WO2013183524A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2013183524A1
WO2013183524A1 PCT/JP2013/064951 JP2013064951W WO2013183524A1 WO 2013183524 A1 WO2013183524 A1 WO 2013183524A1 JP 2013064951 W JP2013064951 W JP 2013064951W WO 2013183524 A1 WO2013183524 A1 WO 2013183524A1
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negative electrode
active material
electrode active
lithium
material layer
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PCT/JP2013/064951
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English (en)
Japanese (ja)
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徹也 梶田
慎 芹澤
入山　次郎
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日本電気株式会社
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0442—Anodisation, Oxidation
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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 a high capacity non-aqueous electrolyte secondary battery using a high capacity active material for a negative electrode.
  • Carbon (C) such as graphite and hard carbon is mainly used for the negative electrode of the lithium ion secondary battery. Although carbon can repeat charge / discharge cycles satisfactorily, the capacity has already been used up to near the theoretical capacity, so a significant increase in capacity cannot be expected in the future. On the other hand, there is a strong demand for improving the capacity of lithium ion secondary batteries, and negative electrode materials having a higher capacity than carbon are being studied.
  • An example of a negative electrode material capable of realizing a high capacity is silicon (Si).
  • Si silicon
  • the negative electrode using Si has a large amount of occlusion and release of lithium ions per unit volume and a high capacity, when the lithium ions are occluded and released, the electrode active material itself has a large expansion and contraction, so that the pulverization proceeds.
  • the irreversible capacity in the first charge / discharge is large, and a portion not used for charge / discharge is formed on the positive electrode side. There is also a problem that the charge / discharge cycle life is short.
  • Patent Document 1 proposes a method using Si oxide as a negative electrode active material as a measure for reducing the initial irreversible capacity using Si and improving the charge / discharge cycle life.
  • Si oxide as a negative electrode active material
  • improvement in cycle characteristics has been confirmed.
  • the conductivity of the oxide is low, the current collecting property is lowered, and the irreversible capacity in charge / discharge is large.
  • Patent Document 2 proposes a method using particles obtained by combining a carbon material with Si and Si oxide as a negative electrode active material. Although the improvement of the cycle characteristics is confirmed by this, it is still insufficient, and the improvement of the initial charge / discharge efficiency is insufficient.
  • the method of charging electrochemically is excellent in that it can be charged according to the purpose by controlling the amount of energized electricity, but it is complicated and productivity because it is reassembled as a battery after charging the electrode once. Very low.
  • Patent Document 3 proposes a non-aqueous electrolyte lithium ion secondary battery using a mixed active material with a product.
  • the lithium-containing composite nitride is excellent in terms of compensating the irreversible capacity of the Si oxide, but the capacity per mass of the lithium-containing composite nitride is about 800 mAh / g, which is small compared to the Si oxide, and only the Si oxide is used. There is a problem that the energy density of the battery is smaller than the energy density of the battery when used as the negative electrode active material.
  • Patent Document 4 proposes a method of doping Li to the negative electrode in advance by attaching Li metal to the negative electrode and heating, but the doping time tends to be long, the doping tends to be non-uniform. There is a problem that is high.
  • an object of the present invention is to provide a negative electrode for a non-aqueous electrolyte secondary battery having a high capacity, a manufacturing method thereof, and a non-aqueous electrolyte secondary battery having the negative electrode.
  • the present invention is a negative electrode having a negative electrode active material layer containing at least one selected from the group consisting of silicon, silicon oxide and carbon, and in the presence of an ionic liquid, the negative electrode active material layer and the lithium source
  • the present invention relates to a negative electrode that is doped with lithium by performing a heat treatment by contacting the same, and a method for producing the same.
  • a negative electrode for a non-aqueous electrolyte secondary battery having a high capacity can be provided, and the manufacturing time of the negative electrode can be shortened.
  • FIG. 3 is a schematic cross-sectional view showing a structure of an electrode element included in a laminated laminate type secondary battery. It is sectional drawing of the negative electrode for nonaqueous electrolyte secondary batteries which concerns on this invention.
  • an electrode element in which a positive electrode and a negative electrode are arranged to face each other, and an electrolytic solution are included in an outer package.
  • the shape of the secondary battery may be any of a cylindrical type, a flat wound square type, a laminated square type, a coin type, a flat wound laminated type, and a laminated laminate type, and a laminated laminate type is preferable.
  • a laminated laminate type secondary battery will be described.
  • FIG. 1 is a schematic cross-sectional view showing the structure of an electrode element included in a laminated laminate type secondary battery.
  • This electrode element is formed by alternately stacking a plurality of positive electrodes c and a plurality of negative electrodes a with a separator b interposed therebetween.
  • the positive electrode current collector e of each positive electrode c is welded to and electrically connected to each other at an end portion not covered with the positive electrode active material, and a positive electrode terminal f is welded to the welded portion.
  • a negative electrode current collector d of each negative electrode a is welded and electrically connected to each other at an end portion not covered with the negative electrode active material, and a negative electrode terminal g is welded to the welded portion.
  • the negative electrode has a negative electrode active material layer containing a negative electrode active material containing at least one selected from the group consisting of silicon, silicon oxide, and carbon, and in the presence of an ionic liquid, Lithium is doped by performing a heat treatment by bringing the negative electrode active material layer and the lithium source into contact with each other.
  • the negative electrode before being doped with lithium may be referred to as a “negative electrode structure”.
  • the inventors of the present invention as a result of earnestly studying the problem that when doping Li by a method of heating Li metal in contact with the negative electrode in advance, the doping time is long and tends to be non-uniform, It was found that the low ionic conductivity was the cause. Then, the knowledge which can perform this Li dope process rapidly and uniformly by introduce
  • the negative electrode active material includes at least one selected from the group consisting of silicon, silicon oxide, and carbon, preferably includes silicon, and more preferably includes all of silicon, silicon oxide, and carbon.
  • the silicon oxide include silicon dioxide (SiO 2 ) and SiOx (x> 0, preferably 0 ⁇ x ⁇ 2).
  • the carbon include carbon that performs charging and discharging, such as graphite and hard carbon. These may use only 1 type and may use 2 or more types together.
  • the negative electrode active material may include at least one of silicon, silicon oxide, and carbon. These contents are not particularly limited.
  • the contents of silicon, silicon oxide, and carbon with respect to the total of silicon, silicon oxide, and carbon are 5% by mass to 90% by mass, and 5% by mass, respectively. % To 90% by mass and 2% to 80% by mass are preferable.
  • the content of each silicon, silicon oxide, and carbon with respect to the total of silicon, silicon oxide, and carbon is 20% by mass to 50% by mass, 40% by mass to 70% by mass, and 2% by mass, respectively. More preferably, it is 30 mass% or less.
  • the negative electrode structure is produced by forming a negative electrode active material layer on a negative electrode current collector using a mixture in which a negative electrode active material and a negative electrode binder are mixed.
  • the negative electrode binder include thermosetting compounds represented by polyimide, polyamide, polyamideimide, polyacrylic acid resin, polymethacrylic acid resin, and the like.
  • the content of the negative electrode binder is preferably in the range of 1 to 30% by mass and more preferably 2 to 25% by mass with respect to the total amount of the negative electrode active material and the negative electrode binder.
  • the mixture containing the negative electrode active material and the negative electrode binder can further contain a solvent such as N-methyl-2-pyrrolidone (NMP).
  • NMP N-methyl-2-pyrrolidone
  • a paste prepared by kneading the mixture and solvent is applied onto a negative electrode current collector such as a copper foil and rolled to form a coated electrode plate, or directly pressed to form a pressure molded electrode plate.
  • the negative electrode structure can be fabricated by processing into the form. Specifically, for example, silicon powder, silicon oxide powder, carbon powder, and a negative electrode binder are dispersed in a solvent and kneaded.
  • the kneaded product is applied onto a negative electrode current collector made of a metal foil, and dried in a high-temperature atmosphere to produce a negative electrode structure in which a negative electrode active material layer is formed on the negative electrode current collector. it can.
  • the negative electrode active material layer a material that does not charge and discharge, such as carbon black and acetylene black, may be mixed in order to impart conductivity as necessary.
  • the electrode density of the negative electrode active material layer is preferably 0.5 g / cm 3 or more and 2.0 g / cm 3 or less. When the electrode density is less than 0.5 g / cm 3 , the absolute value of the discharge capacity is small, and there are cases where the merit for the carbon material cannot be obtained. On the other hand, when the electrode density exceeds 2.0 g / cm 3 , it is difficult to impregnate the electrode with the electrolytic solution, and the discharge capacity may be reduced.
  • the negative electrode current collector aluminum, nickel, copper, silver, and alloys thereof are preferable in view of electrochemical stability.
  • Examples of the shape include foil, flat plate, and mesh.
  • the thickness of the negative electrode current collector is preferably 4 to 100 ⁇ m because it is preferable to maintain the strength, and more preferably 5 to 30 ⁇ m in order to increase the energy density.
  • lithium pre-doping treatment in the presence of an ionic liquid, lithium is doped by bringing the negative electrode active material layer in the negative electrode structure into contact with the lithium source and performing a heat treatment (hereinafter referred to as “lithium pre-doping treatment”). May be described).
  • lithium pre-doping treatment a heat treatment
  • the ionic liquid is a salt composed of a cation and an anion that shows a liquid state at ⁇ 10 ° C. to 100 ° C.
  • the ionic liquid preferably has lithium ion conductivity. Since the ionic liquid generally has a high decomposition temperature, it is stable even when heated when doping the negative electrode structure with lithium.
  • anion constituting the ionic liquid examples include (CF 3 SO 2 ) 2 N ⁇ (also referred to as TFSI), (C 2 F 5 SO 2 ) 2 N ⁇ (also referred to as BETI), and (FSO 2 ) 2 N ⁇ .
  • CF 2 SO 2 ) 2 N ⁇ referred to as C-TFSI
  • CF 2 ) 3 (SO 2 ) 2 N ⁇ a cyclic anion such as (CF 2 SO 2 ) 2 N ⁇ (referred to as C-TFSI) or (CF 2 ) 3 (SO 2 ) 2 N ⁇ .
  • TFSI, BETI, FSI or (C 4 F 9 SO 2) 2 N - imide anion are preferable, TFSI or FSI is more preferable.
  • Examples of the cation constituting the ionic liquid include lithium, imidazolium, ammonium, pyridinium, pyrrolidinium, piperidinium, phosphonium, and sulfonium.
  • Examples of the imidazolium include 1-ethyl-3-methylimidazolium (EMI), 1-methyl-3-octylimidazolium (MOI), 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1 Examples include -propyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, or 1-ethyl-2,3-dimethylimidazolium.
  • ammonium examples include tetrabutylammonium, tetraethylammonium, triethylmethylammonium, N, N-dimethyl-N-methyl-N- (2-methoxyethyl) ammonium (DEME), trimethylhexylammonium (TMHA), or N, N, N-trimethyl-N-propylammonium and the like can be mentioned.
  • Examples of pyridinium include 1-butyl-3-methylpyridinium and 1-butylpyridinium.
  • Examples of pyrrolidinium include 1-methyl-1-propyl-pyrrolidinium (MPPy), 1-butyl-1-methylpyrrolidinium (BMP), and N-methyl-N-propylpyrrolidinium (P13). It is done.
  • Examples of piperidinium include 1-methyl-1-propyl-piperidinium (MPPi), 1-ethyl-1-methylpiperidinium, N-methyl-N-propylpiperidinium (PP13), and the like.
  • Examples of phosphonium include triethylmethoxyethylphosphonium (TEMEP), triethylmethylphosphonium, triethylhexylphosphonium, and the like.
  • sulfonium examples include triethylsulfonium (TES), triethylmethylsulfonium, triethylhexylsulfonium, and the like. Of these, lithium, MPPy, EMI, PP13, and P13 are preferable.
  • each of these anions and cations may be used alone or in combination of two or more.
  • MPPy-TFSI, BMP-TFSI, EMI-TFSI, TEMEP-TFSI or TES-TFSI are preferable, and MPPy-TFSI, BMP-TFSI or EMI-TFSI are more preferable.
  • an ionic liquid may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • the negative electrode is subjected to a lithium pre-doping process in the presence of an ionic liquid.
  • an ionic liquid As a method for causing the ionic liquid to be present on the negative electrode, it is preferable to apply the ionic liquid on the negative electrode active material layer of the negative electrode structure.
  • the ionic liquid may be sprayed and sprayed on the negative electrode active material layer of the negative electrode structure, or the negative electrode structure may be immersed in the ionic liquid.
  • the ionic liquid is preferably applied to part or all of the surface of the negative electrode active material layer of the negative electrode structure.
  • Examples of a method for applying the ionic liquid include a doctor blade method and a large coater method.
  • FIG. 2 is a schematic cross-sectional view showing a negative electrode structure.
  • a negative electrode active material layer 1 is formed on a negative electrode current collector 2, and an ionic liquid 3 is immersed in the negative electrode active material.
  • the lithium source is preferably in the form of a sheet in order to uniformly contact the negative electrode structure, and examples thereof include metal foils mainly composed of lithium such as rolled lithium foil and vapor-deposited lithium foil.
  • the base material of the sheet include metals such as copper and plastic films such as PET. If the heating temperature exceeds the melting point of metallic lithium (180.5 ° C), the molten lithium will flow out to places other than the electrodes, and efficient diffusion will not be performed. It is more preferable to carry out at 60 ° C. or higher and 120 ° C. or lower, and 60 ° C.
  • the heating time is not particularly limited, but is preferably 10 minutes to 48 hours, more preferably 10 minutes to 30 minutes, and even more preferably 10 minutes to 15 minutes.
  • the presence of the ionic liquid makes it possible to perform the lithium doping process uniformly in a short time. Since metallic lithium reacts violently with moisture, all operations are preferably performed in a low humidity environment.
  • the positive electrode is formed, for example, by binding a positive electrode active material so as to cover the positive electrode current collector with a positive electrode binder.
  • the positive electrode active material is not particularly limited, LiMnO 2, LixMn 2 O 4 (0 ⁇ x ⁇ 2), Li 2 MnO 3, LixMn 1.5 Ni 0.5 O 4 (0 ⁇ x ⁇ 2) or the like Lithium manganate having a layered structure or lithium manganate having a spinel structure; LiCoO 2 , LiNiO 2 or a part of these transition metals replaced with another metal; LiNi 1/3 Co 1/3 Mn 1 / Lithium transition metal oxides in which more than half of specific transition metals such as 3 O 2 are present; Li in excess of the stoichiometric composition in these lithium transition metal oxides; Lithium oxide such as LiFePO 4 Etc.
  • these metal oxides were partially substituted with Al, Fe, P, Ti, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, etc. Materials can also be used.
  • a positive electrode active material can be used individually by 1 type or in combination of 2 or more types.
  • radical materials or the like can be used as the positive electrode active material.
  • the same negative electrode binder can be used.
  • polyvinylidene fluoride is preferable from the viewpoint of versatility and low cost.
  • the amount of the positive electrode binder to be used is preferably 2 to 15 parts by mass with respect to 100 parts by mass of the positive electrode active material from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. .
  • the positive electrode current collector the same as the negative electrode current collector can be used.
  • a conductive auxiliary material may be added to the positive electrode active material layer containing the positive electrode active material for the purpose of reducing impedance.
  • the conductive auxiliary material include carbonaceous fine particles such as graphite, carbon black, and acetylene black.
  • Electrode As the electrolytic solution, a solution in which a lithium salt is dissolved as an electrolyte in a solvent can be used.
  • Solvents include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC).
  • Chain carbonates such as dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate, ⁇ -lactones such as ⁇ -butyrolactone, 1,2-diethoxyethane (DEE), chain ethers such as ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylform Amide, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, dioxolane derivative, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, And apro
  • propylene carbonate, ethylene carbonate, ⁇ -butyrolactone, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are preferably used alone or in combination.
  • lithium salt examples include LiPF 6 , LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 CO 3 , LiC (CF 3 SO 2 ) 2 , LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2, LiB 10 Cl 10, lower aliphatic lithium carboxylate, chloroborane lithium, lithium tetraphenylborate, LiBr, include LiI, LiSCN, LiCl, imides and the like It is done. These can be used alone or in combination of two or more.
  • the electrolyte concentration of the electrolytic solution can be, for example, 0.5 mol / l to 1.5 mol / l. If electrolyte concentration is 1.5 mol / l or less, the increase in the density and viscosity of electrolyte solution can be suppressed. Moreover, if electrolyte concentration is 0.5 mol / l or more, the electrical conductivity of electrolyte solution can be made enough. A polymer electrolyte may be used instead of the electrolyte.
  • a porous film such as polypropylene or polyethylene or a nonwoven fabric can be used.
  • a separator what laminated
  • polyimide, polyamideimide, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, or glass fiber having high heat resistance can be used.
  • the textile separator which bundled those fibers and made it into a thread form and made it into a textile fabric can also be used.
  • the exterior body can be appropriately selected as long as it is stable to the electrolytic solution and has a sufficient water vapor barrier property.
  • a laminated laminate type secondary battery a laminate film made of aluminum, silica-coated polypropylene, polyethylene, or the like can be used as the outer package.
  • an aluminum laminate film from the viewpoint of suppressing volume expansion.
  • Example 1 and 2 Preparation of negative electrode
  • a mixture in which the molar ratio of Si, SiO 2 and carbon (C) was 1: 1: 0.8 was used as the negative electrode active material.
  • This negative electrode active material was mixed with polyimide as a negative electrode binder at a weight ratio of 85:15 (negative electrode active material: negative electrode binder), and an electrode material mixed with NMP as a solvent had a thickness of 10 ⁇ m. This was coated on a copper foil and dried at 125 ° C. for 5 minutes. Thereafter, compression molding was performed with a roll press, and drying was performed again in a drying furnace at 350 ° C. for 30 minutes in an N 2 atmosphere. The copper foil on which the negative electrode active material layer was formed was punched out to 30 ⁇ 28 mm to produce a negative electrode.
  • Li dope An ionic liquid of 1.0 mol / L LiTFSI / MPPy-TFSI was applied to the negative electrode surface, and a 3.2 ⁇ 3.4 mm Li foil was attached to the negative electrode. The laminate was sealed and left in a high-temperature bath at 60 ° C. for 10 minutes.
  • Example 2 it carried out like Example 1 except the temperature of the thermostat having been 80 degreeC. The results are shown in Table 2.
  • a model cell was similarly produced in the case where Li was doped under the same conditions as in Example 1 except that a carbonate-based electrolyte was introduced instead of the ionic liquid and Li was attached to the negative electrode.
  • the results are shown in Table 6.
  • the Li metal is pasted in the presence of the ionic liquid and the temperature is increased.
  • the heating temperature was preferably 60 ° C. to 80 ° C. from the viewpoint of the amount of lithium to be doped.
  • negative electrode b separator c positive electrode d negative electrode current collector e positive electrode current collector f positive electrode terminal g negative electrode terminal 1 negative electrode active material layer 2 negative electrode current collector 3 ionic liquid

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Abstract

La présente invention concerne une électrode négative qui possède une couche de matériau actif d'électrode négative qui contient au moins une substance choisie parmi le groupe comprenant du silicium, de l'oxyde de silicium et du carbone, et qui est caractérisée en ce que l'électrode négative est dopée au lithium en amenant la couche de matériau actif d'électrode négative en contact avec une source de lithium et en effectuant un traitement thermique en présence d'un liquide ionique.
PCT/JP2013/064951 2012-06-04 2013-05-29 Batterie secondaire à électrolyte non aqueux WO2013183524A1 (fr)

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