WO2016043061A1 - MATÉRIAU D'ÉLECTRODE NÉGATIVE EN ALLIAGE À BASE DE Si POUR DISPOSITIFS DE STOCKAGE D'ÉLECTRICITÉ ET ÉLECTRODE UTILISANT CELUI-CI - Google Patents

MATÉRIAU D'ÉLECTRODE NÉGATIVE EN ALLIAGE À BASE DE Si POUR DISPOSITIFS DE STOCKAGE D'ÉLECTRICITÉ ET ÉLECTRODE UTILISANT CELUI-CI Download PDF

Info

Publication number
WO2016043061A1
WO2016043061A1 PCT/JP2015/075119 JP2015075119W WO2016043061A1 WO 2016043061 A1 WO2016043061 A1 WO 2016043061A1 JP 2015075119 W JP2015075119 W JP 2015075119W WO 2016043061 A1 WO2016043061 A1 WO 2016043061A1
Authority
WO
WIPO (PCT)
Prior art keywords
phase
negative electrode
crystallite size
electrode material
based alloy
Prior art date
Application number
PCT/JP2015/075119
Other languages
English (en)
Japanese (ja)
Inventor
友紀 廣野
哲嗣 久世
哲朗 仮屋
澤田　俊之
Original Assignee
山陽特殊製鋼株式会社
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 山陽特殊製鋼株式会社 filed Critical 山陽特殊製鋼株式会社
Priority to KR1020177004242A priority Critical patent/KR20170057235A/ko
Priority to CN201580046199.4A priority patent/CN106605322A/zh
Publication of WO2016043061A1 publication Critical patent/WO2016043061A1/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
    • 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
    • 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
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a Si-based alloy negative electrode material that is excellent in conductivity of an electricity storage device that involves movement of lithium ions during charge and discharge, such as a lithium ion secondary battery, a hybrid capacitor, and an all solid lithium ion secondary battery, and an electrode using the same Is.
  • Si is attracting attention as a material that can replace carbonaceous materials.
  • the reason is that Si forms a compound represented by Li22Si5 and can occlude a large amount of lithium, so that the capacity of the negative electrode can be greatly increased as compared with the case of using a carbonaceous material. This is because there is a possibility that the storage capacity of the lithium ion secondary battery, the hybrid capacitor, and the all solid state battery can be increased.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2001-297757
  • Patent Document 2 Japanese Patent Application Laid-Open No. 10-318044
  • an electrode in which a phase of an active material containing a Si phase is coated with a conductive material such as Cu that is not alloyed with lithium, and a manufacturing method thereof are disclosed in, for example, Japanese Patent Application Laid-Open No. 2004-228059 (Patent Document). 3) and Japanese Patent Laid-Open No. 2005-44672 (Patent Document 4).
  • the problem to be solved by the present invention is to control the chemical composition, structure, structure size, etc. of the Si phase or intermetallic compound phase in the Si-based alloy at a high level, thereby enabling the lithium ion secondary battery or hybrid to be controlled. It is to propose a Si-based alloy negative electrode material that is excellent in charge / discharge characteristics with respect to an electricity storage device that moves lithium ions during charge / discharge, such as a capacitor and an all solid state battery.
  • the inventors have intensively developed, and as a result, refinement of the structure, excellent ion conductivity and electron conductivity, control of the component system that enhances the stress relaxation effect, Si phase and
  • the present inventors have found a Si-based alloy negative electrode material capable of obtaining excellent battery characteristics by controlling the crystallite size of the intermetallic compound phase.
  • a negative electrode material made of a Si-based alloy for an electricity storage device accompanied by movement of lithium ions during charge and discharge is Having a Si main phase composed of Si and a compound phase composed of one or more elements other than Si and Si;
  • the compound phase has a phase comprising Si and Cr, or a phase comprising Si, Cr and Ti;
  • Si crystallite size of the Si main phase is 30 nm or less,
  • the crystallite size of the compound phase comprising Si and Cr or Si, Cr and Ti is 40 nm or less,
  • the total content of Cr and Ti is 21.1 to 40 at. %
  • a negative electrode material made of a Si-based alloy having a Cr / Ti ratio of Cr% / (Cr% + Ti%) in the range of 0.15 to 1.00.
  • a negative electrode material made of a Si-based alloy for an electricity storage device that involves movement of lithium ions during charge and discharge, wherein the negative electrode material made of the Si-based alloy is a Si main phase made of Si. And a compound phase comprising one or more elements other than Si and Si, the compound phase having a phase comprising Si and Cr, or a phase comprising Si, Cr and Ti,
  • the Si crystallite size is 30 nm or less
  • the crystallite size of the compound phase composed of Si and Cr, or Si, Cr and Ti is 40 nm or less
  • the total content of Cr and Ti is 21.1 to 40 at.
  • a negative electrode material made of a Si-based alloy for an electricity storage device is provided, in which Cr% / (Cr% + Ti%), which is a ratio of Cr and Ti, is 0.15 to 1.00. .
  • Cu, V, Mn, Fe, Ni, Nb, Zn, Al are included in the compound phase of the negative electrode material made of the Si-based alloy for an electricity storage device described in the other embodiment. At least one element selected from the group consisting of a total content of 0.05 at. % To 5 at. %, A negative electrode material made of a Si-based alloy for power storage devices is provided.
  • the total content is 0.05 at. % To 5 at. %, A negative electrode material made of a Si-based alloy for power storage devices is provided.
  • a negative electrode made of an alloy is provided.
  • Cr is an essential element for generating Si 2 Cr effective for the formation of a Si phase and a fine eutectic structure.
  • Ti is substituted by Cr to increase the lattice constant of Si 2 Cr, thereby improving lithium ion conductivity. Presumed to increase.
  • the crystallite size of the Si phase is inserting the crystallite size of the Si phase to 30 nm or less and the crystallite size of the compound phase of Si and Cr or the compound phase of Si, Cr and Ti to 40 nm or less, occlusion / release of lithium to Si is performed. It plays the role of relieving the stress caused by the volume expansion at the time and preventing electrical isolation due to the pulverization of Si, and provides excellent charge / discharge cycle characteristics.
  • one or more of additive elements such as Cu, V, Mn, Fe, Ni, Nb, Pd, Zn, and Al are added to a sample made of Si and Cr, or Si and Cr and Ti, which are Si-based alloy negative electrode materials for power storage devices.
  • Si and Cr, or Si and Cr and Ti which are Si-based alloy negative electrode materials for power storage devices.
  • the compound phase surrounds the periphery of the fine Si phase, and mitigates the stress caused by the pulverization of Si and the volume expansion at the time of insertion and extraction of lithium into and from the Si. It plays a role in preventing collapse and electrical isolation of Si.
  • excellent battery characteristics are provided.
  • a sample made of Si and Cr, or Si and Cr and Ti, which are Si-based alloy negative electrode materials for electricity storage devices contains one or more additive elements such as Mg, B, P and Ga in a total of 0.05 at. % To 5 at.
  • the compound phase surrounds the periphery of the fine Si phase, and mitigates the stress caused by the pulverization of Si and the volume expansion at the time of insertion and extraction of lithium into and from the Si. It plays a role in preventing collapse and electrical isolation of Si.
  • P-type semiconductor structure by adding B it plays a role of improving the electrical conductivity of Si.
  • N-type semiconductor structure by adding P it plays a role of improving the electrical conductivity of Si.
  • excellent battery characteristics are provided.
  • Cross-sectional SEM image of the Si-Si 2 Cr eutectic alloy is a diagram showing a. XRD of Si—Si 2 Cr eutectic alloy with varying Cr / Ti ratio.
  • the present invention is described in detail below.
  • the charge / discharge capacity of a lithium ion secondary battery is determined by the amount of lithium transferred.
  • Si causes volume expansion of about 400% when lithium is occluded / released, Si is peeled off or dropped from the electrode, or Si cannot maintain contact with the current collector. A sudden drop in capacity occurs.
  • Si phase size is too large, Si does not react with lithium up to the internal Si phase, but expands from the surface layer that easily reacts with lithium of Si, cracks occur, and then the internal unreacted Si phase expands.
  • the Si is pulverized repeatedly such that cracks occur. As a result, Si peels off from the electrode, or Si cannot maintain contact with the current collector, resulting in a rapid decrease in charge / discharge capacity associated with the cycle.
  • FIG. 1 is a cross-sectional structure diagram of a Si—Si 2 Cr eutectic alloy according to the present invention, taken by a scanning electron micrograph, wherein the black phase is the Si phase and the white phase is the Si 2 Cr phase. As shown in FIG. 1, both the Si phase and the CrSi 2 phase are extremely fine. In addition, compared with other elements, such as Fe and V, the following is estimated about the cause by which Cr addition produces an extremely fine eutectic structure
  • the amount of additive element necessary to obtain the eutectic of the Si phase and silicide is determined by the type of element, for example, 26.5% for Fe and 3% for V. These can be read from the phase diagrams of Si and additive elements.
  • the amount of silicide is inevitably increased and coarsening is likely, and the proportion of the Si phase that occludes / releases Li decreases.
  • a high discharge capacity cannot be obtained.
  • the Si—Si 2 Cr eutectic alloy can have both a high discharge capacity and an excellent cycle life.
  • the charge / discharge characteristics can be further improved by replacing a part of Cr with Ti.
  • replacing Cr with Ti in the Si—Si 2 Cr eutectic alloy the inventor found that Ti was replaced with Cr in Si 2 Cr, and the lattice constant was changed without changing its crystal structure. I thought it would increase.
  • FIG. 2 is a diagram showing X-ray diffraction of a Si—Si 2 Cr eutectic alloy with a changed Cr / Ti ratio. As shown in this figure, by replacing a part of Cr with Ti, the diffraction peak position of Si 2 Cr is shifted to the lower angle side without changing the crystal structure, and the lattice constant is increased. It is considered a thing.
  • the characteristics of the lithium ion secondary battery can be further improved by controlling the crystallite size. If the Si phase size is too large, Si does not react with lithium up to the internal Si phase, but expands from the surface layer that reacts easily with lithium of Si, cracks occur, and then the internal unreacted Si phase expands, Moreover, the pulverization of Si which repeats that a crack arises is caused. As a result, Si peels off from the electrode, or Si cannot maintain contact with the current collector, resulting in a rapid decrease in charge / discharge capacity associated with the cycle.
  • the crystallite size of the Si phase of the negative electrode material for a lithium ion secondary battery it is necessary to refine the structure of the Si phase to a size at which pulverization does not occur, and it is preferable to control the crystallite size of the Si phase of the negative electrode material for a lithium ion secondary battery to 30 nm or less. More preferably, it is 25 nm or less. In particular, it is preferably 10 nm or less.
  • the crystallite size it is preferable to control the crystallite size to 40 nm or less. More preferably, it is 20 nm or less. In particular, it is preferably 10 nm or less.
  • Examples of the production method include water atomization, single-roll quenching method, twin-roll quenching method, gas atomization method, disk atomization method, and centrifugal atomization, but are not limited thereto. Further, when the cooling effect is insufficient in the above process, mechanical milling or the like can be performed. Examples of the milling method include a ball mill, a bead mill, a planetary ball mill, an attritor, and a vibration ball mill, but are not limited thereto.
  • the Si compound phase can relax the volume expansion and contraction of Si during charge and discharge, and the electrical and electronic isolation of the active material in the electrode It is possible to prevent the cycle characteristics from being significantly deteriorated. Furthermore, if the total amount of Cr and Ti is 40% or less, a reduction in the proportion of the Si phase that occludes and releases Li is prevented, and a high discharge capacity is obtained. Therefore, by making the total content of Cr and Ti 21.1 to 40%, the amount of the Si compound can be increased to increase the electron conductivity of the electrode and to suppress the stress due to the volume expansion and contraction of the Si phase during charge and discharge. It becomes possible to secure the phase.
  • the total range of Cr and Ti is preferably 22 to 35%, more preferably 23 to 30%.
  • the preferable range of Cr% / (Cr% + Ti%) is 0.15 to 0.90, more preferably 0.20 to 0.80.
  • the composition of the Six (Cr, Ti) y phase is x> It must be y.
  • a fine Si phase is obtained by forming a eutectic alloy with Si in addition to Cr and Ti, so that the intermetallic compound is more conductive and flexible than Si.
  • One or more additive elements such as Cu, V, Mn, Fe, Ni, Nb, Zn, and Al can be further included.
  • the total content of Cu, V, Mn, Fe, Ni, Nb, Pd, Zn and Al is 0.05 at. % Or more, 5 at. % Or less, the amount of the lithium inert element does not increase, and a decrease in charge / discharge capacity can be prevented. Therefore, the total content of additive elements contained at least one of Cu, V, Mn, Fe, Ni, Nb, Pd, Zn, and Al is 0.05 at. % To 5 at. % Is desirable. More preferably, 0.1 at. % To 3 at. %.
  • Co, Zr, Pd, Bi, In, Sb, Sn, and Mo aiming at the same effect are also set to 0.05 at. % To 5 at. % Is desirable.
  • the total content of Mg, B, P and Ga is 0.05 at. % Or more, 5 at. % Or less, the amount of the lithium inert element does not increase, and a decrease in charge / discharge capacity can be prevented.
  • the total content of additive elements contained at least one of Mg, B, P and Ga is 0.05 at. % To 5 at. % Is desirable. More preferably, 0.1 at. % To 3 at. %.
  • Co, Zr, Pd, Bi, In, Sb, Sn, and Mo aiming at similar effects also have a total content of at least one additive element of 0.05 at. % To 5 at. % Is desirable.
  • Negative electrode material powders for lithium ion secondary batteries having the compositions shown in Tables 1 and 2 were prepared by a single roll quenching method, a gas atomizing method, or the like described below.
  • a liquid quenching method which is a single roll quenching method
  • a raw material having a predetermined composition is placed in a quartz tube having pores at the bottom, melted at a high frequency in an Ar atmosphere to form a molten metal, and a copper roll that rotates this molten metal.
  • a quenching ribbon was prepared in which the crystallite size of the Si phase was refined by the quenching effect of the copper roll.
  • the milled ribbon is then sealed in an Ar atmosphere together with zirconia balls, SUS304 balls, or SUJ2 balls in a zirconia, SUS304, or SUJ2 pot container and milled for the purpose of processing into particles. It was.
  • a ball mill, a bead mill, a planetary ball mill, an attritor, a vibrating ball mill, and the like can be given.
  • a raw material having a predetermined composition is placed in a quartz crucible having pores at the bottom, heated and melted in a high-frequency induction melting furnace in an Ar gas atmosphere, and then subjected to gas injection in an Ar gas atmosphere and a tapping hot water. Then, gas atomized fine powder was obtained by rapid solidification.
  • a raw material having a predetermined composition is placed in a quartz crucible having pores at the bottom, heated and melted in a high-frequency induction melting furnace in an Ar gas atmosphere, and then in an Ar gas atmosphere, 40000 to 60000 r. p. m.
  • the hot water was discharged onto a rotating disk of No.
  • the produced atomized fine powder is sealed in a zirconia or SUS304 / SUJ2 pot container in an Ar atmosphere together with zirconia balls, SUS304 balls, or SUJ2 balls, and powdered by mechanical milling to control the crystallite size.
  • mechanical milling include a ball mill, a bead mill, a planetary ball mill, an attritor, and a vibrating ball mill.
  • the crystallite size of the atomized powder and the intermetallic compound using rapid solidification can be controlled by setting the milling time and the number of rotations.
  • a so-called bipolar coin-type cell using lithium metal as a counter electrode was used.
  • a negative electrode active material Si—Cr—Ti, etc.
  • a conductive material acetylene black
  • a binder material polyimide, polyvinylidene fluoride, etc.
  • a dispersion N-methylpyrrolidone
  • the solvent was evaporated by vacuum drying with a vacuum dryer, and then roll-pressed as necessary, and then punched into a shape suitable for the coin cell.
  • lithium for the counter electrode was punched into a shape suitable for the coin cell.
  • the vacuum drying of the slurry-coated electrode when the polyimide binder material was used, it was dried at a temperature of 200 ° C. or higher in order to fully exhibit the performance.
  • polyvinylidene fluoride or the like it was dried at a temperature of about 160 ° C.
  • the electrolyte used for the lithium ion battery was a 3: 7 mixed solvent of ethylene carbonate and dimethyl carbonate, LiPF 6 (lithium hexafluorophosphate) was used as the supporting electrolyte, and 1 mol was dissolved in the electrolyte. Since the electrolyte solution must be handled in an inert atmosphere with dew point control, the cells were all assembled in a glove box with an inert atmosphere. The separator was cut out in a shape suitable for a coin cell and then held in the electrolyte for several hours under reduced pressure in order to sufficiently permeate the electrolyte into the separator. Thereafter, the negative electrode punched out in the previous step, the separator, and the counter electrode lithium were combined in this order, and the inside of the battery was sufficiently filled with the electrolytic solution.
  • LiPF 6 lithium hexafluorophosphate
  • the measurement of charge capacity and discharge capacity was performed using the above-mentioned bipolar cell, at a temperature of 25 ° C., and charged at a current density of 0.50 mA / cm 2 until the same potential (0 V) as that of the metal lithium electrode. At a current value (0.50 mA / cm 2 ), discharging was performed up to 1.5 V, and this charging-discharging was defined as one cycle. The cycle life was evaluated by repeating the above measurement.
  • No. of the present invention example. 1 to 12 include the Si main phase and the phase composed of Si, Cr and Ti, the crystallite size of Si is 30 nm or less, and the crystallite size of the compound phase composed of Si, Cr and Ti satisfies the condition of 40 nm or less is doing.
  • Invention Example No. No. 4 contains Si main phase, Si, Cr, and Ti, the crystallite size of Si is 3 nm, and the condition that the crystallite size of Si is 30 nm or less is satisfied.
  • the crystallite size of the compound phase composed of Si, Cr, and Ti is 31 nm, and the condition that the crystallite size of the compound phase composed of Si, Cr, and Ti is 40 nm or less is satisfied.
  • the present invention conditions were satisfied, the initial discharge capacity was 789 mAh / g, the discharge capacity retention rate after 50 cycles was 92%, and both the charge / discharge capacity and the cycle life showed good characteristics.
  • No. of the present invention example. 13 to 18 include a Si main phase and a phase composed of Si and Cr, the crystallite size of Si is 30 nm or less, and the crystallite size of the compound phase composed of Si and Cr satisfies the condition of 40 nm or less.
  • Invention Example No. No. 14 contains a Si main phase, Si, and Cr, the Si crystallite size is 5 nm, and satisfies the condition that the Si crystallite size is 30 nm or less. And the crystallite size of the compound phase consisting of Si and Cr is 14 nm, and the crystallite size of the compound phase consisting of Si and Cr is 40 nm or less. Further, as described above, the present invention conditions were satisfied, the discharge capacity was 989 mAh / g, the discharge capacity retention rate after 50 cycles was 83%, and both the charge / discharge capacity and the cycle life showed good characteristics.
  • No. of the present invention example. 19 to 24 include a Si main phase and a phase composed of Si, Cr, and Ti.
  • the crystallite size of Si is 30 nm or less, and the crystallite size of the compound phase composed of Si, Cr, and Ti is 40 nm or less. is doing.
  • Invention Example No. No. 23 includes Si main phase, Si, Cr, and Ti, the Si crystallite size is 9 nm, and satisfies the condition that the Si crystallite size is 30 nm or less.
  • the crystallite size of the compound phase composed of Si, Cr and Ti is 15 nm, and the crystallite size of the compound phase composed of Si, Cr and Ti is 40 nm or less.
  • the discharge capacity was 674 mAh / g
  • the discharge capacity retention rate after 50 cycles was 84%
  • both the charge / discharge capacity and the cycle life showed good characteristics.
  • No. of the present invention example. 25 to 55 include a Si main phase and a phase composed of Si and Cr, or Si, Cr and Ti.
  • the Si main phase has a Si crystallite size of 30 nm or less, and is composed of Si and Cr, or Si, Cr and Ti.
  • the crystallite size of the compound phase satisfies the condition of 40 nm or less.
  • the total content of additive elements contained at least one of Cu, V, Mn, Fe, Ni, Nb, Zn and Al is 0.05 at. % To 5 at. %. Further, the total content of additive elements contained at least one or more of Mg, B, P and Ga is 0.05 at. % To 5 at. %. Including a small amount of addition of Co, Zr, Pd, Bi, In, Sb, Sn, etc. aiming at the same effect.
  • No. No. 39 contains Si main phase, Si, Cr, and Ti, the crystallite size of Si is 15 nm, and satisfies the condition that the crystallite size of Si is 30 nm or less.
  • the crystallite size of the compound phase composed of Si, Cr and Ti is 32 nm, and the crystallite size of the compound phase composed of Si, Cr and Ti is 40 nm or less.
  • 0.01 at. % Cu, 0.03 at. % V, 0.01 at. % Mn, 0.01 at. % Fe, 0.01 at. % Ni, 0.02 at. % Zn, 0.02 at. % Al is contained.
  • Comparative Example No. 49 does not contain Cr, and the total content of Cr and Ti is 21.1 to 40 at. %, And the Cr / Ti ratio Cr% / (Cr% + Ti%) is not in the range of 0.15 to 1.00, so the conditions of the present invention are not satisfied.
  • Comparative Example No. 81 the total content of Cr and Ti is 21.1 to 40 at. %, The ratio of Cr to Ti, Cr% / (Cr% + Ti%) is not in the range of 0.15 to 1.00, and does not satisfy the condition of the Si crystallite size of 30 nm or less. Therefore, the conditions of the present invention are not satisfied.
  • Comparative Example No. 106 the total content of Cr and Ti is 21.1 to 40 at.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

La présente invention concerne : un matériau d'électrode négative en alliage à base de Si qui permet l'obtention d'excellentes caractéristiques de batterie; et une électrode. Ce matériau d'électrode négative est un matériau d'électrode négative qui est formé d'un alliage à base de Si et est pour utilisation dans des dispositifs de stockage d'électricité dans lesquels des ions lithium se déplacent pendant la charge et la décharge. Le matériau d'électrode négative qui est formé d'un alliage à base de Si a une phase principale de Si qui est composée de Si et une phase composite qui est composée de Si et un ou plusieurs éléments autres que Si. La phase composite comprend une phase contenant une phase composée de Si et Cr ou une phase composée de Si, Cr et Ti. La taille de cristallite de Si dans la phase principale est de 30 nm ou moins, et la taille de cristallite dans la phase composite composée de Si et Cr ou dans la phase composite composée de Si, Cr et Ti est de 40 nm ou moins. La teneur totale de Cr et Ti est de 21,1 à 40 % at., et le rapport de Cr à Ti, spécifiquement Cr %/ (Cr % + Ti %) est dans la plage de 0,15 à 1,00.
PCT/JP2015/075119 2014-09-16 2015-09-03 MATÉRIAU D'ÉLECTRODE NÉGATIVE EN ALLIAGE À BASE DE Si POUR DISPOSITIFS DE STOCKAGE D'ÉLECTRICITÉ ET ÉLECTRODE UTILISANT CELUI-CI WO2016043061A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020177004242A KR20170057235A (ko) 2014-09-16 2015-09-03 축전 디바이스용 Si계 합금 음극 재료 및 이것을 사용한 전극
CN201580046199.4A CN106605322A (zh) 2014-09-16 2015-09-03 蓄电器件用Si系合金负极材料及使用其的电极

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-187238 2014-09-16
JP2014187238A JP6735060B2 (ja) 2014-09-16 2014-09-16 蓄電デバイス用Ｓｉ系合金負極材料およびそれを用いた電極

Publications (1)

Publication Number Publication Date
WO2016043061A1 true WO2016043061A1 (fr) 2016-03-24

Family

ID=55533101

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/075119 WO2016043061A1 (fr) 2014-09-16 2015-09-03 MATÉRIAU D'ÉLECTRODE NÉGATIVE EN ALLIAGE À BASE DE Si POUR DISPOSITIFS DE STOCKAGE D'ÉLECTRICITÉ ET ÉLECTRODE UTILISANT CELUI-CI

Country Status (5)

Country Link
JP (1) JP6735060B2 (fr)
KR (1) KR20170057235A (fr)
CN (1) CN106605322A (fr)
TW (1) TW201616707A (fr)
WO (1) WO2016043061A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017221693A1 (fr) * 2016-06-21 2017-12-28 山陽特殊製鋼株式会社 Matériau d'électrode négative pour dispositifs de stockage d'électricité

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6859930B2 (ja) * 2017-09-14 2021-04-14 株式会社豊田自動織機 Ａｌ含有シリコン材料
WO2019053984A1 (fr) * 2017-09-14 2019-03-21 株式会社豊田自動織機 Substance active d'électrode négative comprenant un matériau de silicium contenant de l'al
WO2019053983A1 (fr) * 2017-09-14 2019-03-21 株式会社豊田自動織機 Matériau actif d'électrode négative contenant un matériau de silicium contenant de l'aluminium
JP7119895B2 (ja) * 2018-10-24 2022-08-17 トヨタ自動車株式会社 負極活物質
KR102654226B1 (ko) 2023-05-08 2024-04-03 김경민 개선된 생산성을 가진 소방 배관 제조 시스템

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001297757A (ja) * 2000-04-14 2001-10-26 Sumitomo Metal Ind Ltd 非水電解質二次電池用負極材料およびその製造方法
JP2005071771A (ja) * 2003-08-22 2005-03-17 Samsung Sdi Co Ltd リチウム二次電池用負極活物質及びその製造方法並びにリチウム二次電池
JP2012150910A (ja) * 2011-01-17 2012-08-09 Sanyo Special Steel Co Ltd リチウムイオン二次電池負極用Ｓｉ合金粉末およびその製造方法
JP2012234788A (ja) * 2011-04-20 2012-11-29 Sanyo Special Steel Co Ltd Ｓｉ系合金負極材料
JP2013125743A (ja) * 2011-12-13 2013-06-24 Samsung Sdi Co Ltd 負極活物質及びそれを含む二次電池
JP2013191529A (ja) * 2012-02-16 2013-09-26 Hitachi Chemical Co Ltd 複合材料、複合材料の製造方法、リチウムイオン二次電池用電極材料、リチウムイオン二次電池用負極、及びリチウムイオン二次電池
JP2014038832A (ja) * 2012-07-20 2014-02-27 Sanyo Special Steel Co Ltd 蓄電デバイスの負極材料

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6322362B2 (ja) * 2012-02-01 2018-05-09 山陽特殊製鋼株式会社 Ｓｉ系合金負極材料
JP6371504B2 (ja) * 2013-02-19 2018-08-08 山陽特殊製鋼株式会社 蓄電デバイス用Ｓｉ系合金負極材料およびそれを用いた電極

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001297757A (ja) * 2000-04-14 2001-10-26 Sumitomo Metal Ind Ltd 非水電解質二次電池用負極材料およびその製造方法
JP2005071771A (ja) * 2003-08-22 2005-03-17 Samsung Sdi Co Ltd リチウム二次電池用負極活物質及びその製造方法並びにリチウム二次電池
JP2012150910A (ja) * 2011-01-17 2012-08-09 Sanyo Special Steel Co Ltd リチウムイオン二次電池負極用Ｓｉ合金粉末およびその製造方法
JP2012234788A (ja) * 2011-04-20 2012-11-29 Sanyo Special Steel Co Ltd Ｓｉ系合金負極材料
JP2013125743A (ja) * 2011-12-13 2013-06-24 Samsung Sdi Co Ltd 負極活物質及びそれを含む二次電池
JP2013191529A (ja) * 2012-02-16 2013-09-26 Hitachi Chemical Co Ltd 複合材料、複合材料の製造方法、リチウムイオン二次電池用電極材料、リチウムイオン二次電池用負極、及びリチウムイオン二次電池
JP2014038832A (ja) * 2012-07-20 2014-02-27 Sanyo Special Steel Co Ltd 蓄電デバイスの負極材料

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017221693A1 (fr) * 2016-06-21 2017-12-28 山陽特殊製鋼株式会社 Matériau d'électrode négative pour dispositifs de stockage d'électricité
JP2017228403A (ja) * 2016-06-21 2017-12-28 山陽特殊製鋼株式会社 蓄電デバイス用負極材料
CN108701821A (zh) * 2016-06-21 2018-10-23 山阳特殊制钢株式会社 蓄电器件用负极材料

Also Published As

Publication number Publication date
JP6735060B2 (ja) 2020-08-05
KR20170057235A (ko) 2017-05-24
TW201616707A (zh) 2016-05-01
JP2016062660A (ja) 2016-04-25
CN106605322A (zh) 2017-04-26

Similar Documents

Publication Publication Date Title
JP6322362B2 (ja) Ｓｉ系合金負極材料
JP6371504B2 (ja) 蓄電デバイス用Ｓｉ系合金負極材料およびそれを用いた電極
JP6374678B2 (ja) 蓄電デバイスの負極材料
WO2012144424A1 (fr) MATIÈRE D'ÉLECTRODE NÉGATIVE EN ALLIAGE À BASE DE Si
TWI569497B (zh) 鋰離子電池用之負極活性材料及使用該材料之鋰離子電池用之負極
WO2016043061A1 (fr) MATÉRIAU D'ÉLECTRODE NÉGATIVE EN ALLIAGE À BASE DE Si POUR DISPOSITIFS DE STOCKAGE D'ÉLECTRICITÉ ET ÉLECTRODE UTILISANT CELUI-CI
JP4739462B1 (ja) 導電性に優れるＳｉ系合金負極材料
JP2007149604A (ja) リチウム二次電池用負極及びリチウム二次電池
JP6076772B2 (ja) 蓄電デバイス用Ｓｉ系合金負極材料およびそれを用いた電極
WO2012008540A1 (fr) Matériau d'électrode négative en alliage de si présentant une excellente conductivité électrique, et procédé de fabrication de celui-ci
JP2017224499A (ja) リチウムイオン電池用負極活物質およびリチウムイオン電池
JP2004235057A (ja) リチウム二次電池用負極及びリチウム二次電池
JP2009193686A (ja) 非水系電解質二次電池用正極活物質とその製造方法
JP6371635B2 (ja) 蓄電デバイス用Ｓｉ系合金負極材料およびそれを用いた電極
JP4763970B2 (ja) 非水電解質二次電池用負極材料、非水電解質二次電池用負極及び非水電解質二次電池
JPWO2013168786A1 (ja) リチウムイオン二次電池用負極
JP6245954B2 (ja) リチウムイオン二次電池用負極活物質
JP4703110B2 (ja) 非水電解質二次電池用負極材料、非水電解質二次電池用負極及び非水電解質二次電池
JP6630632B2 (ja) 蓄電デバイス用負極材料
WO2018193864A1 (fr) Matériau d'électrode négative pour dispositif de stockage d'énergie
JP6045879B2 (ja) リチウムイオン二次電池の負極活物質の原料として用いるＳｎ合金粉末およびその製造方法。
JP2006155903A (ja) 非水電解質電池用負極材料、負極、およびそれを用いた非水電解質電池
JP2008270130A (ja) 非水電解質電池用負極材料およびそれを用いた負極並びに非水電解質電池

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: 15841850

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20177004242

Country of ref document: KR

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: 15841850

Country of ref document: EP

Kind code of ref document: A1