WO2013042421A1 - Batterie secondaire - Google Patents

Batterie secondaire Download PDF

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Publication number
WO2013042421A1
WO2013042421A1 PCT/JP2012/066787 JP2012066787W WO2013042421A1 WO 2013042421 A1 WO2013042421 A1 WO 2013042421A1 JP 2012066787 W JP2012066787 W JP 2012066787W WO 2013042421 A1 WO2013042421 A1 WO 2013042421A1
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Prior art keywords
secondary battery
negative electrode
peak
discharge
respect
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PCT/JP2012/066787
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English (en)
Japanese (ja)
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入山　次郎
徹也 梶田
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日本電気株式会社
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Priority to JP2013534622A priority Critical patent/JP6179404B2/ja
Publication of WO2013042421A1 publication Critical patent/WO2013042421A1/fr

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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This embodiment relates to a secondary battery.
  • Patent Document 1 discloses a lithium secondary battery having a negative electrode using silicon oxide as a negative electrode active material.
  • Patent Document 2 discloses a method of discharging a non-aqueous electrolyte secondary battery using a silicon oxide containing lithium as a negative electrode active material, and the negative electrode voltage with respect to a lithium reference electrode does not exceed 0.6V.
  • a discharge control method for a non-aqueous electrolyte secondary battery, characterized by controlling the discharge so as to be discharged, is disclosed.
  • Patent Document 3 discloses a nonaqueous secondary battery including a negative electrode, a positive electrode, and a nonaqueous electrolyte, wherein the active material of the negative electrode has a general formula MxSi (0 ⁇ x ⁇ 0.5, M: Ag, Au, A crystal represented by Zn, Cd, Hg, Al, Ga, In, Tl, Sn, Pb, Sb, Bi) and calculated by differential scanning calorimetry.
  • a non-aqueous secondary battery characterized by being a silicon compound having a degree of conversion in the range of 10 to 60% is disclosed.
  • the charging method of the said non-aqueous secondary battery characterized by ending charge in the range from which the electric potential of the negative electrode with respect to metallic lithium becomes an electric potential higher than 100 mV is disclosed.
  • Patent Document 4 discloses a method for using a lithium secondary battery in which an electrode provided with an active material layer containing silicon on a current collector made of a metal that is not alloyed with lithium is used as a negative electrode.
  • a method for using a lithium secondary battery is disclosed, in which the negative electrode is charged and discharged in a range where the potential of the negative electrode is 0.8 V (vs. Li / Li + ) or less.
  • Patent Document 5 discloses a battery including a negative electrode capable of inserting and extracting lithium (Li) containing silicon (Si) as a constituent element, a positive electrode capable of inserting and extracting lithium, and an electrolyte.
  • the battery is characterized in that the molar ratio of lithium atom to silicon atom (Li / Si) is 4.0 or less.
  • the lithium secondary battery using silicon oxide as the negative electrode active material disclosed in Patent Document 1 the amount of lithium doping tends to be locally high in the negative electrode when lithium is doped, and lithium is contained at a high concentration. Locations and locations that do not contain lithium are likely to be mixed. This is because the lithium ion conductivity of silicon oxide is extremely low before doping with lithium and increases as the amount of lithium doped increases. Therefore, the lithium secondary battery has a low capacity retention rate in the charge / discharge cycle. Similar problems exist in the secondary batteries and methods disclosed in Patent Documents 2 to 5.
  • This embodiment is intended to provide a secondary battery having a high capacity retention rate in a charge / discharge cycle.
  • the secondary battery according to the present embodiment is a secondary battery including a negative electrode containing silicon oxide, and a VdQ / dV curve (V: potential of the negative electrode with respect to Li: mV) at the time of discharging the secondary battery.
  • DQ / dV the peak area (P1) of a peak having a peak top in the range of 100 to 210 mV in the capacity change (mAh / mV) of the secondary battery with respect to the potential change (mV) of the negative electrode with respect to Li, 285 to 325 mV
  • the peak area (P2) of the peak having a peak top in the range of and the peak area (P3) of the peak having a peak top in the range of 410 to 520 mV satisfy 0 ⁇ P1 / (P2 + P3) ⁇ 0.05.
  • a method for manufacturing a secondary battery according to the present embodiment is a method for manufacturing a secondary battery including a negative electrode containing silicon oxide, the step of assembling a secondary battery before initial charge, and the secondary battery before initial charge.
  • V-dQ / dV curve at the time of discharging the secondary battery (V: potential of negative electrode with respect to Li (mV), dQ / dV: potential of negative electrode with respect to Li)
  • the area (P2) and the peak area (P3) of a peak having a peak top in the range of 410 to 520 mV satisfy 0 ⁇ P1 / (P2 + P3) ⁇ 0.05.
  • the secondary battery according to the present embodiment can provide a secondary battery having a high capacity retention rate in the charge / discharge cycle.
  • FIG. 4 is a diagram showing a V-dQ / dV curve at the time of initial discharge in Example 1.
  • 6 is a diagram showing a V-dQ / dV curve at the time of first discharge in Example 2.
  • FIG. 6 is a diagram showing a V-dQ / dV curve at the time of first discharge in Example 3.
  • FIG. 10 is a diagram showing a V-dQ / dV curve at the time of first discharge in Example 4.
  • FIG. 10 is a diagram showing a V-dQ / dV curve at the time of first discharge in Example 5.
  • FIG. 4 is a diagram showing a V-dQ / dV curve at the time of initial discharge in Example 1.
  • 6 is a diagram showing a V-dQ / dV curve at the time of first discharge in Example 2.
  • FIG. 6 is a diagram showing a V-dQ / dV curve at the time of first discharge in Example 3.
  • FIG. 10 is a diagram showing a
  • FIG. 12 is a diagram showing a V-dQ / dV curve at the time of first discharge in Example 6.
  • 6 is a diagram showing a V-dQ / dV curve at the time of initial discharge in Comparative Example 1.
  • FIG. 6 is a diagram showing a V-dQ / dV curve at the time of first discharge in Comparative Example 2.
  • FIG. 10 is a diagram showing a V-dQ / dV curve at the time of first discharge in Comparative Example 3.
  • the secondary battery according to the present embodiment is a secondary battery including a negative electrode containing silicon oxide, and a VdQ / dV curve (V: potential of the negative electrode with respect to Li: mV) at the time of discharging the secondary battery.
  • DQ / dV the peak area (P1) of a peak having a peak top in the range of 100 to 210 mV in the capacity change (mAh / mV) of the secondary battery with respect to the potential change (mV) of the negative electrode with respect to Li, 285 to 325 mV
  • the peak area (P2) of the peak having a peak top in the range of and the peak area (P3) of the peak having a peak top in the range of 410 to 520 mV satisfy 0 ⁇ P1 / (P2 + P3) ⁇ 0.05.
  • a secondary battery including a negative electrode including a silicon oxide the present inventors, when doping a lithium into the negative electrode, when a location containing lithium at a high concentration occurs in the negative electrode, electrochemically removes lithium from the location. It was found that a peak having a peak top appears in the range of 100 to 210 mV on the V-dQ / dV curve when dedoping. Moreover, the secondary battery with a large peak area (P1) of the peak was found to have a significantly reduced capacity with charge / discharge cycles.
  • peaks are considered to occur because some oxidation-reduction reaction occurs when lithium doped to the negative electrode silicon oxide is dedoped. It is considered that the composition ratio of Li and Si is different for each peak, and it is estimated that the peak having the peak top in the range of 100 to 210 mV has a composition with a high ratio of Li to Si. Therefore, a secondary battery in which the peak area (P1) of a peak having a peak top in the range of 100 to 210 mV is relatively smaller than the peak areas (P2, P3) of other peaks is a local battery in the silicon oxide of the negative electrode. In particular, it is considered that there are few places where lithium is doped, and lithium is doped relatively uniformly.
  • V-dQ / dV curve during secondary battery discharge P1 / (P2 + P3) satisfies 0 ⁇ P1 / (P2 + P3) ⁇ 0.05 in the V-dQ / dV curve when the secondary battery is discharged.
  • V represents the potential (mV) of the negative electrode with respect to Li.
  • DQ / dV represents a change in capacity (mAh / mV) of the secondary battery with respect to a change in potential (mV) of the negative electrode with respect to Li.
  • P1 / (P2 + P3) exceeds 0.05, it is considered that there are many locations where lithium is locally doped in the silicon oxide of the negative electrode, and the capacity retention rate greatly increases with charge / discharge cycles. descend.
  • P1 / (P2 + P3) is preferably 0.005 ⁇ P1 / (P2 + P3) ⁇ 0.045, more preferably 0.01 ⁇ P1 / (P2 + P3) ⁇ 0.04, and 0.015 ⁇ More preferably, P1 / (P2 + P3) ⁇ 0.035, and particularly preferably 0.02 ⁇ P1 / (P2 + P3) ⁇ 0.03.
  • the discharge for measuring the V-dQ / dV curve is preferably the first discharge that is performed after the first charge and before the second charge. However, the discharge may be performed after the second or third charge.
  • the discharge conditions for the discharge for measuring the V-dQ / dV curve are not particularly limited. Depending on the discharge conditions, the peak top potential of each peak may slightly change, but the number of peaks, the peak area ratio, etc. basically do not change. As discharge conditions, for example, the discharge is a discharge from a fully charged state, and the current density of the discharge is 0.01 mA / cm 2 per area of the negative electrode, so that the change in the peak top potential of each peak is further reduced. Is preferable.
  • a peak having a peak top in the range of 100 to 210 mV does not have to occur in the V-dQ / dV curve during discharge.
  • the peak area (P1) is 0, P1 / (P2 + P3) is 0, which satisfies the range of P1 / (P2 + P3) defined in the present embodiment.
  • a peak having a peak top in the range of 410 to 520 mV may not occur.
  • the peak area (P3) is zero.
  • P2 + P3 does not become zero.
  • Each peak area on the V-dQ / dV curve when the secondary battery is discharged is calculated by the following method.
  • the original data By fitting the original data by superimposing Gaussian functions, the potential and peak area of each peak top are obtained.
  • noise is removed by smoothing the data.
  • a SABITZKY-GOLAY algorithm, an adjacent averaging process, or the like is used.
  • each peak area is obtained.
  • ORIGIN data analysis software manufactured by ORIGINLAB CORPORATION, http://www.lightstone.co.jp/origin /Pa.htm
  • ORIGIN data analysis software manufactured by ORIGINLAB CORPORATION, http://www.lightstone.co.jp/origin /Pa.htm
  • the software has an NLSF (NONLINEAR LEAST SQUARES FITTER-nonlinear curve fitting mechanism) to which a least square method is applied, and can fit a curve having an arbitrary plurality of peaks with a Gaussian function.
  • NLSF NONLINEAR LEAST SQUARES FITTER-nonlinear curve fitting mechanism
  • the area is calculated for the portion where the peak appears by the above method, and the value is used as the peak area.
  • the peak top potential of a peak where no peak top appears is specified by extrapolating a Gaussian function that forms the peak.
  • the configuration of the secondary battery according to the present embodiment is not particularly limited as long as the secondary battery includes a negative electrode containing silicon oxide and P1 / (P2 + P3) in the V-dQ / dV curve during discharge satisfies the above range.
  • a laminated secondary battery is shown in FIG.
  • the secondary battery shown in FIG. 1 includes a positive electrode composed of a positive electrode active material layer 1 and a positive electrode current collector 3, and a negative electrode composed of a negative electrode active material layer 2 containing silicon oxide and a negative electrode current collector 4.
  • the separator 5 is sandwiched.
  • the positive electrode current collector 3 is connected to the positive electrode tab 8.
  • the negative electrode current collector 4 is connected to the negative electrode tab 7.
  • a laminate film 6 is used for the exterior body.
  • the inside of the secondary battery is filled with an electrolyte solution (not shown).
  • the secondary battery according to the present embodiment may be a lithium secondary battery or a lithium ion secondary battery. Further, in this specification, a battery that has been initially charged is referred to as a “secondary battery”, and a battery before the first charge is performed is referred to as a “secondary battery before first charge”.
  • the negative electrode according to the present embodiment includes silicon oxide as a negative electrode active material.
  • the silicon oxide is not particularly limited, but is represented by, for example, SiO x (0 ⁇ x ⁇ 2). Further, the silicon oxide may contain Li.
  • the silicon oxide containing Li is represented by, for example, SiLi y O z (0 ⁇ y, 0 ⁇ z ⁇ 2).
  • the silicon oxide may contain a trace amount of metallic elements and nonmetallic elements other than Li.
  • the silicon oxide can contain, for example, 0.1 to 5% by mass of at least one element selected from the group consisting of nitrogen, boron and sulfur. By containing a trace amount of metal elements and non-metal elements, the electrical conductivity of the silicon oxide is improved.
  • SiO silicon monoxide
  • These silicon oxides may be used alone or in combination of two or more.
  • the peak top potential of each peak may slightly change in the V-dQ / dV curve at the time of discharge as compared with the case where it is not added. However, there is no change in that the peak top enters the predetermined potential range defined in this embodiment. Therefore, P1 / (P2 + P3) can be calculated also in this case.
  • the silicon oxide may be crystalline or amorphous. However, it is preferable that all or part of the silicon oxide has an amorphous structure.
  • a silicon oxide having an amorphous structure is considered to have relatively few elements due to non-uniformity such as grain boundaries and defects. It can be confirmed by X-ray diffraction measurement (general XRD measurement) that all or part of the silicon oxide has an amorphous structure. Specifically, when all or part of the silicon oxide has an amorphous structure, a peak specific to the silicon oxide is observed as a broad peak.
  • the negative electrode according to the present embodiment may include natural graphite, artificial graphite, amorphous carbon, and the like as a negative electrode active material in addition to silicon oxide.
  • the content of the silicon oxide in the negative electrode is preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 95% by mass or less, from the viewpoint of improving energy density, More preferably, it is at least 90% by mass.
  • the negative electrode according to this embodiment can contain a negative electrode conductivity imparting agent and a negative electrode binder in addition to silicon oxide.
  • the negative electrode conductivity-imparting agent known materials can be used.
  • a carbon material can be used.
  • the carbon material include graphite, amorphous carbon, diamond-like carbon, carbon black, ketjen black, acetylene black, vapor grown carbon fiber, fullerene, carbon nanotube, and a composite thereof.
  • These negative electrode conductivity-imparting agents may be used alone or in combination of two or more. Note that graphite with high crystallinity has high electrical conductivity, and is excellent in adhesion to a current collector made of a metal such as copper and voltage flatness.
  • amorphous carbon with low crystallinity has a relatively small volume expansion, so it has a high effect of reducing the volume expansion of the entire negative electrode and is less likely to deteriorate due to non-uniformity such as grain boundaries and defects. .
  • the addition amount of the negative electrode conductivity-imparting agent is preferably 1 to 25% by mass and more preferably 2 to 20% by mass with respect to the total mass of the negative electrode active material, the negative electrode conductivity-imparting agent and the negative electrode binder. Preferably, it is 5 to 15% by mass. When the addition amount is 1% by mass or more, sufficient conductivity can be maintained. Moreover, since the ratio of negative electrode active material mass can be enlarged when this addition amount is 25 mass% or less, the capacity
  • the negative electrode binder known materials can be used.
  • the negative electrode binder include polyvinylidene fluoride (PVdF), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, polytetrafluoroethylene, Polypropylene, polyethylene, polyimide (PI), polyamideimide (PAI) and the like can be used.
  • PVdF polyvinylidene fluoride
  • PI polyimide
  • PAI polyamideimide
  • these negative electrode binder may be used alone or in combination of two or more.
  • the addition amount of the negative electrode binder is preferably 1 to 25% by mass and more preferably 2 to 20% by mass with respect to the total mass of the negative electrode active material, the negative electrode conductivity imparting agent and the negative electrode binder. Preferably, it is 5 to 15% by mass.
  • production of electrode peeling can be prevented because this addition amount is 1 mass% or more.
  • the ratio of negative electrode active material mass can be enlarged when this addition amount is 25 mass% or less, the capacity
  • the material of the negative electrode current collector is not particularly limited, but aluminum, nickel, copper, silver, and alloys thereof are preferable from the viewpoint of electrochemical stability.
  • Examples of the shape of the negative electrode current collector include foil, flat plate, and mesh.
  • the negative electrode according to the present embodiment can be produced, for example, by the following method.
  • a negative electrode is produced by mixing a silicon oxide, a negative electrode conductivity-imparting agent, and a negative electrode binder, and applying the mixture onto a negative electrode current collector to form a negative electrode active material layer.
  • Examples of the method for forming the negative electrode active material layer include a doctor blade method, a die coater method, a CVD method, and a sputtering method.
  • the negative electrode may be produced by forming a thin film of aluminum, nickel, copper, or an alloy thereof by a method such as vapor deposition or sputtering.
  • the positive electrode which concerns on this embodiment is not specifically limited, It is preferable that it is a positive electrode containing Li. Specifically, it is preferable to use a positive electrode including a positive electrode active material containing Li. Examples of the positive electrode active material containing Li include lithium manganate having a layered structure such as LiMnO 2 and Li x Mn 2 O 4 (0 ⁇ x ⁇ 2) or lithium manganate having a spinel structure, or LiCoO 2 and LiNiO 2. Or the compound etc. which substituted some of these transition metals with the other metal are mentioned.
  • LiM1O 2 (M1 is at least one element selected from the group consisting of Mn, Fe, Co, and Ni, and M1 may be partially substituted with Mg, Al, or Ti.
  • LiMn 2 ⁇ x M2 x O 4 (M2 is at least one element selected from the group consisting of Mg, Al, Co, Ni, Fe and B, and 0 ⁇ x ⁇ 2).
  • the cathode active material LiFePO 4 having a crystal structure of olivine may also be mentioned.
  • These positive electrode active materials can be used alone or in combination of two or more.
  • the positive electrode according to the present embodiment can contain a positive electrode conductivity imparting agent and a positive electrode binder in addition to the positive electrode active material.
  • the positive electrode conductivity-imparting agent in addition to the carbon material exemplified as the negative electrode conductivity-imparting agent, metal materials such as aluminum, conductive oxide powder, and the like can be used.
  • the addition amount of the positive electrode conductivity-imparting agent is preferably 1 to 25% by mass and more preferably 2 to 20% by mass with respect to the total mass of the positive electrode active material, the positive electrode conductivity-imparting agent and the positive electrode binder. Preferably, it is 5 to 15% by mass. When the addition amount is 1% by mass or more, sufficient conductivity can be maintained. Moreover, since the ratio of positive electrode active material mass can be enlarged when this addition amount is 25 mass% or less, the capacity
  • the positive electrode binder the same as the negative electrode binder can be used. However, from the viewpoint of versatility and low cost, polyvinylidene fluoride (PVdF) is preferable.
  • the addition amount of the positive electrode binder is preferably 1 to 25% by mass and more preferably 2 to 20% by mass with respect to the total mass of the positive electrode active material, the positive electrode conductivity imparting agent and the positive electrode binder. Preferably, it is 5 to 15% by mass. Generation
  • the positive electrode current collector the same as the negative electrode current collector can be used.
  • a positive electrode active material containing Li, a positive electrode conductivity imparting agent, and a positive electrode binder are mixed, and the mixture is applied onto the positive electrode current collector to form a positive electrode active material layer. It can produce by doing.
  • the method for forming the positive electrode active material layer include a doctor blade method, a die coater method, a CVD method, and a sputtering method.
  • a positive electrode may be produced by forming a thin film of aluminum, nickel, copper, or an alloy thereof by a method such as vapor deposition or sputtering.
  • the secondary battery according to the present embodiment preferably includes a reference electrode from the viewpoint of controlling the lower limit voltage of the negative electrode in initial charging described later.
  • the reference electrode is preferably a Li reference electrode.
  • a reference electrode obtained by bonding a copper foil and lithium metal can be used.
  • the reference electrode can be placed in the secondary battery by overlapping with the negative electrode through a separator, for example.
  • the electrolytic solution is not particularly limited as long as it is stable at a metallic lithium potential, but a solution in which an electrolyte salt is dissolved in a nonaqueous electrolytic solvent is preferable.
  • the nonaqueous electrolytic solvent is not particularly limited. However, from the viewpoint of being stable at a metallic lithium potential, cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, and vinylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, and dipropyl carbonate; ⁇ -Lactones such as butyrolactone.
  • a non-aqueous electrolysis solvent can be used individually by 1 type or in combination of 2 or more types.
  • electrolyte salt examples include LiPF 6 , LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , Li (CF 3 SO 2 ) 2 , LiN (CF 3 SO 2).
  • a lithium salt such as 2 .
  • the electrolyte salt can be used alone or in combination of two or more.
  • an ionic liquid can also be used as an electrolytic solution.
  • the ionic liquid include quaternary ammonium-imide salts.
  • a solid electrolyte may be used instead of the electrolytic solution.
  • a separator is not specifically limited, A well-known separator can be employ
  • porous films and nonwoven fabrics such as a polypropylene and polyethylene, can be used, for example.
  • a polyimide or aramid film, a cellulose film, or the like can be used.
  • the exterior body is not particularly limited as long as it is stable to the electrolytic solution and has a sufficient water vapor barrier property.
  • a metal can such as iron or aluminum alloy, a laminate film, or the like can be used.
  • a laminate film a laminate film in which aluminum or silica is deposited is preferable from the viewpoint of water vapor barrier properties.
  • a method for manufacturing a secondary battery according to the present embodiment is a method for manufacturing a secondary battery including a negative electrode containing silicon oxide, the step of assembling a secondary battery before initial charge, and the secondary battery before initial charge.
  • V-dQ / dV curve at the time of discharging the secondary battery (V: potential of negative electrode with respect to Li (mV), dQ / dV: potential of negative electrode with respect to Li)
  • V potential of negative electrode with respect to Li
  • dQ / dV potential of negative electrode with respect to Li
  • the area (P2) and the peak area (P3) of a peak having a peak top in the range of 410 to 520 mV satisfy 0 ⁇ P1 / (P2 + P3) ⁇ 0.05. Details of each step will be described below.
  • the secondary battery before the first charge is assembled.
  • the secondary battery before the first charge can be assembled by the following method, for example.
  • the positive electrode and the negative electrode are arranged opposite to each other with the separator interposed therebetween, and an electrode laminate is produced in which the positive electrode and the negative electrode are laminated.
  • a positive electrode tab and a negative electrode tab are connected to the positive electrode and the negative electrode through a positive electrode current collector and a negative electrode current collector, respectively.
  • the electrode laminate is accommodated in the exterior body.
  • An electrolytic solution is injected into the exterior body, and the electrode laminate is immersed in the electrolytic solution.
  • the exterior body is sealed so that a part of the positive electrode tab and the negative electrode tab protrudes to the outside.
  • the secondary battery before the first charge may include the reference electrode.
  • the first charging process Next, the assembled secondary battery before the first charge is charged for the first time to obtain a secondary battery.
  • the first charge is a charge performed before the first discharge.
  • the current density per negative electrode area is preferably 0.1 mA / cm 2 or less.
  • the P1 / (P2 + P3) in the V-dQ / dV curve during discharge can satisfy the range defined in the present embodiment. It said current density 0.001 mA / cm 2 or more, more preferably 0.05 mA / cm 2 or less, 0.003mA / cm 2 or more, more preferably 0.03 mA / cm 2 or less, 0. It is particularly preferably 005 mA / cm 2 or more and 0.01 mA / cm 2 or less.
  • the Li doping amount with respect to the silicon oxide is 2400 mAh / g or less in the initial charge.
  • the P1 / (P2 + P3) in the V-dQ / dV curve at the time of discharge can satisfy the predetermined range in the present embodiment.
  • the doping amount of Li is preferably 1600 mAh / g or more and 2300 mAh / g or less, more preferably 1800 mAh / g or more and 2250 mAh / g or less, and 2000 mAh / g or more and 2200 mAh / g or less. Is particularly preferred.
  • the lower limit voltage of the negative electrode is ⁇ 5 mV or more with respect to the Li reference electrode.
  • the initial charge is performed while maintaining the battery voltage at a predetermined potential.
  • the P1 / (P2 + P3) in the V-dQ / dV curve at the time of discharge can be set within the range defined in the present embodiment. it can.
  • the lower limit potential of the negative electrode is more preferably ⁇ 2 mV or more and 10 mV or less, further preferably ⁇ 1 mV or more and 7 mV or less, and particularly preferably 0 mV or more and 5 mV or less.
  • the initial charging conditions have been described above, the initial charging conditions are not limited to these, and are not particularly limited as long as P1 / (P2 + P3) is within the range defined in the present embodiment.
  • the slurry was applied to a copper foil having a thickness of 10 ⁇ m using a doctor blade.
  • the copper foil coated with the slurry was heated at 120 ° C. for 7 minutes to dry the NMP. Then, it heated for 30 minutes at 350 degreeC using the electric furnace in nitrogen atmosphere. This obtained the negative electrode.
  • Lithium cobaltate manufactured by Nichia Corporation
  • carbon black trade name: “# 3030B”, manufactured by Mitsubishi Chemical Corporation
  • polyvinylidene fluoride trade name: “# 2400”, Co., Ltd.
  • Kureha Lithium cobaltate
  • carbon black trade name: “# 3030B”, manufactured by Mitsubishi Chemical Corporation
  • polyvinylidene fluoride trade name: “# 2400”, Co., Ltd.
  • Kureha Lithium cobaltate (manufactured by Nichia Corporation), carbon black (trade name: “# 3030B”, manufactured by Mitsubishi Chemical Corporation), and polyvinylidene fluoride (trade name: “# 2400”, Co., Ltd.) Kureha) were weighed at a mass ratio of 95: 2: 3, respectively.
  • NMP were mixed to obtain a slurry.
  • the mass ratio of NMP to solids was 52:48.
  • the slurry was applied to an aluminum foil having a thickness of 15 ⁇ m using a doctor blade.
  • a polypropylene film was used as the separator.
  • As the laminate film a polypropylene film on which aluminum was deposited was used.
  • As the electrolytic solution a 7: 3 (volume ratio) mixed solvent of ethylene carbonate and diethyl carbonate containing 1.0 mol / l LiPF 6 electrolyte salt was used.
  • the first charge of the secondary battery before the first charge The produced secondary battery before the first charge was charged for the first time, and the negative electrode was doped with Li. Specifically, the current density per negative electrode area was set to 0.01 mA / cm 2 until the battery voltage was 4.2 V or the potential of the negative electrode with respect to the reference electrode was 0 V. After the battery voltage became 4.2V or the negative electrode potential with respect to the reference electrode became 0V, the negative electrode potential with respect to the reference electrode was kept at -5 mV or more by decreasing the current value. In this example, since the battery voltage reached 4.2 V earlier, after the battery voltage reached 4.2 V, the potential of the negative electrode with respect to the reference electrode was kept at -5 mV or more by decreasing the current value.
  • the amount of lithium released from the positive electrode reached 160 mAh / g per lithium cobaltate, the initial charge was terminated. Thereby, a secondary battery was obtained. At this time, the doping amount of Li with respect to SiO in the negative electrode was 1800 mAh / g.
  • V represents the potential (mV) of the negative electrode with respect to Li
  • dQ / dV represents the change in capacity of the secondary battery (mAh / mV) with respect to the potential change (mV) of the negative electrode with respect to Li.
  • Example 2 At the end of the first charge, the masses of the positive electrode and the negative electrode were adjusted so that the Li doping amount with respect to SiO in the negative electrode was 2000 mAh / g, and the Li doping amount after the first charging was 2000 mAh / g. Other than that produced the secondary battery similarly to Example 1, and performed the charging / discharging cycle test.
  • the potential of the negative electrode with respect to the reference electrode was earlier than 0 V in the initial charge, the potential of the negative electrode with respect to the reference electrode was reduced by reducing the current value after the potential of the negative electrode with respect to the reference electrode became 0 V. Was kept above -5 mV.
  • Example 3 At the end of the first charge, the masses of the positive electrode and the negative electrode were adjusted so that the Li doping amount relative to SiO in the negative electrode was 2200 mAh / g, and the Li doping amount after the first charging was 2200 mAh / g. Other than that produced the secondary battery similarly to Example 1, and performed the charging / discharging cycle test.
  • the potential of the negative electrode with respect to the reference electrode was earlier than 0 V in the initial charge, the potential of the negative electrode with respect to the reference electrode was reduced by reducing the current value after the potential of the negative electrode with respect to the reference electrode became 0 V. Was kept above -5 mV.
  • Example 4 At the end of the initial charge, the masses of the positive electrode and the negative electrode were adjusted so that the Li doping amount with respect to SiO in the negative electrode was 2400 mAh / g, and the Li doping amount after the initial charging was 2400 mAh / g. Other than that produced the secondary battery similarly to Example 1, and performed the charging / discharging cycle test.
  • the potential of the negative electrode with respect to the reference electrode was earlier than 0 V in the initial charge, the potential of the negative electrode with respect to the reference electrode was reduced by reducing the current value after the potential of the negative electrode with respect to the reference electrode became 0 V. Was kept above -5 mV.
  • Example 5 The current density per negative electrode area at the first charge was set to 0.1 mA / cm 2 . Moreover, the mass of the positive electrode and the negative electrode was adjusted so that the doping amount of Li with respect to SiO in the negative electrode was 1900 mAh / g at the end of the initial charging, and the doping amount of Li after the initial charging was 1900 mAh / g. Other than that produced the secondary battery similarly to Example 1, and performed the charging / discharging cycle test. In the present embodiment, since the potential of the negative electrode with respect to the reference electrode was earlier than 0 V in the initial charge, the potential of the negative electrode with respect to the reference electrode was reduced by reducing the current value after the potential of the negative electrode with respect to the reference electrode became 0 V. Was kept above -5 mV.
  • Example 6 SiO 2 and Si were mixed at a molar ratio of 1: 1. A mixture obtained by mixing 100 parts by mass of the mixture and 9 parts by mass of MgO was heat-treated at 900 ° C. under reduced pressure. Then, it cooled rapidly by the twin roller rapid cooling method. Thereby, Si 0.9 Mg 0.1 O was prepared.
  • a secondary battery was produced in the same manner as in Example 4 except that the Si 0.9 Mg 0.1 O was used instead of SiO, and a charge / discharge cycle test was performed.
  • the potential of the negative electrode with respect to the reference electrode was earlier than 0 V in the initial charge, the potential of the negative electrode with respect to the reference electrode was reduced by reducing the current value after the potential of the negative electrode with respect to the reference electrode became 0 V. Was kept above -5 mV.
  • the secondary battery according to the example had a higher capacity retention rate than the secondary battery according to the comparative example.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne une batterie secondaire qui présente une rétention à haute capacité durant le cycle de charge/de décharge de la batterie. La batterie secondaire comporte une électrode négative qui comprend un oxyde de silicium. Dans une courbe V-dQ/dV (V étant le potentiel (mV) de l'électrode négative par rapport à Li, et dQ/dV étant le changement de capacitance (mAh/mV) de la batterie secondaire par rapport à un changement de potentiel (mV) de l'électrode négative par rapport à Li) lorsque la batterie secondaire se décharge, 0 ≤ P1/(P2+P3) ≤ 0,05 peut être satisfait par la zone de crête (P1) d'une crête qui possède une valeur maximale au sein de la plage allant de 100 à 210 mV, la zone de crête (P2) d'une crête qui possède une valeur maximale au sein de la plage allant de 285 à 325 mV, et la zone de crête (P3) d'une crête qui possède une valeur maximale au sein de la plage allant de 410 à 520 mV.
PCT/JP2012/066787 2011-09-21 2012-06-29 Batterie secondaire WO2013042421A1 (fr)

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CN106067543A (zh) * 2015-04-22 2016-11-02 信越化学工业株式会社 非水电解质二次电池及其负极材料的制造方法、其负极活性物质及该物质的制造方法
JP6306767B1 (ja) * 2017-03-20 2018-04-04 デジュ・エレクトロニック・マテリアルズ・カンパニー・リミテッドＤａｅｊｏｏ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． リチウム二次電池陰極材用シリコン複合酸化物及びその製造方法
US10553910B2 (en) 2016-03-25 2020-02-04 Toyota Motor Europe Lithium-ion battery formation process
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WO2023044866A1 (fr) * 2021-09-26 2023-03-30 宁德时代新能源科技股份有限公司 Matériau d'électrode négative au silicium-carbone, plaque d'électrode négative, batterie secondaire, module de batterie, bloc-batterie et appareil électrique

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WO2014199554A1 (fr) * 2013-06-14 2014-12-18 信越化学工業株式会社 Matériau contenant du silicium, électrode négative de batterie secondaire à électrolyte non aqueux et son procédé de fabrication, et batterie secondaire à électrolyte non aqueux et son procédé de fabrication
JP2015002036A (ja) * 2013-06-14 2015-01-05 信越化学工業株式会社 珪素含有材料、非水電解質二次電池用負極及びその製造方法並びに非水電解質二次電池及びその製造方法
CN105283986A (zh) * 2013-06-14 2016-01-27 信越化学工业株式会社 含硅材料、非水电解质二次电池用负极及其制造方法、以及非水电解质二次电池及其制造方法
EP2991141A4 (fr) * 2013-06-14 2016-10-12 Shinetsu Chemical Co Matériau contenant du silicium, électrode négative de batterie secondaire à électrolyte non aqueux et son procédé de fabrication, et batterie secondaire à électrolyte non aqueux et son procédé de fabrication
CN106067543A (zh) * 2015-04-22 2016-11-02 信越化学工业株式会社 非水电解质二次电池及其负极材料的制造方法、其负极活性物质及该物质的制造方法
JP2016207446A (ja) * 2015-04-22 2016-12-08 信越化学工業株式会社 非水電解質二次電池用負極活物質及びその製造方法、並びにその負極活物質を用いた非水電解質二次電池及び非水電解質二次電池用負極材の製造方法
US10553910B2 (en) 2016-03-25 2020-02-04 Toyota Motor Europe Lithium-ion battery formation process
JP6306767B1 (ja) * 2017-03-20 2018-04-04 デジュ・エレクトロニック・マテリアルズ・カンパニー・リミテッドＤａｅｊｏｏ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． リチウム二次電池陰極材用シリコン複合酸化物及びその製造方法
JP2018156922A (ja) * 2017-03-20 2018-10-04 デジュ・エレクトロニック・マテリアルズ・カンパニー・リミテッドＤａｅｊｏｏ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． リチウム二次電池陰極材用シリコン複合酸化物及びその製造方法
WO2021082291A1 (fr) * 2019-10-29 2021-05-06 宁德新能源科技有限公司 Matériau d'électrode négative, électrode négative le comprenant et procédé de préparation d'électrode négative
WO2023044866A1 (fr) * 2021-09-26 2023-03-30 宁德时代新能源科技股份有限公司 Matériau d'électrode négative au silicium-carbone, plaque d'électrode négative, batterie secondaire, module de batterie, bloc-batterie et appareil électrique

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