intercouche (d002) est supérieure ou égale à 0,340 nm et dont le rapport de forme elliptique moyen d'une section transversale de particule observée avec un microscope électronique à balayage est de 0,20 à 0,31, et des particules de graphite dont le rapport de forme elliptique moyen d'une section transversale de particule est supérieur ou égal à 0,37 sont mélangées à un rapport massique allant de 40:60 à 5:95 ; et, dans une batterie secondaire au lithium-ion utilisant ce matériau actif d'électrode négative en tant qu'électrode négative, le rapport de résistance en courant continu (DCR-20 °C/DCR23 °C) entre la résistance en courant continu (DCR23 °C) lorsqu'elle est chargée à une intensité de charge de 60 % à 23 °C et la résistance en courant continu (DCR-20 °C) lorsqu'elle est chargée à une intensité de charge de 60 % à -20 °C est inférieur ou égal à 6,0.
PCT/JP2016/055416 2015-02-25 2016-02-24 Matériau actif pour électrode négative de batterie secondaire au lithium-ion, électrode négative de batterie secondaire l'utilisant, et batterie secondaire WO2016136803A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-035567 2015-02-25
JP2015035567 2015-02-25

Publications (1)

Publication Number Publication Date
WO2016136803A1 true WO2016136803A1 (fr) 2016-09-01

Family

ID=56788736

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/055416 WO2016136803A1 (fr) 2015-02-25 2016-02-24 Matériau actif pour électrode négative de batterie secondaire au lithium-ion, électrode négative de batterie secondaire l'utilisant, et batterie secondaire

Country Status (2)

Country Link
TW (1) TW201705594A (fr)
WO (1) WO2016136803A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109952672A (zh) * 2016-11-14 2019-06-28 日立化成株式会社 锂离子二次电池用负极材、锂离子二次电池用负极和锂离子二次电池
WO2020105598A1 (fr) * 2018-11-19 2020-05-28 昭和電工株式会社 Particules de carbone composites ainsi que procédé de fabrication de celles-ci, et batterie secondaire au lithium-ion
CN114079033A (zh) * 2020-08-11 2022-02-22 泰星能源解决方案有限公司 非水电解质二次电池

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11339806A (ja) * 1999-04-23 1999-12-10 Sharp Corp 電極及び電極の製造方法
JP2000226206A (ja) * 1999-02-04 2000-08-15 Kansai Coke & Chem Co Ltd 黒鉛粒子組成物およびそれを用いた塗布体の製造法
JP2011054371A (ja) * 2009-09-01 2011-03-17 Hitachi Vehicle Energy Ltd リチウムイオン二次電池
JP2012015051A (ja) * 2010-07-05 2012-01-19 Hitachi Vehicle Energy Ltd リチウムイオン二次電池、及びリチウムイオン二次電池用負極
JP2012084519A (ja) * 2010-09-16 2012-04-26 Mitsubishi Chemicals Corp 非水電解液二次電池用負極材及びこれを用いた負極並びに非水電解液二次電池
WO2012077176A1 (fr) * 2010-12-06 2012-06-14 トヨタ自動車株式会社 Accumulateur lithium ion et processus de fabrication d'un accumulateur lithium ion
WO2013051155A1 (fr) * 2011-10-07 2013-04-11 トヨタ自動車株式会社 Batterie secondaire au lithium-ion

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000226206A (ja) * 1999-02-04 2000-08-15 Kansai Coke & Chem Co Ltd 黒鉛粒子組成物およびそれを用いた塗布体の製造法
JPH11339806A (ja) * 1999-04-23 1999-12-10 Sharp Corp 電極及び電極の製造方法
JP2011054371A (ja) * 2009-09-01 2011-03-17 Hitachi Vehicle Energy Ltd リチウムイオン二次電池
JP2012015051A (ja) * 2010-07-05 2012-01-19 Hitachi Vehicle Energy Ltd リチウムイオン二次電池、及びリチウムイオン二次電池用負極
JP2012084519A (ja) * 2010-09-16 2012-04-26 Mitsubishi Chemicals Corp 非水電解液二次電池用負極材及びこれを用いた負極並びに非水電解液二次電池
WO2012077176A1 (fr) * 2010-12-06 2012-06-14 トヨタ自動車株式会社 Accumulateur lithium ion et processus de fabrication d'un accumulateur lithium ion
WO2013051155A1 (fr) * 2011-10-07 2013-04-11 トヨタ自動車株式会社 Batterie secondaire au lithium-ion

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109952672A (zh) * 2016-11-14 2019-06-28 日立化成株式会社 锂离子二次电池用负极材、锂离子二次电池用负极和锂离子二次电池
WO2020105598A1 (fr) * 2018-11-19 2020-05-28 昭和電工株式会社 Particules de carbone composites ainsi que procédé de fabrication de celles-ci, et batterie secondaire au lithium-ion
CN114079033A (zh) * 2020-08-11 2022-02-22 泰星能源解决方案有限公司 非水电解质二次电池
US11996543B2 (en) 2020-08-11 2024-05-28 Prime Planet Energy & Solutions, Inc. Nonaqueous electrolyte secondary battery including negative electrode active material layer with reasonable large tortuosity ratio

Also Published As

Publication number Publication date
TW201705594A (zh) 2017-02-01

Similar Documents

Publication Publication Date Title
JP6464252B2 (ja) 黒鉛２次粒子及びこれを含むリチウム二次電池
KR101930127B1 (ko) 리튬 2 차 전지 및 그것에 사용하는 비수계 전해액
CN107528053B (zh) 锂离子二次电池用负极材料、锂离子二次电池用负极以及锂离子二次电池
CN107210424B (zh) 锂离子二次电池用负极及锂离子二次电池
KR20170075661A (ko) 리튬 이차전지용 음극활물질 및 이를 포함하는 리튬 이차전지용 음극
KR20170002302A (ko) 리튬이온 이차전지용 부극 및 이차전지
KR20190062319A (ko) 음극 활물질, 이를 포함하는 음극 및 리튬 이차전지
JPWO2015152113A1 (ja) 黒鉛系負極活物質材料、負極及びリチウムイオン二次電池
CN113571772A (zh) 锂二次电池以及其中使用的非水电解液
CN115863618A (zh) 非水二次电池用负极材料、非水二次电池用负极及非水二次电池
KR20140128307A (ko) 비수계 2차 전지용 복층 구조 탄소재 및 이를 이용한 비수계 2차 전지용 음극 및 비수계 2차 전지
WO2012176873A1 (fr) Élément rechargeable au lithium
JP2015187926A (ja) リチウム二次電池
EP2876722B1 (fr) Batterie rechargeable au lithium
JP7334735B2 (ja) 非水系二次電池用負極材、非水系二次電池用負極及び非水系二次電池
JP2022550820A (ja) 球状化カーボン系負極活物質、その製造方法、それを含む負極、及びリチウム二次電池
JP2018006270A (ja) リチウムイオン二次電池負極用黒鉛質炭素材料、その製造方法、それを用いた負極又は電池
WO2016136226A1 (fr) Procédé de fabrication de batterie secondaire à l'électrolyte non aqueux
CN111656580B (zh) 锂二次电池用负极活性材料、包含其的负极以及包含所述负极的锂离子二次电池
WO2016136803A1 (fr) Matériau actif pour électrode négative de batterie secondaire au lithium-ion, électrode négative de batterie secondaire l'utilisant, et batterie secondaire
JP7009049B2 (ja) リチウムイオン二次電池負極用炭素材料、その中間体、その製造方法、及びそれを用いた負極又は電池
KR20150107674A (ko) 리튬이온 이차전지용 부극 활물질 및 그것을 사용한 리튬이온 이차전지 부극 및 리튬이온 이차전지
CN108878880B (zh) 非水二次电池用负极活性物质以及非水二次电池
WO2019186829A1 (fr) Matériau d'électrode négative de batterie secondaire au lithium-ion, procédé de production de matériau d'électrode négative de batterie secondaire au lithium-ion, suspension épaisse de matériau d'électrode négative de batterie secondaire au lithium-ion, électrode négative de batterie secondaire au lithium-ion et batterie secondaire au lithium-ion
JP2010267629A (ja) リチウム二次電池用負極及びリチウム二次電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16755547

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 16755547

Country of ref document: EP

Kind code of ref document: A1