WO2016098213A1 - Matériau actif d'électrode négative pour un dispositif électrique et dispositif électrique utilisant ce dernier - Google Patents

Matériau actif d'électrode négative pour un dispositif électrique et dispositif électrique utilisant ce dernier Download PDF

Info

Publication number
WO2016098213A1
WO2016098213A1 PCT/JP2014/083479 JP2014083479W WO2016098213A1 WO 2016098213 A1 WO2016098213 A1 WO 2016098213A1 JP 2014083479 W JP2014083479 W JP 2014083479W WO 2016098213 A1 WO2016098213 A1 WO 2016098213A1
Authority
WO
WIPO (PCT)
Prior art keywords
active material
negative electrode
electrode active
silicon
silicide
Prior art date
Application number
PCT/JP2014/083479
Other languages
English (en)
Japanese (ja)
Inventor
文博 三木
渡邉　学
智裕 蕪木
千葉　啓貴
Original Assignee
日産自動車株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産自動車株式会社 filed Critical 日産自動車株式会社
Priority to JP2016564520A priority Critical patent/JPWO2016098213A1/ja
Priority to PCT/JP2014/083479 priority patent/WO2016098213A1/fr
Publication of WO2016098213A1 publication Critical patent/WO2016098213A1/fr

Links

Images

Classifications

    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode active material for an electric device and an electric device using the same.
  • the negative electrode active material for an electric device and the electric device using the same according to the present invention include, for example, a driving power source and an auxiliary power source for a motor of a vehicle such as an electric vehicle, a fuel cell vehicle, and a hybrid electric vehicle as a secondary battery or a capacitor Used for.
  • Motor drive secondary batteries are required to have extremely high output characteristics and high energy compared to consumer lithium ion secondary batteries used in mobile phones and notebook computers. Therefore, lithium ion secondary batteries having the highest theoretical energy among all the batteries are attracting attention, and are currently being developed rapidly.
  • a lithium ion secondary battery includes a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector using a binder, and a negative electrode in which a negative electrode active material or the like is applied to both surfaces of a negative electrode current collector using a binder.
  • a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector using a binder
  • a negative electrode in which a negative electrode active material or the like is applied to both surfaces of a negative electrode current collector using a binder.
  • it has the structure connected through an electrolyte layer and accommodated in a battery case.
  • a battery using a material that is alloyed with Li for the negative electrode is expected as a negative electrode material for vehicle use because the energy density is improved as compared with a conventional carbon / graphite negative electrode material.
  • a lithium ion secondary battery using a material that is alloyed with Li for the negative electrode has a large expansion and contraction in the negative electrode during charge and discharge.
  • the volume expansion is about 1.2 times in graphite materials
  • Si materials when Si and Li are alloyed, transition from the amorphous state to the crystalline state causes a large volume change. (Approximately 4 times), there was a problem of reducing the cycle life of the electrode.
  • 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.
  • Japanese Patent No. 5079334 discloses an invention that aims to provide a non-aqueous electrolyte secondary battery having a negative electrode pellet having a high capacity and excellent cycle life.
  • a silicon-containing alloy obtained by mixing silicon powder and titanium powder by a mechanical alloying method and wet-pulverizing the first phase mainly composed of silicon and a silicide of titanium (such as TiSi 2 ) ) Containing a second phase containing) is disclosed as a negative electrode active material.
  • a silicon-containing alloy obtained by mixing silicon powder and titanium powder by a mechanical alloying method and wet-pulverizing the first phase mainly composed of silicon and a silicide of titanium (such as TiSi 2 ) ) Containing a second phase containing) is disclosed as a negative electrode active material.
  • at least one of these two phases is amorphous or low crystalline.
  • an electric device such as a lithium ion secondary battery using the negative electrode pellet described in Japanese Patent No. 5079334 can exhibit good cycle durability. Nevertheless, it has been found that the cycle durability may not be sufficient.
  • an object of the present invention is to provide means capable of improving cycle durability of an electric device such as a lithium ion secondary battery.
  • the present inventors have conducted intensive research to solve the above problems.
  • a negative electrode active material made of a silicon-containing alloy having a structure in which a silicide phase containing a transition metal silicide is dispersed in a parent phase mainly composed of amorphous or low crystalline silicon It has been found that the above problem can be solved by controlling the closest distance between the silicide phases to a predetermined value or less, and the present invention has been completed.
  • the present invention relates to a negative electrode active material for electric devices.
  • the negative electrode active material for an electric device is made of a silicon-containing alloy having a structure in which a silicide phase containing a silicide of a transition metal is dispersed in a parent phase mainly composed of amorphous or low crystalline silicon. Is.
  • the negative active material for an electric device is characterized in that the closest distance between adjacent silicide phases is 300 nm or less.
  • FIG. 1 is a schematic cross-sectional view schematically showing an outline of a laminated flat non-bipolar lithium ion secondary battery which is a typical embodiment of an electric device according to the present invention.
  • FIG. 1 is a perspective view schematically showing the appearance of a stacked flat lithium ion secondary battery that is a representative embodiment of an electric device according to the present invention.
  • 2 is a photograph obtained by EDX analysis (energy dispersive X-ray analysis) of the silicon-containing alloy (negative electrode active material) powder obtained in Example 1.
  • FIG. 3A red indicates the presence site of Ti, green indicates the presence site of Sn, and blue indicates the presence site of Si.
  • FIG. 2 is a photograph obtained by EDX analysis (energy dispersive X-ray analysis) of the silicon-containing alloy (negative electrode active material) powder obtained in Example 1.
  • FIG. 3B red indicates a site where Ti is present. It is the diffraction pattern of the site
  • FIG. It is the diffraction pattern of the site
  • One embodiment of the present invention includes a silicon-containing alloy having a structure in which a silicide phase including a silicide of a transition metal is dispersed in a parent phase mainly composed of amorphous or low crystalline silicon.
  • a negative electrode active material for an electrical device wherein the closest distance between the silicide phases is less than 300 nm.
  • an amorphous-crystal phase transition (to Li 15 Si 4) when Si and Li are alloyed due to a shortest closest distance between adjacent silicide phases. Crystallization) is suppressed.
  • contraction of the silicon containing alloy which comprises the negative electrode active material in the charging / discharging process of an electrical device are suppressed.
  • cycle durability of an electric device using the negative electrode active material can be improved.
  • a negative electrode for a lithium ion secondary battery which is a typical embodiment of a negative electrode including a negative electrode active material for an electric device according to the present invention, and a lithium ion secondary battery using the same
  • a cell (single cell layer) ) Voltage is large, and high energy density and high power density can be achieved. Therefore, the lithium ion secondary battery using the negative electrode active material for the lithium ion secondary battery of the present embodiment is excellent as a vehicle driving power source or an auxiliary power source.
  • it can be suitably used as a lithium ion secondary battery for a vehicle driving power source or the like.
  • the present invention can be sufficiently applied to lithium ion secondary batteries for portable devices such as mobile phones.
  • the lithium ion secondary battery that is the subject of the present embodiment may be any one that uses the negative electrode active material for the lithium ion secondary battery of the present embodiment described below. It should not be restricted in particular.
  • the lithium ion secondary battery when distinguished by form / structure, it can be applied to any conventionally known form / structure such as a stacked (flat) battery or a wound (cylindrical) battery. Is.
  • a stacked (flat) battery structure By adopting a stacked (flat) battery structure, long-term reliability can be secured by a sealing technique such as simple thermocompression bonding, which is advantageous in terms of cost and workability.
  • a solution electrolyte type battery using a solution electrolyte such as a nonaqueous electrolyte solution for the electrolyte layer, a polymer battery using a polymer electrolyte for the electrolyte layer, etc. It can be applied to any conventionally known electrolyte layer type.
  • the polymer battery is further divided into a gel electrolyte type battery using a polymer gel electrolyte (also simply referred to as gel electrolyte) and a solid polymer (all solid) type battery using a polymer solid electrolyte (also simply referred to as polymer electrolyte). It is done.
  • the non-bipolar (internal parallel connection type) lithium ion secondary battery using the negative electrode active material for the lithium ion secondary battery of this embodiment will be described very simply with reference to the drawings.
  • the technical scope of the lithium ion secondary battery of the present embodiment should not be limited to these.
  • FIG. 1 schematically shows the overall structure of a flat (stacked) lithium ion secondary battery (hereinafter also simply referred to as “stacked battery”), which is a typical embodiment of the electrical device of the present invention.
  • stacked battery a flat (stacked) lithium ion secondary battery
  • the stacked battery 10 of the present embodiment has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside a laminate sheet 29 that is an exterior body.
  • the positive electrode in which the positive electrode active material layer 15 is disposed on both surfaces of the positive electrode current collector 12, the electrolyte layer 17, and the negative electrode active material layer 13 is disposed on both surfaces of the negative electrode current collector 11. It has a configuration in which a negative electrode is laminated. Specifically, the negative electrode, the electrolyte layer, and the positive electrode are laminated in this order so that one positive electrode active material layer 15 and the negative electrode active material layer 13 adjacent thereto face each other with the electrolyte layer 17 therebetween. .
  • the adjacent positive electrode, electrolyte layer, and 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 single battery layers 19 are stacked and electrically connected in parallel.
  • the positive electrode current collector 15 located on both outermost layers of the power generation element 21 has the positive electrode active material layer 15 disposed only on one side, but the active material layers may be provided on both sides. . That is, instead of using a current collector dedicated to the outermost layer provided with an active material layer only on one side, a current collector having an active material layer on both sides may be used as it is as an outermost current collector. Further, by reversing the arrangement of the positive electrode and the negative electrode as compared with FIG. 1, the outermost negative electrode current collector is positioned on both outermost layers of the power generation element 21, and one side of the outermost negative electrode current collector or A 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 that are electrically connected to the respective electrodes (positive electrode and negative electrode), and are sandwiched between the end portions of the laminate sheet 29. Thus, it has a structure led out of the laminate sheet 29.
  • the positive electrode current collector 27 and the negative electrode current collector 25 are ultrasonically welded to the positive electrode current collector 12 and the negative electrode current collector 11 of each electrode via a positive electrode lead and a negative electrode lead (not shown), respectively, as necessary. Or resistance welding or the like.
  • the lithium ion secondary battery described above is characterized by a 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 necessary.
  • the positive electrode active material layer 15 includes a positive electrode active material.
  • the positive electrode active material examples include LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , Li (Ni—Mn—Co) O 2, and lithium-- such as those in which some of these transition metals are substituted with other elements.
  • Examples include transition metal composite oxides, lithium-transition metal phosphate compounds, and lithium-transition metal sulfate compounds.
  • two or more positive electrode active materials may be used in combination.
  • a lithium-transition metal composite oxide is used as the positive electrode active material.
  • a composite oxide containing lithium and nickel is used, and more preferably Li (Ni—Mn—Co) O 2 and a part of these transition metals substituted with other elements (hereinafter, referred to as “following”) Simply referred to as “NMC composite oxide”).
  • the NMC composite oxide has a layered crystal structure in which a lithium atomic layer and a transition metal (Mn, Ni, and Co are arranged in order) are stacked alternately via an oxygen atomic layer.
  • One Li atom is contained, and the amount of Li that can be taken out is twice that of the spinel lithium manganese oxide, that is, the supply capacity is doubled, so that a high capacity can be obtained.
  • the NMC composite oxide includes a composite oxide in which a part of the transition metal element is substituted with another metal element.
  • Other elements in that case include Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, Fe, B, Ga, In, Si, Mo, Y, Sn, V, Cu , Ag, Zn, etc., preferably Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, more preferably Ti, Zr, P, Al, Mg, From the viewpoint of improving cycle characteristics, Ti, Zr, Al, Mg, and Cr are more preferable.
  • a represents the atomic ratio of Li
  • b represents the atomic ratio of Ni
  • c represents the atomic ratio of Mn
  • d represents the atomic ratio of Co
  • x represents the atomic ratio of M. Represents. From the viewpoint of cycle characteristics, it is preferable that 0.4 ⁇ b ⁇ 0.6 in the general formula (1).
  • the composition of each element can be measured by, for example, inductively coupled plasma (ICP) emission spectrometry.
  • ICP inductively coupled plasma
  • Ni nickel
  • Co cobalt
  • Mn manganese
  • Ti or the like partially replaces the transition metal in the crystal lattice. From the viewpoint of cycle characteristics, it is preferable that a part of the transition element is substituted with another metal element, and it is particularly preferable that 0 ⁇ x ⁇ 0.3 in the general formula (1). Since at least one selected from the group consisting of Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr is dissolved, the crystal structure is stabilized. It is considered that the battery capacity can be prevented from decreasing even if the above is repeated, and that excellent cycle characteristics can be realized.
  • b, c and d are 0.44 ⁇ b ⁇ 0.51, 0.27 ⁇ c ⁇ 0.31, 0.19 ⁇ d ⁇ 0.26. It is preferable from the viewpoint of improving the balance between capacity and life characteristics.
  • LiNi 0.5 Mn 0.3 Co 0.2 O 2 is LiCoO 2 , LiMn 2 O 4 , LiNi 1/3 Mn 1/3 Co 1/3 O 2, etc. that have been proven in general consumer batteries.
  • the capacity per unit weight is large, and the energy density can be improved, so that a battery having a compact and high capacity can be produced, which is preferable from the viewpoint of cruising distance.
  • LiNi 0.8 Co 0.1 Al 0.1 O 2 is more advantageous in terms of a larger capacity, but there are difficulties in life characteristics.
  • LiNi 0.5 Mn 0.3 Co 0.2 O 2 has life characteristics as excellent as LiNi 1/3 Mn 1/3 Co 1/3 O 2 .
  • two or more positive electrode active materials may be used in combination.
  • a lithium-transition metal composite oxide is used as the positive electrode active material.
  • positive electrode active materials other than those described above may be used.
  • the average particle diameter 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 increasing the output.
  • the “particle diameter” refers to the outline of the active material particles (observation surface) observed using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). It means the maximum distance among any two points.
  • the value of “average particle diameter” is the value of particles observed in several to several tens of fields using observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The value calculated as the average value of the particle diameter shall be adopted.
  • the particle diameters and average particle diameters of other components can be defined in the same manner.
  • the positive electrode active material layer 15 may contain a binder.
  • Binder is added for the purpose of maintaining the electrode structure by binding the active materials or the active material and the current collector.
  • 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, have a very wide potential window, are stable at 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.
  • 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 it is preferably 0.5 to 15% by mass with respect to the active material layer. More preferably, it is 1 to 10% by mass.
  • the positive electrode (positive electrode active material layer) can be applied by any one of a kneading method, a sputtering method, a vapor deposition method, a CVD method, a PVD method, an ion plating method, and a thermal spraying method in addition to a method of applying (coating) a normal slurry. Can be formed.
  • the negative electrode active material layer 13 includes a negative electrode active material.
  • the negative electrode active material is made of a silicon-containing alloy having a structure in which a silicide phase containing a silicide of a transition metal is dispersed in a parent phase mainly composed of amorphous or low crystalline silicon. It is characterized in that the closest distance between adjacent silicide phases is 300 nm or less.
  • the silicon-containing alloy constituting the negative electrode active material in the present embodiment is first provided with a parent phase mainly composed of amorphous or amorphous silicon.
  • a parent phase mainly composed of amorphous or amorphous silicon.
  • the parent phase constituting the silicon-containing alloy may be a phase containing silicon as a main component, and is preferably a Si single phase (phase consisting of only Si).
  • This parent phase (phase containing Si as a main component) is a phase involved in occlusion / release of lithium ions during operation of the electrical device (lithium ion secondary battery) of the present embodiment, and electrochemically reacts with Li. It is a possible phase.
  • the Si single phase it is possible to occlude and release a large amount of Li per weight and per volume.
  • the parent phase may contain a small amount of additive elements such as phosphorus and boron, transition metals, and the like.
  • the silicon-containing alloy constituting the negative electrode active material in the present embodiment includes a silicide phase dispersed in the parent phase in addition to the parent phase.
  • This silicide phase is a phase containing a transition metal silicide. Since this silicide phase contains silicide (silicide), it has excellent affinity with the parent phase and can suppress cracks at the crystal interface particularly during volume expansion during charging. Furthermore, the silicide phase is superior in terms of electron conductivity and hardness compared to the parent phase. For this reason, the silicide phase plays a role of improving the low electron conductivity of the parent phase and maintaining the shape of the active material against the stress during expansion.
  • a plurality of phases may exist in the silicide phase.
  • two or more phases for example, MSi 2 and MSi
  • two or more phases may exist by including a silicide with different transition metal elements.
  • the type of transition metal contained in the silicide phase is not particularly limited, but is preferably at least one selected from the group consisting of Ti, Zr, Ni, Cu, and Fe, and more preferably Ti or Zr. Yes, particularly preferably Ti.
  • These elements have a higher electron conductivity and higher strength than silicides of other elements when silicides are formed.
  • TiSi 2 which is silicide when the transition metal element is Ti is preferable because it exhibits very excellent electron conductivity.
  • composition of the silicon-containing alloy which comprises a negative electrode active material It is preferable that it has a composition represented by following Chemical formula (1).
  • A is an inevitable impurity
  • M is one or more transition metal elements
  • the “inevitable impurities” means an Si-containing alloy that exists in a raw material or is inevitably mixed in a manufacturing process. The inevitable impurities are originally unnecessary impurities, but are a very small amount and do not affect the characteristics of the Si alloy.
  • Ti is selected as an additive element (M; transition metal) to the negative electrode active material (silicon-containing alloy), and Sn is added as a second additive element as necessary.
  • M is selected as an additive element (M; transition metal) to the negative electrode active material (silicon-containing alloy)
  • Sn is added as a second additive element as necessary.
  • M is preferably titanium (Ti)
  • M is a ternary system of Si—Sn—Ti containing titanium. More preferably.
  • the amorphous-crystal phase transition is suppressed because, in the Si material, when Si and Li are alloyed, the amorphous state transitions to the crystalline state and a large volume change (about 4 times) occurs. This is because the particles themselves are broken and the function as an active material is lost. Therefore, by suppressing the amorphous-crystal phase transition, it is possible to suppress the collapse of the particles themselves, maintain the function as the active material (high capacity), and improve the cycle life. By selecting such an additive element, a Si alloy negative electrode active material having a high capacity and high cycle durability can be provided.
  • the composition ratio z of the transition metal M (particularly Ti) is preferably 7 ⁇ z ⁇ 100, more preferably 10 ⁇ z ⁇ 100, and 15 ⁇ z ⁇ 100. It is more preferable that 20 ⁇ z ⁇ 100.
  • the x, y, and z in the chemical formula (1) are the following formulas (1) or (2):
  • the content of the transition metal M is preferably in the range of more than 7% by mass. That is, the x, y, and z are represented by the following formula (3) or (4):
  • the x, y, and z are represented by the following formula (5) or (6):
  • the x, y, and z are expressed by the following formula (7):
  • A is an impurity (unavoidable impurity) other than the above three components derived from the raw materials and the manufacturing method.
  • the a is 0 ⁇ a ⁇ 0.5, and preferably 0 ⁇ a ⁇ 0.1.
  • the silicon-containing alloy constituting the negative electrode active material in this embodiment is characterized in that the closest distance between adjacent silicide phases is 300 nm or less.
  • the “closest distance between adjacent silicide phases” means a distance (shortest distance) between adjacent silicide phases in the cross section of the alloy, and HAADF-STEM (high angle scattering annular dark field scanning transmission microscopy; -Angle
  • the combination of adjacent silicide phases is preferably 10% or more, more preferably 30% or more, still more preferably 50% or more, still more preferably 70% or more, and particularly preferably 90% or more. Most preferably, 100% satisfies “the closest distance is 300 nm or less”.
  • HAADF-STEM is a method for obtaining an image of a sample by applying a finely focused electron beam while scanning the sample and detecting the scattered electrons scattered at a high angle with a ring detector. is there.
  • a HAADF-STEM image is obtained under the following conditions.
  • FIB focused ion beam
  • Microsampling system Hitachi FB-2000A
  • Use Al grid (measuring equipment and conditions)
  • Apparatus Atomic resolution analytical electron microscope (JEM-JEM-ARM200F) JED2 JED-2300 (100mm 2 silicon drift (SDD) type)
  • the closest distance between the silicide phases is preferably 200 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, and particularly preferably 25 nm or less.
  • the combinations of adjacent silicide phases preferably 10% or more, more preferably 30% or more, still more preferably 50% or more, and even more preferably 70% or more, Particularly preferably, 90% or more, and most preferably 100%, may be included in a preferable range regarding these closest distances.
  • the lower limit value of the closest distance between adjacent silicide phases is not particularly limited, but is usually 1 nm or more.
  • the present inventors examined the cycle durability of a half cell (counter electrode: metallic lithium) using an amorphous silicon thin film produced by sputtering as a negative electrode.
  • the film thickness of the negative electrode silicon thin film
  • the cycle durability was greatly improved when the film thickness of the negative electrode (silicon thin film) was 100 nm compared to when the film thickness of the negative electrode (silicon thin film) was 300 nm. did.
  • the present inventors have found that even when using a silicon-containing alloy in which amorphous silicon is used as a parent phase and a silicide phase is dispersed in the parent phase as a negative electrode active material, an amorphous silicon existing between silicide phases.
  • the hypothesis was set that the same cycle durability could be improved by setting the interval between the silicon phases to 300 nm or less. Then, as described in the Examples section described later, the above hypothesis was verified by confirming that high cycle durability can be achieved by the configuration of the present invention (the closest distance between adjacent silicide phases is 300 nm or less). The present invention has been completed.
  • the mechanism by which cycle durability is improved by the closest distance between the silicide phases in the silicon-containing alloy constituting the negative electrode active material being 300 nm or less is estimated as follows. That is, when the distance between the silicide phases is small, the amorphous-crystal phase transition (crystallization to Li 15 Si 4 ) when Si and Li are alloyed is suppressed. Thereby, the expansion
  • the Si negative electrode is in an amorphous state and has a small volume change unless the Li in the active material increases with charge and does not exceed the charge capacity (3580 mAh / g) of the Li 15 Si 4 composition.
  • the charge capacity 3580 mAh / g
  • Li 15 Si 4 when Li increases beyond this composition, it crystallizes, thereby causing particle collapse. From this, it is considered that the production of crystalline Li 15 Si 4 by charging adversely affects the cycle durability of the negative electrode.
  • nucleation free energy is a function of the radius R of the nucleus
  • ns is a fixed molecular number density and ⁇ is a constant. It is represented by In other words, it is shown that nucleation is more dominant as R increases at a certain critical concentration. Therefore, it is considered that the narrower the region of amorphous or low crystalline silicon that reacts with Li in the silicon-containing alloy, the more the crystallization to Li 15 Si 4 is suppressed and the cycle durability is improved. .
  • the diffraction showing the crystallinity of the silicide phase is performed by performing electron diffraction measurement under the following measuring device and conditions.
  • the presence or absence of the spot may be confirmed, and the presence of such a spot supports the presence of the silicide phase.
  • the presence of the halo pattern confirms that the matrix is amorphous or low crystalline.
  • the particle diameter of the silicon-containing alloy constituting the negative electrode active material in the present embodiment is not particularly limited, but the average particle diameter is preferably 0.1 to 20 ⁇ m, more preferably 0.2 to 10 ⁇ m.
  • Method for producing negative electrode active material There is no particular limitation on the method for manufacturing the negative electrode active material for an electrical device according to the present embodiment, and conventionally known knowledge can be referred to as appropriate. In this application, the closest distance between adjacent silicide phases is set to 300 nm or less. As an example of the manufacturing method for the above, the following manufacturing method is provided. That is, according to the present invention, an electricity comprising a silicon-containing alloy having a structure in which a silicide phase containing a silicide of a transition metal is dispersed in a parent phase mainly composed of amorphous or low crystalline silicon. A method for producing a negative electrode active material for a device is provided.
  • the manufacturing method mixes the raw material of the said silicon containing alloy, and obtains mixed powder,
  • the negative electrode for electric devices which consists of said silicon containing alloy by performing alloying process with respect to the said mixed powder for 24 hours or more And a step of obtaining an active material.
  • it demonstrates in order of a process.
  • a process for obtaining a mixed powder by mixing raw materials of a silicon-containing alloy is performed.
  • raw materials for the alloy are mixed.
  • the raw material of the alloy is not particularly limited as long as the ratio of elements necessary as the negative electrode active material can be realized.
  • raw materials in a powder state are mixed. Thereby, the mixed powder which consists of a raw material is obtained.
  • Examples of alloying methods include a solid phase method, a liquid phase method, and a gas phase method.
  • a mechanical alloy method for example, a mechanical alloy method, an arc plasma melting method, a casting method, a gas atomizing method, a liquid quenching method, an ion beam sputtering method, a vacuum method, and the like.
  • Examples include vapor deposition, plating, and gas phase chemical reaction.
  • a step of melting the raw material and a step of rapidly cooling and solidifying the molten material may be included.
  • the alloying process described above is performed for 24 hours or more. Thereby, it can be set as the structure which consists of a mother phase / silicide phase as mentioned above.
  • the alloying treatment time is less than 24 hours, it becomes difficult to make the average distance between silicide phases 300 nm or less, and a negative electrode active material (silicon-containing alloy) capable of exhibiting desired cycle durability is obtained. May not be possible.
  • the alloying treatment time is preferably 30 hours or more, more preferably 36 hours or more, still more preferably 42 hours or more, and particularly preferably 48 hours or more.
  • the upper limit of the time for alloying process is not set in particular, it may usually be 72 hours or less.
  • the alloying treatment by the method described above is usually performed in a dry atmosphere, but the particle size distribution after the alloying treatment may be very large or small. For this reason, it is preferable to perform the grinding
  • the predetermined alloy included in the negative electrode active material layer has been described, but the negative electrode active material layer may contain other negative electrode active materials.
  • the negative electrode active material other than the predetermined alloy include natural graphite, artificial graphite, carbon black, activated carbon, carbon fiber, coke, soft carbon, carbon such as hard carbon, pure metal such as Si and Sn, and the predetermined composition.
  • Alloy-based active material out of ratio or metal oxide such as TiO, Ti 2 O 3 , TiO 2 , SiO 2 , SiO, SnO 2 , lithium such as Li 4/3 Ti 5/3 O 4 or Li 7 MnN And transition metal complex oxides (composite nitrides), 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 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 includes a binder.
  • Binder is added for the purpose of maintaining the electrode structure by binding the active materials or the active material and the current collector.
  • the amount of the binder contained in the negative electrode active material layer is not particularly limited as long as it can bind the active material, but is preferably 0.5 to 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 include a conductive additive, an electrolyte salt (lithium salt), an ion conductive polymer, and the like as necessary.
  • the negative electrode active material layer 13 essentially includes a conductive additive.
  • Conductive auxiliary agent means the additive mix
  • Examples of the conductive assistant 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, more preferably 3% by mass or more, and further preferably 5% by mass or more with respect to the total amount of the active material layer.
  • the content of the conductive additive mixed in the active material layer is 15% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less with respect to the total amount of the active material layer. is there.
  • the conductive binder having the functions of the conductive assistant and the binder may be used in place of the conductive assistant and the binder, or may be used in combination with one or both of the conductive assistant and the binder.
  • Commercially available TAB-2 (manufactured by Hosen 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 conductive polymer examples include 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 mixing ratio can be adjusted by appropriately referring to known knowledge about the non-aqueous solvent secondary battery.
  • each active material layer (active material layer on one side of the current collector) is not particularly limited, and conventionally known knowledge about the battery can be appropriately referred to.
  • the thickness of each active material layer is usually about 1 to 500 ⁇ m, preferably 2 to 100 ⁇ m, taking into consideration the intended use of the battery (emphasis on output, energy, 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 intended use of the battery. For example, if it is used for a large battery that requires a high energy density, a current collector having a large area is used.
  • 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 (such as an expanded grid) can be used.
  • the negative electrode active material is formed directly on the negative electrode current collector 12 by sputtering or the like, it is desirable to use a current collector foil.
  • a metal or a resin in which a conductive filler is added to a conductive polymer material or a non-conductive polymer material can be employed.
  • examples of the metal include aluminum, nickel, iron, stainless steel, titanium, and copper.
  • a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material of a combination of these metals can be preferably used.
  • covered on the metal surface may be sufficient.
  • aluminum, stainless steel, copper, and nickel are preferable from the viewpoints of electronic conductivity, battery operating potential, and adhesion of the negative electrode active material by sputtering to the current collector.
  • examples of the conductive polymer material include polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polyacrylonitrile, and polyoxadiazole. Since such a conductive polymer material has sufficient conductivity without adding a conductive filler, it is advantageous in terms of facilitating the manufacturing process or reducing the weight of the current collector.
  • Non-conductive polymer materials include, 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) , 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 polytetraflu
  • a conductive filler may be added to the conductive polymer material or the non-conductive polymer material as necessary.
  • a conductive filler is inevitably necessary to impart conductivity to the resin.
  • the conductive filler can be used without particular limitation as long as it has a conductivity.
  • metals, conductive carbon, etc. are mentioned as a material excellent in electroconductivity, electric potential resistance, or lithium ion barrier
  • 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 these metals It is preferable to contain an alloy or metal oxide containing.
  • it includes at least one selected from the group consisting of acetylene black, vulcan, black pearl, carbon nanofiber, ketjen black, carbon nanotube, carbon nanohorn, carbon nanoballoon, and fullerene.
  • the amount of the conductive filler added is not particularly limited as long as it is an amount capable of imparting sufficient conductivity to the current collector, and is generally about 5 to 35% by mass.
  • a liquid electrolyte or a polymer electrolyte can 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), Examples include carbonates such as methylpropyl carbonate (MPC).
  • 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 electrolytic solution and intrinsic polymer electrolytes not containing an electrolytic solution.
  • the gel electrolyte has a configuration in which the above liquid electrolyte (electrolytic solution) is injected into a matrix polymer made of an ion conductive polymer.
  • the use of a gel polymer electrolyte as the electrolyte is superior in that the fluidity of the electrolyte is lost and it is easy to block ion conduction between the layers.
  • Examples of the ion conductive polymer used as the matrix polymer include polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers thereof.
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • electrolyte salts such as lithium salts can be well dissolved.
  • the ratio of the liquid electrolyte (electrolytic solution) in the gel electrolyte is not particularly limited, but is preferably about several mass% to 98 mass% from the viewpoint of ionic conductivity.
  • the gel electrolyte having a large amount of electrolytic solution having a ratio of the electrolytic solution of 70% by mass or more is particularly effective.
  • a separator may be used for the electrolyte layer.
  • the separator include a microporous film made of polyolefin such as polyethylene and polypropylene, a porous flat plate, and a non-woven fabric.
  • the intrinsic polymer electrolyte has a structure in which a supporting salt (lithium salt) is dissolved in the above matrix polymer, and does not contain an organic solvent that is a plasticizer. Therefore, when the electrolyte layer is composed of an intrinsic polymer electrolyte, there is no fear of liquid leakage from the battery, and the reliability of the battery can be improved.
  • a supporting salt lithium salt
  • the matrix polymer of the gel electrolyte or the intrinsic polymer electrolyte can express excellent mechanical strength by forming a crosslinked structure.
  • thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam polymerization, etc. are performed on a polymerizable polymer (for example, PEO or PPO) for forming a polymer electrolyte using an appropriate polymerization initiator.
  • a polymerization treatment may be performed.
  • a current collecting plate may be used for the purpose of taking out the current outside the battery.
  • the current collector plate is electrically connected to the current collector and the lead, and is taken out of the laminate sheet that is a battery exterior material.
  • the material constituting the current collector plate is not particularly limited, and a known highly conductive material conventionally used as a current collector plate for a lithium ion secondary battery can be used.
  • 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, and aluminum is more preferable from the viewpoint of light weight, corrosion resistance, and high conductivity. Copper or the like is preferable. Note that 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.
  • ⁇ Use positive terminal lead and negative terminal lead as required.
  • a terminal lead used in a known lithium ion secondary battery can be used.
  • the part taken out from the battery outer packaging material 29 has a heat insulating property so as not to affect the product (for example, automobile parts, particularly electronic devices) by contacting with peripheral devices or wiring and causing leakage. It is preferable to coat with a heat shrinkable tube or the like.
  • ⁇ Battery exterior material> As the battery exterior material 29, a known metal can case can be used, and a bag-like case using a laminate film containing aluminum that can cover the power generation element can be used.
  • a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used as the laminate film, but the laminate film is not limited thereto.
  • a laminate film is desirable from the viewpoint that it is excellent in high output and cooling performance, and can be suitably used for a battery for large equipment for EV and HEV.
  • said lithium ion secondary battery can be manufactured with a conventionally well-known manufacturing method.
  • FIG. 2 is a perspective view showing the appearance of a stacked flat lithium ion secondary battery.
  • the stacked flat lithium ion secondary battery 50 has a rectangular flat shape, and a positive current collector 59 for taking out power from both sides thereof, a negative current collector, and the like.
  • the electric plate 58 is pulled out.
  • the power generation element 57 is wrapped by the battery outer packaging material 52 of the lithium ion secondary battery 50 and the periphery thereof is heat-sealed.
  • the power generation element 57 pulls out the positive electrode current collector plate 59 and the negative electrode current collector plate 58 to the outside. Sealed.
  • 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 laminating a plurality of single battery layers (single cells) 19 including a positive electrode (positive electrode active material layer) 13, an electrolyte layer 17, and a negative electrode (negative electrode active material layer) 15.
  • the lithium ion secondary battery is not limited to a laminated flat shape (laminate cell).
  • a cylindrical shape coin cell
  • a prismatic shape square cell
  • it may be a cylindrical cell, and is not particularly limited.
  • the cylindrical or prismatic shape is not particularly limited, for example, a laminate film or a conventional cylindrical can (metal can) may be used as the exterior material.
  • the power generation element is covered with an aluminum laminate film. With this configuration, weight reduction can be achieved.
  • 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 of parts and taken out from each side. It is not limited to the one shown in FIG.
  • a terminal instead of the current collector plate, for example, a terminal may be formed using a cylindrical can (metal can).
  • the negative electrode and the lithium ion secondary battery using the negative electrode active material for the lithium ion secondary battery of the present embodiment are large vehicles such as electric vehicles, hybrid electric vehicles, fuel cell vehicles, and hybrid fuel cell vehicles. It can be suitably used as a capacity power source. That is, it can be suitably used for a vehicle driving power source and an auxiliary power source that require high volume energy density and high volume output density.
  • the lithium ion battery is exemplified as the electric device.
  • the present invention is not limited to this, and can be applied to other types of secondary batteries and further to primary batteries. Moreover, it can be applied not only to batteries but also to capacitors.
  • Example 1 [Manufacture of silicon-containing alloys] A silicon-containing alloy (Si 59 Sn 22 Ti 19 ) was produced by a mechanical alloy method. Specifically, using a planetary ball mill device P-6 manufactured by Fricht, Germany, zirconia pulverized balls and alloy raw material powders were put into a zirconia pulverized pot and alloyed at 600 rpm for 50 hours (alloying treatment). ), And then pulverization was performed at 400 rpm for 1 hour. In addition, the average particle diameter of the obtained silicon-containing alloy (negative electrode active material) powder was 0.3 ⁇ m.
  • lithium (LiPF 6) was used dissolved at a concentration of 1 mol / L.
  • Example 2 Except for changing the composition of the silicon-containing alloy to Si 90 Sn 5 Ti 5 and changing the alloying treatment time to 48 hours, a negative electrode active material, a negative electrode, and A lithium ion secondary battery (coin cell) was produced. In addition, the average particle diameter of the obtained silicon-containing alloy (negative electrode active material) powder was 0.3 ⁇ m.
  • Example 3 A negative electrode active material, a negative electrode, and a lithium ion secondary battery (coin cell) were prepared in the same manner as in Example 1 except that the alloying treatment time for producing the silicon-containing alloy was changed to 25 hours. Produced. In addition, the average particle diameter of the obtained silicon-containing alloy (negative electrode active material) powder was 0.3 ⁇ m.
  • Example 4 A negative electrode active material, a negative electrode, and a lithium ion secondary battery (coin cell) were prepared in the same manner as in Example 2 described above, except that the alloying treatment time for producing the silicon-containing alloy was changed to 24 hours. Produced. In addition, the average particle diameter of the obtained silicon-containing alloy (negative electrode active material) powder was 0.3 ⁇ m.
  • Example 5 A negative electrode active material, a negative electrode, and lithium ions were obtained in the same manner as in Example 1 except that the composition of the silicon-containing alloy was changed to Si 90 Ti 10 and the alloying time was changed to 24 hours. A secondary battery (coin cell) was produced. In addition, the average particle diameter of the obtained silicon-containing alloy (negative electrode active material) powder was 0.3 ⁇ m.
  • FIGS. 3A and 3B photographs obtained by EDX analysis (energy dispersive X-ray analysis) of the silicon-containing alloy (negative electrode active material) powder obtained in Example 1 are shown in FIGS. 3A and 3B.
  • red indicates the presence site of Ti
  • green indicates the presence site of Sn
  • blue indicates the presence site of Si.
  • red indicates a site where Ti is present.
  • part assumed to be an amorphous silicon phase obtained by the electron diffraction analysis about the silicon containing alloy (negative electrode active material) powder obtained in Example 1 is shown in FIG.
  • the diffraction pattern of the assumed part is shown in FIG. 3D. From the results shown in these figures, it was confirmed that the portion assumed to be an amorphous silicon phase was amorphous, and the portion assumed to be a silicide phase was crystalline.
  • the evaluation cell is in a constant current / constant voltage mode in the charging process (referring to the Li insertion process to the evaluation electrode) in a thermostat set to the above evaluation temperature using a charge / discharge tester.
  • the battery was charged from 2 V to 10 mV at 0.1 mA.
  • a constant current mode was set and discharge was performed from 0.3 C, 10 mV to 2 V.
  • the charge / discharge test was conducted from the initial cycle (1 cycle) to 50 cycles under the same charge / discharge conditions with the above charge / discharge cycle as one cycle.
  • the results of determining the ratio of the discharge capacity at the 50th cycle to the discharge capacity at the first cycle are shown in Table 1 below.
  • the lithium ion battery using the negative electrode active material according to the present invention has a high discharge capacity retention rate and is excellent in cycle durability.
  • Lithium ion secondary battery (stacked battery), 11 negative electrode current collector, 12 positive electrode current collector, 13 negative electrode active material layer, 15 positive electrode active material layer, 17 electrolyte layer, 19 cell layer, 21, 57 power generation element, 25, 58 negative electrode current collector plate, 27, 59 positive current collector, 29, 52 Battery exterior material (laminate film).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

Le problème à résoudre dans le cadre de la présente invention vise à pourvoir à des moyens qui peuvent améliorer la durabilité de cycle d'un dispositif électrique tel qu'une batterie rechargeable au lithium-ion. La solution consiste à utiliser, pour un dispositif électrique, un matériau actif d'électrode négative composé d'un alliage contenant du silicium ayant une structure dans laquelle des phases de siliciure comprenant un siliciure d'un métal de transition sont dispersées dans une phase matricielle comprenant du silicium amorphe ou faiblement cristallin comme composant principal, la distance la plus faible entre des phases de siliciure adjacentes parmi lesdites phases de siliciure étant égale ou inférieure à 300 nm.
PCT/JP2014/083479 2014-12-17 2014-12-17 Matériau actif d'électrode négative pour un dispositif électrique et dispositif électrique utilisant ce dernier WO2016098213A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2016564520A JPWO2016098213A1 (ja) 2014-12-17 2014-12-17 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
PCT/JP2014/083479 WO2016098213A1 (fr) 2014-12-17 2014-12-17 Matériau actif d'électrode négative pour un dispositif électrique et dispositif électrique utilisant ce dernier

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2014/083479 WO2016098213A1 (fr) 2014-12-17 2014-12-17 Matériau actif d'électrode négative pour un dispositif électrique et dispositif électrique utilisant ce dernier

Publications (1)

Publication Number Publication Date
WO2016098213A1 true WO2016098213A1 (fr) 2016-06-23

Family

ID=56126136

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/083479 WO2016098213A1 (fr) 2014-12-17 2014-12-17 Matériau actif d'électrode négative pour un dispositif électrique et dispositif électrique utilisant ce dernier

Country Status (2)

Country Link
JP (1) JPWO2016098213A1 (fr)
WO (1) WO2016098213A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019185908A (ja) * 2018-04-04 2019-10-24 日産自動車株式会社 電極活物質スラリーの製造方法
JP2020145053A (ja) * 2019-03-05 2020-09-10 株式会社豊田中央研究所 負極活物質材料及び蓄電デバイス

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005088761A1 (fr) * 2004-03-16 2005-09-22 Matsushita Electric Industrial Co., Ltd. Pile secondaire de lithium
JP2006236887A (ja) * 2005-02-28 2006-09-07 Matsushita Electric Ind Co Ltd 非水電解質二次電池
JP2007157704A (ja) * 2005-11-09 2007-06-21 Matsushita Electric Ind Co Ltd コイン型リチウム二次電池用負極とその製造方法、およびコイン型リチウム二次電池
JP2008198391A (ja) * 2007-02-08 2008-08-28 Sony Corp 負極活物質および電池
JP2009521792A (ja) * 2005-12-23 2009-06-04 スリーエム イノベイティブ プロパティズ カンパニー リチウム−イオン電池の電極に有用なシリコン含有合金
JP2010080285A (ja) * 2008-09-26 2010-04-08 Panasonic Corp 扁平型非水電解質二次電池およびその製造方法
JP2012526920A (ja) * 2009-05-14 2012-11-01 スリーエム イノベイティブ プロパティズ カンパニー 低エネルギー粉砕方法、低結晶性合金、及び負極組成物
JP2013131432A (ja) * 2011-12-22 2013-07-04 Panasonic Corp 非水電解液二次電池
WO2014080888A1 (fr) * 2012-11-22 2014-05-30 日産自動車株式会社 Électrode négative pour un dispositif électrique et dispositif électrique pourvu de cette dernière

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005088761A1 (fr) * 2004-03-16 2005-09-22 Matsushita Electric Industrial Co., Ltd. Pile secondaire de lithium
JP2006236887A (ja) * 2005-02-28 2006-09-07 Matsushita Electric Ind Co Ltd 非水電解質二次電池
JP2007157704A (ja) * 2005-11-09 2007-06-21 Matsushita Electric Ind Co Ltd コイン型リチウム二次電池用負極とその製造方法、およびコイン型リチウム二次電池
JP2009521792A (ja) * 2005-12-23 2009-06-04 スリーエム イノベイティブ プロパティズ カンパニー リチウム−イオン電池の電極に有用なシリコン含有合金
JP2008198391A (ja) * 2007-02-08 2008-08-28 Sony Corp 負極活物質および電池
JP2010080285A (ja) * 2008-09-26 2010-04-08 Panasonic Corp 扁平型非水電解質二次電池およびその製造方法
JP2012526920A (ja) * 2009-05-14 2012-11-01 スリーエム イノベイティブ プロパティズ カンパニー 低エネルギー粉砕方法、低結晶性合金、及び負極組成物
JP2013131432A (ja) * 2011-12-22 2013-07-04 Panasonic Corp 非水電解液二次電池
WO2014080888A1 (fr) * 2012-11-22 2014-05-30 日産自動車株式会社 Électrode négative pour un dispositif électrique et dispositif électrique pourvu de cette dernière

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019185908A (ja) * 2018-04-04 2019-10-24 日産自動車株式会社 電極活物質スラリーの製造方法
JP7042144B2 (ja) 2018-04-04 2022-03-25 日産自動車株式会社 電極活物質スラリーの製造方法
JP2020145053A (ja) * 2019-03-05 2020-09-10 株式会社豊田中央研究所 負極活物質材料及び蓄電デバイス
JP6998335B2 (ja) 2019-03-05 2022-02-10 株式会社豊田中央研究所 負極活物質材料及び蓄電デバイス

Also Published As

Publication number Publication date
JPWO2016098213A1 (ja) 2017-11-02

Similar Documents

Publication Publication Date Title
JP6098719B2 (ja) 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
JP6493414B2 (ja) 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
JP6040997B2 (ja) リチウムイオン二次電池用負極、及びこれを用いたリチウムイオン二次電池
JP6327362B2 (ja) 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
JP6112200B2 (ja) 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
WO2016098209A1 (fr) Matière active d'électrode négative pour dispositif électrique et dispositif électrique l'utilisant
JP6459479B2 (ja) 電気デバイス用負極、およびこれを用いた電気デバイス
JP6488690B2 (ja) 電気デバイス用負極、およびこれを用いた電気デバイス
JP6561461B2 (ja) 電気デバイス用負極、およびこれを用いた電気デバイス
WO2016098210A1 (fr) Matière active d'électrode négative pour dispositif électrique et dispositif électrique l'utilisant
JP6488689B2 (ja) 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
WO2016098213A1 (fr) Matériau actif d'électrode négative pour un dispositif électrique et dispositif électrique utilisant ce dernier
JP6485028B2 (ja) 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
JP6112199B2 (ja) 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
JP6083471B2 (ja) 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
JP6555278B2 (ja) リチウムイオン二次電池用負極活物質、およびこれを用いたリチウムイオン二次電池
JP6292317B2 (ja) 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
JP6736999B2 (ja) 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
WO2016098208A1 (fr) Matériau actif d'électrode négative destiné à être utilisé dans un dispositif électrique et dispositif électrique utilisant ledit matériau
JP2016115630A (ja) 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

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14908423

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016564520

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14908423

Country of ref document: EP

Kind code of ref document: A1