WO2010058990A2 - 이차 전지용 전극활물질 및 그 제조방법 - Google Patents

이차 전지용 전극활물질 및 그 제조방법 Download PDF

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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
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active material
electrode active
lithium
metal
oxide
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PCT/KR2009/006846
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English (en)
French (fr)
Korean (ko)
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WO2010058990A3 (ko
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이용주
김제영
권오중
오병훈
엄인성
최승연
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주식회사 엘지화학
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Priority to JP2011537364A priority Critical patent/JP5558482B2/ja
Priority to CN200980155046.8A priority patent/CN102292854B/zh
Priority to US13/130,153 priority patent/US8546019B2/en
Priority to EP09827755.1A priority patent/EP2360759B1/de
Publication of WO2010058990A2 publication Critical patent/WO2010058990A2/ko
Publication of WO2010058990A3 publication Critical patent/WO2010058990A3/ko

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G13/00—Compounds of mercury
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G17/00—Compounds of germanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • H01M6/5088—Initial activation; predischarge; Stabilisation of initial voltage
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 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.

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PCT/KR2009/006846 2008-11-20 2009-11-20 이차 전지용 전극활물질 및 그 제조방법 WO2010058990A2 (ko)

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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
US13/130,153 US8546019B2 (en) 2008-11-20 2009-11-20 Electrode active material for secondary battery and method for preparing the same
EP09827755.1A EP2360759B1 (de) 2008-11-20 2009-11-20 Aktives elektrodenmaterial für eine sekundärbatterie und herstellungsverfahren dafür

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

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