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WO2014061881A1 - Matériau actif d'électrode négative pour batterie rechargeable au lithium, procédé de préparation de matériau d'électrode négative pour batterie rechargeable au lithium et batterie rechargeable au lithium comprenant ledit matériau actif d'électrode négative pour batterie rechargeable au lithium - Google Patents

Matériau actif d'électrode négative pour batterie rechargeable au lithium, procédé de préparation de matériau d'électrode négative pour batterie rechargeable au lithium et batterie rechargeable au lithium comprenant ledit matériau actif d'électrode négative pour batterie rechargeable au lithium Download PDF

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Publication number
WO2014061881A1
WO2014061881A1 PCT/KR2013/001010 KR2013001010W WO2014061881A1 WO 2014061881 A1 WO2014061881 A1 WO 2014061881A1 KR 2013001010 W KR2013001010 W KR 2013001010W WO 2014061881 A1 WO2014061881 A1 WO 2014061881A1
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Prior art keywords
secondary battery
lithium secondary
active material
negative electrode
titanium
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English (en)
Korean (ko)
Inventor
박수진
박옥지
이정인
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UNIST Academy Industry Research Corp
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UNIST Academy Industry Research Corp
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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

  • Lithium secondary batteries which are in the spotlight as the power source of recent portable small electronic devices, have a discharge voltage that is two times higher than that of a battery using an alkaline aqueous solution, and thus have a high energy density.
  • lithium and a transition metal having a structure capable of intercalating lithium ions such as LiCoO 2 , LiMn 2 O 4 , and LiNi 1-x Co x O 2 (0 ⁇ x ⁇ 1) Oxides are mainly used.
  • the negative electrode active material various types of carbon-based materials including artificial, natural graphite, and hard carbon capable of inserting / desorbing lithium have been applied.
  • the graphite of the carbon series has a low discharge voltage of -0.2V compared to lithium, and the battery using this negative electrode active material exhibits a high discharge voltage of 3.6V, which provides an advantage in terms of energy density of the lithium battery and also has excellent reversibility in lithium secondary. It is most widely used to ensure the long life of the battery.
  • the graphite active material has a problem of low capacity in terms of energy density per unit volume of the electrode plate due to the low graphite density (theoretical density of 2.2 g / cc) in the production of the electrode plate, and side reaction with the organic electrolyte used at high discharge voltage is likely to occur. There was a problem of occurrence of swelling of the battery and consequent decrease in capacity.
  • negative electrode active materials such as silicon and tin have been recently developed.
  • silicon-based negative active material it has the advantage of realizing a high capacity when reacting with lithium ions, but there is a problem that the capacity decreases gradually as the contact between the current collector and the active material becomes weak due to a volume change of 300% or more during charge and discharge.
  • the low electrical conductivity of silicon does not occur smoothly the charge transfer reaction that occurs during the insertion / desorption of lithium.
  • a titanium silicide layer formed on an outer surface of a core including a material capable of doping and undoping lithium, and a core including a material capable of doping and undoping lithium. It provides a negative electrode active material for a lithium secondary battery comprising a.
  • the material capable of doping and undoping lithium may be a silicon-based compound.
  • the titanium silicide may be represented by the following Chemical Formula 1.
  • the titanium silicide may be TiSi, TiSi 2 , Ti 3 Si, Ti 5 Si 3 , Ti 5 Si 4, or a combination thereof.
  • the material capable of doping and undoping lithium may be silicon (Si), SiO x1 , Si-C composite, or Si-Q alloy.
  • X1 is greater than or equal to 0 and less than 2, wherein Q is an alkali metal, an alkaline earth metal, a group 13 to 16 element, a transition metal, a rare earth element, or a combination thereof, and silicon is excluded from Q.
  • the material capable of doping and undoping lithium may be in powder form, wafer form, or nanowire form.
  • the titanium silicide may be partially or wholly formed on the outer surface of the core including a material capable of doping and undoping lithium.
  • the amount of titanium included in the negative electrode active material for the lithium secondary battery may be 1 wt% to 5 wt% with respect to 100 wt% of the negative electrode active material for the lithium secondary battery.
  • a surface of a material capable of doping and undoping lithium is prepared by mixing a material capable of doping and undoping lithium, a titanium precursor, and a solvent, and heat treating the obtained mixture. It provides a method for producing a negative electrode active material for a lithium secondary battery comprising the step of forming a titanium silicide layer.
  • the material capable of doping and undoping lithium may be a silicon-based compound.
  • the titanium silicide may be represented by the following Chemical Formula 1.
  • the material capable of doping and undoping lithium may be silicon (Si), SiO x1 , Si-C composite, or Si-Q alloy.
  • X1 is greater than or equal to 0 and less than 2, wherein Q is an alkali metal, an alkaline earth metal, a group 13 to 16 element, a transition metal, a rare earth element, or a combination thereof, and silicon is excluded from Q.
  • the titanium precursor may be titanium alkoxide, titanium halide, titanium hydroxide, titanium alkylamide, or a combination thereof.
  • the titanium precursor is titanium tetrabutoxide (Ti (OCH 2 CH 2 CH 2 CH 3 ) 4 ), titanium tetraisopropoxide (Titanium tetraisopropoxide, Ti [OCH (CH 3 ) 2 ] 4 ), titanium tetrachloride (TiCl 4 ), titanium tetrafluoride (TiF 4 ), tetrakis dimethyl amino titanium, TDMAT, Ti [N (CH 3 ) 2 ] 4 ) or a combination thereof.
  • the solvent may be water, alcohol, ketone, weak acid, amide or a combination thereof.
  • the heat treatment may be performed at 400 °C to 1100 °C.
  • the heat treatment may be made at 400 ° C to 500 ° C and then once again at 900 ° C to 1000 ° C.
  • the heat treatment may be performed in air or in an inert gas atmosphere.
  • the heat treatment may be performed for 0.5 hours to 12 hours.
  • the method for preparing a negative active material for a lithium secondary battery includes introducing a hydrophilic group onto a surface of a material capable of doping and undoping lithium before mixing the material capable of doping and undoping the lithium, a titanium precursor, and a solvent. It may further comprise a step.
  • Introducing a hydrophilic group on the surface of the material capable of doping and undoping the lithium may be performed by a method of acid treating the material capable of dope and undoping the lithium.
  • a lithium secondary battery negative electrode including the negative electrode active material for the lithium secondary battery; A positive electrode including a positive electrode active material; A separator present between the cathode and the anode; And it provides a lithium secondary battery comprising an electrolyte.
  • a lithium secondary battery negative active material a method of manufacturing a negative active material for a lithium secondary battery, and a lithium secondary battery including the negative active material for a lithium secondary battery may achieve high capacity and excellent lifespan characteristics.
  • FIG. 1 is an exploded perspective view of a rechargeable lithium battery according to one embodiment.
  • FIG. 2 is a scanning electron microscope (SEM) photograph of a negative electrode active material according to an embodiment of the present invention.
  • SEM scanning electron microscope
  • FIG. 3 is an enlarged SEM photograph of FIG. 2.
  • FIG. 4 is a spectrum obtained by analyzing the SEM image of FIG. 2 with Energy Dispersive x-ray Spectroscopy (EDAX).
  • EDAX Energy Dispersive x-ray Spectroscopy
  • FIG 5 is an X-ray diffraction graph of an anode active material according to an embodiment of the present invention.
  • FIG. 6 is an enlarged graph of the titanium silicide peak in FIG. 5.
  • FIG. 7 is an X-ray diffraction graph of an anode active material according to another embodiment of the present invention.
  • FIG. 8 is an enlarged graph of the titanium silicide peak in FIG. 7.
  • FIG. 9 is a graph showing charge and discharge capacity of a rechargeable lithium battery according to one embodiment of the present invention.
  • FIG. 10 is a graph illustrating life characteristics of a rechargeable lithium battery according to one embodiment of the present invention.
  • FIG. 11 is a graph of charge and discharge capacity of a lithium secondary battery according to a comparative example of the present invention.
  • FIG. 12 is a graph of life characteristics of a lithium secondary battery according to a comparative example of the present invention.
  • an "alkyl group” means a “saturated alkyl group” that does not include any alkene or alkyne; Or “unsaturated alkyl group” containing at least one alkene group or alkyne group.
  • the "alkene group” refers to a substituent in which at least two carbon atoms form at least one carbon-carbon double bond
  • the “alkyne group” refers to a substituent in which at least two carbon atoms form at least one carbon-carbon triple bond. it means.
  • the alkyl group may be branched, straight chain or cyclic.
  • the alkyl group may be an alkyl group of C1 to C20, specifically, a lower alkyl group of C1 to C6, a middle alkyl group of C7 to C10, and a higher alkyl group of C11 to C20.
  • a C1 to C4 alkyl group means that there are 1 to 4 carbon atoms in the alkyl chain, which is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl Selected from the group consisting of:
  • Typical alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl and cyclo Pentyl group, cyclohexyl group, and the like.
  • Aromatic group means a substituent in which all elements of the cyclic substituent have p-orbitals, and these p-orbitals form a conjugate. Specific examples include an aryl group and a heteroaryl group.
  • a titanium silicide layer formed on an outer surface of a core including a material capable of doping and undoping lithium, and a core including a material capable of doping and undoping lithium. It provides a negative electrode active material for a lithium secondary battery comprising a.
  • the material capable of doping and undoping lithium may be a silicon-based compound.
  • the negative electrode active material for a lithium secondary battery has a fast reaction rate with lithium ions, is effective in suppressing a volume change of the negative electrode active material generated during charging and discharging of a lithium secondary battery, and may improve electron transfer speed in an electrolyte.
  • the lithium secondary battery including the negative electrode active material may realize high capacity, excellent charge and discharge efficiency, and lifespan characteristics.
  • the silicide means a compound of an element and silicon that are more electrically positive than silicon.
  • the electrically positive element may be a single element or a plurality of elements.
  • the electrically positive element may be a metal.
  • the titanium silicide is a compound containing titanium (Ti) and silicon (Si), which is a kind of metal silicide and a kind of titanium alloy.
  • the titanium silicide may be represented by the following Chemical Formula 1.
  • the titanium silicide may be specifically TiSi, TiSi 2 , Ti 3 Si, Ti 5 Si 3 , Ti 5 Si 4 or a combination thereof, but is not limited thereto.
  • the material capable of doping and undoping lithium may be silicon (Si), SiO x1 , Si-C composite, or Si-Q alloy.
  • X1 is greater than or equal to 0 and less than 2, wherein Q is an alkali metal, an alkaline earth metal, a group 13 to 16 element, a transition metal, a rare earth element, or a combination thereof, and silicon is excluded from Q.
  • Q Specific elements of Q include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof is mentioned.
  • a lithium secondary battery including the same may realize high capacity.
  • the material capable of doping and undoping lithium may be in various forms, and specifically, may be in powder form, wafer form, or nanowire form.
  • the material capable of doping and undoping lithium may be in the form of a porous powder, a porous wafer, or a porous nanowire.
  • the reaction area with the electrolyte may be increased.
  • the titanium silicide may be formed partially, ie, discontinuously on the outside of the core including a material capable of doping and undoping lithium. That is, the titanium silicide may be formed in an island type on the outer side of the core including a material capable of doping and undoping lithium.
  • the titanium silicide may be formed on the entire surface of the core including a material capable of doping and undoping lithium, that is, continuously. That is, the titanium silicide may cover the entire outer periphery of the core including a material capable of doping and undoping lithium.
  • the amount of titanium contained in the negative electrode active material for the lithium secondary battery may be 1 wt% to 5 wt%, specifically 2 wt% to 5 wt%, 1 wt% to 4 wt% with respect to 100 wt% of the negative active material for the lithium secondary battery. , 2% to 4% by weight.
  • the negative electrode active material for the lithium secondary battery When the content of titanium contained in the negative electrode active material for the lithium secondary battery satisfies the above range, the negative electrode active material for the lithium secondary battery has a fast reaction rate with lithium ions and changes in volume of the negative electrode active material generated during charging and discharging of the lithium secondary battery. It is effective in suppressing the reaction rate and can improve the electron transfer speed in the electrolyte.
  • the lithium secondary battery including the negative electrode active material may realize high capacity, excellent charge and discharge efficiency, and lifespan characteristics.
  • a surface of a material capable of doping and undoping lithium is prepared by mixing a material capable of doping and undoping lithium, a titanium precursor, and a solvent, and heat treating the obtained mixture. It provides a method for producing a negative electrode active material for a lithium secondary battery comprising the step of forming a titanium silicide layer.
  • the material capable of doping and undoping lithium may be a silicon-based compound.
  • a titanium precursor reacts with a material capable of doping and undoping lithium and a titanium precursor to produce a titanium silicide layer on the surface of the material capable of doping and undoping lithium.
  • the portion of the titanium precursor that can dope and undo lithium is the outermost surface of the material that can dope and undo lithium.
  • the interior of materials that can dope and undo lithium do not react with titanium.
  • the material capable of doping and undoping lithium becomes the core and the titanium silicide layer becomes the shell to form the core-shell structure.
  • the negative active material for a lithium secondary battery manufactured by the above-described manufacturing method has a fast reaction rate with lithium ions, is effective in suppressing a volume change of the negative electrode active material generated during charging and discharging of a lithium secondary battery, and improves the electron transfer rate in the electrolyte. Can be improved.
  • the lithium secondary battery including the negative electrode active material may realize high capacity, excellent charge and discharge efficiency, and lifespan characteristics.
  • the titanium silicide may be represented by the following Chemical Formula 1.
  • the titanium silicide may be specifically TiSi, TiSi 2 , Ti 3 Si, Ti 5 Si 3 , Ti 5 Si 4 or a combination thereof, but is not limited thereto.
  • the material capable of doping and undoping lithium may be silicon (Si), SiO x1 , Si-C composite, or Si-Q alloy.
  • X1 is greater than or equal to 0 and less than 2, wherein Q is an alkali metal, an alkaline earth metal, a group 13 to 16 element, a transition metal, a rare earth element, or a combination thereof, and silicon is excluded from Q.
  • Q Specific elements of Q include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof is mentioned.
  • a lithium secondary battery including the same may realize high capacity.
  • the material capable of doping and undoping lithium may be in various forms, and specifically, may be in powder form, wafer form, or nanowire form.
  • the material capable of doping and undoping lithium may be in the form of a porous powder, a porous wafer, or a porous nanowire.
  • the reaction area with the electrolyte may be increased.
  • the titanium silicide may be discontinuously formed on the outer surface of the core including a material capable of doping and undoping lithium. That is, the titanium silicide may be formed in an island type on the outer side of the core including a material capable of doping and undoping lithium.
  • the titanium silicide may be continuously formed on the outer side of the core including a material capable of doping and undoping lithium. That is, the titanium silicide may cover the entire outer periphery of the core including a material capable of doping and undoping lithium.
  • the titanium precursor may be titanium alkoxide, titanium halide, titanium hydroxide, titanium alkylamide, or a combination thereof.
  • the titanium precursor is specifically, titanium tetrabutoxide (Ti (OCH 2 CH 2 CH 2 CH 3 ) 4 ), titanium tetraisopropoxide (Ti (OCH (CH 3 ) 2 ] 4 ) , Titanium tetrachloride (TiCl 4 ), titanium tetrafluoride (TiF 4 ), tetrakis dimethyl amino titanium, TDMAT, Ti [N (CH 3 ) 2 ] 4 ), or a combination thereof, but is not limited thereto. It doesn't happen.
  • the content of titanium included in the negative electrode active material for a lithium secondary battery manufactured by the manufacturing method may be 1 wt% to 5 wt% with respect to 100 wt% of the negative electrode active material for the lithium secondary battery.
  • the negative electrode active material for the lithium secondary battery When the content of titanium contained in the negative electrode active material for the lithium secondary battery satisfies the above range, the negative electrode active material for the lithium secondary battery has a fast reaction rate with lithium ions and changes in volume of the negative electrode active material generated during charging and discharging of the lithium secondary battery. It is effective in suppressing the reaction rate and can improve the electron transfer speed in the electrolyte.
  • the lithium secondary battery including the negative electrode active material may realize high capacity, excellent charge and discharge efficiency, and lifespan characteristics.
  • the titanium precursor may be set in an amount of 1 wt% to 5 wt% based on 100 wt% of the negative active material for the lithium secondary battery. As the content of the titanium precursor increases, the amount of titanium in the negative electrode active material increases. By adjusting the content of the titanium precursor within the above range it is possible to control the amount of titanium silicide formed on the surface of the material capable of doping and undoping the lithium.
  • the solvent may be water, alcohol, ketone, weak acid, amide or a combination thereof.
  • the solvent is methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butyl alcohol, ethylene glycol (ethylene glycol, EG), dimethylformamide (dimethylformamide, DMF), methylpyrrolidone, NMP ) Or a combination thereof, but is not limited thereto.
  • the solvent may be a solvent in which ethylene glycol and ethanol are mixed.
  • titanium oxide is formed on the surface of the material capable of doping and undoping lithium from the titanium precursor, and at the same time, titanium and material capable of doping and undoping lithium are formed. Reaction with each other produces a titanium silicide layer on the surface of the material capable of doping and undoping lithium.
  • the solvent may be removed through the heat treatment.
  • the heat treatment may be made at 400 °C to 1100 °C, specifically 450 °C to 1100 °C, 400 °C to 1000 °C, 450 °C to 1000 °C.
  • the temperature range of the heat treatment is a temperature at which the titanium precursor can react with a material capable of doping and undoping lithium to form titanium silicide. That is, the titanium precursor begins to transition to titanium silicide at 400 ° C. to 450 ° C., and all titanium precursors are transitioned to titanium silicide at 1000 ° C. to 1100 ° C.
  • the heat treatment may be made at 400 ° C to 500 ° C, and then once again at 900 ° C to 1000 ° C. In this case, aggregation of the titanium precursor may be suppressed.
  • the heat treatment may be performed in air or in an inert gas atmosphere. Specifically, the heat treatment may be performed once more in an inert gas atmosphere after being made in the atmosphere.
  • the inert gas include nitrogen, neon, argon, krypton, xenon, radon, and the like.
  • the heat treatment time may vary depending on the heat treatment temperature. Specifically, the heat treatment may be performed for 0.5 to 12 hours, or 1 to 3 hours.
  • heat treatment at 450 ° C. does not change all titanium precursors to titanium silicides even after 12 hours of reaction.
  • some titanium precursors are stabilized with titanium oxide, while others are converted to titanium silicides.
  • the heat treatment temperature is for example 1000 ° C., all titanium precursors are transferred to titanium silicides in 30 minutes to 1 hour.
  • the heat treatment may be performed in the air for 0.5 to 2 hours, or may be performed in an inert gas atmosphere for 0.5 to 5 hours.
  • titanium silicide It is possible to control the type, form and amount of titanium silicide by adjusting the temperature and time of the heat treatment within the range of the substrate.
  • TiSi 2 , Ti 5 Si 3 and the like are formed, mainly TiSi 2 is formed.
  • heat-treated for 4 hours at 1000 °C argon atmosphere TiSi 2 and Ti 5 Si 3 and the like are formed, mainly Ti 5 Si 3 is formed.
  • a hydrophilic group is introduced to a surface of a material capable of doping and undoping lithium before mixing a material capable of doping and undoping lithium, a titanium precursor, and a solvent. It may further comprise the step.
  • the hydrophilic group include a hydroxy group (-OH), a carboxy group (-COOH), an amino group (-NH 2 ), a sulfone group (-SO 3 H), and the like.
  • the reason for introducing the hydrophilic group is to bind the titanium evenly dispersed in the surface of the material capable of doping and undoping the lithium.
  • Introducing a hydrophilic group on the surface of the material capable of doping and undoping the lithium may be performed by a method of acid treating the material capable of dope and undoping the lithium.
  • the acid includes, for example, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, and the like.
  • a lithium secondary battery negative electrode including the negative electrode active material for the lithium secondary battery; A positive electrode including a positive electrode active material; A separator present between the cathode and the anode; And it provides a lithium secondary battery comprising an electrolyte.
  • the lithium secondary battery may be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery according to the type of separator and electrolyte used, and may be classified into a cylindrical shape, a square shape, a coin type, a pouch type, and the like, Depending on the size, it can be divided into bulk type and thin film type. Since the structure and manufacturing method of these batteries are well known in the art, detailed description thereof will be omitted.
  • the lithium secondary battery 100 is cylindrical and has a negative electrode 112, a positive electrode 114, a separator 113 disposed between the negative electrode 112 and the positive electrode 114, and the negative electrode 112. ), The electrolyte impregnated in the positive electrode 114 and the separator 113, the battery container 120, and the sealing member 140 which encloses the said battery container 120 are comprised as a main part.
  • the lithium secondary battery 100 is configured by stacking the negative electrode 112, the separator 113, and the positive electrode 114 in order, and then storing the lithium secondary battery 100 in the battery container 120 in a state wound in a spiral shape.
  • the negative electrode includes a current collector and a negative electrode active material layer formed on the current collector, and the negative electrode active material layer includes a negative electrode active material.
  • the negative electrode active material is as described above.
  • the negative electrode active material layer also includes a binder, and optionally may further include a conductive material.
  • the binder adheres the anode active material particles to each other well, and also serves to adhere the anode active material to the current collector well, and representative examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, and carboxylation.
  • Polyvinylchloride, polyvinylfluoride, polymers including ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylic ray Tied styrene-butadiene rubber, epoxy resin, nylon, and the like may be used, but is not limited thereto.
  • the conductive material is used to impart conductivity to the electrode, and may be used as long as it is an electronic conductive material without causing chemical change in the battery to be constructed. Examples thereof include natural graphite, artificial graphite, carbon black, acetylene black, and ketjen black. Carbon-based materials such as carbon fibers; Metal materials such as metal powder or metal fibers such as copper, nickel, aluminum and silver; Conductive polymers such as polyphenylene derivatives; Or a conductive material containing a mixture thereof.
  • the current collector may be copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam (foam), copper foam, a polymer substrate coated with a conductive metal, or a combination thereof.
  • the positive electrode includes a current collector and a cathode active material layer formed on the current collector.
  • a compound (lithiated intercalation compound) capable of reversible intercalation and deintercalation of lithium may be used.
  • one or more of complex oxides of metal and lithium of cobalt, manganese, nickel or a combination thereof may be used, and specific examples thereof may be a compound represented by any one of the following formulas.
  • Li a A 1-b R b D 2 (wherein 0.90 ⁇ a ⁇ 1.8 and 0 ⁇ b ⁇ 0.5); Li a E 1-b R b O 2-c D c (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); LiE 2-b R b 0 4-c D c (wherein 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); Li a Ni 1-bc Co b R c D ⁇ (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ ⁇ 2); Li a Ni 1-bc Co b R c O 2- ⁇ Z ⁇ (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05 and 0 ⁇ ⁇ 2); Li a
  • A is Ni, Co, Mn or a combination thereof;
  • R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements or combinations thereof;
  • D is O, F, S, P or a combination thereof;
  • E is Co, Mn or a combination thereof;
  • Z is F, S, P or a combination thereof;
  • G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V or a combination thereof;
  • Q is Ti, Mo, Mn or a combination thereof;
  • T is Cr, V, Fe, Sc, Y or a combination thereof;
  • J is V, Cr, Mn, Co, Ni, Cu or a combination thereof.
  • the coating layer may include an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxycarbonate of a coating element.
  • the compounds constituting these coating layers may be amorphous or crystalline.
  • the coating element included in the coating layer Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr or a mixture thereof may be used.
  • the coating layer forming process may use any coating method as long as it does not adversely affect the physical properties of the positive electrode active material by using such elements in the compound (for example, spray coating, dipping, etc.). Details that will be well understood by those in the field will be omitted.
  • the positive electrode active material layer also includes a binder and a conductive material.
  • the binder adheres the positive electrode active material particles to each other well, and also serves to adhere the positive electrode active material to the current collector well, and representative examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and polyvinyl. Chloride, carboxylated polyvinylchloride, polyvinylfluoride, polymer comprising ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene- Butadiene rubber, acrylic styrene-butadiene rubber, epoxy resin, nylon and the like can be used, but is not limited thereto.
  • the conductive material is used to impart conductivity to the electrode, and any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery.
  • any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery.
  • Metal powders such as black, carbon fiber, copper, nickel, aluminum, silver, metal fiber, etc. can be used, and 1 type (s) or 1 or more types can be mixed and used for conductive materials, such as a polyphenylene derivative.
  • Al may be used as the current collector, but is not limited thereto.
  • the negative electrode and the positive electrode are each prepared by mixing an active material, a conductive material and a binder in a solvent to prepare an active material composition, and applying the composition to a current collector. Since such an electrode manufacturing method is well known in the art, detailed description thereof will be omitted. N-methylpyrrolidone may be used as the solvent, but is not limited thereto.
  • the electrolyte contains a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the cell can move.
  • the non-aqueous organic solvent may be a carbonate, ester, ether, ketone, alcohol or aprotic solvent.
  • the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), and ethylene carbonate ( EC), propylene carbonate (PC), butylene carbonate (BC) and the like
  • the ester solvent may be methyl acetate, ethyl acetate, n-propyl acetate, 1,1-dimethylethyl acetate, methylpropionate.
  • Ethyl propionate, ⁇ -butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone and the like may be used.
  • Dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran may be used as the ether solvent, and cyclohexanone may be used as the ketone solvent.
  • R-CN R is a C2 to C20 linear, branched or cyclic hydrocarbon group
  • Amides such as nitriles, dimethylformamide, and dioxolanes, such as 1,3-dioxolane, and sulfolanes, such as 1,3-dioxolane, and the like.
  • the non-aqueous organic solvent may be used alone or in combination of one or more, and the mixing ratio in the case of mixing one or more may be appropriately adjusted according to the desired battery performance, which is widely understood by those skilled in the art. Can be.
  • the carbonate solvent it is preferable to use a mixture of a cyclic carbonate and a chain carbonate.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of about 1: 1 to about 1: 9, so that the performance of the electrolyte may be excellent.
  • the non-aqueous organic solvent may further include the aromatic hydrocarbon organic solvent in the carbonate solvent.
  • the carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of about 1: 1 to about 30: 1.
  • an aromatic hydrocarbon compound of Formula 2 may be used as the aromatic hydrocarbon organic solvent.
  • R 1 to R 6 are each independently hydrogen, halogen, C1 to C10 alkyl group, C1 to C10 haloalkyl group, or a combination thereof.
  • the aromatic hydrocarbon organic solvent is benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene , 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2, 4-trichlorobenzene, iodobenzene, 1,2-dioodobenzene, 1,3-dioodobenzene, 1,4-dioiobenzene, 1,2,3-triiodobenzene, 1,2,4 -Triiodobenzene, toluene, fluorotoluene, 1,2-difluorotoluene, 1,3-difluorotoluene
  • the non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate-based compound of Formula 3 to improve battery life.
  • R 7 and R 8 are each independently hydrogen, a halogen group, a cyano group (CN), a nitro group (NO 2 ), or a fluoroalkyl group of C1 to C5, and at least one of R 7 and R 8 Is a halogen group, cyano group (CN), nitro group (NO 2 ) or a fluoroalkyl group of C1 to C5.
  • ethylene carbonate compounds include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, fluoroethylene carbonate, and the like. Can be. When the vinylene carbonate or the ethylene carbonate-based compound is further used, the amount thereof may be appropriately adjusted to improve life.
  • the lithium salt is dissolved in the non-aqueous organic solvent, acts as a source of lithium ions in the battery to enable the operation of the basic lithium secondary battery, and serves to promote the movement of lithium ions between the positive electrode and the negative electrode to be.
  • Representative examples of the lithium salt are LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y +1 SO 2 ), where x and y are natural numbers, LiCl, LiI, LiB (C 2 O 4 ) 2 (lithium bis (oxalato) borate (LiBOB) or combinations thereof
  • the lithium salt may be used within the range of 0.1 to 2.0 M. When the concentration of the lithium salt is included in the above range, the electrolyte has an appropriate conductivity and viscosity. It can exhibit excellent electro
  • the separator 113 separates the negative electrode 112 and the positive electrode 114 and provides a moving passage for lithium ions, and any separator can be used as long as it is commonly used in a lithium battery. In other words, those having low resistance to ion migration of the electrolyte and excellent electrolyte-wetting ability can be used.
  • it is selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or a combination thereof, and may be in a nonwoven or woven form.
  • a polyolefin-based polymer separator such as polyethylene or polypropylene is mainly used for a lithium ion battery, and a coated separator including a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength. Can be used as a structure.
  • the silicon is treated with nitric acid to introduce silanol groups to the silicon surface.
  • 1 g of the activated silicon and 0.3 g of titanium tetrabutoxide (Ti (OCH 2 CH 2 CH 2 CH 3 ) 4 ) were added to 20 mL of a solution in which ethylene glycol and ethanol were mixed at a 4: 1 weight ratio, and maintained at 60 ° C. do. After washing several times with ethanol and centrifuged to remove ethylene glycol.
  • the material thus obtained is dried and heat-treated at 450 ° C. for 1 hour in an air atmosphere to prepare a cathode active material for a lithium secondary battery having a core-shell structure in which titanium silicide is formed on a silicon surface.
  • the mixed solvent (3: 7 volume ratio of ethylene carbonate (EC) and dimethyl carbonate (DMC) in which 1.3 M of LiPF 6 was melt
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • Example 1 the lithium secondary cell (half cell) in the same manner as in Example 1 except that after the heat treatment for 1 hour at 450 °C in an air atmosphere, further heat treatment at 1000 °C in an argon atmosphere To prepare.
  • a lithium secondary cell was manufactured in the same manner as in Example 1, except that silicon was treated with nitric acid and silicon introduced with a silanol group on the surface was used as a negative electrode active material.
  • Example 2 The negative electrode active material prepared in Example 2 and Comparative Example 1 was photographed by a scanning electron microscope (Hitachi, Fe-SEM).
  • FIG. 2 is an SEM photograph of the nanoparticles prepared in Example 2
  • FIG. 3 is an enlarged photograph 10 times of FIG. 2 and 3, it can be seen that the titanium silicide is formed on the surface of the silicon core.
  • Example 4 is a spectrum obtained by analyzing the SEM image of FIG. 2 with EDAX (Energy Dispersive x-ray Spectroscopy).
  • EDAX Electronic Dispersive x-ray Spectroscopy
  • the content of each element in the negative electrode active material for a lithium secondary battery prepared in Example 2 can be seen through FIG. 4.
  • the titanium element is contained 2.06% by weight in 100% by weight of the negative electrode active material for a lithium secondary battery prepared in Example 2.
  • Example 5 is an X-ray diffraction analysis (X-ray diffraction, light source CuK ⁇ ) graph of the negative electrode active material for a lithium secondary battery prepared in Example 1. 5, it can be seen that the strength of the silicon peak is high and the peak of the titanium silicide is low. That is, it can be seen that the negative electrode active material for the lithium secondary battery manufactured in Example 1 is mostly silicon and a small amount of titanium is formed.
  • FIG. 6 is an enlarged graph of peaks of titanium silicide having a relatively low strength in FIG. 5 to see what kind of titanium silicide is formed.
  • the formed titanium silicide is TiSi 2 and Ti 3 Si 5 It can be seen that a lot of TiSi 2 is produced.
  • Example 7 is an X-ray diffraction graph of a negative active material for a lithium secondary battery prepared in Example 2; As shown in FIG. 5, the strength of the silicon peak is high and the peak of the titanium silicide is low, so that the negative active material for the lithium secondary battery prepared in Example 2 is mostly silicon and a small amount of titanium is formed.
  • FIG. 8 is an enlarged graph of the titanium silicide peak in FIG. 7.
  • FIG. 8 has an increased strength of Ti 5 Si 3 compared to FIG. 6. Through this, the heat treatment temperature increases when TiSi 2 portion is switched to Ti 5 Si 3 it can be seen that the amount of the Ti 5 Si 3 increases.
  • Example 9 is a graph measuring charge and discharge capacity of the lithium secondary battery prepared in Example 2;
  • the voltage profile at 0.1C rate shows a discharge capacity of 2970 mAh / g and a charge capacity of 2680 mAh / g. It can be seen that the efficiency is very high as 90.2%. This suggests that the titanium silicide layer has sufficient electrical conductivity.
  • FIG. 11 is a graph measuring charge and discharge capacity of the lithium secondary battery manufactured in Comparative Example 1.
  • FIG. The voltage profile at 0.1C rate shows a discharge capacity of 2930 mAh / g and a charge capacity of 2530 mAh / g with an efficiency of 80.2%. It can be seen that the efficiency is very low compared to the case of the lithium secondary battery prepared in Example 2. This is a phenomenon that occurs due to the low electrical conductivity of silicon.
  • Example 10 is a graph showing the life characteristics of the lithium secondary battery prepared in Example 2.
  • the first cycle is the result at 0.1C, and the second to 50th cycles show a 0.2C rate.
  • the charging capacity in the second cycle is 2100 mAh / g, and the 50th cycle is 1750 mAh / g, showing a capacity retention of about 83% or more after 50 cycles.
  • lithium secondary battery 112 negative electrode

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Abstract

La présente invention concerne un matériau actif d'électrode négative pour une batterie rechargeable au lithium, comprenant : un noyau comprenant un matériau qui permet le dopage et le dédopage du lithium ; et une couche de siliciure de titane formée le long de la périphérie extérieure du noyau comprenant le matériau qui permet le dopage et le dédopage du silicium. L'invention concerne en outre un procédé de préparation du matériau actif d'électrode négative pour batterie rechargeable au lithium et ladite batterie rechargeable au lithium comprenant le matériau actif d'électrode négative pour batterie rechargeable au lithium.
PCT/KR2013/001010 2012-10-16 2013-02-07 Matériau actif d'électrode négative pour batterie rechargeable au lithium, procédé de préparation de matériau d'électrode négative pour batterie rechargeable au lithium et batterie rechargeable au lithium comprenant ledit matériau actif d'électrode négative pour batterie rechargeable au lithium Ceased WO2014061881A1 (fr)

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KR1020120115076A KR101456201B1 (ko) 2012-10-16 2012-10-16 리튬 이차 전지용 음극 활물질, 리튬 이차 전지용 음극 활물질의 제조 방법 및 상기 리튬 이차 전지용 음극 활물질을 포함하는 리튬 이차 전지

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KR102356936B1 (ko) 2014-12-31 2022-02-03 삼성전자주식회사 복합 음극 활물질, 그 제조방법, 이를 포함하는 음극 및 리튬이차전지
KR101766020B1 (ko) * 2015-07-07 2017-08-08 한국과학기술원 미세기공을 포함하는 고전도성 탄소와 금속 초박막이 코팅된 전도성 단결정 실리콘 입자, 이를 포함하는 고용량 이차전지용 음극활물질 및 그 제조방법
WO2017209561A1 (fr) * 2016-06-02 2017-12-07 주식회사 엘지화학 Matériau cathode actif, cathode le comprenant et batterie secondaire au lithium comprenant ce même matériau
US11133524B2 (en) 2016-06-02 2021-09-28 Lg Chem, Ltd. Negative electrode active material, negative electrode including the same and lithium secondary battery including the same
KR20190037119A (ko) 2017-09-28 2019-04-05 주식회사 엘지화학 리튬 이차 전지용 전극 활물질 복합체 및 상기 전극 활물질 복합체의 제조방법
CN111146409B (zh) * 2018-11-05 2021-02-26 宁德时代新能源科技股份有限公司 负极活性材料、其制备方法及二次电池
CN111146410B (zh) * 2018-11-05 2021-03-02 宁德时代新能源科技股份有限公司 负极活性材料及电池

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