WO2013180083A1 - Batterie secondaire au lithium-ion - Google Patents

Batterie secondaire au lithium-ion Download PDF

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Publication number
WO2013180083A1
WO2013180083A1 PCT/JP2013/064681 JP2013064681W WO2013180083A1 WO 2013180083 A1 WO2013180083 A1 WO 2013180083A1 JP 2013064681 W JP2013064681 W JP 2013064681W WO 2013180083 A1 WO2013180083 A1 WO 2013180083A1
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negative electrode
lithium
secondary battery
active material
doping
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PCT/JP2013/064681
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English (en)
Japanese (ja)
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川崎　大輔
慎 芹澤
恵美子 藤井
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日本電気株式会社
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Priority to JP2014518443A priority Critical patent/JPWO2013180083A1/ja
Publication of WO2013180083A1 publication Critical patent/WO2013180083A1/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
    • H01M4/04—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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • 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

  • the present invention relates to a lithium ion secondary battery produced by reacting lithium ions with a negative electrode active material and performing a lithium pre-doping treatment in a process of producing a lithium ion secondary battery, particularly a lithium ion secondary battery. It relates to batteries.
  • Patent Document 1 discloses that a silicon oxide or a silicate compound is used as a negative electrode active material of a secondary battery.
  • Patent Document 2 and Patent Document 3 disclose that lithium is diffused into a non-carbon-based negative electrode by attaching a metal lithium foil to the non-carbon-based negative electrode and heating.
  • Patent Documents 4 and 5 disclose a technique of doping lithium into silicon-silicon oxide composite particles coated with carbon.
  • Patent Document 6 discloses a negative electrode material made of silicon having an oxidation number of 0, silicon having an oxidation number of 0 to +4, and silicon having an oxidation number of +4. Further, Li 2 SiO 3, Li 4 SiO 4, Li 4 Si 3 O 8, Li 2 Si 2 O 5 is disclosed as lithium silicate.
  • Patent Document 7 discloses a negative electrode for a secondary battery provided with an active material layer containing carbon material particles capable of inserting and extracting lithium ions, metal particles capable of being alloyed with lithium, and oxide particles capable of inserting and extracting lithium ions. Is disclosed. In addition, a technique for bonding lithium metal to the negative electrode surface is disclosed.
  • Patent Document 8 discloses a negative electrode material for a secondary battery in which the surface of particles having a structure in which silicon microcrystals are dispersed in a silicon compound is coated with carbon.
  • Patent Documents 9 and 10 disclose that when the negative electrode active material contains silicon, a thermosetting resin or polyimide that causes a dehydration condensation reaction by heating is used as a negative electrode binder.
  • the secondary battery using the oxide of silicon described in Patent Document 1 as the negative electrode active material has a problem that when the charge / discharge is performed at 45 ° C. or higher, the capacity reduction accompanying the charge / discharge cycle is remarkably large. .
  • Patent Document 2 discloses a method for manufacturing a negative electrode for a secondary battery in which a metal lithium foil is attached to a non-carbon negative electrode and heated at 30 to 160 ° C.
  • the purpose of Patent Document 2 is to solve the problem of “lithium depletion” by dissolving and supplying lithium from the metal lithium layer even when lithium is consumed during charging and discharging. That is, it is not intended to produce a lithium ion secondary battery having a high energy and a long life by forming lithium silicate with controlled valence of silicon by lithium pre-doping.
  • the study on the negative electrode active material and the study on the binder, the electrode element structure, and the exterior body that are indispensable for forming the lithium ion secondary battery are not sufficiently performed. Many were seen.
  • Patent Document 3 as a method of manufacturing a secondary battery, a metal film mainly composed of lithium is brought into contact with the surface of a layer containing an active material of a non-carbon-based negative electrode to react lithium with the active material of the negative electrode.
  • a process is disclosed.
  • studies on forming lithium silicate with controlled valence of silicon by lithium pre-doping are insufficient.
  • many studies have been made on the negative electrode active material and on the binder, electrode element structure, and exterior body, which are indispensable for forming a lithium ion secondary battery. It was.
  • the negative electrode materials for secondary batteries described in Patent Document 4 and Patent Document 5 can also improve the energy density of the secondary battery.
  • the binder, electrolyte solution, electrode element structure, and exterior body, which are indispensable for forming a lithium ion secondary battery, have not been fully studied.
  • Patent Document 4 Patent Document 5
  • a technique of doping lithium into a silicon-based negative electrode active material in advance by a lithium doping process for a so-called powdered negative electrode active material is for improving energy density. It is effective for.
  • only the lithium doping method described in these documents increases (1) the number of active sites on the negative electrode surface due to the reaction with lithium, and (2) the moisture content in the battery.
  • the amount of gas generated increases due to reasons such as increased reactivity, (3) the irreversible capacity of the negative electrode decreases and the charge / discharge range of the positive electrode widens, and the deterioration of the positive electrode proceeds, especially when the cell is a laminate type It has been found that it causes cell characteristic deterioration.
  • lithium doping alone with respect to the so-called powdered negative electrode active material is insufficient, and there is a demand for further improving the energy density.
  • Patent Document 2 Patent Document 3, Patent Document 4, and Patent Document 5, as a lithium pre-doping method, a non-carbon-based negative electrode active material is reacted with lithium at a powder stage, and after the electrode is manufactured, a metal lithium foil is used. The method of reacting with lithium by using lithium and the effect thereof have not been studied at all.
  • Patent Document 6 aims to produce a lithium ion secondary battery having a high energy and a long life by forming a lithium silicate in which the valence of silicon is controlled.
  • the study on the negative electrode active material and the method for producing the lithium ion secondary battery were insufficient.
  • the negative electrode for a secondary battery described in Patent Document 7 has an effect of relaxing the volume change of the entire negative electrode when lithium is occluded and released due to the difference in charge / discharge potential of the three components. Further, by bonding lithium metal to the negative electrode surface, there is an effect of eliminating the irreversible capacity sites of the negative electrode active material.
  • Patent Document 7 as a method of lithium pre-doping, there are many points that have not been fully studied on the study of the technology of reacting with lithium at the negative electrode active material stage and the relationship in the coexistence state of the three components. It was.
  • the binder, electrolyte solution, electrode element structure, and exterior body which are indispensable for forming a lithium ion secondary battery, have not been fully studied.
  • Patent Document 8 The negative electrode material for a secondary battery described in Patent Document 8 also has an effect of reducing volume change as a whole of the negative electrode.
  • Patent Document 8 does not discuss the lithium pre-doping technique at all.
  • Patent Document 9 and Patent Document 10 describe a binder for a negative electrode.
  • studies on the state of the negative electrode active material and studies on the lithium pre-doping technology have been insufficient.
  • the electrolyte solution, the electrode element structure, and the exterior body, which are indispensable for forming a lithium ion secondary battery are often not fully studied.
  • the lithium ion secondary battery using a non-carbon material as the negative electrode active material has a high capacity, but has many capacity components that are irreversible during the first charge, and is charged and discharged in a high temperature environment. As a result, the secondary battery swells and the cycle characteristics such as the capacity retention rate decrease, which is a problem. Further development of a technology capable of solving the problem has been desired.
  • an object of the embodiment of the present invention is to provide a secondary battery having a high energy density and good high-temperature cycle characteristics.
  • the present invention A secondary battery having a negative electrode subjected to lithium pre-doping, Producing a negative electrode comprising a negative electrode active material containing at least a metal capable of alloying with lithium (a), a negative electrode binder, and a negative electrode current collector (negative electrode production step); A step of producing an electrode element including the negative electrode produced by the negative electrode production step, a positive electrode, and a separator, wherein the positive electrode and the negative electrode are arranged opposite to each other (electrode element production step); Manufactured through (Time of i) Before the negative electrode manufacturing process, (Time of ii) After the negative electrode preparation step and before the electrode element preparation step, (Time of iii) during the electrode element manufacturing process, and (time of iv) after the electrode element manufacturing process, The present invention relates to a secondary battery in which a lithium pre-doping process is performed by contacting a lithium source at least at two times selected from the group consisting of:
  • a secondary battery having a high energy density and good high-temperature cycle characteristics can be provided.
  • FIG. 3 is a schematic cross-sectional view showing a structure of an electrode element included in a laminated laminate type secondary battery.
  • lithium pre-doping may be simply referred to as “pre-doping” or “doping”.
  • the secondary battery according to this embodiment is A secondary battery having a negative electrode subjected to lithium pre-doping, Producing a negative electrode comprising a negative electrode active material containing at least a metal capable of alloying with lithium (a), a negative electrode binder, and a negative electrode current collector (negative electrode production step); A step of producing an electrode element including the negative electrode produced by the negative electrode production step, a positive electrode, and a separator, wherein the positive electrode and the negative electrode are arranged opposite to each other (electrode element production step); Manufactured through (Time of i) Before the negative electrode manufacturing process, (Time of ii) After the negative electrode preparation step and before the electrode element preparation step, (Time of iii) during the electrode element manufacturing process, and (time of iv) after the electrode element manufacturing process, It is obtained by a production method in which a lithium pre-doping treatment is performed by contacting a lithium source at least at two times selected from the group consisting of:
  • the negative electrode includes a negative electrode active material, a negative electrode binder, and a negative electrode current collector, and the negative electrode active material is bound so as to cover the negative electrode current collector with the negative electrode binder.
  • the negative electrode active material includes at least a metal (a) that can be alloyed with lithium.
  • the negative electrode active material preferably further contains a metal oxide (b) that can occlude and release lithium ions and / or a carbon material (c) that can occlude and release lithium ions.
  • the metal (a) Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, or an alloy of two or more thereof can be used. .
  • silicon (Si) is included as the metal (a).
  • the content of the metal (a) in the negative electrode active material is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and more preferably 20% by mass to 50% by mass. More preferably, it is as follows.
  • silicon oxide, aluminum oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, or a composite of two or more of these can be used.
  • silicon oxide is preferably included as the metal oxide (b). This is because silicon oxide is relatively stable and hardly causes a reaction with other compounds.
  • one or more elements selected from nitrogen, boron and sulfur may be added to the metal oxide (b), for example, 0.1 to 5% by mass. By carrying out like this, the electrical conductivity of a metal oxide (b) can be improved.
  • the content of the metal oxide (b) in the negative electrode active material is not particularly limited and may be 0% by mass, but is preferably 5% by mass to 90% by mass, and preferably 40% by mass to 80% by mass. It is more preferable to set it as mass% or less, and it is still more preferable to set it as 50 mass% or more and 70 mass% or less.
  • the metal oxide (b) preferably has an amorphous structure in whole or in part.
  • the metal oxide (b) having an amorphous structure can suppress the volume expansion of the carbon material (c) and the metal (a), which are other negative electrode active materials, and can suppress the decomposition of the electrolytic solution. Although this mechanism is not clear, it is presumed that the metal oxide (b) has some influence on the formation of a film on the interface between the carbon material (c) and the electrolytic solution due to the amorphous structure.
  • the amorphous structure is considered to have relatively few elements due to non-uniformity such as crystal grain boundaries and defects.
  • the metal oxide (b) has an amorphous structure. Specifically, when the metal oxide (b) does not have an amorphous structure, a peak specific to the metal oxide (b) is observed, but all or part of the metal oxide (b) is amorphous. In the case of having a structure, the intrinsic peak is observed broad in the metal oxide (b).
  • the negative electrode active material contains a metal (a) and a metal oxide (b)
  • the metal (a) is entirely or partially dispersed in the metal oxide (b).
  • volume expansion as the whole negative electrode can be further suppressed, and decomposition of the electrolytic solution can also be suppressed.
  • all or part of the metal (a) is dispersed in the metal oxide (b) because of observation with a transmission electron microscope (general TEM observation) and energy dispersive X-ray spectroscopy (general). This can be confirmed by using a combination of a standard EDX measurement.
  • the cross section of the sample containing the metal particles (a) is observed, the oxygen concentration of the metal particles (a) dispersed in the metal oxide (b) is measured, and the metal particles (a) are configured. It can be confirmed that the metal being used is not an oxide.
  • the metal oxide (b) is preferably an oxide of a metal constituting the metal (a).
  • the ratio of the metal (a) and the metal oxide (b) is not particularly limited. It is preferable that a metal (a) shall be 5 to 90 mass% with respect to the sum total of a metal (a) and a metal oxide (b), and it is preferable to set it as 30 to 60 mass%.
  • the metal oxide (b) is preferably 10% by mass or more and 95% by mass or less, and preferably 40% by mass or more and 70% by mass or less with respect to the total of the metal (a) and the metal oxide (b). preferable.
  • the carbon material (c) graphite, amorphous carbon, diamond-like carbon, carbon nanotube, or a composite of two or more of these can be used.
  • graphite with high crystallinity has high electrical conductivity, and is excellent in adhesiveness and voltage flatness with a negative electrode current collector made of a metal such as copper.
  • amorphous carbon having low crystallinity has a relatively small volume expansion, it has a high effect of relaxing the volume expansion of the entire negative electrode, and deterioration due to non-uniformity such as crystal grain boundaries and defects hardly occurs.
  • the content of the carbon material (c) in the negative electrode active material may be 0% by mass, but is preferably 2% by mass or more and 50% by mass or less, and more preferably 2% by mass or more and 30% by mass or less. preferable.
  • the ratio of the metal (a), the metal oxide (b), and the carbon material (c) is not particularly limited.
  • the metal (a) is preferably 5% by mass or more and 90% by mass or less, and 20% by mass or more and 50% by mass or less with respect to the total of the metal (a), the metal oxide (b), and the carbon material (c). It is preferable that The metal oxide (b) is preferably 5% by mass or more and 90% by mass or less, and 40% by mass or more and 70% by mass with respect to the total of the metal (a), the metal oxide (b), and the carbon material (c). % Or less is preferable.
  • the carbon material (c) is preferably 2% by mass or more and 50% by mass or less, preferably 2% by mass or more and 30% by mass or less with respect to the total of the metal (a), the metal oxide (b) and the carbon material (c). The following is preferable.
  • the metal (a), the metal oxide (b) and the carbon material (c) are not particularly limited, but particulate materials can be used.
  • the average particle diameter of the metal (a) may be smaller than the average particle diameter of the metal oxide (b) and the average particle diameter of the carbon material (c). In this way, the metal (a) having a large volume change during charging and discharging has a relatively small particle size, and the metal oxide (b) and the carbon material (c) having a small volume change have a relatively large particle size. Therefore, dendrite formation and alloy pulverization are more effectively suppressed.
  • the average particle diameter of the metal (a) can be, for example, 10 ⁇ m or less, and is preferably 5 ⁇ m or less.
  • the carbon material (c) may be localized in the vicinity of the surface of the particle composed of the metal (a) and the metal oxide (b) in a state like a coating. By localizing, carbon aggregation can be prevented, and from the viewpoint of the electrode as a whole, there is an effect on relaxation of volume expansion and equalization of electronic conductivity.
  • the negative electrode active material includes a metal (a), a metal oxide (b), and a carbon material (c), and all or part of the metal oxide (b) has an amorphous structure, and all or one part of the metal (a)
  • the negative electrode active material in which the part is dispersed in the metal oxide (b) and the carbon material (c) is localized is produced by, for example, a method disclosed in Patent Document 8. Can do. That is, by performing a CVD process on the metal oxide (b) in an atmosphere containing an organic gas such as methane gas, the metal (a) in the metal oxide (b) is nanoclustered and the surface is a carbon material (c ) Can be obtained. Moreover, the said negative electrode active material is producible also by mixing a metal (a), a metal oxide (b), and a carbon material (c) by mechanical milling in steps.
  • the negative electrode active material is preferably a negative electrode active material mainly composed of silicon.
  • Lithium silicate can be formed by performing lithium pre-doping on silicon and silicon oxide as described later. At that time, by controlling the valence of silicon, a negative electrode having a high capacity and a long life can be produced.
  • silicon having an oxidation number of 0, a silicon compound having a silicon atom having an oxidation number of +4, and a silicon atom having an oxidation number of greater than 0 and less than +4 By forming a silicon lower oxide, a negative electrode having a high capacity and a long life can be produced.
  • binder for the negative electrode generally, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, polytetrafluoroethylene Polypropylene, polyethylene, polyimide, polyamideimide, and the like are used. In this embodiment, it is preferable to use polyimide or polyamideimide.
  • the content of the binder for the negative electrode to be used is the ratio of the mass% ratio of the negative electrode active material and the negative electrode binder from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. Is preferably 95: 5 to 80:20, more preferably 92: 8 to 85:15.
  • 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 negative electrode can be manufactured by forming a negative electrode active material layer including a negative electrode active material and a negative electrode binder on the negative electrode current collector.
  • 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.
  • a thin film of aluminum, nickel, or an alloy thereof may be formed by a method such as vapor deposition or sputtering to form a negative electrode current collector.
  • the electrode element includes at least a negative electrode, a positive electrode, and a separator, and the positive electrode and the negative electrode are arranged to face each other.
  • 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.
  • an electrode element included in a laminated laminate type secondary battery will be described.
  • FIG. 1 is a schematic cross-sectional view showing a 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 electrode element having such a planar laminated structure does not have a portion with a small R (a region close to the core of the concentric winding structure or a folded region corresponding to the end of the flat winding structure), Compared to an electrode element having a rotating structure, there is an advantage that it is less likely to be adversely affected by the volume change of the electrode accompanying charge / discharge. That is, it is effective as an electrode element using an active material that easily causes volume expansion.
  • an electrode element having a wound structure since the electrode is curved, the structure is easily distorted when a volume change occurs.
  • a negative electrode active material having a large volume change due to charge / discharge such as silicon oxide, it is considered that a secondary battery using an electrode element having a wound structure has a large capacity drop due to charge / discharge. .
  • the electrode element having a planar laminated structure has a problem that when the gas is generated between the electrodes, the generated gas tends to stay between the electrodes. This is because, in the case of an electrode element having a wound structure, the distance between the electrodes is difficult to widen because tension is applied to the electrodes, whereas in the case of an electrode element having a laminated structure, the distance between the electrodes is widened. This is because it is easy. This problem is particularly noticeable when the outer package is an aluminum laminate film.
  • the above-described problems can be solved, and a long-life driving is possible even in a laminated laminate type lithium ion secondary battery using a high energy type negative electrode.
  • an electrode element manufacturing step for example, when an electrode element having the structure of FIG. 1 is manufactured, three positive electrode layers and four negative electrode layers are alternately overlapped with a separator interposed therebetween, and a positive electrode collector not covered with a positive electrode active material.
  • An electrode element can be produced by welding the end portions of the negative electrode current collector not covered with the electric body and the negative electrode active material, respectively, and further welding the positive electrode terminal and the negative electrode terminal respectively to the welded portions.
  • time to perform lithium pre-doping refers to contacting a negative electrode active material with a lithium source (metallic lithium or a lithium compound having an activity similar thereto) that has not been in contact with the negative electrode active material until then. This is the time when the new lithium source is brought into contact with the negative electrode active material for the first time.
  • a lithium source metallic lithium or a lithium compound having an activity similar thereto
  • the lithium pre-doping treatment lithium can be doped (inserted) into the negative electrode active material from the lithium source to collapse the irreversible capacity. Further, as a result of the lithium pre-doping treatment, the metal or metal oxide in the electrode can react to generate a lithium metal oxide.
  • the lithium pre-doping performed before the negative electrode manufacturing step refers to the lithium pre-doping performed before or during the negative electrode manufacturing step. That is.
  • Examples of the lithium pre-doping performed before the negative electrode preparation step include pre-doping performed in the state of the negative electrode active material alone.
  • Examples of the lithium pre-doping performed during the negative electrode preparation step include lithium pre-doping performed in a state where a negative electrode active material and a negative electrode binder are mixed.
  • the lithium pre-doping process time of i
  • the form of a negative electrode active material may be a powder state or a slurry state, it is preferable that it is a powder state.
  • the powdered negative electrode active material include a powder of the negative electrode active material alone or a powder obtained by mixing a negative electrode active material and a negative electrode binder.
  • a negative electrode active material in a slurry state a slurry obtained by mixing a negative electrode active material and an organic solvent such as n-methylpyrrolidone, or a negative electrode active material, a negative electrode binder, and an organic solvent such as n-methylpyrrolidone And a slurry obtained by mixing the.
  • an organic solvent such as n-methylpyrrolidone
  • a negative electrode active material a negative electrode active material in a slurry state
  • the method described in Patent Document 4 or Patent Document 5 can be used as the lithium pre-doping method performed at (time i).
  • the specific molar ratio is not particularly limited, but the molar ratio of “metal contained in the powdered negative electrode active material” and “lithium contained in the lithium source” is preferably 5: 1 to 0.00.
  • the molar ratio is 5: 1, more preferably 2: 1 to 0.8: 1.
  • heat processing temperature is not specifically limited, 100 to 800 degreeC is preferable and 200 to 800 degreeC is more preferable.
  • the lithium source include lithium metal, an organic lithium compound, lithium hydride, and lithium aluminum hydride. Among these, lithium hydride and lithium aluminum hydride are more preferable.
  • the negative electrode active material is in a slurry state
  • a slurry containing the negative electrode active material is mixed with a lithium source in an atmosphere at a temperature of 60 ° C. to 125 ° C. to thereby convert lithium into the negative electrode active material.
  • the molar ratio between the “metal contained in the negative electrode active material” and the “lithium contained in the lithium source” in the slurry is preferably a molar ratio of 5: 1 to 0.5: 1. More preferred is a molar ratio of 1 to 0.8 to 1.
  • lithium source to be mixed with the negative electrode active material in the slurry state examples include lithium metal, organic lithium compound, lithium hydride, lithium aluminum hydride, and among these, lithium metal, lithium hydride, lithium aluminum hydride are more. preferable. Moreover, these lithium sources may be used individually by 1 type, or may use 2 or more types together.
  • lithium pre-doping performed after the negative electrode preparation step and before the electrode element preparation step refers to the negative electrode and the positive electrode by winding or stacking.
  • lithium pre-doping performed in a state of only the negative electrode preferably in a state where the negative electrode is in the electrode plate state
  • a method in which a negative electrode is disposed in an electrolyte together with a lithium source, lithium is doped using a potential difference between the negative electrode and the lithium source, and lithium diffusion by heat is utilized.
  • a method of doping lithium into the negative electrode see Patent Document 3
  • a lithium battery with the lithium source placed on the negative electrode by vapor deposition or the like are used as a secondary battery, and the secondary battery is heated at a low temperature (approximately 70 to 80 ° C. or lower) and a method of doping lithium with a potential difference.
  • the negative electrode obtained by applying the negative electrode active material together with the negative electrode binder and the conductive auxiliary agent on the negative electrode current collector may be pressed before the electrode element manufacturing step.
  • the lithium pre-doping time of ii
  • the diffusion of lithium is improved, but the electrode tends to peel off during pressing.
  • peeling of the electrode during pressing is less likely to occur, but lithium diffusion tends to be delayed.
  • the lithium source is preferably in the form of a sheet.
  • the sheet-like lithium source include 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. Heating is performed after the lithium source is brought into contact with the electrode.
  • the heating temperature is preferably 70 ° C. or higher and 180.5 ° C. or lower, more preferably 80 ° C. or higher and 130 ° C. or lower, and further preferably 80 ° C. or higher and 125 ° C. or lower.
  • the heating time depends on the heating temperature, it is generally 1 to 48 hours, preferably 8 to 16 hours. Since metallic lithium reacts violently with moisture, all operations are preferably performed in a low humidity environment.
  • the pre-doping performed during the electrode element manufacturing process (hereinafter sometimes referred to as “time of iii”) is a process of manufacturing an electrode element including a negative electrode, a positive electrode, and a separator. It is a pre-dope performed between.
  • the pre-doping performed at (iii) can reduce the process time because the lithium source can be arranged simultaneously with the lamination of the electrode and the separator. However, it cannot be accelerated at high temperatures to prevent the separator from melting.
  • a pre-doping method to be performed at (iii) for example, when laminating a negative electrode, a positive electrode, and a separator, at least one surface of the surface covered with the negative electrode active material of the negative electrode, preferably a lithium metal foil or the like on both surfaces
  • the method of laminating a lithium source is mentioned.
  • a lithium source is laminated on both sides of all the negative electrodes to be formed.
  • a laminate in which a negative electrode, a lithium source, a positive electrode, a separator, and the like are combined.
  • the heating temperature may be lower than the melting point of the separator to be used, and for example, heating at 60 to 120 ° C. is preferable.
  • the heating time is not particularly limited, but is preferably 1 hour to 48 hours, for example.
  • the pre-doping performed after the electrode element manufacturing step preferably means that after the electrode element is manufactured, the electrode element and the electrolyte are It is a pre-doping performed in the process of completing the secondary battery by enclosing it in the exterior body.
  • the pre-doping performed at (iv time) can increase the diffusion speed of lithium by injecting an electrolytic solution.
  • Examples of the pre-doping method performed at (iv time) include a method of laminating a lithium source such as a lithium metal foil on the outermost negative electrode of the electrode element.
  • the electrode element in which the lithium source is laminated on the outermost negative electrode in this manner is enclosed in an outer package such as a metal can or an aluminum laminate film together with the electrolytic solution, and is incorporated into a secondary battery. Then, when this laminated electrode element touches the electrolyte in the secondary battery, a kind of local battery is formed and self-discharged, and lithium is doped electrochemically into the negative electrode active material.
  • lithium pre-doping is performed at least two times out of the above (i time) to (iv time).
  • the combination of the periods when the lithium pre-doping is performed includes at least (ii period), that is, (ii period), (i period), (iii period) and (iv period) A combination with at least one period is preferable, and a combination of the period (i) and the period (ii) is more preferable.
  • lithium pre-doping is performed on the negative electrode active material in the powder state (time i), and lithium pre-doping is performed on the negative electrode state (time ii). It is further preferable to combine with the above. This makes it easier to control the valence of silicon.
  • “only when the negative electrode active material is doped with lithium in the state of (i)”, an attempt to dope a sufficient amount of lithium increases the active sites on the negative electrode surface due to the reaction with lithium. This increases the reactivity with moisture in the battery, causing a deterioration of the service life.
  • the target lithium pre-doping Of the amount, in the “powder state” at (time i), the weight ratio is about 3/4 or less, preferably 2/3 or less, more preferably 1/2 or less, and the remaining deficiency is ( It is particularly preferable to dope in the state of the negative electrode at the time of ii). Thereby, a secondary battery with various battery characteristics can be manufactured.
  • 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.
  • lithium manganate having a layered structure such as LiMnO 2 , Li x Mn 2 O 4 (0 ⁇ x ⁇ 2) or lithium manganate having a spinel structure; LiCoO 2 , LiNiO 2 or a transition metal thereof Lithium transition metal oxides in which a specific transition metal such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 does not exceed half the lithium transition metal oxides; In which Li is made excessive in comparison with the stoichiometric composition.
  • a positive electrode active material can be used individually by 1 type or in combination of 2 or more types.
  • the positive electrode binder the same as the 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 used is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material from the viewpoints of “sufficient binding force” and “higher 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.
  • the electrolytic solution used in the present embodiment includes a nonaqueous electrolytic solution that is stable at the operating potential of the battery and a supporting salt.
  • the non-aqueous electrolyte include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC); dimethyl carbonate (DMC), diethyl carbonate (DEC) Chain carbonates such as ethyl methyl carbonate (EMC) and dipropyl carbonate (DPC); propylene carbonate derivatives; aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate; diethyl ether and ethyl propyl ether And aprotic organic solvents such as phosphate esters.
  • the fluorinated aprotic organic solvent which substituted some of them with the fluorine is mentioned.
  • non-aqueous electrolytes include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (MEC).
  • Cyclic or chain carbonates such as dipropyl carbonate (DPC) are preferred.
  • a non-aqueous electrolyte can be used individually by 1 type or in combination of 2 or more types.
  • the supporting salt used in the present embodiment include LiPF 6 , LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ). 2 and lithium salts such as LiN (CF 3 SO 2 ) 2 .
  • the supporting salt can be used alone or in combination of two or more. LiPF 6 is preferable from the viewpoint of low cost.
  • ⁇ Separator> As the separator, a porous film such as polypropylene or polyethylene or a nonwoven fabric can be used. Moreover, what laminated
  • 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.
  • the distortion of the electrode element becomes very large when gas is generated, compared to a secondary battery using a metal can as the exterior body. This is because the laminate film is more easily deformed by the internal pressure of the secondary battery than the metal can. Furthermore, when sealing a secondary battery using a laminate film as an exterior body, the internal pressure of the battery is usually lower than the atmospheric pressure, so there is no extra space inside, and if gas is generated, it is immediately It tends to lead to battery volume changes and electrode element deformation.
  • the secondary battery according to the present embodiment can overcome the above problem. Therefore, according to the present invention, it is possible to provide a laminated laminate type lithium ion secondary battery that is inexpensive and excellent in design flexibility of cell capacity by changing the number of laminated layers.
  • Example 1 [Preparation of positive electrode] Lithium nickelate (LiNi 0.80 Co 0.15 Al 0.05 O 2 ) as a positive electrode active material, carbon black as a conductive auxiliary, and polyvinylidene fluoride as a positive electrode binder: They were weighed at a mass ratio of 5: 5 and mixed with n-methylpyrrolidone to obtain a positive electrode slurry. The positive electrode slurry was applied to an aluminum foil having a thickness of 20 ⁇ m at a basis weight of 5 mg / cm 2 , dried, and further pressed to produce a positive electrode.
  • Lithium nickelate LiNi 0.80 Co 0.15 Al 0.05 O 2
  • carbon black as a conductive auxiliary
  • polyvinylidene fluoride as a positive electrode binder
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • a negative electrode was doped with lithium by flowing a current of 1 mA for 50 hours in a room temperature environment.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • Example 2 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by vapor deposition. That is, lithium pre-doping was performed by arranging a metal lithium wire and a negative electrode in a vacuum chamber and heating the metal lithium wire in a vacuum.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, the lithium foil rolled on Cu foil was affixed facing the negative electrode, vacuum-sealed in an aluminum laminate bag, and heat-treated at 130 ° C. for 12 hours in a vacuum thermostat.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, the lithium foil rolled on Cu foil was affixed and bonded to the negative electrode, vacuum sealed in an aluminum laminate bag, and heat-treated at 130 ° C. for 12 hours in a vacuum thermostat.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, a lithium foil rolled on a Cu foil was affixed to the negative electrode and opposed, vacuum sealed in an aluminum laminate bag, and heat-treated at 185 ° C. for 12 hours in a vacuum thermostat.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 5 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, the lithium foil rolled on Cu foil was affixed and bonded to the negative electrode, vacuum sealed in an aluminum laminate bag, and heat-treated at 130 ° C. for 12 hours in a vacuum thermostat.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 6 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, a lithium foil rolled on a Cu foil was affixed to the negative electrode and faced, vacuum sealed in an aluminum laminate bag, and heat-treated at 170 ° C. for 12 hours in a vacuum thermostat.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 7 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, a lithium foil rolled on a Cu foil was affixed to the negative electrode and opposed, vacuum sealed in an aluminum laminate bag, and heat-treated at 100 ° C. for 12 hours in a vacuum thermostat.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 8 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, a lithium foil rolled on a Cu foil was affixed to the negative electrode, faced in an aluminum laminate bag, and heat-treated at 70 ° C. for 12 hours in a vacuum thermostat.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 9 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, the lithium foil rolled on Cu foil was affixed and bonded to the negative electrode, vacuum sealed in an aluminum laminate bag, and heat-treated at 130 ° C. for 12 hours in a vacuum thermostat.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 10 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • a metal (a) was obtained by mixing tin with an average particle diameter of 7 ⁇ m and silicon with an average particle diameter of 7 ⁇ m at a weight ratio of 80:20 and performing mechanical milling in an argon atmosphere.
  • this metal material was measured with a particle size distribution measuring apparatus manufactured by Nikkiso Co., Ltd., the average particle size was about 5 to 6 ⁇ m.
  • Lithium hydride was mixed with the metal (a) at a mass ratio (1:10), and heat treatment was performed in an argon gas at 600 ° C. for 1 hour to perform lithium pre-doping.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, a lithium foil rolled on a Cu foil was affixed to the negative electrode and opposed, vacuum sealed in an aluminum laminate bag, and heat-treated at 100 ° C. for 12 hours in a vacuum thermostat.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 11 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • a metal (a) was obtained by mixing tin with an average particle diameter of 7 ⁇ m and silicon with an average particle diameter of 7 ⁇ m at a weight ratio of 80:20 and performing mechanical milling in an argon atmosphere.
  • this metal material was measured with a particle size distribution measuring apparatus manufactured by Nikkiso Co., Ltd., the average particle size was about 5 to 6 ⁇ m.
  • Lithium hydride was mixed with the metal (a) at a mass ratio (1:10), and heat treatment was performed in an argon gas at 600 ° C. for 1 hour to perform lithium pre-doping.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, a lithium foil rolled on a Cu foil was affixed to the negative electrode and opposed, vacuum sealed in an aluminum laminate bag, and heat-treated at 100 ° C. for 12 hours in a vacuum thermostat.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 12 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • a metal (a) was obtained by mixing tin having an average particle diameter of 7 ⁇ m and silicon having an average particle diameter of 7 ⁇ m at a weight ratio of 80:20 and performing mechanical milling in an argon atmosphere.
  • this metal material was measured with a particle size distribution measuring apparatus manufactured by Nikkiso Co., Ltd., the average particle size was about 5 to 6 ⁇ m.
  • Lithium hydride was mixed with the metal (a) at a mass ratio (1:10), and heat treatment was performed in an argon gas at 600 ° C. for 1 hour to perform lithium pre-doping.
  • the obtained mixture was mechanically milled in an argon atmosphere to obtain a mixture.
  • the metal (a) was dispersed in the oxide (b), and the oxide (b) had an amorphous structure.
  • the obtained mixture was subjected to CVD treatment at 1150 ° C. for 6 hours in an atmosphere containing methane gas to obtain a negative electrode active material in which carbon was localized near the surface of the negative electrode active material.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, a lithium foil rolled on a Cu foil was affixed to the negative electrode and opposed, vacuum sealed in an aluminum laminate bag, and heat-treated at 100 ° C. for 12 hours in a vacuum thermostat.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 13 [Preparation of positive electrode] A positive electrode was produced in the same manner as in Example 1.
  • a silicon-silicon oxide mixed powder represented by the general formula SiO (a mixture of silicon oxide and silicon) is subjected to CVD treatment at 1150 ° C. for 6 hours in an atmosphere containing methane gas, so that silicon in the silicon oxide is converted into an oxide matrix.
  • a negative electrode active material in which the oxide was amorphous and the carbon particles were localized near the surface of the silicon-silicon oxide mixed powder was obtained.
  • the mass ratio of silicon / silicon oxide / carbon was adjusted to be approximately 32/63/5.
  • This negative electrode active material was mixed with lithium hydride at a mass ratio (1:10), and heat-treated in argon gas at 600 ° C. for 1 hour to perform lithium pre-doping.
  • This negative electrode active material and a polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Viromax (registered trademark)) as a negative electrode binder are weighed at a mass ratio of 85:15, and they are n —Mixed with pyrrolidone to form negative electrode slurry.
  • the negative electrode slurry was applied to a copper foil having a thickness of 15 ⁇ m at a basis weight of 2 mg / cm 2 , dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to produce a negative electrode.
  • the lithium negative electrode was subjected to lithium pre-doping.
  • Lithium pre-doping was performed by a lithium pasting method. That is, a lithium foil rolled on a Cu foil was affixed to the negative electrode and opposed, vacuum sealed in an aluminum laminate bag, and heat-treated at 100 ° C. for 12 hours in a vacuum thermostat.
  • the obtained positive electrode 3 layers and negative electrode 4 layers were alternately stacked while sandwiching a polypropylene porous film as a separator.
  • the ends of the positive electrode current collector that is not covered with the positive electrode active material and the negative electrode current collector that is not covered with the negative electrode active material are welded, and the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are further welded to the welded portions. Were respectively welded to obtain an electrode element having a planar laminated structure.
  • the electrode element was wrapped with an aluminum laminate film as an exterior body, an electrolyte solution was poured into the inside, and then sealed while reducing the pressure to 0.1 atm to prepare a secondary battery.
  • the fabricated secondary battery was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 14 Production and evaluation were performed in the same manner as in Example 13 except that Ube Industries polyimide (U-varnish) was used as the negative electrode binder.
  • Example 15 Manufactured in the same manner as in Example 13 except that a 1: 1 weight ratio mixture of polyimide (U-varnish) manufactured by Ube Industries, Ltd. and polyamideimide (Vilomax) manufactured by Toyobo Co., Ltd. was used as the negative electrode binder. ⁇ Evaluated.
  • Example 11 when the metal (a) of the negative electrode was dispersed in the amorphous oxide (b), a more remarkable effect was observed (Example 11). Furthermore, when carbon (c) was localized near the surface of the negative electrode active material, a more remarkable effect was observed (Example 12). Furthermore, when the metal was silicon and the oxide was silicon oxide, a more remarkable effect was observed (Example 13). Further, it was confirmed that the same effect was obtained even if the type of the negative electrode binder was changed (Examples 14 and 15).
  • This embodiment can be used in all industrial fields that require a power source and in industrial fields related to the transport, storage, and supply of electrical energy.
  • power supplies for mobile devices such as mobile phones and notebook computers
  • power supplies for transportation and transportation media such as trains, satellites, and submarines, including electric vehicles such as electric cars, hybrid cars, electric bikes, and electric assist bicycles
  • a backup power source such as a UPS
  • a power storage facility for storing power generated by solar power generation, wind power generation, etc .

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

La présente invention concerne une batterie secondaire qui comporte une électrode négative qui a été soumise à un traitement de dopage préalable au lithium. Cette batterie secondaire est caractérisée en ce qu'elle est produite par les étapes suivantes : la formation d'une électrode négative qui comprend un matériau actif d'électrode négative contenant au moins un métal (a) qui peut constituer un alliage avec du lithium, un liant pour électrodes négatives, et un collecteur d'électrode négative (étape de formation d'électrode négative) ; la formation d'un élément d'électrode qui comporte l'électrode négative, qui a été formée par l'étape de formation d'électrode négative, une électrode positive et un séparateur de telle sorte que l'électrode positive et l'électrode négative sont agencées de façon à se faire face (étape de formation d'élément d'électrode). Cette batterie secondaire est également caractérisée en ce que le traitement de dopage préalable au lithium est effectué en amenant l'électrode négative en contact avec une source de lithium pendant au moins deux périodes qui sont choisies dans le groupe comprenant (période i) la période avant l'étape de formation d'électrode négative, (période ii) la période après l'étape de formation d'électrode négative mais avant l'étape de formation d'élément d'électrode, (période iii) la période durant l'étape de formation d'élément d'électrode, et (période iv) la période après l'étape de formation d'élément d'électrode.
PCT/JP2013/064681 2012-05-29 2013-05-27 Batterie secondaire au lithium-ion WO2013180083A1 (fr)

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JP2015164105A (ja) * 2014-02-28 2015-09-10 株式会社Ｇｓユアサ 蓄電素子
JP2017174803A (ja) * 2016-03-16 2017-09-28 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の製造方法及び非水電解質二次電池用負極の製造方法
JP2019096561A (ja) * 2017-11-27 2019-06-20 株式会社豊田自動織機 リチウムイオン二次電池
US20200220178A1 (en) * 2019-01-08 2020-07-09 Commissariat à l'énergie atomique et aux énergies alternatives Negative electrodes for use in accumulators operating according to the ion insertion and deinsertion or alloy formation principle and accumulator comprising such an electrode

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JP2008300214A (ja) * 2007-05-31 2008-12-11 Fuji Heavy Ind Ltd 電極、蓄電デバイスおよびこれらの製造方法
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JP2007214109A (ja) * 2006-01-10 2007-08-23 Matsushita Electric Ind Co Ltd 非水電解質二次電池およびその製造方法
JP2008300214A (ja) * 2007-05-31 2008-12-11 Fuji Heavy Ind Ltd 電極、蓄電デバイスおよびこれらの製造方法
JP2011222153A (ja) * 2010-04-05 2011-11-04 Shin Etsu Chem Co Ltd 非水電解質二次電池用負極材及び非水電解質二次電池用負極材の製造方法並びにリチウムイオン二次電池

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015164105A (ja) * 2014-02-28 2015-09-10 株式会社Ｇｓユアサ 蓄電素子
JP2017174803A (ja) * 2016-03-16 2017-09-28 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の製造方法及び非水電解質二次電池用負極の製造方法
JP2019096561A (ja) * 2017-11-27 2019-06-20 株式会社豊田自動織機 リチウムイオン二次電池
US20200220178A1 (en) * 2019-01-08 2020-07-09 Commissariat à l'énergie atomique et aux énergies alternatives Negative electrodes for use in accumulators operating according to the ion insertion and deinsertion or alloy formation principle and accumulator comprising such an electrode

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