+

WO2010058990A2 - Matériau actif d'électrode pour batterie rechargeable et son procédé de fabrication - Google Patents

Matériau actif d'électrode pour batterie rechargeable et son procédé de fabrication Download PDF

Info

Publication number
WO2010058990A2
WO2010058990A2 PCT/KR2009/006846 KR2009006846W WO2010058990A2 WO 2010058990 A2 WO2010058990 A2 WO 2010058990A2 KR 2009006846 W KR2009006846 W KR 2009006846W WO 2010058990 A2 WO2010058990 A2 WO 2010058990A2
Authority
WO
WIPO (PCT)
Prior art keywords
active material
electrode active
lithium
metal
oxide
Prior art date
Application number
PCT/KR2009/006846
Other languages
English (en)
Korean (ko)
Other versions
WO2010058990A3 (fr
Inventor
이용주
김제영
권오중
오병훈
엄인성
최승연
Original Assignee
주식회사 엘지화학
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 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2011537364A priority Critical patent/JP5558482B2/ja
Priority to CN200980155046.8A priority patent/CN102292854B/zh
Priority to EP09827755.1A priority patent/EP2360759B1/fr
Priority to US13/130,153 priority patent/US8546019B2/en
Publication of WO2010058990A2 publication Critical patent/WO2010058990A2/fr
Publication of WO2010058990A3 publication Critical patent/WO2010058990A3/fr

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G13/00Compounds of mercury
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00Compounds of gallium, indium or thallium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G17/00Compounds of germanium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00Compounds of bismuth
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00Compounds of antimony
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00Compounds of zinc
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/50Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • H01M6/5088Initial activation; predischarge; Stabilisation of initial voltage
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/40Electric properties
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the present invention relates to an electrode active material for a secondary battery and a secondary battery comprising the electrode active material.
  • Lithium secondary batteries are manufactured by using a material capable of inserting and detaching lithium ions as a positive electrode and a negative electrode, and filling an organic or polymer electrolyte between a positive electrode and a negative electrode, and when lithium ions are inserted and desorbed from a positive electrode and a negative electrode. Electrical energy is generated by oxidation and reduction.
  • metal Si, Sn, etc. which exhibit higher charge and discharge capacity than carbonaceous materials and which can be electrochemically alloyed with lithium, as an electrode active material.
  • a metal-based electrode active material has a severe change in volume associated with lithium charging and discharging, resulting in cracking and micronization. Therefore, the capacity of the secondary battery using the metal-based electrode active material decreases rapidly as the charge-discharge cycle progresses, and the cycle Life is shortened.
  • an electrode active material comprising a first particulate form of an oxide of a (semi) metal capable of alloying with lithium, and a second particulate form of an oxide containing a (semi) metal and lithium identical to the (semi) metal. Since lithium is already contained in the second particulate phase due to the reaction of lithium and the (qua) metal oxide in the preparation of the electrode active material, it is formed by the reaction of the lithium ion and the (qua) metal oxide during the initial charging of the battery. It was confirmed that irreversible phases such as lithium oxide or lithium metal oxide can be reduced.
  • the present invention is based on this.
  • the present invention is (a) a first particulate form of an oxide of a (semi) metal capable of alloying with lithium; And (b) an electrode active material comprising a second particulate form of an oxide containing the same (semi) metal and lithium as the (semi) metal at the same time, and a secondary battery comprising the electrode active material.
  • the present invention comprises the steps of chemically or mechanically mixing a lithium salt that does not contain oxygen, and an oxide of a (semi) metal capable of alloying with lithium; And it provides a method for producing the above-mentioned electrode active material comprising the step of heat-treating the mixture in an inert atmosphere.
  • the present invention comprises the steps of chemically or mechanically mixing a lithium salt that does not contain oxygen, and an oxide of a (semi) metal capable of alloying with lithium; And it provides a method for producing the above-mentioned electrode active material comprising the step of mechanical alloying (Mechanical Alloying) the mixture.
  • the electrode active material in addition to the first particulate form of the oxide of the first (semiconductor) metal capable of alloying with lithium, a second oxide composed of the same (semiconductor) metal and lithium as the (semiconductor) metal at the same time
  • a second oxide composed of the same (semiconductor) metal and lithium as the (semiconductor) metal at the same time
  • Example 1 is a scanning electron microscope (Scanning Electron Microscopy, SEM) photograph of the electrode active material prepared in Example 1.
  • FIG. 5 is a Si-Nuclear Magnetic Resonance (NMR) spectrum of the electrode active material of Example 1 of the present invention, the heat-treated SiO used in Comparative Example 2, and the unheated SiO used in Comparative Example 3.
  • FIG. 5 is a Si-Nuclear Magnetic Resonance (NMR) spectrum of the electrode active material of Example 1 of the present invention, the heat-treated SiO used in Comparative Example 2, and the unheated SiO used in Comparative Example 3.
  • Example 6 is a Li-NMR spectrum of the electrode active material of Example 1 of the present invention and LiCl of the control group 3.
  • Example 7 is an XRD graph of the electrode active material of Example 1 of the present invention and control group 2 (untreated SiO used in Comparative Example 3).
  • the present invention relates to an electrode active material for a secondary battery, comprising: a first particulate form of an oxide of a first (semi) metal capable of alloying with lithium, and a second particulate form of an oxide containing (semi) metal and lithium identical to the (semi) metal. Characterized in that it comprises a.
  • lithium oxide is caused by the reaction of lithium ions (Li + ) and (semi) metal oxides inserted into the cathode during initial charge and discharge of the battery. Or an irreversible phase such as lithium metal oxide is formed.
  • an electrode active material including a (quasi) metal oxide capable of alloying with lithium such as SiO, SnO, etc.
  • electrode active materials including metals such as Si and Sn cracks and micronization are less likely to occur due to volume change of the electrode active materials.
  • the initial efficiency of the battery is reduced because lithium is consumed due to the formation of lithium oxide or lithium metal oxide that is irreversible, thereby reducing the amount of lithium that can be actually used. Not only is it lowered, but the capacity of the battery is lowered.
  • the capacity of the battery is lowered.
  • the negative irreversible capacity of the negative electrode when the negative irreversible capacity of the negative electrode is large, a dead volume increase of the positive electrode side occurs through the irreversible negative electrode, so that the capacity of the actual positive electrode is less than that available in the positive electrode. The capacity is shown, which causes the capacity of the battery to decrease.
  • the low battery capacity and low charge and discharge efficiency in each cycle due to this dead volume the battery life characteristics are reduced.
  • metal lithium such as lithium foil or lithium powder
  • a (quasi) metal oxide in the manufacturing step of the electrode active material to suppress the dead volume of the positive electrode due to the irreversibility of the negative electrode
  • the metal lithium was applied to the surface of the (quasi) metal oxide electrode prepared in the manufacturing step to suppress the dead volume of the positive electrode due to the irreversibility of the negative electrode.
  • the electrode after applying the metal lithium to the surface of the electrode of the (qua) metal oxide, the electrode is manufactured by applying a predetermined pressure to the metal lithium and the electrode so that the metal lithium adheres well to the electrode surface, This electrode was used as the cathode to suppress the dead volume of the anode.
  • lithium ions (Li + ) detached from the positive electrode are inserted into the negative electrode during charging
  • lithium ions are also deposited in the metal lithium stacked on the negative electrode surface.
  • Desorbed, and the desorbed lithium ions are inserted into the cathode together with the desorbed lithium ions at the positive electrode to compensate for the lithium ions consumed due to the irreversible phase formed during the reaction of the lithium ions with the (qua) metal oxide, and the ratio of the negative electrode Minimization of dead volume of anode due to reversed phase was attempted.
  • the conventional electrode simply does not reduce the formation of an irreversible phase due to the reaction of lithium and the (qua) metal oxide during charging of the battery, since the metal lithium simply exists on the surface of the (qua) metal oxide electrode.
  • the electrode active material of the conventional electrode is composed only of the particulate form of the (semi) metal oxide, there is no particle shape containing both (semi) metal and lithium at the same time as the electrode active material of the present invention.
  • the electrode active material according to the present invention is an oxide containing the same (semi) metal and lithium as the (semi) metal simultaneously with the first particulate form of the (semi) metal (ex. Si, Sn, etc.). A second particulate form.
  • the electrode active material of the present invention contains lithium in the second particulate phase prior to the initial charge and discharge of the battery, lithium oxide or lithium due to the reaction of the lithium ion and the (quasi) metal oxide during the initial charge and discharge of the battery. Less irreversible phases, such as metal oxides, can be produced to improve the initial efficiency.
  • the secondary battery using the electrode active material according to the present invention may have a high capacity while having an initial efficiency of about 50% or more.
  • Examples of the (quasi) metal oxide on the first particle include an oxide of a metal or metal such as Si, Sn, Al, Sb, Bi, As, Ge, Pb, Zn, Cd, In, Ga, and the like.
  • the metal is not particularly limited as long as it is a metal or metal oxide that can be alloyed with the metal.
  • examples of the (partial) metal and the lithium-containing oxide on the second particles include Li 2 SiO, Li 2 SnO, Li 4 SiO 4 , Li 2 Si 2 O 5 , Li 6 Si 2 O 7 , Li 2 Si 3 O 7 , Li 8 SiO 6 , Li 2 SnO 3, Li 5 AlO 4 , LiAlO 2 , LiAl 5 O 8 , LiSbO 3 , LiSb 3 O 8 , Li 3 SbO 4 , Li 5 SbO 5 , Li 7 SbO 6 , LiSb 3 O 8 , Li 0.62 Bi 7.38 O 11.38 , LiBiO 2 , LiBiO 3 , Li 3 BiO 4 , Li 5 BiO 5 , Li 7 BiO 6 , LiBi 12 O 18.50 , LiAsO 3 , Li 3 AsO 4 , Li 4 As 2 O 7 , Li 2 GeO 5 , Li 2 Ge 4 O 9 , Li 2 Ge 7 O 15 , Li 2 GeO 3 , Li 2
  • the present invention is not limited thereto, and the lithium is not particularly limited as long as lithium is contained in the (quasi) metal oxide.
  • the lithium is not particularly limited as long as lithium is contained in the (quasi) metal oxide.
  • the first particulate form of the (quasi) metal oxide and the second particulate form of the oxide containing (semi) metal and lithium may be mixed with each other in the electrode active material. It is preferred that the aggregate of one first particulate or two or more first particulates can be surrounded by second particulates.
  • the size of the first particulate phase may range from about 0.1 nm to 5 ⁇ m
  • the size of the second particulate phase may range from about 0.1 nm to 20 ⁇ m
  • the electrode active material consisting of the second particles may have a size (average particle diameter) of about 0.1 to 100 ⁇ m range, but is not limited thereto.
  • the secondary battery including the electrode active material of the present invention the initial efficiency is improved compared to the secondary battery containing a conventional electrode active material containing only a particulate form of (quasi) metal oxide.
  • the initial efficiency is about 50% or more, preferably 65% or more, and more. Preferably it was 70% or more.
  • the electrode active material of the present invention has a volume change rate of about 300% or less compared to the initial stage, compared to an initial electrode active material made of metal such as Si or Sn, which has a volume change rate of about 400% or more. .
  • the above-mentioned 1st particulate form and 2nd particulate form are contained by 5: 95-95: 5 weight ratio. If the weight ratio of the first particle phase is too low, the reversible capacity is small and the effect as a high-capacity electrode active material is inadequate, and the lithium particles are excessively contained in the second particle phase, which may cause safety problems due to reaction with moisture. . On the other hand, if the weight ratio of the first particulate phase is too high, too much irreversible lithium oxide or lithium metal oxide due to reaction with lithium ions during charging and discharging of the battery may generate an initial efficiency.
  • the electrode active material of the present invention comprises the steps of chemically or mechanically mixing a lithium salt that does not contain oxygen and a (semi) metal oxide capable of alloying with lithium; And heat-treating the mixture in an inert atmosphere.
  • the (semi) metal oxide is not particularly limited as long as it is an oxide of a metal or metalloid capable of alloying with lithium.
  • Non-limiting examples thereof include oxides such as Si, Sn, Al, Sb, Bi, As, Ge, Pb, Zn, Cd, In, Ga, and alloys thereof.
  • a lithium salt containing no oxygen may be used as the lithium salt mixed with the (quasi) metal oxide to form the second particulate part. This is because, when the lithium salt contains oxygen, lithium oxide is generated in the heat treatment step, and oxygen together with lithium may react with the metal oxide, thereby lowering the initial efficiency of the battery.
  • lithium salts that do not contain oxygen include LiCl, LiBF 4 , LiAlCl 4 , LiSCN, LiSbF 6 , LiPF 6 , LiAsF 6 , LiB 10 Cl 10 , LiF, LiBr, LiI, and the like, but are not limited thereto.
  • the lithium salt and (semi) metal oxide which do not contain oxygen mentioned above are mixed in a weight ratio of 5: 95-80: 20. If the weight ratio of the lithium salt containing no oxygen is too small, the amount of lithium reacting with the (quasi) metal oxide is not sufficient, so that a small amount of lithium-containing second particulate phase is formed, which leads to an initial stage of the battery. When charging and discharging, too much irreversible lithium oxide or lithium metal oxide is generated due to the reaction of lithium ions inserted into the negative electrode and the (quasi) metal oxide, and thus an initial efficiency increase effect of the battery may be insufficient.
  • the weight ratio of the lithium salt that does not contain oxygen is too high, excessive amounts of lithium may be contained in the second particles, which may cause battery safety problems, or the amount of lithium that may be contained in the second particles is exceeded. Lithium may precipitate.
  • the chemical mixing method of the first embodiment of the present invention comprises the steps of forming a dispersion by dispersing a metal oxide in a solution prepared by dissolving a lithium salt containing no oxygen in a solvent; And it may include the step of drying the dispersion.
  • the solvent or dispersion medium for dissolving the lithium salt which does not contain the above-mentioned oxygen and for dispersing the alloyable (quasi) metal oxide is not particularly limited, whereby dissolution and mixing can be made uniform, and then easily removed. It is desirable to be able to.
  • Non-limiting examples of the solvent or dispersion medium is distilled water; Alcohols such as ethanol and methanol; Acetone, tetrahydrofuran, methylene chloride, chloroform, dimethylformamide, N-methyl-2-pyrrolidone, cyclohexane, dichloromethane, dimethylsulfoxide, acetonitrile, pyridine, amines and the like, or a mixture thereof.
  • the (semi) metal oxide may be generally dispersed using a dispersion apparatus known in the art.
  • the dispersing device is not particularly limited as long as it disperses the material to be dispersed in the dispersion medium, and examples thereof include an ultrasonic dispersing device, a magnetic sterling device and a spray dryer device.
  • the formed dispersion is dried at a room temperature of 25 to 28 ° C. or at a temperature of 50 to 200 ° C. to remove the solvent or the dispersion medium, thereby obtaining a mixture in which a lithium salt is formed on the surface of the (quasi) metal oxide.
  • the method of removing the solvent or the dispersion medium may use methods known in the art.
  • mechanical mixing uses mechanical mixing devices such as high energy ball mills, planetary mills, stirred ball mills, vibrating mills, and the like.
  • Process parameters such as ball-to-powder weight ratio, ball size, mixing time, mixing temperature and atmosphere can be varied according to conventional conditions known in the art.
  • alcohol such as ethanol
  • higher fatty acids such as stearic acid (stearic acid) may be added as a processing control agent (processing control agent).
  • processing control agent may be added in an amount of about 2.0 parts by weight or less, preferably 0.5 parts by weight or less, based on 100 parts by weight of the mixture. When the process control agent is added, the mixing time can be reduced.
  • the alloying with lithium salt and lithium that does not contain oxygen can be performed simultaneously with grinding and mixing the (quasi) metal oxide as much as possible.
  • the present invention can obtain an electrode active material in the form of an alloy of a uniform composition. In this case, the heat treatment may not be performed in an inert atmosphere later.
  • a mixture of lithium salts containing no oxygen and a (quasi) metal oxide with a ball about 5 mm in diameter is introduced into a ball-mill apparatus, and then rotated at room temperature to mechanically mix and alloy.
  • the mixture of lithium salts and (semi) metal oxides which do not contain oxygen can be pulverized and mixed more uniformly, and the (semi) metal oxide can be mixed by appropriate rpm and time
  • An electrode active material having a structure in which a first particulate form of and a second particulate form of an oxide containing (semi) metal and lithium same as the (semi) metal are mixed can be obtained.
  • the mixture of the lithium salt and the (quasi) metal oxide and oxygen containing no oxygen (Ball) is 1: 1 to 20 to 20 by weight ratio is appropriately added to the ball-mill apparatus. If it is out of the above range, the compressive stress can not be transmitted to the mixture, or more than necessary balls may be used to lower the yield.
  • the ball may be a stainless ball or zirconia ball having a diameter in the range of about 0.1 to 10 mm.
  • the rotational speed of the device is suitably in the range of about 300 to 3000 rpm, but is preferably adjusted according to whether it is a mechanical mixing process or a mechanical alloying process.
  • the mechanical alloy treatment time is preferably about 30 minutes or more, specifically 3 to 100 hours. This is because an electrode active material having a structure in which the first particulate form and the second particulate form are mixed can be obtained.
  • the mechanical alloy treatment time is too short, the mixture of lithium salt and (quasi) metal oxide containing no oxygen is not properly pulverized and uniformly mixed so that the first and second particulate phases in the obtained electrode active material are uniform. It may not be mixed.
  • impurities may flow from the mechanical alloying device may degrade the performance of the electrode active material obtained.
  • the atmosphere in which contact with oxygen is blocked includes an inert atmosphere in which nitrogen gas, hydrogen gas, argon gas, helium gas, krypton gas, or xenon gas is present, or a vacuum atmosphere, but is not limited thereto.
  • the (semi) metal oxide and lithium of lithium salts formed on the surface react with each other to form new bonds, and as a result, the (semi) metal oxide capable of alloying. And a reactant in which the same (semi) metal and the same oxide containing lithium at the same time as the (semi) metal oxide are mixed with each other. In this process, the anion portion of the lithium salt is released as a gas.
  • the heat treatment temperature range is not particularly limited as long as it is a temperature between the melting point of the lithium salt not containing oxygen and the boiling point of the lithium salt, and may vary depending on the type of lithium salt not containing oxygen. If the lithium salt is less than the melting point of the lithium salt, the reaction between the lithium salt and the (quasi) metal oxide may not occur. If the boiling point of the lithium salt exceeds the lithium salt, the lithium salt is gas before the lithium salt sufficiently reacts with the (quasi) metal oxide. Can be released in form. Therefore, it is appropriate that the heat treatment temperature range is in the range of 500 to 2000 ° C.
  • the temperature below 1300 degreeC is preferable.
  • SiO tends to grow separately from SiO 2 and SiO, thereby reducing the advantage of controlling the thickness of SiO. Therefore, the heat treatment is performed at a temperature between the melting point of the lithium salt containing no oxygen and the boiling point of the lithium salt, but it is preferable to consider the kind of (quasi) metal oxide.
  • the heat treatment of the mixture is preferably performed in an inert atmosphere in which nitrogen gas, argon gas, helium gas, krypton gas, xenon gas, or the like is present to block contact with oxygen. If the mixture is in contact with oxygen during heat treatment of the mixture, since lithium and oxygen react with the metal oxide to form lithium oxide or lithium metal oxide, the initial efficiency increase effect of the battery may be reduced.
  • the electrode can be prepared by conventional methods known in the art.
  • a slurry may be prepared by mixing and stirring a binder and a solvent, a conducting agent, and a dispersant in an electrode active material of the present invention, and then applying the same to a current collector of a metal material, compressing, and drying the electrode. have.
  • the binder may be suitably used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the electrode active material, and the conductive agent may be suitably used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the electrode active material.
  • binders examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinylacetate, polyetherylene oxide, polypyrrolidone, polyvinyl alcohol, polyacrylonitrile, poly Aqueous binders such as polyacrylic acid (PAA), carboxymethylcellulose (CMC), and styrene-butadiene rubber (SBR).
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylacetate
  • polyetherylene oxide polypyrrolidone
  • polyvinyl alcohol polyacrylonitrile
  • PAA polyacrylic acid
  • CMC carboxymethylcellulose
  • SBR styrene-butadiene rubber
  • carbon black may be used as the conductive agent.
  • acetylene black series such as Chevron Chemical Company or Gulf Oil Company.
  • Ketjen Black EC series from Armak Company
  • Vulcan XC-72 from Cabot Company, etc.
  • Super P from MMM
  • fiber There is also a linear conductive agent such as fiber.
  • the current collector of the metal material is a highly conductive metal, and the slurry of the electrode active material can be easily adhered, and any material can be used as long as it is not reactive in the voltage range of the battery.
  • Representative examples include meshes, foils, and the like, which are made of copper, gold, nickel, or a combination thereof.
  • the method of applying the slurry to the current collector is also not particularly limited.
  • it can be applied by a method such as a doctor blade, dipping, brushing, and the like, but the coating amount is not particularly limited, but the thickness of the active material layer formed after removing the solvent or the dispersion medium is usually 0.005 to 5 mm, preferably 0.05 to 2 mm. It is preferable that the amount to be.
  • the method of removing the solvent or the dispersion medium is not particularly limited, but the solvent or the dispersion medium may be added as quickly as possible within the speed range in which stress concentration occurs and cracks occur in the active material layer or the active material layer does not peel off from the current collector. It is preferable to use a method of adjusting to remove to volatilize. As a non-limiting example it may be dried in a vacuum oven at 50 to 200 °C for 0.5 to 3 days.
  • the electrode active material of the present invention can be used in all devices that undergo an electrochemical reaction.
  • the secondary battery of the present invention can be produced by a conventional method known in the art, including the electrode produced using the electrode active material of the present invention.
  • a porous separator may be inserted between the positive electrode and the negative electrode to add an electrolyte solution.
  • Secondary batteries include lithium ion secondary batteries, lithium polymer secondary batteries or lithium ion polymer secondary batteries.
  • the electrolyte may include a nonaqueous solvent and an electrolyte salt.
  • the nonaqueous solvent is not particularly limited as long as it is normally used as a nonaqueous solvent for nonaqueous electrolyte, and cyclic carbonate, linear carbonate, lactone, ether, ester or ketone can be used.
  • Examples of the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BE), and the like.
  • Examples of the linear carbonate include diethyl carbonate (DEC), dimethyl carbonate (DMC), and dipropyl carbonate. (DPC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC), and the like.
  • Examples of the lactone include gamma butyrolactone (GBL), and examples of the ether include dibutyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, and the like. There is this.
  • ester examples include n-methyl acetate, n-ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl pivalate, and the like.
  • vinyl ketone There is a vinyl ketone.
  • the electrolyte salt is not particularly limited as long as it is usually used as an electrolyte salt for nonaqueous electrolyte.
  • Non-limiting examples of the electrolyte salt is A + B - A salt of the structure, such as, A + is Li +, Na +, and comprising an alkali metal cation or an ion composed of a combination thereof, such as K +, B - is PF 6 -, BF 4 -, Cl - , Br -, I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, C (CF 2 SO 2 ) salts containing ions consisting of anions such as 2 - or a combination thereof.
  • lithium salts are preferred.
  • These electrolyte salts can be used individually or in mixture of 2 or more types.
  • the secondary battery of the present invention may include a separator.
  • a separator There is no restriction
  • the secondary battery of the present invention is not limited in appearance, but may be cylindrical, square, pouch or coin using a can.
  • the parts by weight are based on 100 parts by weight of a mixture of a lithium salt (not containing oxygen) and a (quasi) metal oxide.
  • the above-mentioned electrode active material powder, polyvinylidene fluoride (PVdF) as a binder, and acetylene black as a conductive agent were mixed in a weight ratio of 85: 10: 5, and these were used as a solvent, N-methyl-2-pyrrolidone ( N-methyl-2-pyrrolidone: NMP) was added and mixed to prepare a uniform electrode slurry.
  • NMP N-methyl-2-pyrrolidone
  • the prepared electrode slurry was coated on one surface of a copper (Cu) current collector to a thickness of 65 ⁇ m, dried and rolled, and then punched to a required size to prepare an electrode.
  • Cu copper
  • Ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed in a volume ratio of 30:70. Thereafter, 1 M of LiPF 6 was added to the nonaqueous electrolyte solvent to prepare a nonaqueous electrolyte.
  • the prepared electrode was used as a cathode, a Li metal foil was used as a counter electrode, a polyolefin separator was interposed between both electrodes, and the electrolyte was injected to prepare a coin-type battery of the present invention.
  • An electrode active material and a battery were prepared in the same manner as in Example 1, except that 80 parts by weight of lithium chloride and 20 parts by weight of silicon monoxide were used instead of 50 parts by weight of lithium chloride and 50 parts by weight of silicon monoxide.
  • An electrode active material and a battery were prepared in the same manner as in Example 1 except that instead of 50 parts by weight of lithium chloride, 76 parts by weight of lithium iodide (LiI) was used as a lithium salt containing no oxygen.
  • LiI lithium iodide
  • An electrode active material and a battery were manufactured in the same manner as in Example 1, except that 25 parts by weight of lithium chloride and 75 parts by weight of tin monoxide (SnO) were used instead of 50 parts by weight of lithium chloride and 50 parts by weight of silicon monoxide.
  • SnO tin monoxide
  • An electrode active material and a battery were prepared in the same manner as in Example 1, except that 47 parts by weight of lithium carbonate (Li 2 CO 3 ) and 53 parts by weight of silicon monoxide were used instead of 50 parts by weight of lithium chloride and 50 parts by weight of silicon monoxide. Prepared. At this time, a scanning electron microscope (Scanning Electron Microscopy, SEM) of the prepared electrode active material is shown in FIG.
  • a battery was manufactured in the same manner as in Example 1, except that 100 parts by weight of silicon monoxide (SiO), which was not heat-treated, was used instead of the electrode active material obtained by heat-treating the mixture of lithium chloride and silicon monoxide.
  • SiO silicon monoxide
  • lithium hydroxide LiOH
  • silicon monoxide instead of 50 parts by weight of lithium chloride and 50 parts by weight of silicon monoxide, 36 parts by weight of lithium hydroxide (LiOH) and 64 parts by weight of silicon monoxide were used as lithium salts containing oxygen, in the same manner as in Example 1 Active materials and batteries were prepared.
  • the electrode active material and the battery were prepared in the same manner as in Example 1 except that 100 parts by weight of tin monoxide (SnO) was heat-treated at a temperature of 800 ° C. Prepared.
  • a battery was prepared in the same manner as in Example 1, except that 100 parts by weight of tin oxide (SnO), which was not heat-treated, was used instead of the electrode active material obtained by heat-treating a mixture of 50 parts by weight of lithium chloride and 50 parts by weight of silicon monoxide. .
  • SnO tin oxide
  • Discharge of battery Discharge was performed by constant current to 1.0V.
  • Table 1 a molar ratio of b Discharge Capacity (mAh / g) Charge capacity (mAh / g) Initial Efficiency (%) M: O molar ratio
  • Comparative Example 2 100: 0 1745 2710 64.4 1: 1 Comparative Example 3 100: 0 1750 2713 64.5 1: 1 Comparative Example 4 55: 45 1427 2718 52.5 1: 2
  • the secondary battery manufactured in Example 1 As can be seen in Table 1 and Figure 4, the secondary battery manufactured in Example 1, the charge capacity is reduced compared to the battery prepared in Comparative Examples 2 or 3, the initial efficiency is about 14% Improved. In addition, the secondary battery manufactured in Example 4 also improved the initial efficiency compared with the batteries produced in Comparative Examples 5 and 6. From this, it can be seen that when the heat treatment after mixing the SiO and LiCl containing no oxygen, less irreversible phase due to the reaction of lithium ions and SiO during the charge and discharge of the battery was generated.
  • the electrode active material prepared in Example 1 showed a peak at the same position as that of the control 2 (SiO) pattern, but no peak at another position. .
  • the peak appeared between 20 ⁇ 30 ° is a typical peak coming out by the nanostructure of SiO, this peak also appeared in the electrode active material prepared in Example 1.
  • the width of the peak indicates that the grain size of the electrode active material and the control 2 of Example 1 is about 5 nm or less.
  • the electrode active material of Example 1 having fine grains of 5 nm or less may be referred to as an amorphous material rather than a crystalline material. From these XRD results, it was found that not only the first particulate phase made of (quasi) metal oxide but also the second particulate phase made of oxide containing both (quasi) metal and lithium at the same time were in an amorphous state.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne une batterie rechargeable comprenant : (a) des granules primaires d'un oxyde non métallique pouvant s'allier au lithium; et (b) des granules secondaires d'un oxyde contenant le même élément non-métallique que celui de (a), ainsi que du lithium, et une batterie rechargeable comprenant ce matériau actif d'électrode. Lorsque le matériau actif d'électrode de cette invention est utilisé comme un matériau actif de l'anode, on obtient des quantités réduites d'une phase irréversible telle qu'un oxyde de lithium ou un oxyde métallique de lithium au cours d'une charge-décharge initiale d'une batterie puisque le lithium est déjà contenu dans les granules secondaires avant la charge-décharge initiale, ce qui permet de minimiser un volume mort sur le côté d'une cathode et de fabriquer une batterie de haute capacité.
PCT/KR2009/006846 2008-11-20 2009-11-20 Matériau actif d'électrode pour batterie rechargeable et son procédé de fabrication WO2010058990A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2011537364A JP5558482B2 (ja) 2008-11-20 2009-11-20 二次電池用電極活物質及びその製造方法
CN200980155046.8A CN102292854B (zh) 2008-11-20 2009-11-20 二次电池用电极活性材料及其制备方法
EP09827755.1A EP2360759B1 (fr) 2008-11-20 2009-11-20 Matériau actif d'électrode pour batterie rechargeable et son procédé de fabrication
US13/130,153 US8546019B2 (en) 2008-11-20 2009-11-20 Electrode active material for secondary battery and method for preparing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR2008006836 2008-11-20
KRPCT/KR2008/006836 2008-11-20
KR2008006929 2008-11-24
KRPCT/KR2008/006929 2008-11-24

Publications (2)

Publication Number Publication Date
WO2010058990A2 true WO2010058990A2 (fr) 2010-05-27
WO2010058990A3 WO2010058990A3 (fr) 2010-08-12

Family

ID=42198683

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2009/006846 WO2010058990A2 (fr) 2008-11-20 2009-11-20 Matériau actif d'électrode pour batterie rechargeable et son procédé de fabrication

Country Status (5)

Country Link
US (1) US8546019B2 (fr)
EP (1) EP2360759B1 (fr)
JP (1) JP5558482B2 (fr)
CN (1) CN102292854B (fr)
WO (1) WO2010058990A2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013129850A1 (fr) * 2012-02-28 2013-09-06 주식회사 엘지화학 Matériau actif d'électrode pour batterie secondaire au lithium et procédé de fabrication de celui-ci
WO2014010973A1 (fr) * 2012-07-13 2014-01-16 주식회사 엘지화학 Matériau actif d'anode de type bimodal et batterie secondaire au lithium comprenant celui-ci
WO2014084679A1 (fr) * 2012-11-30 2014-06-05 주식회사 엘지화학 Matière active d'anode, batterie secondaire au lithium la comprenant et procédé de fabrication de matière active d'anode
KR101558044B1 (ko) 2012-07-13 2015-10-07 주식회사 엘지화학 바이모달 타입의 음극 활물질 및 이를 포함하는 리튬 이차전지
WO2018084431A1 (fr) * 2016-11-01 2018-05-11 주식회사 아모그린텍 Électrode, accumulateur l'utilisant, et procédé de fabrication d'électrode
CN109155409A (zh) * 2016-05-30 2019-01-04 信越化学工业株式会社 负极活性物质、混合负极活性物质材料、及负极活性物质的制备方法

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5450182B2 (ja) * 2010-03-12 2014-03-26 株式会社半導体エネルギー研究所 二次電池および電子機器
US20120003541A1 (en) * 2010-07-02 2012-01-05 Samsung Sdi Co., Ltd. Positive active material for lithium secondary battery and lithium secondary battery using the same
CN102569812B (zh) * 2011-12-24 2013-11-27 西北工业大学 聚合物掺杂锡酸锂负极材料的制备方法
EP2894699B1 (fr) * 2012-09-03 2018-07-11 Nippon Chemi-Con Corporation Matériau d'électrode pour batteries secondaires au lithium-ion, procédé de production de matériau d'électrode pour batteries secondaires au lithium-ion, et batterie secondaire au lithium-ion
GB2508218A (en) * 2012-11-26 2014-05-28 Leclanch S A Electrode for the reduction of gassing in lithium titanate cells
KR102685472B1 (ko) 2013-05-15 2024-07-17 퀀텀스케이프 배터리, 인코포레이티드 배터리용 고상 캐소라이트 또는 전해질
US9761861B1 (en) 2013-06-25 2017-09-12 Quantumscape Corporation Pulse plating of lithium material in electrochemical devices
US9935309B2 (en) 2013-08-21 2018-04-03 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, raw material for a negative electrode active material, negative electrode, lithium ion secondary battery, method for producing a negative electrode active material, and method for producing a lithium ion secondary battery
CN105580171B (zh) 2013-09-24 2017-10-03 三洋电机株式会社 非水电解质二次电池用负极活性物质及使用了该负极活性物质的非水电解质二次电池
JP5839733B2 (ja) * 2013-12-25 2016-01-06 株式会社半導体エネルギー研究所 二次電池の作製方法
JP6359836B2 (ja) * 2014-02-07 2018-07-18 信越化学工業株式会社 非水電解質二次電池用負極材、非水電解質二次電池用負極及びその製造方法並びに非水電解質二次電池
JP6181590B2 (ja) * 2014-04-02 2017-08-16 信越化学工業株式会社 非水電解質二次電池用負極及び非水電解質二次電池
CN106605329B (zh) 2014-06-04 2020-08-25 昆腾斯科普公司 具有混合粒度的电极材料
JP2016062860A (ja) * 2014-09-22 2016-04-25 株式会社東芝 非水電解質二次電池用電極活物質およびそれを備えた非水電解質二次電池
US10116003B2 (en) 2015-02-03 2018-10-30 Quantumscape Corporation Metal sulfide anolytes for electrochemical cells
EP3979382A1 (fr) 2015-06-24 2022-04-06 QuantumScape Battery, Inc. Cellule électrochimique avec un électrolyte composite
US10116001B2 (en) 2015-12-04 2018-10-30 Quantumscape Corporation Lithium, phosphorus, sulfur, and iodine including electrolyte and catholyte compositions, electrolyte membranes for electrochemical devices, and annealing methods of making these electrolytes and catholytes
JP6746526B2 (ja) * 2016-04-06 2020-08-26 信越化学工業株式会社 負極活物質、混合負極活物質材料、及び負極活物質の製造方法
EP3467912B1 (fr) * 2016-05-30 2023-01-18 Shin-Etsu Chemical Co., Ltd. Matière active d'électrode négative, matière active d'électrode négative mixte et procédé de production d'une matière active d'électrode négative
CN108292745B (zh) * 2016-06-02 2021-10-12 株式会社Lg化学 负极活性材料、包含它的负极和包含该负极的锂二次电池
US11342630B2 (en) 2016-08-29 2022-05-24 Quantumscape Battery, Inc. Catholytes for solid state rechargeable batteries, battery architectures suitable for use with these catholytes, and methods of making and using the same
WO2018165606A1 (fr) 2017-03-10 2018-09-13 Quantumscape Corporation Charge ultrasonique d'électrode négative métallique
JP6911545B2 (ja) * 2017-06-05 2021-07-28 株式会社Gsユアサ 負極及び非水電解質蓄電素子
US10431700B2 (en) * 2017-06-09 2019-10-01 Giga Solar Materials Corp. Conductive paste composition for providing enhanced adhesion strength to a semiconductor substrate and its use
KR102244904B1 (ko) 2017-07-13 2021-04-26 주식회사 엘지화학 전극 보호층을 포함하는 음극 및 이를 적용한 리튬 이차전지
CN108717977B (zh) * 2018-05-29 2021-10-08 哈尔滨工业大学 一种具有优良零伏存储性能的锂离子电池
CN110556525B (zh) * 2019-08-21 2022-03-29 华南理工大学 一种锗酸锂、锗酸锂/石墨复合负极材料及其制备方法与在组装锂电池中的应用
CN112751027B (zh) * 2019-10-30 2024-08-09 贝特瑞新材料集团股份有限公司 一种负极材料及其制备方法和锂离子电池
CN111848132A (zh) * 2020-07-30 2020-10-30 电子科技大学 易烧结高Q值Li3Mg2SbO6基微波介质陶瓷材料及其制备方法
CN115440944A (zh) * 2021-06-04 2022-12-06 中伟新材料股份有限公司 锂电池正极活性材料和制备方法,及其正极和锂电池
JP7040832B1 (ja) 2021-08-11 2022-03-23 日本重化学工業株式会社 リチウムイオン二次電池用負極活物質、その製造方法、及びリチウムイオン二次電池用負極電極
CN114292088B (zh) * 2021-12-30 2022-10-11 安徽大学 一种氚-中子复合增殖剂铅酸锂共晶陶瓷球粒及制备方法
KR102729470B1 (ko) * 2022-10-12 2024-11-13 포스코홀딩스 주식회사 리튬 함유 화합물을 포함하는 조성물 및 배터리 처리 방법

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3252414B2 (ja) * 1991-11-29 2002-02-04 松下電器産業株式会社 非水電解液二次電池
JP2997741B2 (ja) * 1992-07-29 2000-01-11 セイコーインスツルメンツ株式会社 非水電解質二次電池及びその製造方法
JP4768901B2 (ja) 1999-06-03 2011-09-07 チタン工業株式会社 リチウムチタン複合酸化物及びその製造方法、並びにその用途
KR100417251B1 (ko) 1999-12-15 2004-02-05 주식회사 엘지화학 전기화학적 성능이 향상된 리튬망간 스피넬 산화물의 제조방법
JP4702510B2 (ja) * 2001-09-05 2011-06-15 信越化学工業株式会社 リチウム含有酸化珪素粉末及びその製造方法
EP1624509A4 (fr) 2003-05-13 2010-03-24 Mitsubishi Chem Corp Poudre d'oxyde composite a base de nickel/lithium en couches et son procede de production
JP4650603B2 (ja) * 2003-12-22 2011-03-16 日本電気株式会社 二次電池用負極材料及びその製造方法並びにそれを用いた二次電池
JP2005285545A (ja) * 2004-03-30 2005-10-13 Ngk Insulators Ltd リチウム二次電池
KR20050114516A (ko) 2004-06-01 2005-12-06 브이케이 주식회사 이종금속 산화물이 코팅된 리튬 2차 전지용 양극 활물질및 이를 포함한 리튬 2차 전지
JP4533822B2 (ja) * 2005-08-24 2010-09-01 株式会社東芝 非水電解質電池および負極活物質
US7776473B2 (en) * 2006-03-27 2010-08-17 Shin-Etsu Chemical Co., Ltd. Silicon-silicon oxide-lithium composite, making method, and non-aqueous electrolyte secondary cell negative electrode material
KR100830612B1 (ko) 2006-05-23 2008-05-21 강원대학교산학협력단 리튬 이차 전지용 음극 활물질, 그의 제조 방법 및 그를포함하는 리튬 이차 전지
KR101451801B1 (ko) * 2007-02-14 2014-10-17 삼성에스디아이 주식회사 음극 활물질, 그 제조 방법 및 이를 채용한 음극과 리튬전지

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None
See also references of EP2360759A4

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2806488A4 (fr) * 2012-02-28 2015-10-28 Lg Chemical Ltd Matériau actif d'électrode pour batterie secondaire au lithium et procédé de fabrication de celui-ci
JP2015512130A (ja) * 2012-02-28 2015-04-23 エルジー・ケム・リミテッド リチウム二次電池用電極活物質及びその製造方法
WO2013129850A1 (fr) * 2012-02-28 2013-09-06 주식회사 엘지화학 Matériau actif d'électrode pour batterie secondaire au lithium et procédé de fabrication de celui-ci
KR101555932B1 (ko) 2012-02-28 2015-09-25 주식회사 엘지화학 리튬 이차전지용 전극활물질 및 그 제조방법
US20140363741A1 (en) * 2012-02-28 2014-12-11 Lg Chem, Ltd. Electrode active material for lithium secondary battery and preparation thereof
US9397335B2 (en) 2012-07-13 2016-07-19 Lg Chem, Ltd. Bimodal type anode active material and lithium secondary battery including the same
KR101558044B1 (ko) 2012-07-13 2015-10-07 주식회사 엘지화학 바이모달 타입의 음극 활물질 및 이를 포함하는 리튬 이차전지
WO2014010973A1 (fr) * 2012-07-13 2014-01-16 주식회사 엘지화학 Matériau actif d'anode de type bimodal et batterie secondaire au lithium comprenant celui-ci
US20140027679A1 (en) * 2012-07-13 2014-01-30 Lg Chem, Ltd. Bimodal type anode active material and lithium secondary battery including the same
WO2014084679A1 (fr) * 2012-11-30 2014-06-05 주식회사 엘지화학 Matière active d'anode, batterie secondaire au lithium la comprenant et procédé de fabrication de matière active d'anode
US9419276B2 (en) 2012-11-30 2016-08-16 Lg Chem, Ltd. Anode active material, lithium secondary battery comprising the same, and method of manufacturing anode active material
CN109155409A (zh) * 2016-05-30 2019-01-04 信越化学工业株式会社 负极活性物质、混合负极活性物质材料、及负极活性物质的制备方法
CN109155409B (zh) * 2016-05-30 2021-08-31 信越化学工业株式会社 负极活性物质、混合负极活性物质材料、及负极活性物质的制备方法
US11139469B2 (en) 2016-05-30 2021-10-05 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method for producing negative electrode active material
US11658289B2 (en) 2016-05-30 2023-05-23 Shin-Etsu Chemical Co., Ltd. Negative electrode active material, mixed negative electrode active material, and method for producing negative electrode active material
WO2018084431A1 (fr) * 2016-11-01 2018-05-11 주식회사 아모그린텍 Électrode, accumulateur l'utilisant, et procédé de fabrication d'électrode
US11018379B2 (en) 2016-11-01 2021-05-25 Amogreentech Co., Ltd. Electrode, secondary battery using same, and method for manufacturing electrode

Also Published As

Publication number Publication date
JP2012509564A (ja) 2012-04-19
EP2360759A2 (fr) 2011-08-24
US8546019B2 (en) 2013-10-01
JP5558482B2 (ja) 2014-07-23
EP2360759A4 (fr) 2013-03-06
CN102292854B (zh) 2015-01-14
US20110311875A1 (en) 2011-12-22
EP2360759B1 (fr) 2017-07-12
WO2010058990A3 (fr) 2010-08-12
CN102292854A (zh) 2011-12-21

Similar Documents

Publication Publication Date Title
WO2010058990A2 (fr) Matériau actif d'électrode pour batterie rechargeable et son procédé de fabrication
WO2019151813A1 (fr) Matériau actif d'anode, anode comprenant ce dernier et batterie rechargeable au lithium
WO2019151814A1 (fr) Matériau actif d'anode, anode le comprenant, et batterie secondaire au lithium
WO2013129850A1 (fr) Matériau actif d'électrode pour batterie secondaire au lithium et procédé de fabrication de celui-ci
WO2016108384A1 (fr) Matériau actif de cathode pour batteries secondaires lithium-ion, procédé de fabrication de celui-ci et batterie secondaire lithium-ion comprenant celui-ci
WO2011019218A9 (fr) MATÉRIAU ACTIF D'ANODE AMORPHE, PROCÉDÉ DE PRÉPARATION D'ÉLECTRODE METTANT EN œUVRE UN TEL MATÉRIAU, ET BATTERIE RECHARGEABLE EN CONTENANT, ET CONDENSATEUR HYBRIDE
WO2019151778A1 (fr) Matériau actif d'anode destiné à une batterie secondaire au lithium, anode le comprenant, et batterie secondaire au lithium-ion comprenant une telle anode
WO2012011785A2 (fr) Procédé de production d'une matière active d'anode utile pour un accumulateur au lithium, matière active d'anode pour un accumulateur au lithium produite au moyen du procédé et accumulateur au lithium utilisant ladite matière active d'anode
WO2015099233A1 (fr) Matériau actif d'anode, batterie secondaire comprenant ledit matériau et procédé de fabrication du matériau actif d'anode
WO2021125870A1 (fr) Matériau actif d'électrode positive, procédé destiné à le produire, et batterie secondaire au lithium l'incluant
WO2010143805A1 (fr) Matériau cathodique pour une batterie secondaire au lithium, son procédé de fabrication et batterie secondaire au lithium le comprenant
WO2022080762A1 (fr) Poudre de structure nanocomposite de siliicum pour matériau d'électrode négative, et son procédé de fabrication
WO2014061974A1 (fr) Composite oxyde de silicium - carbone et procédé de préparation de celui-ci
KR101194911B1 (ko) 이차 전지용 전극활물질 및 그 제조방법
WO2015088248A1 (fr) Matériau d'électrode négative pour batterie rechargeable, et batterie rechargeable utilisant ledit matériau
KR101102651B1 (ko) 이차 전지용 전극활물질 및 그 제조방법
WO2019027215A2 (fr) Précurseur d'oxyde composite de lithium, procédé de préparation associé et oxyde composite de lithium préparé en l'utilisant
WO2019066275A2 (fr) Matériau actif d'électrode positive pour accumulateur au lithium et procédé de fabrication d'un matériau actif d'électrode positive
WO2018155744A1 (fr) Matériau actif d'anode, batterie secondaire le comprenant, et procédé de fabrication de matériau actif d'anode
WO2021182926A1 (fr) Matériau actif négatif, son procédé de fabrication, et batterie secondaire au lithium ayant un matériau actif négatif
WO2018038509A1 (fr) Matériau actif de cathode pour batterie secondaire au lithium, son procédé de préparation et batterie secondaire au lithium le comprenant
WO2023101078A1 (fr) Procédé de fabrication d'un matériau actif d'électrode, matériau actif d'électrode et batterie au lithium-ion le comprenant
WO2016053031A1 (fr) Matériau actif d'anode pour batterie secondaire au lithium, son procédé de fabrication, et batterie secondaire au lithium le comprenant
WO2024128543A1 (fr) Matériau actif d'électrode positive pour batterie au lithium rechargeable, son procédé de préparation, et batterie au lithium rechargeable le comprenant
WO2022075748A1 (fr) Procédé de préparation d'un matériau actif de cathode pour batterie secondaire au lithium, et matériau actif de cathode ainsi préparé

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980155046.8

Country of ref document: CN

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

Ref document number: 09827755

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 2011537364

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2009827755

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2009827755

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 13130153

Country of ref document: US

点击 这是indexloc提供的php浏览器服务,不要输入任何密码和下载