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WO2014199781A1 - Matériau actif d'électrode négative destiné à être utilisé dans un dispositif électrique et dispositif électrique faisant intervenir ledit matériau - Google Patents

Matériau actif d'électrode négative destiné à être utilisé dans un dispositif électrique et dispositif électrique faisant intervenir ledit matériau Download PDF

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Publication number
WO2014199781A1
WO2014199781A1 PCT/JP2014/063247 JP2014063247W WO2014199781A1 WO 2014199781 A1 WO2014199781 A1 WO 2014199781A1 JP 2014063247 W JP2014063247 W JP 2014063247W WO 2014199781 A1 WO2014199781 A1 WO 2014199781A1
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WIPO (PCT)
Prior art keywords
active material
negative electrode
electrode active
alloy
battery
Prior art date
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PCT/JP2014/063247
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English (en)
Japanese (ja)
Inventor
智裕 蕪木
渡邉　学
文博 三木
千葉　啓貴
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
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Priority to JP2015522676A priority Critical patent/JP6112199B2/ja
Publication of WO2014199781A1 publication Critical patent/WO2014199781A1/fr
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a negative electrode active material for an electrical device, and an electrical device using the same.
  • the negative electrode active material for an electric device according to the present invention and an electric device using the same are, for example, driving power sources and auxiliary power sources for motors of vehicles such as electric vehicles, fuel cell vehicles and hybrid electric vehicles as secondary batteries and capacitors. Used for
  • a motor drive secondary battery As a motor drive secondary battery, it is required to have extremely high output characteristics and high energy as compared with a consumer lithium ion secondary battery used for a mobile phone, a notebook personal computer and the like. Therefore, a lithium ion secondary battery having the highest theoretical energy among all the batteries has attracted attention, and is currently being rapidly developed.
  • a lithium ion secondary battery comprises a positive electrode obtained by applying a positive electrode active material etc. on both sides of a positive electrode current collector using a binder, and a negative electrode obtained by applying a negative electrode active material etc. on both sides of a negative electrode current collector using a binder Are connected via the electrolyte layer and stored in the battery case.
  • a battery using a material that is alloyed with Li for the negative electrode is expected to be a negative electrode material for use in vehicles because the energy density is improved as compared to conventional carbon / graphite based negative electrode materials.
  • a lithium ion secondary battery using a material that is alloyed with Li for the negative electrode has a large amount of expansion and contraction at the negative electrode during charge and discharge.
  • the volume expansion when occluding Li ions is about 1.2 times in the case of a graphite material, while in the case of Si material, when Si and Li are alloyed, it changes from an amorphous state to a crystalline state and a large volume change
  • the capacity and the cycle durability are in a trade-off relationship, and there is a problem that it is difficult to improve the cycle durability while exhibiting a high capacity.
  • a negative electrode active material for a lithium ion secondary battery including an amorphous alloy having a formula; Si x M y Al z has been proposed (for example, JP-A-2009-517850 (International Publication 2007/064531))).
  • M is Mn, Mo, Nb, W, Ta, Fe, Cu, It is a metal consisting of at least one of Ti, V, Cr, Ni, Co, Zr, and Y.
  • JP-A-2009-517850 it is described that, in addition to the high capacity, a good cycle life is exhibited by minimizing the content of the metal M in the paragraph “0008”.
  • the objective of this invention is providing the negative electrode active material for electric devices, such as a lithium ion secondary battery which has high cycle durability.
  • the present inventors diligently studied to solve the above-mentioned problems. As a result, it is found that the above problems can be solved by using a ternary Si alloy which is a combination of predetermined elements and has a predetermined composition, and by setting the BET specific surface area of the alloy to a predetermined range.
  • the present invention has been completed.
  • the present invention relates to a negative electrode active material for an electric device.
  • the negative electrode active material for an electric device has the following chemical formula (1):
  • M is at least one metal selected from the group consisting of Ti, Zn, C, and a combination thereof
  • A is an unavoidable impurity
  • It It is characterized in that it contains an alloy represented by Further, in the alloy, BET specific surface area, is characterized in that it is less than 100 m 2 / g exceed 3m 2 / g.
  • 1, 10 is a lithium ion secondary battery (stacked battery); 11 is a negative electrode current collector; 12 is a positive electrode current collector; 13 is a negative electrode active material layer; 15 is a positive electrode active material layer; Reference numeral 17 denotes an electrolyte layer, 19 denotes a single cell layer, 21 denotes a power generation element, 25 denotes a negative electrode current collector plate, 27 denotes a positive electrode current collector plate, and 29 denotes a battery exterior material (laminated film).
  • BRIEF DESCRIPTION OF THE DRAWINGS It is the perspective view which represented typically the external appearance of the lamination-type flat lithium ion secondary battery which is typical embodiment of the electric device which concerns on this invention. In FIG.
  • 50 represents a lithium ion secondary battery (laminated battery); 57 represents a power generation element; 58 represents a negative electrode current collector; 59 represents a positive electrode current collector; and 52 represents a battery exterior material (laminate film) Respectively.
  • FIG. It is a figure which shows the influence of the negative electrode active material alloy composition on the discharge capacity maintenance factor of the 100th cycle of the battery obtained by the reference example A.
  • FIG. It is a ternary composition chart which plots and shows the alloy component formed into a film by the reference example B with the preferable composition range of Si-Sn-Zn type alloy which comprises the negative electrode active material for electric devices of this invention.
  • It is a ternary composition figure which shows the more preferable composition range of Si-Sn-Zn type alloy which comprises the negative electrode active material for electric devices of this invention.
  • FIG. 1 It is a ternary composition figure which shows the especially preferable composition range of the Si-Sn-Zn type alloy which comprises the negative electrode active material for electric devices of this invention. It is drawing which shows the influence of the negative electrode active material alloy composition on the initial stage discharge capacity of the battery obtained by the reference example B.
  • FIG. It is drawing which shows the relationship between the discharge capacity maintenance factor of the 50th cycle of the battery obtained by the reference example B, and an anode active material alloy composition. It is a figure which shows the relationship of the discharge capacity maintenance factor of a 100th cycle of the battery obtained by the reference example B, and an anode active material alloy composition.
  • the “electrode layer” means a mixture layer containing a negative electrode active material, a conductive additive, and a binder, but may also be referred to as a “negative electrode active material layer” in the description of this specification.
  • the electrode layer on the positive electrode side is also referred to as a “positive electrode active material layer”.
  • a negative electrode for a lithium ion secondary battery which is a representative embodiment of a negative electrode including the negative electrode active material for an electric device according to the present invention, and a lithium ion secondary battery using the same High energy density, high power density can be achieved. Therefore, the lithium ion secondary battery using the negative electrode active material for a lithium ion secondary battery of the present embodiment is excellent for use as a driving power supply or an auxiliary power supply of a vehicle. As a result, it can be suitably used as a lithium ion secondary battery for driving power supply of a vehicle. In addition to this, it is sufficiently applicable to lithium ion secondary batteries for mobile devices such as mobile phones.
  • the lithium ion secondary battery to be a target of the present embodiment may be one using the negative electrode active material for the lithium ion secondary battery of the present embodiment described below, and the other constituent requirements will be described. It should not be particularly limited.
  • the lithium ion secondary battery when the lithium ion secondary battery is distinguished by form and structure, it can be applied to any conventionally known form and structure such as a laminated (flat) battery and a wound (cylindrical) battery. It is a thing.
  • a laminated (flat type) battery structure By employing a laminated (flat type) battery structure, long-term reliability can be secured by seal technology such as simple thermocompression bonding, which is advantageous in terms of cost and workability.
  • the solution electrolyte type battery using solution electrolytes such as non-aqueous electrolyte solution, in the electrolyte layer, the polymer battery using polymer electrolyte in the electrolyte layer, etc. It can be applied to any of the conventionally known electrolyte layer types.
  • the polymer battery is further divided into a gel electrolyte type battery using a polymer gel electrolyte (also simply referred to as a gel electrolyte), and a solid polymer (all solid) type battery using a polymer solid electrolyte (also simply referred to as a polymer electrolyte).
  • FIG. 1 schematically shows the entire structure of a flat (stacked) lithium ion secondary battery (hereinafter, also simply referred to as “stacked battery”), which is a representative embodiment of the electrical device of the present invention. It is the cross-sectional schematic represented.
  • stacked battery lithium ion secondary battery
  • the laminated battery 10 of this embodiment has a structure in which a substantially rectangular power generating element 21 in which the charge and discharge reaction actually proceeds is sealed inside a laminate sheet 29 which is an exterior body.
  • the adjacent positive electrode, the electrolyte layer, and the negative electrode constitute one unit cell layer 19. Therefore, it can be said that the stacked battery 10 shown in FIG. 1 has a configuration in which a plurality of unit cell layers 19 are stacked and electrically connected in parallel.
  • the positive electrode active material layer 15 is arrange
  • the outermost negative electrode current collector is positioned in both outermost layers of the power generation element 21, and one side of the outermost negative electrode current collector or The negative electrode active material layer may be disposed on both sides.
  • the positive electrode current collector 12 and the negative electrode current collector 11 are attached to the positive electrode current collector plate 27 and the negative electrode current collector plate 25 respectively, which are conducted to the respective electrodes (positive electrode and negative electrode), and held between the ends of the laminate sheet 29 And the structure of being derived to the outside of the laminate sheet 29.
  • the positive electrode current collector plate 27 and the negative electrode current collector plate 25 are ultrasonically welded to the positive electrode current collector 12 and the negative electrode current collector 11 of each electrode via the positive electrode lead and the negative electrode lead (not shown), respectively, as necessary. Or may be attached by resistance welding or the like.
  • the lithium ion secondary battery described above is characterized by the negative electrode.
  • main components of the battery including the negative electrode will be described.
  • the active material layer 13 or 15 contains an active material, and further contains other additives as needed.
  • the positive electrode active material layer 15 contains a positive electrode active material.
  • Positive electrode active material for example, metal lithium, lithium-transition metal complex oxide, lithium-transition metal phosphate compound, lithium-transition metal sulfate compound, solid solution type, ternary system, NiMn type, NiCo type, spinel Mn type Etc.
  • lithium-transition metal complex oxides examples include LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , Li (Ni, Mn, Co) O 2 , Li (Li, Ni, Mn, Co) O 2 , LiFePO 4 and What has some of these transition metals substituted by other elements etc. are mentioned.
  • xLiMO 2 ⁇ (1-x) Li 2 NO 3 (0 ⁇ x ⁇ 1, M is an average oxidation state of 3+, N is one or more transition metals having an average oxidation state of 4+), LiRO 2- LiMn 2 O 4 (R transition metal element such as Ni, Mn, Co, Fe, etc.) and the like.
  • ternary system examples include nickel-cobalt-manganese (composite) positive electrode materials and the like.
  • NiMn-based material examples include LiNi 0.5 Mn 1.5 O 4 and the like.
  • NiCo Li (NiCo) O 2, and the like.
  • LiMn 2 O 4 etc. are mentioned as spinel Mn type
  • two or more positive electrode active materials may be used in combination.
  • a lithium-transition metal complex oxide is used as a positive electrode active material.
  • positive electrode active materials other than those described above may be used.
  • the particle sizes optimum for expressing the unique effects of each material may be blended and used. It is not necessary to make the particle size uniform.
  • the average particle size of the positive electrode active material contained in the positive electrode active material layer 15 is not particularly limited, but is preferably 1 to 30 ⁇ m, more preferably 5 to 20 ⁇ m from the viewpoint of achieving high output.
  • particle diameter refers to active material particles (observation using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM)). Of the distances between any two points on the contour line of a surface), this means the largest distance. Further, in the present specification, unless otherwise stated, the value of “average particle diameter” may be within a few to several tens of fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). A value calculated as an average value of particle diameters of particles observed in The particle sizes and average particle sizes of other components can be defined in the same manner.
  • the positive electrode active material layer 15 can include a binder.
  • Binder is added for the purpose of binding the active materials or the active material and the current collector to maintain the electrode structure.
  • a binder used for a positive electrode active material layer For example, the following materials are mentioned.
  • polyvinylidene fluoride, polyimide, styrene butadiene rubber, carboxymethyl cellulose, polypropylene, polytetrafluoroethylene, polyacrylonitrile, polyamide, and polyamideimide are more preferable.
  • These suitable binders are excellent in heat resistance, and furthermore, the potential window is very wide and stable to both the positive electrode potential and the negative electrode potential, and can be used for the active material layer.
  • These binders may be used alone or in combination of two or more.
  • the amount of the binder contained in the positive electrode active material layer is not particularly limited as long as it can bind the active material, but preferably 0.5 to 15% by mass with respect to the active material layer And more preferably 1 to 10% by mass.
  • the positive electrode (positive electrode active material layer) can be prepared by any method of kneading, sputtering, vapor deposition, CVD, PVD, ion plating, and thermal spraying, in addition to the usual method of coating (coating) slurry. It can be formed.
  • the negative electrode active material layer 13 contains a negative electrode active material.
  • the negative electrode active material essentially contains a predetermined alloy.
  • the negative electrode using the negative electrode active material according to the present invention has a useful effect of having high cycle durability.
  • alloy In the present embodiment, the alloy is represented by the following chemical formula (1).
  • M is at least one metal selected from the group consisting of Ti, Zn, C, and a combination thereof.
  • A is an unavoidable impurity.
  • the above-mentioned "unavoidable impurities” mean those which are present in the raw material in the Si alloy or are inevitably mixed in the manufacturing process. Although the inevitable impurities are unnecessary originally, they are trace amounts and are allowable impurities because they do not affect the characteristics of the Si alloy.
  • Sn which is the first additive element
  • M which is the second additive element (at least one metal selected from the group consisting of Ti, Zn, C, and a combination thereof) are used.
  • Sn which is the first additive element
  • M which is the second additive element (at least one metal selected from the group consisting of Ti, Zn, C, and a combination thereof)
  • M is at least one metal selected from the group consisting of Ti, Zn, C, and combinations thereof. Therefore, hereinafter, Si x Sn y Ti z A a, the Si x Sn y Zn z A a , and Si x Sn y C z A a Si alloy will be described respectively.
  • Si x Sn y Ti z Si alloys represented by A a The Si x Sn y Ti z A a, as described above, and Sn is a first additional element, by selecting the Ti as the second additional element, when Li alloying, amorphous - crystalline phases Transition can be suppressed to improve cycle life.
  • the capacity is higher than that of a conventional negative electrode active material, for example, a carbon-based negative electrode active material.
  • the x, y, and z are the following formula (1) or (2):
  • the first region is 35% by mass or more and 78% by mass or less of silicon (Si), 7% by mass or more It is preferable that the region contains 30% by mass or less of tin (Sn) and more than 0% by mass and 37% by mass or less of titanium (Ti). Further, as indicated by symbol B in FIG. 3, the second region is 35% by mass or more and 52% by mass or less Si, 30% by mass or more and 51% by mass or less Sn, more than 0% by mass and 35% by mass or less It is preferable that the region contains Ti. When the content of each component is in the above range, an initial discharge capacity of over 1000 Ah / g can be obtained, and the cycle life can also exceed 90% (50 cycles).
  • the content of titanium is preferably in the range of 7% by mass or more. That is, as indicated by the symbol C in FIG. 4, the first region is 35% by mass or more and 78% by mass or less of silicon (Si), 7% by mass or more and 30% by mass or less of tin (Sn), 7% by mass or more It is preferable that the region contains titanium (Ti) of 37% by mass or less.
  • the second region is 35% by mass or more and 52% by mass or less Si, 30% by mass or more and 51% by mass or less Sn, and 7% by mass or more and 35% by mass or less Ti It is preferably a region containing That is, the x, y, and z are the following formula (3) or (4):
  • the discharge capacity retention rate after 50 cycles can be 43% or more.
  • the first region is 35% by mass or more and 68% by mass or less of Si, and 7% by mass or more and 30% by mass or less It is preferable that it is an area
  • the second region is 39% by mass or more and 52% by mass or less Si, 30% by mass or more and 51% by mass or less Sn, and 7% by mass or more and 20% by mass or less Ti It is desirable that the region contains That is, the x, y, and z are the following formula (5) or (6):
  • the negative electrode active material of the present embodiment contains an alloy of a region indicated by symbol G in FIG. 6 and the balance is an unavoidable impurity.
  • symbol G is an area
  • A is an impurity (an unavoidable impurity) other than the above three components derived from the raw material and the manufacturing method. It is preferable that a is 0 ⁇ a ⁇ 0.5, and 0 ⁇ a ⁇ 0.1.
  • Si alloy represented by Si x Sn y Zn z A a is a phase transition between amorphous and crystalline when Li is alloyed by selecting Sn as the first additive element and Zn as the second additive element. Can be suppressed to improve the cycle life.
  • the capacity is higher than that of a conventional negative electrode active material, for example, a carbon-based negative electrode active material.
  • x is more than 23 and less than 64
  • y is 4 or more and 58 or less
  • z is more than 0 and less than 65. Note that this numerical range corresponds to the range indicated by the symbol X in FIG.
  • this negative electrode active material of Si alloy is used for the negative electrode of an electric device, for example, the negative electrode of a lithium ion secondary battery.
  • the alloy contained in the negative electrode active material absorbs lithium ions at the time of charge of the battery, and releases lithium ions at the time of discharge.
  • the negative electrode active material is a negative electrode active material of a Si alloy
  • tin (Sn) as a first additive element and zinc (Zn) as a second additive element are added thereto. It is a thing.
  • Sn as the first additive element
  • Zn zinc
  • the capacity can be made higher than that of the carbon-based negative electrode active material.
  • Si-Sn-Zn system Si-Sn-Zn system alloy provided with a good cycle life even after 100 cycles after 50 cycles by optimizing the composition range of Sn and Zn which are the 1st and 2nd addition elements respectively
  • the negative electrode active material can be obtained.
  • the first cycle discharge capacity can be sufficiently secured.
  • y is 4 or more, a good discharge capacity maintenance rate at the 50th cycle can be sufficiently secured.
  • cycle durability is improved, and a good discharge capacity maintenance rate (for example, 50% or more) at the 100th cycle can be sufficiently secured.
  • the range indicated by the symbol E in FIG. 13 satisfying 23 ⁇ x ⁇ 58, 4 ⁇ y ⁇ 24, 38 ⁇ z ⁇ 61, and 23 ⁇ x ⁇ 38, 24 ⁇ y ⁇ 35, 27 ⁇ z ⁇ 53 are satisfied.
  • the range indicated by the symbol F in FIG. 13 the range indicated by the symbol G in FIG. 13 that satisfies 23 ⁇ x ⁇ 38, 35 ⁇ y ⁇ 40, 27 ⁇ z ⁇ 44, or 23 ⁇ x ⁇ 29, 40 ⁇ y ⁇ 58, It is desirable to set the range indicated by the symbol H in FIG. 13 that satisfies 13 ⁇ z ⁇ 37. This improves the cycle durability, and as shown in Table 2, it is possible to obtain a discharge capacity retention rate exceeding 75% in 100 cycles.
  • A is an impurity (an unavoidable impurity) other than the above three components derived from the raw material and the manufacturing method. It is more preferable that a is 0 ⁇ a ⁇ 0.5, and 0 ⁇ a ⁇ 0.1.
  • Si alloy represented by Si x Sn y C z A a is an amorphous-crystalline phase during Li alloying by selecting Sn as the first additive element and C as the second additive element. Transition can be suppressed to improve cycle life.
  • the capacity is higher than that of a conventional negative electrode active material, for example, a carbon-based negative electrode active material.
  • x is preferably 29 or more. Note that this numerical range corresponds to the range indicated by the symbol A in FIG. By having the above composition, not only high capacity can be expressed, but also after 50 cycles, high discharge capacity can be maintained after 100 cycles.
  • x is 29 or more and 63 or less
  • y is 14 or more and 48 or less
  • z is 11 or more and 48 or less. This numerical range corresponds to the range indicated by the symbol B in FIG.
  • x is 29 or more and 44 or less
  • y is 14 or more and 48 or less
  • z is 11 or more and 48 or less. Note that this numerical range corresponds to the range indicated by the symbol C in FIG.
  • x is 29 or more and 40 or less, and y is 34 or more and 48 or less (therefore, 12 ⁇ z ⁇ 37).
  • This numerical range corresponds to the range indicated by the symbol D in FIG.
  • A is an impurity (an unavoidable impurity) other than the above three components derived from the raw material and the manufacturing method. It is preferable that a is 0 ⁇ a ⁇ 0.5, and 0 ⁇ a ⁇ 0.1.
  • BET specific surface area of Si alloy Si alloy according to the present invention, BET specific surface area, has a feature that exceed 3m 2 / g is less than 100 m 2 / g.
  • An electrical device such as a lithium ion secondary battery using a negative electrode active material containing a Si alloy having such characteristics has high cycle durability.
  • BET specific surface area is, in the case of using the Si alloy is less than 100 m 2 / g as the active material beyond the 3m 2 / g, since there is adequate space between the Si alloy particles, during charging and discharging The influence of expansion and contraction of the negative electrode active material can be alleviated. Also, for example, even when applied to the negative electrode of a lithium ion secondary battery, since the Si alloy (negative electrode active material) is in an appropriate contact state with the electrolytic solution, the progress of the decomposition reaction of the electrolytic solution is effectively suppressed. ⁇ Can be prevented.
  • the Si alloy according to the present invention has a microstructure (amorphous structure). Therefore, in the amorphous Si alloy, Li can be inserted and released while maintaining the fine structure (amorphous structure). Therefore, it is considered that cycle durability can be improved by the negative electrode using the negative electrode active material according to the present invention.
  • the cycle durability is reduced.
  • the BET specific surface area is preferably 8 to 40 m 2 / g, more preferably 10 to 35 m 2 / g.
  • BET specific surface area adopts a value measured and calculated by the following method.
  • the BET specific surface area of the Si alloy (negative electrode active material) is measured by a BET specific surface area measuring device (manufactured by HORIBA, Ltd., model: SA-9601) (BET single point method).
  • the BET specific surface area of Si alloy does not change substantially before and after being applied to an electric device (for example, battery).
  • the BET specific surface area of the Si alloy (powder) as a negative electrode active material collected from the disassembling electrode after assembling the electrical device (for example, battery) according to the present invention is more than 3 m 2 / g and 100 m 2 It is less than 1 / g, preferably 8 to 40 m 2 / g, and more preferably 10 to 35 m 2 / g.
  • Method of controlling the BET specific surface area 100m less than 2 / g exceed 3m 2 / g is not particularly limited.
  • the average particle diameter of the raw material metal particles is preferably 0.01 to 10 ⁇ m, more preferably more than 0.05 ⁇ m and 1 ⁇ m or less.
  • At least one of Si particles, Sn particles, and M particles used as a raw material at the time of producing the Si alloy may have the above average particle diameter.
  • two of the Si particles, the Sn particles and the M particles have the above average particle diameter, and more preferably, all the Si particles, the Sn particles and the M particles have the above average particle diameter.
  • the “average particle size” of the Si alloy or the raw material metal particles is the value of the average particle size (D50) (diameter) of each particle (secondary particle) measured by the laser diffraction method.
  • the Si alloy according to the present invention may be subjected to a pulverization treatment and / or a calcination treatment, if necessary, after an alloying treatment (for example, a mechanical alloy method) as described in detail below.
  • an alloying treatment for example, a mechanical alloy method
  • the pulverizing conditions are not particularly limited, but the pulverizing treatment can be carried out usually at a speed of 400 to 800 rpm for 5 minutes to 100 hours, preferably 30 minutes to 4 hours.
  • the firing conditions in the case of performing the firing treatment after the alloying treatment or after the pulverizing treatment are not particularly limited.
  • the BET specific surface area of the Si alloy can be reduced by performing the baking treatment. Therefore, particularly when the BET specific surface area of the obtained Si alloy is large, the BET specific surface area of the Si alloy can be controlled within the predetermined range according to the present invention by appropriately adjusting the firing conditions.
  • the firing temperature is preferably 80 to 300 ° C.
  • the firing time is preferably 0.5 to 3 hours.
  • the size of the Si alloy according to the present invention is not particularly limited, but the D50 value of the secondary particle diameter obtained by the laser diffraction method is preferably more than 0.01 ⁇ m and less than 20 ⁇ m.
  • An electrical device such as a lithium ion secondary battery using a negative electrode active material containing a Si alloy of such a size has high cycle durability.
  • the D50 value of the secondary particle diameter is preferably 0.4 to 10 ⁇ m, more preferably 2 to 7.5 ⁇ m, from the viewpoint of cycle durability.
  • the D50 value is calculated based on particle size distribution data calculated by a laser type particle size distribution meter, D50; median diameter, that is, particle diameter of intermediate value is calculated, and that value is adopted.
  • the laser type particle size distribution analyzer uses a laser diffraction / scattering type particle size distribution measuring apparatus (manufactured by Horiba, Ltd., model: LA-920).
  • Si alloy The shape of the Si alloy is not particularly limited, and may be spherical, elliptical, cylindrical, polygonal columnar, scaly, indeterminate, or the like.
  • the method of producing the alloy having the composition formula Si x Sn y M z A a according to the present embodiment is not particularly limited, and production may be performed using various conventionally known production methods. it can. That is, since there is almost no difference in alloy state and characteristics depending on the manufacturing method, any and all manufacturing methods can be applied.
  • a method for producing the particle form of the alloy having the composition formula Si x Sn y M z A a there are a solid phase method, a liquid phase method and a gas phase method.
  • a plasma melting method or the like can be used.
  • a binder, a conductive auxiliary agent, and a viscosity control solvent may be added to the particles to prepare a slurry, and a slurry electrode may be formed using the slurry. Therefore, it is excellent in that it is easy to mass-produce (mass production) and easy to put to practical use as a battery electrode.
  • the negative electrode active material layer may contain the other negative electrode active material.
  • negative electrode active materials other than the above-mentioned predetermined alloy natural graphite, artificial graphite, carbon black, activated carbon, carbon fiber, coke, soft carbon or carbon such as hard carbon, pure metal such as Si or Sn, or the above predetermined composition Alloy based active material out of the ratio, or TiO, Ti 2 O 3 , TiO 2 , or SiO 2 , metal oxides such as SiO 2 , SiO, SnO 2 , lithium such as Li 4/3 Ti 5/3 O 4 or Li 7 MnN And complex oxides of lithium and transition metals, Li-Pb alloys, Li-Al alloys, Li and the like.
  • the content of the predetermined alloy in the total amount of 100% by mass of the negative electrode active material is preferably from the viewpoint of sufficiently exerting the effects exhibited by using the predetermined alloy as the negative electrode active material. It is 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, particularly preferably 95 to 100% by mass, and most preferably 100% by mass.
  • the negative electrode active material layer 13 contains a binder.
  • Binder The binder is added for the purpose of binding the active materials or the active material and the current collector to maintain the electrode structure.
  • the binder used in the negative electrode active material layer There is no particular limitation on the type of the binder used in the negative electrode active material layer, and those described above as the binder used in the positive electrode active material layer can be used similarly. Therefore, the detailed description is omitted here.
  • the amount of binder contained in the negative electrode active material layer is not particularly limited as long as it can bind the active material, it is preferably 0.5 to the negative electrode active material layer. It is 20% by mass, more preferably 1 to 15% by mass.
  • the positive electrode active material layer 15 and the negative electrode active material layer 13 contain, as necessary, a conductive additive, an electrolyte salt (lithium salt), an ion conductive polymer, and the like.
  • the negative electrode active material layer 13 essentially contains a conductive additive.
  • the conductive support agent refers to an additive compounded to improve the conductivity of the positive electrode active material layer or the negative electrode active material layer.
  • the conductive aid include carbon materials such as carbon black such as acetylene black, graphite and vapor grown carbon fiber.
  • the content of the conductive additive mixed into the active material layer is in the range of 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more based on the total amount of the active material layer.
  • the content of the conductive additive mixed into the active material layer is 15% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less based on the total amount of the active material layer is there.
  • the following effects are expressed by defining the compounding ratio (content) of the conductive aid in the active material layer in which the electron conductivity of the active material itself is low and the electrode resistance can be reduced by the amount of the conductive aid within the above range Ru. That is, without inhibiting the electrode reaction, the electron conductivity can be sufficiently ensured, the reduction of the energy density due to the reduction of the electrode density can be suppressed, and the energy density can be improved by the improvement of the electrode density. .
  • a conductive binder having both the functions of the conductive aid and the binder may be used instead of the conductive aid and the binder, or one or both of the conductive aid and the binder may be used in combination.
  • a commercially available TAB-2 (manufactured by Takasen Co., Ltd.) can be used as the conductive binder.
  • Electrolyte salt lithium salt
  • Examples of the electrolyte salt (lithium salt) include Li (C 2 F 5 SO 2 ) 2 N, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 and the like.
  • Ion Conducting Polymers include, for example, polyethylene oxide (PEO) based and polypropylene oxide (PPO) based polymers.
  • the compounding ratio of the components contained in the positive electrode active material layer and the negative electrode active material layer is not particularly limited.
  • the compounding ratio can be adjusted by appropriately referring to known knowledge of non-aqueous solvent secondary batteries.
  • each active material layer active material layer on one side of the current collector
  • the thickness of each active material layer is usually about 1 to 500 ⁇ m, preferably 2 to 100 ⁇ m, in consideration of the purpose of use of the battery (power emphasis, energy emphasis, etc.) and ion conductivity.
  • the current collectors 11 and 12 are made of a conductive material.
  • the size of the current collector is determined according to the use application of the battery. For example, if it is used for a large battery where high energy density is required, a large-area current collector is used.
  • the thickness of the current collector is also not particularly limited.
  • the thickness of the current collector is usually about 1 to 100 ⁇ m.
  • the shape of the current collector is not particularly limited.
  • a mesh shape expansion grid etc. or the like can be used besides the current collector foil.
  • the thin film alloy is directly formed on the negative electrode current collector 12 by sputtering or the like, it is desirable to use a current collector foil.
  • the material constituting the current collector there is no particular limitation on the material constituting the current collector.
  • a metal or a resin in which a conductive filler is added to a conductive polymer material or a nonconductive polymer material may be employed.
  • the metal aluminum, nickel, iron, stainless steel, titanium, copper and the like can be mentioned.
  • a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plated material of a combination of these metals can be preferably used.
  • it may be a foil in which a metal surface is coated with aluminum.
  • aluminum, stainless steel, copper, and nickel are preferable from the viewpoint of electron conductivity, battery operation potential, adhesion of the negative electrode active material by sputtering to a current collector, and the like.
  • Examples of the conductive polymer material include polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polyacrylonitrile, and polyoxadiazole. Such a conductive polymer material has sufficient conductivity even without the addition of a conductive filler, and thus is advantageous in facilitating the manufacturing process or reducing the weight of the current collector.
  • nonconductive polymer material for example, polyethylene (PE; high density polyethylene (HDPE), low density polyethylene (LDPE), etc.), polypropylene (PP), polyethylene terephthalate (PET), polyether nitrile (PEN), polyimide (PI), polyamideimide (PAI), polyamide (PA), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA) And polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF), or polystyrene (PS).
  • PE polyethylene
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PEN polyether nitrile
  • PI polyimide
  • PAI polyamideimide
  • PA polyamide
  • PTFE polytetrafluoroethylene
  • a conductive filler may be added to the above-mentioned conductive polymer material or non-conductive polymer material as required.
  • the conductive filler is necessarily essential to impart conductivity to the resin.
  • the conductive filler can be used without particular limitation as long as it is a substance having conductivity.
  • metals, conductive carbon and the like can be mentioned as materials excellent in conductivity, potential resistance, or lithium ion blocking properties.
  • the metal is not particularly limited, but at least one metal selected from the group consisting of Ni, Ti, Al, Cu, Pt, Fe, Cr, Sn, Zn, In, Sb, and K or a metal thereof Preferably, it contains an alloy or a metal oxide.
  • it contains at least one selected from the group consisting of acetylene black, vulcan, black pearl, carbon nanofibers, ketjen black, carbon nanotubes, carbon nanohorns, carbon nanoballoons, and fullerenes.
  • the addition amount of the conductive filler is not particularly limited as long as it can impart sufficient conductivity to the current collector, and is generally about 5 to 35% by mass.
  • a liquid electrolyte or a polymer electrolyte may be used as the electrolyte constituting the electrolyte layer 17.
  • the liquid electrolyte has a form in which a lithium salt (electrolyte salt) is dissolved in an organic solvent.
  • organic solvent include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), Carbonates such as methyl propyl carbonate (MPC) are exemplified.
  • Li (CF 3 SO 2) 2 N Li (C 2 F 5 SO 2) 2 N, LiPF 6, LiBF 4, LiAsF 6, LiTaF 6, LiClO 4, LiCF 3 SO 3 , etc.
  • a compound that can be added to the active material layer of the electrode can be employed.
  • polymer electrolytes are classified into gel electrolytes containing an electrolyte solution and intrinsic polymer electrolytes not containing an electrolyte solution.
  • the gel electrolyte has a configuration in which the above-mentioned liquid electrolyte (electrolyte solution) is injected into a matrix polymer made of an ion conductive polymer.
  • a gel polymer electrolyte as the electrolyte is excellent in that the fluidity of the electrolyte is lost and the ion conduction between each layer can be easily blocked.
  • Examples of the ion conductive polymer used as a matrix polymer include polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers of these. Electrolyte salts such as lithium salts can be well dissolved in such polyalkylene oxide polymers.
  • the proportion of the liquid electrolyte (electrolyte solution) in the gel electrolyte should not be particularly limited, but is preferably about several mass% to about 98 mass% from the viewpoint of ion conductivity and the like.
  • the present embodiment is particularly effective for a gel electrolyte containing a large amount of electrolyte solution in which the ratio of the electrolyte solution is 70% by mass or more.
  • a separator may be used for the electrolyte layer.
  • the separator include, for example, a microporous film made of a polyolefin such as polyethylene and polypropylene, a porous flat plate, and a non-woven fabric.
  • the intrinsic polymer electrolyte has a constitution in which a support salt (lithium salt) is dissolved in the above-mentioned matrix polymer, and does not contain an organic solvent which is a plasticizer. Therefore, when the electrolyte layer is composed of an intrinsic polymer electrolyte, there is no concern of liquid leakage from the battery, and the reliability of the battery can be improved.
  • a support salt lithium salt
  • a gel electrolyte or a matrix polymer of an intrinsic polymer electrolyte can exhibit excellent mechanical strength by forming a crosslinked structure.
  • thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam polymerization, etc. may be performed on a polymerizable polymer (eg, PEO or PPO) for forming a polymer electrolyte using an appropriate polymerization initiator.
  • a polymerization treatment may be applied.
  • a current collector may be used for the purpose of extracting current outside the battery.
  • the current collector plate is electrically connected to the current collector and the leads, and is taken out of the laminate sheet which is a battery exterior material.
  • the material which comprises a current collection board is not restrict
  • a constituent material of the current collector plate for example, metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS) and alloys thereof are preferable, more preferably aluminum from the viewpoint of light weight, corrosion resistance and high conductivity. Copper is preferred.
  • the same material may be used for the positive electrode current collector plate and the negative electrode current collector plate, or different materials may be used.
  • the positive electrode terminal lead and the negative electrode terminal lead are also used as needed.
  • terminal leads used in known lithium ion secondary batteries can be used.
  • the heat-resistant insulation property does not affect the product (for example, automobile parts, especially electronic devices etc.) because the portion taken out from the battery exterior material 29 contacts with peripheral devices or wiring to cause electric leakage. It is preferable to coat with a heat-shrinkable tube or the like.
  • a known metal can case can be used as the battery exterior material 29, and a bag-like case using a laminate film containing aluminum that can cover the power generation element can be used.
  • the laminate film for example, a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used, but it is not limited thereto.
  • a laminate film is desirable from the viewpoint of being excellent in high output and cooling performance and being suitably usable for a battery for large-sized devices for EV and HEV.
  • the above lithium ion secondary battery can be manufactured by a conventionally known manufacturing method.
  • FIG. 2 is a perspective view showing the appearance of a laminated flat lithium ion secondary battery.
  • the laminated flat lithium ion secondary battery 50 has a rectangular flat shape, and the positive electrode current collector plate 59 for taking out electric power from both sides thereof and the negative electrode collector The electric plate 58 is pulled out.
  • the power generation element 57 is wrapped by the battery exterior material 52 of the lithium ion secondary battery 50, and the periphery thereof is heat-fused, and the power generation element 57 draws the positive electrode current collector plate 59 and the negative electrode current collector plate 58 to the outside. It is sealed tightly.
  • the power generation element 57 corresponds to the power generation element 21 of the lithium ion secondary battery (stacked battery) 10 shown in FIG.
  • the power generation element 57 is formed by stacking a plurality of unit cell layers (single cells) 19 each including the positive electrode (positive electrode active material layer) 13, the electrolyte layer 17, and the negative electrode (negative electrode active material layer) 15.
  • the said lithium ion secondary battery is not restrict
  • a wound type lithium ion battery one having a cylindrical shape (coin cell) or one having a prismatic shape (square cell), or such one obtained by deforming such a cylindrical shape into a rectangular flat shape
  • cylindrical cells there is no particular limitation, such as cylindrical cells.
  • a laminate film may be used as the exterior material, or a conventional cylindrical can (metal can) may be used, and the like.
  • the power generation element is coated with an aluminum laminate film. Weight reduction can be achieved by the form.
  • the removal of the positive electrode current collector plate 59 and the negative electrode current collector plate 58 shown in FIG. 2 is not particularly limited.
  • the positive electrode current collector plate 59 and the negative electrode current collector plate 58 may be drawn out from the same side, or the positive electrode current collector plate 59 and the negative electrode current collector plate 58 may be divided into a plurality and taken out from each side.
  • the terminal may be formed using, for example, a cylindrical can (metal can) instead of the current collector plate.
  • the negative electrode and the lithium ion secondary battery using the negative electrode active material for a lithium ion secondary battery of the present embodiment are large in such as electric vehicles, hybrid electric vehicles, fuel cell vehicles and hybrid fuel cell vehicles. It can be suitably used as a capacitive power source. That is, it can be suitably used for a vehicle drive power supply or an auxiliary power supply where high volume energy density and high volume output density are required.
  • the lithium ion battery was illustrated as an electric device in the said embodiment, it is not necessarily restricted to this, It is applicable also to the secondary battery of another type, and also a primary battery. Moreover, it can apply not only to a battery but to a capacitor.
  • Target manufactured by High Purity Chemical Laboratory Co., Ltd., Purity: 4 N
  • Si 50.8 mm diameter, 3 mm thickness (with 2 mm thick oxygen free copper backing plate)
  • Sn 50.8 mm diameter, 5 mm thickness
  • Ti 50.8 mm diameter, 5 mm thickness.
  • the sputtering time is fixed at 10 minutes, and the power of the DC power source is changed in the above range, respectively, thereby forming an amorphous alloy on the Ni substrate.
  • a thin film was formed to obtain a negative electrode sample provided with alloy thin films of various compositions.
  • discharge capacity at the 50th and 100th cycles was determined, and the maintenance rate for the discharge capacity at the first cycle was calculated.
  • the results are shown in Table 1 together.
  • discharge capacity has shown the value computed per alloy weight.
  • “discharge capacity (mAh / g)” is per pure Si or alloy weight, and when Li reacts with Si-Sn-M alloy (Si-M alloy, pure Si or Si-Sn alloy) Indicates the capacity of the
  • initial capacity in the present specification corresponds to "discharge capacity (mAh / g)" of the initial cycle (first cycle).
  • discharge capacity maintenance rate (%) at the 50th or 100th cycle represents an index of “how much capacity is maintained from the initial capacity”.
  • the formula for calculating the discharge capacity retention rate (%) is as follows.
  • FIG. 7 shows the relationship between the discharge capacity at the first cycle and the alloy composition.
  • FIG. 8 and FIG. 9 the relationship between the discharge capacity maintenance rate at 50 cycles and 100 cycles and the alloy composition is shown, respectively.
  • discharge capacity has shown the value computed per alloy weight.
  • the battery of Reference Example A (see Table 1) using an Si-Sn-Ti alloy as a negative electrode active material, each component being in a specific range, that is, in a range A or a range B shown in FIG. , As shown in FIG. 7, with an initial capacity of at least 1000 mAh / g. Then, as shown in FIGS. 8 and 9, it was confirmed that the discharge capacity retention ratio of 91% or more after 50 cycles and 43% or more even after 100 cycles.
  • the sputtering time was fixed to 10 minutes using the Si target, the Sn target and the Zn target as described above, and the power of the DC power source was changed in the above range.
  • an alloy thin film in an amorphous state was formed on a Ni substrate to obtain a negative electrode sample provided with alloy thin films of various compositions.
  • the DC power supply 1 (Si target) is 185 W
  • the DC power supply 3 (Zn target) was 100 W.
  • the DC power supply 1 (Si target) is 185 W
  • the DC power supply 2 (Sn target) is 30 W
  • the DC power supply 3 (Zn target) is 0 W.
  • the DC power supply 1 (Si target) is 185 W
  • the DC power supply 2 (Sn target) is 0 W
  • the DC power supply 3 (Zn target) is 25 W.
  • the component compositions of these alloy thin films are shown in Table 2.
  • the analysis of the obtained alloy thin film was performed by the same analysis method and analyzer as in Reference Example A.
  • the DC power supply 1 (Si target) is 185 W
  • the DC power supply 2 (Sn target) is 35 W
  • the DC power supply 3 (C target) in Reference Example 3-16. ) was 110W.
  • the DC power supply 1 (Si target) is 185 W
  • the DC power supply 2 (Sn target) is 22 W
  • the DC power supply 3 (C target) is 0 W.
  • the DC power supply 1 (Si target) is 185 W
  • the DC power supply 2 (Sn target) is 0 W
  • the DC power supply 3 (C target) is 30 W.
  • performance evaluation is performed on a negative electrode for an electrical device having a negative electrode active material layer using Si 60 Sn 20 Ti 20 as a negative electrode active material.
  • Si 60 Sn 20 Ti 20 and alloys used in the present invention Si x Sn y Ti z A a , Si x Sn y Zn z A a , and Si x Sn y C z A a , Also for Si 60 Sn 20 Ti 20 ), the same or similar results as in the following example using Si 60 Sn 20 Ti 20 can be obtained.
  • the reason for this is that the BET specific surface area of the alloy (negative electrode active material) is important to improve the cycle durability of the Si alloy. Further, in addition to the BET specific surface area of the alloy (negative electrode active material), the progress of the amorphization of Si in the active material is considered to be important for improving the cycle durability of the Si alloy.
  • the second additive element is for alloying the Si material to facilitate advancing the amorphous state. Therefore, it is considered that the cycle durability is improved as the amorphous state of Si progresses even in Si x Sn y Zn z A a and Si x Sn y C z A a using Zn and C other than Ti. . That is, when an alloy having such similar characteristics is used, similar results can be obtained even if the type of alloy is changed.
  • Example 1 Manufacturing of Si alloy
  • the Si alloy was manufactured by mechanical alloying (or arc plasma melting).
  • grains whose average particle diameter (D50) is 0.5 micrometer were used as a raw material.
  • the zirconia ground ball and each raw material powder of each alloy are charged into a zirconia ground pot and alloyed at 600 rpm for 24 hours (alloy Treatment) and then grinding treatment at 400 rpm for 40 minutes.
  • the BET specific surface area and the average particle size (D50) of the obtained Si alloy were measured according to the following method, and the results are shown in Table 4 below.
  • Li 1.85 Ni 0.18 Co 0.10 Mn 0.87 O 3 which is a positive electrode active material was produced by the method described in Example 1 (paragraph 0046) of JP 2012-185913A. Then, 90 parts by mass of the positive electrode active material, 5 parts by mass of acetylene black as a conductive additive, and 5 parts by mass of polyvinylidene fluoride as a binder are mixed and dispersed in N-methylpyrrolidone to obtain a positive electrode slurry. The Next, the obtained positive electrode slurry was uniformly coated on both surfaces of a positive electrode current collector made of aluminum foil so that the thickness of the positive electrode active material layer was 30 ⁇ m, and dried to obtain a positive electrode.
  • Lithium (LiPF 6 ) was used at a concentration of 1 mol / L.
  • Example 2 A negative electrode and a battery were produced in the same manner as in Example 1 except that Si particles having an average particle diameter (D50) of 0.1 ⁇ m were used as a raw material in the production of the Si alloy.
  • D50 average particle diameter
  • Example 3 A negative electrode and a battery were produced in the same manner as in Example 1 except that Si particles having an average particle diameter (D50) of 0.08 ⁇ m were used as a raw material in the production of the Si alloy.
  • D50 average particle diameter
  • Example 4 A negative electrode and a battery were produced in the same manner as in Example 1 except that Si particles having an average particle diameter (D50) of 0.3 ⁇ m were used as a raw material in the production of the Si alloy.
  • D50 average particle diameter
  • Example 5 The same method as in Example 1 was used except that Si particles having an average particle diameter (D50) of 0.5 ⁇ m were used as a raw material in the production of the Si alloy and firing was carried out at 100 ° C. for 1 hour after grinding treatment. A negative electrode and a battery were produced.
  • D50 average particle diameter
  • Example 6 The same method as in Example 1 was used except that Si particles having an average particle diameter (D50) of 0.05 ⁇ m were used as a raw material in the production of the Si alloy, and firing was performed at 200 ° C. for 1 hour after grinding. A negative electrode and a battery were produced.
  • D50 average particle diameter
  • Example 1 The same method as in Example 1 was used except that Si particles having an average particle diameter (D50) of 0.5 ⁇ m were used as a raw material in the production of the Si alloy and firing was carried out at 400 ° C. for 1 hour after grinding treatment. A negative electrode and a battery were produced.
  • D50 average particle diameter
  • Example 2 A negative electrode and a battery were produced in the same manner as in Example 1 except that Si particles having an average particle size (D50) of 0.05 ⁇ m were used as a raw material in the production of the Si alloy.
  • D50 average particle size
  • Example 3 A negative electrode and a battery were produced in the same manner as in Example 1 except that Si particles having an average particle diameter (D50) of 0.5 ⁇ m were used as a negative electrode active material instead of the Si alloy in the production of the negative electrode.
  • D50 average particle diameter
  • the particle size distribution data is measured using a laser diffraction / scattering type particle size distribution measuring apparatus (manufactured by Horiba, Ltd., model: LA-920), and based on the data, the average particle size of Si alloy (D50; median Calculate the diameter).
  • the negative electrode active material (powder) was scraped from the electrode used for the evaluation of the cycle durability (battery performance), and was ground in an agate mortar, and the BET specific surface area of the powder was measured by the above method. And the same BET surface area. From this result, it is understood that the BET specific surface area of the negative electrode active material (Si alloy) shown in Table 4 below can be regarded as the BET specific surface area of the negative electrode active material (powder) collected from the disassembling electrode. Therefore, it is considered that the BET specific surface area of the Si alloy (negative electrode active material) can be confirmed from the BET specific surface area of the negative electrode active material (powder) collected from the disassembling electrode after assembling the battery.

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Abstract

La présente invention concerne un matériau actif d'électrode négative destiné à être utilisé dans un dispositif électrique tel qu'une batterie secondaire au lithium-ion et offrant une durabilité de cycle élevée. Ledit matériau actif d'électrode négative destiné à être utilisé dans un dispositif électrique contient un alliage qui peut être représenté par la formule chimique (1). (1) SixSnyMzAa Dans la formule chimique (1), M représente un ou plusieurs métaux choisis dans le groupe constitué par le titane, le zinc, le carbone ainsi que des associations de ces métaux ; A représente les impuretés inévitables ; et x, y, z, et a représentent les pourcentages de masse, avec 0 < x < 100, 0 < y < 100, 0 < z < 100, 0 ≤ a < 0,5, et x+y+z+a = 100. La surface spécifique BET de l'alliage susmentionné est supérieure à 3 m2/g mais inférieure à 100 m2/g.
PCT/JP2014/063247 2013-06-12 2014-05-19 Matériau actif d'électrode négative destiné à être utilisé dans un dispositif électrique et dispositif électrique faisant intervenir ledit matériau Ceased WO2014199781A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2016098206A1 (fr) * 2014-12-17 2016-06-23 日産自動車株式会社 Matériau actif d'électrode négative pour dispositif électrique, et dispositif électrique l'utilisant
JPWO2017081758A1 (ja) * 2015-11-10 2018-06-21 日産自動車株式会社 電気デバイス用負極活物質、およびこれを用いた電気デバイス

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