WO2012108741A2 - Procédé de fabrication d'une électrode composite métal lithié/carbone, électrode composite métal lithié/carbone fabriquée par ce procédé et dispositif électrochimique comprenant l'électrode - Google Patents

Procédé de fabrication d'une électrode composite métal lithié/carbone, électrode composite métal lithié/carbone fabriquée par ce procédé et dispositif électrochimique comprenant l'électrode Download PDF

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WO2012108741A2
WO2012108741A2 PCT/KR2012/001075 KR2012001075W WO2012108741A2 WO 2012108741 A2 WO2012108741 A2 WO 2012108741A2 KR 2012001075 W KR2012001075 W KR 2012001075W WO 2012108741 A2 WO2012108741 A2 WO 2012108741A2
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lithium
carbon composite
electrode
metal
composite electrode
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Korean (ko)
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WO2012108741A3 (fr
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선양국
수크로사티브루노
이동주
아순주세프
이성만
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한양대학교 산학협력단
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Priority to US14/652,656 priority Critical patent/US9985326B2/en
Priority claimed from KR1020120014186A external-priority patent/KR101397415B1/ko
Publication of WO2012108741A2 publication Critical patent/WO2012108741A2/fr
Publication of WO2012108741A3 publication Critical patent/WO2012108741A3/fr

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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium oxide or oxide-forming salts thereof
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/052—Li-accumulators
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
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    • 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 a method for producing a lithiated metal carbon composite electrode, to a lithiated metal carbon composite electrode and an electrochemical device comprising the same, and more particularly to a new having a good charge and discharge characteristics and cycle characteristics
  • Ni-MH (Ni-MH) secondary batteries and lithium secondary batteries are increasing.
  • lithium secondary batteries using lithium and nonaqueous electrolytes have been actively developed due to the high possibility of realizing small, lightweight and high energy density batteries.
  • a transition metal oxide such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 is used as a cathode material of a lithium secondary battery, and lithium metal or carbon is used as an anode material.
  • a lithium secondary battery is comprised using the organic solvent which contains lithium ion as electrolyte between two electrodes.
  • Lithium secondary batteries using metal lithium as a negative electrode tend to generate dendrite crystals when charging and discharging are repeated, and thus there is a high risk of short circuit. Therefore, a carbonized or graphitized carbon material is used for the negative electrode.
  • BACKGROUND ART Lithium secondary batteries having a nonaqueous solvent containing lithium ions as an electrolyte have been put to practical use.
  • the graphitized carbon material has a theoretical lithium storage capacity of 372 mAh / g, which is equivalent to 10% of the lithium metal theory capacity, and has a very small capacity. Therefore, the progress has been actively focused on materials having a higher lithium storage capacity than graphite.
  • silicon-based materials have attracted much attention due to their high capacity (4200 mAhg ⁇ 1 ).
  • the silicon has a problem that the volume change (shrinkage or expansion) occurs during the insertion / de-insertion process of lithium ions, the mechanical stability is lowered, and as a result the cycle characteristics are inhibited. Therefore, it is necessary to develop a material having structural stability and excellent stability when used as an active material of an electrochemical device and ensuring cycle characteristics.
  • a metal alloy-based negative electrode active material which has a higher capacity, has excellent life characteristics, and can replace a conventional carbon-based negative electrode or a lithium metal negative electrode.
  • a metal alloy-based negative electrode material such as Sn, Si, Ge, etc.
  • the performance of the electrochemical device using the metal alloy negative electrode active material is greatly affected by the manufacturing method or structure of the composite, it is necessary to develop a new manufacturing method that can improve the performance of the electrochemical device.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing a lithiated metal carbon composite electrode and a lithiated metal carbon composite electrode produced thereby.
  • Another object of the present invention is to provide an electrochemical device comprising the lithiated metal carbon composite electrode.
  • the present invention to achieve the above object
  • It provides a method for producing a lithiated metal carbon composite electrode consisting of a fourth step of applying a pressure while adding a solution to the current collector is laminated lithium.
  • a metal carbon composite is first prepared in a first step.
  • the metal carbon composite material is not particularly limited, and the metal carbon composite material is selected from the group consisting of Mg, Ca, Al, Si, Ge, Sn, Pb, As, Bi, Ag, Au, Zn, Cd, and Hg. It is a complex of metal and carbon and both are possible.
  • the metal carbon composite material is preferably a silicon carbon composite material or a tin carbon composite material.
  • the production method of the metal carbon composite is not particularly limited and a general production method may be used.
  • a gel of resorcinol and formaldehyde is prepared according to the process described in Italian Application No. RM2008A000381, and after immersing a tin-organic precursor in the gel, It can manufacture by the process of heat processing.
  • a slurry is prepared by mixing the metal carbon composite, the conductive material, and the binder in a solvent, and applied to a current collector.
  • the binder may include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, and ethylene oxide.
  • Polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon and the like can be used, but is not limited thereto.
  • any conductive material may be used as the conductive material without causing chemical change, and examples thereof include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, and carbon fiber; 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 content of the metal carbon composite may be 60% by weight to 90% by weight based on the total weight of solids, the content of the binder is 5% by weight to 20% by weight, and the content of the conductive material is 5% by weight to 20% by weight. Can be%.
  • the current collector may be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and combinations thereof. .
  • the lithium is laminated on the current collector coated with the slurry including the metal carbon composite material.
  • the lithium is in the form of a sheet (sheet), the thickness is preferably 50 or more.
  • the lithium has a sheet (sheet) form is preferable in terms of improving the workability in the manufacturing process, the thickness is 50 or more is advantageous to sufficiently lithiize the metal carbon composite.
  • the solution may be a solution in which lithium salt is dissolved in a non-aqueous organic solvent.
  • a solution in which a lithium salt is dissolved in the non-aqueous organic solvent is added, lithium ions can be well transferred from the lithium metal to the surface and the inside of the metal carbon composite material.
  • the lithium salt may be LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 3 C, and LiBPh At least one selected from the group consisting of four .
  • the non-aqueous organic solvent includes an organic solvent and an ionic solvent, wherein the non-aqueous organic solvent is ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), 1,2-dimethoxyethane (DME), -butyrolactone (GBL), tetrahydrofuran (THF), 1,3-dioxolane (DOXL), dimethylether (DEE), methyl propionate (MP), sulfolane (S), dimethyl sulfoxide (DMSO), acetonitrile (AN), and tetraethylene glycol dimethyl ether (TEGDME) is one or more selected from the group consisting of ionic
  • the solvent is 1-ethyl-3-methylimidazolium (EMI)-(CF 3 SO 2 ) 2 N, 1-butyl-3-methylimidazolium (BMI)-(CF 3 SO 2
  • the concentration of the lithium salt in the solution in which the lithium salt is dissolved in the non-aqueous organic solvent may be in the range of 0.1 to 2.0M.
  • concentration of the lithium salt is included in this range, the ionic conductivity of the electrolyte is increased, and lithium ions are easily moved to the metal carbon composite, thereby promoting the formation of the lithiated metal carbon composite.
  • the pressure applied to the current collector in which lithium is laminated in the fourth step is 300 to 3500 N / m 2.
  • lithium When pressure is applied to the current collector in which lithium is laminated as described above, lithium is transferred from the stacked lithium to the metal carbon composite, a part of lithium forms an alloy with the metal, and the other part of lithium is the carbon crystal structure. Will be inserted into
  • the pressure to add lithium is 300 N / m2 or less takes a long time to the metal carbon composite lithiation process, if the pressure to apply the lithium is more than 3500 N / m2 it is difficult to remove the stacked lithium for lithiation again .
  • the method of applying pressure to the current collector on which lithium is laminated is not particularly limited. That is, after the lithium is laminated on the current collector, the plate is laminated on the upper part, and a weight indicating a certain weight is placed on the plate so that pressure is uniformly applied to the entire current collector.
  • a weight indicating a certain weight is placed on the plate so that pressure is uniformly applied to the entire current collector.
  • lithium can be applied to a metal carbon composite material by such a physical method and used as an electrode of an electrochemical device.
  • the pressure after the pressure is applied to the current collector in which the lithium is laminated, it further comprises a fifth step of removing the laminated lithium.
  • the present invention also provides a lithiated metal carbon composite electrode produced by the production method of the present invention.
  • the lithiated metal carbon composite electrode is characterized in that a portion of the lithium forms an alloy with the metal, the remaining portion of the lithium is inserted into the carbon crystal structure.
  • the present invention also provides an electrochemical device comprising a lithiated metal carbon composite electrode produced by the production method of the present invention.
  • the lithiated metal carbon composite electrode is used as a negative electrode to replace the existing carbon-based negative electrode.
  • the electrochemical device of the present invention comprises a positive electrode and / or a negative electrode comprising the lithiated metal carbon composite electrode; And separators present therebetween. It also includes an electrolyte that is impregnated with the positive electrode, the negative electrode, and the separator.
  • the electrolyte may be a liquid electrolyte or a polymer gel electrolyte.
  • the electrochemical device is characterized in that the lithium sulfur battery, lithium air battery or lithium ion battery.
  • the electrochemical device is characterized in that the lithium air battery containing a polymer composite electrolyte or a liquid electrolyte.
  • the polymer composite electrolyte is a film formed of a first lithium salt and a polymer; And an ion conductive solvent impregnated in the film, wherein the organic solvent comprises a second lithium salt and an organic solvent, wherein the organic solvent is tetraethylene glycol dimethyl ether, ethylene glycol dimethacrylate, polyethylene glycol, polyethylene glycol dialkyl ether. , Polyalkyl glycol dialkyl ethers or combinations thereof.
  • the liquid electrolyte is characterized in that represented by the general formula R 1 (CR 3 2 CR 4 2 O) n R 2 .
  • R 1 and R 2 are each independently H, alkyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkoxy, cyryl, substituted alkyl, substituted cycloalkyl, substituted And aryl, substituted heterocyclyl, substituted heteroaryl, substituted alkoxy, substituted silyl, halogen.
  • R 3 and R 4 are each independently represented by H, halogen, alkyl, cycloalkyl, aryl, substituted alkyl, substituted aryl.
  • the liquid electrolyte is selected from tetraethylene glycol dimethyl ether, ethylene glycol dimethacrylate, polyethylene glycol, polyethylene glycol dialkyl ether, polyalkyl glycol dialkyl ether, or a combination thereof.
  • Lithiumated metal carbon composite electrode according to the present invention since lithium forms an alloy with metal and is inserted into the crystal structure of carbon to form a composite of stable structure, the volume change of the metal during the charging and discharging process is small, thus The cycle characteristics are not deteriorated, the charge and discharge capacity is improved, the irreversible capacity can be controlled during initial charge and discharge, and it has the effect of replacing the lithium metal anode having low safety.
  • Figure 1 shows the results of XRD measurement for the electrode prepared in Examples 1-1 to 1-3 and Comparative Example 1 prepared in accordance with an embodiment of the present invention.
  • Example 5 is a result of measuring the initial charge and discharge characteristics of the lithiated tin carbon composite electrode prepared according to Example 2 of the present invention.
  • Example 6 is a result of measuring the second charge and discharge characteristics of the lithiated tin carbon composite electrode prepared according to Example 2 of the present invention.
  • Example 7 is a result of measuring the charge and discharge characteristics of a lithium air battery using a lithiated tin carbon composite electrode prepared according to Example 2 of the present invention.
  • a silicon graphite composite having a particle size of 5 to 15 ⁇ m was prepared.
  • the prepared silicon graphite composite powder was mixed with NMP in a weight ratio of super P, CMC, SBR and 85: 5: 3.3: 6.7, respectively, to prepare a slurry, and then cast on a copper foil as a current collector.
  • the cast electrode was first dried in an oven at 110 ° C. for 2 hours, and then dried in vacuo for 12 hours in the form of an electrode.
  • the prepared electrode was cut into a size of 2 ⁇ 2 cm 2, and Li metal was laminated on the electrode, and then a solution in which 1.2 M LiPF 6 was dissolved in an EC: DMC-3: 7 mixed solvent was applied, and 46 N / A lithiated silicon carbon composite electrode was prepared by applying a pressure of m 2 for 30 minutes.
  • the size and time of the pressure applied to the stacked Li metals were as in Table 1 below, and the rest was the same as in Example 1 to obtain a lithiated silicon carbon composite electrode.
  • Example 1-1 46 0.5
  • Example 1-2 1588 0.5
  • Example 1-3 3130 0.5
  • Example 1-4 3130
  • Example 1-5 3130
  • Example 1-6 3130 6
  • Example 1-7 3130 12 Comparative Example 1 - - Comparative Example 2 7756 5
  • An electrode was manufactured in the same manner as in Example 1 except that the process of applying pressure after stacking lithium was made as Comparative Example 1.
  • the amount of pressure applied to the stacked Li metals was 7756 N / m. 2 Except that In the same manner as in Example 1, an electrode was manufactured and Comparative Example 2 was obtained.
  • a half cell was prepared including the lithiumated silicon carbon composite electrodes prepared in Examples 1-1 to 1-7.
  • the charging and discharging capacity of the half cell using the lithiated silicon carbon composite electrode of Examples 1-1 to 1-3 and Comparative Example 1 as the negative electrode was started from charging at 100 mA g ⁇ 1 condition between 0.01 and 1.5 V. Charge and discharge were carried out, and the results are shown in FIG. 2. In the case of Comparative Example 2, the amount of pressure applied for lithiation was too large so that lithium metal was not separated into the electrode.
  • the OCV was reduced according to the magnitude of the pressure applied during lithiation, it can be seen that the charge capacity is reduced.
  • the ratio of the discharge capacity to the charge capacity increases as the pressure applied for lithiation increases, thereby adjusting the magnitude of the pressure applied for lithiation.
  • the initial reversible capacity of electricity can be controlled by adjusting the degree of lithiation of the lithiated silicon carbon composite.
  • Examples 1-4 to 1-7 the reverse cell to which the lithiated silicon carbon composite and the silicon carbon composite electrode of Comparative Example 1 is applied in the range of 0.01 ⁇ 1.5 V Example 1-4 to 100 ⁇ g -1
  • the electrode of 1-7 was performed from discharge, the comparative example 1 was implemented from charge, and charge / discharge was shown, and the result is shown in FIG.
  • the discharge capacity of the silicon carbon composite is sufficiently expressed, and the discharge capacity increases as the time for applying pressure for lithiation increases. Can be. Therefore, it can be seen that the fully lithiated silicon carbon composite can be applied to an electrochemical device by replacing the lithium metal anode.
  • a lithiated silicon carbon composite electrode was manufactured in the same manner as the electrode prepared in Example 1-7.
  • a lithiated silicon carbon composite according to the patent filed by the present inventor (Korean Application No. 10-2011-0028246) was used. Specifically, the hard carbon ball and sulfur are mixed at a ratio of 1: 5, the primary heat treatment for 7 hours at 150 °C in an airtight flask in an Ar atmosphere to support sulfur inside the hard carbon ball, and then cooled to room temperature, After the heat treatment at 300 °C for 2 hours while applying a pressure of 1 MPa to prepare a carbon sulfur composite supported therein sulfur.
  • the sulfur-supported carbon sulfur composite prepared as described above was used as the anode, and the lithiated silicon carbon composite electrode prepared in Examples 1-1 to 1-7 was used as the cathode, (TEGDME) 4 LiCF 3 SO 3
  • the electrolyte was produced using a 2032 coin-type cell.
  • the lithiated silicon carbon composite electrode works sufficiently as a negative electrode of a lithium sulfur battery.
  • the prepared tin carbon composite, super P carbon black conductive material, and polyvinylidene fluoride binder were mixed in an N-methylpyrrolidone solvent at a ratio of 80:10 to 10 to prepare a tin-carbon composite slurry.
  • the tin carbon composite slurry was cast on Cu foil, and the resulting product was dried in an oven at 100 ° C. for 2 hours and then vacuum dried for at least 12 hours.
  • the vacuum dried product was cut to an appropriate size, a lithium metal was placed thereon, and an electrolyte solution (a mixed solvent of ethylene carbonate and dimethyl carbonate (3: 7 volume ratio) in which 1.2 M LiPF 6 was dissolved) was evenly sprayed onto the lithium metal.
  • an electrolyte solution a mixed solvent of ethylene carbonate and dimethyl carbonate (3: 7 volume ratio) in which 1.2 M LiPF 6 was dissolved
  • a lithium-ioned tin carbon composite electrode prepared in Example 2 was used as a negative electrode, and a CR2032-sized half-cell was prepared using the same positive electrode and electrolyte as in Preparation Example 1.
  • an electrolyte solution a mixed solvent (3: 7 volume ratio) of ethylene carbonate and dimethyl carbonate in which 1.2 M LiPF 6 was dissolved was used.
  • the half cell prepared in Preparation Example 3 was charged and discharged twice at a current condition of 100 mAg ⁇ 1 at 2.0V to 0.01V.
  • the charge and discharge results of the first charge and discharge are shown in FIG. 4, and the charge and discharge results of the second charge and discharge are shown in FIG. 5.
  • the half cell manufactured in Preparation Example 3 had a charge capacity of 17.4 mAh / g and a discharge capacity of 407.1 mAh / g during one charge / discharge. Since lithium is already present in the active material, almost no charging is performed. It can be seen that the dose was excellent. In addition, the initial open circuit voltage (OCV) is about 0.05 V, which also indicates that lithium ions are already present in the active material.
  • the half cell including the lithiated tin carbon composite electrode prepared in Preparation Example 3 had a charge capacity of 375.0 mAh / g and a discharge capacity of 359.7 mAh / g during two charge / discharge cycles, which was sufficient as a battery. You can see it works.
  • the lithium air battery using the lithiated tin carbon composite electrode prepared in Preparation Example 4 exhibits a charge / discharge capacity of 500 mAh / g, and fully operates as a battery with a discharge potential of about 2.5V. It can be seen.
  • Lithiumated metal carbon composite electrode according to the present invention since lithium forms an alloy with metal and is inserted into the crystal structure of carbon to form a composite of stable structure, the volume change of the metal during the charging and discharging process is small, thus The cycle characteristics are not deteriorated, the charge and discharge capacity is improved, the irreversible capacity can be controlled during initial charge and discharge, and it has the effect of replacing the lithium metal anode having low safety.

Abstract

La présente invention concerne un procédé de fabrication d'une électrode composite métal lithié/carbone, une électrode composite métal lithié/carbone obtenue par le procédé et un dispositif électrochimique comprenant l'électrode. Plus particulièrement, la présente invention concerne un procédé de fabrication d'une électrode composite métal lithié/carbone ayant une nouvelle structure avec des caractéristiques supérieures de charge/décharge et une cyclabilité supérieure, une électrode composite métal lithié/carbone fabriquée par ce procédé, et un dispositif électrochimique comprenant l'électrode. L'électrode composite métal lithié/carbone selon la présente invention est structurée de telle sorte que le lithium et le métal forment un alliage qui est simultanément introduit dans une structure cristalline de carbone de façon à former un composite ayant une structure stable. En conséquence, il se produit moins de variations dans le volume du métal pendant les processus de charge/décharge, et de ce fait, une dégradation en cyclabilité peut être empêchée, la capacité de charge/décharge peut être améliorée, une capacité irréversible peut être contrôlée pendant une charge/décharge initiale, et une électrode négative utilisant un métal de lithium, qui peut être non sûre, peut être remplacée par l'électrode de la présente invention.
PCT/KR2012/001075 2011-02-11 2012-02-13 Procédé de fabrication d'une électrode composite métal lithié/carbone, électrode composite métal lithié/carbone fabriquée par ce procédé et dispositif électrochimique comprenant l'électrode WO2012108741A2 (fr)

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KR20110012436 2011-02-11
KR10-2011-0012436 2011-02-11
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KR20110028246 2011-03-29
KR1020120014186A KR101397415B1 (ko) 2011-02-11 2012-02-13 리튬화된 금속 탄소 복합체 전극의 제조 방법, 이에 의하여 제조된 리튬화된 금속 탄소 복합체 전극 및 이를 포함하는 전기화학소자
KR10-2012-0014186 2012-02-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111417595A (zh) * 2017-12-07 2020-07-14 韩国海洋大学产学合作基金会 在内部形成空洞的锂-碳复合体及其制造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990086308A (ko) * 1998-05-27 1999-12-15 박호군 카본 전극의 전리튬화 방법과 이를 이용한리튬 이차전지 제조방법
JP2008508671A (ja) * 2004-07-30 2008-03-21 コミツサリア タ レネルジー アトミーク リチウム化電極製造方法、本方法により得られるリチウム化電極、ならびに、この使用
WO2009009206A2 (fr) * 2007-04-23 2009-01-15 Applied Sciences, Inc. Procédé de dépôt de silicium sur des matériaux de carbone et de réalisation d'une anode destinée à être utilisée dans des batteries lithium-ion
KR20100012761A (ko) * 2008-07-29 2010-02-08 삼성에스디아이 주식회사 리튬 이온 이차 전지용 전해액 및 이를 포함하는 리튬 이온이차 전지

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990086308A (ko) * 1998-05-27 1999-12-15 박호군 카본 전극의 전리튬화 방법과 이를 이용한리튬 이차전지 제조방법
JP2008508671A (ja) * 2004-07-30 2008-03-21 コミツサリア タ レネルジー アトミーク リチウム化電極製造方法、本方法により得られるリチウム化電極、ならびに、この使用
WO2009009206A2 (fr) * 2007-04-23 2009-01-15 Applied Sciences, Inc. Procédé de dépôt de silicium sur des matériaux de carbone et de réalisation d'une anode destinée à être utilisée dans des batteries lithium-ion
KR20100012761A (ko) * 2008-07-29 2010-02-08 삼성에스디아이 주식회사 리튬 이온 이차 전지용 전해액 및 이를 포함하는 리튬 이온이차 전지

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATTA, MOM KANCHAN ET AL.: 'In situ electrochemical synthesis of lithiated silicon-carbon based composites anode materials for lithium ion batteries' JOURNAL OF POWER SOURCES vol. 194, 21 June 2009, pages 1043 - 1052 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111417595A (zh) * 2017-12-07 2020-07-14 韩国海洋大学产学合作基金会 在内部形成空洞的锂-碳复合体及其制造方法

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