WO2007015508A1 - Alliage pour une électrode négative de batterie secondaire au lithium - Google Patents

Alliage pour une électrode négative de batterie secondaire au lithium Download PDF

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Publication number
WO2007015508A1
WO2007015508A1 PCT/JP2006/315281 JP2006315281W WO2007015508A1 WO 2007015508 A1 WO2007015508 A1 WO 2007015508A1 JP 2006315281 W JP2006315281 W JP 2006315281W WO 2007015508 A1 WO2007015508 A1 WO 2007015508A1
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WIPO (PCT)
Prior art keywords
phase
alloy
negative electrode
secondary battery
lithium secondary
Prior art date
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PCT/JP2006/315281
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English (en)
Japanese (ja)
Inventor
Kenichiro Nakajima
Masataka Takeuchi
Original Assignee
Showa Denko K.K.
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Publication date
Application filed by Showa Denko K.K. filed Critical Showa Denko K.K.
Priority to JP2007529504A priority Critical patent/JPWO2007015508A1/ja
Priority to CN2006800282942A priority patent/CN101233632B/zh
Publication of WO2007015508A1 publication Critical patent/WO2007015508A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 lithium secondary battery negative electrode alloy having a large charge / discharge capacity and excellent cycle characteristics, a method for producing a lithium storage alloy, and a lithium secondary battery using the alloy.
  • Lithium secondary batteries are frequently used in portable electronic devices and the like as high-tech energy density batteries. In order to extend the driving time of this portable electronic device, power saving of elements and the like is being promoted. However, multifunctionalization is progressing at a pace exceeding power saving, power consumption is increasing, and it is becoming difficult to sufficiently lengthen the driving time.
  • Carbon is usually used as a negative electrode material for lithium secondary batteries. However, carbon cannot theoretically occlude more Li than the composition of LiC, and its theoretical capacity is 372
  • Si, Al, Sn, Ge, Sb, etc. have been studied as elements having a large theoretical capacity!
  • Si has a theoretical capacity of 200 mAhZg, and is expected to surpass 3900 mAhZg of metallic lithium, which is attractive for reducing the size and capacity of batteries.
  • Patent Document 1 discloses a negative electrode material having a structure mainly composed of a Li storage phase oc (eg, coexistence of S ⁇ and Sn phase) and an intermetallic compound or a phase ⁇ also having a solid solution force. Yes. This negative electrode material is assembled so that 13 becomes the primary crystal upon solidification, and then ⁇ and j8 precipitate as eutectic. The melt of the raw material selected for composition is rapidly solidified by the atomization method, roll quenching method, etc. It is described that it is obtained by The alloy shown as an example of actual manufacture has a thickness of 20 ⁇ m and an alloy structure with a size of several nm. Patent Document 1: JP 2001-297757 A
  • Patent Document 2 includes a layer containing Sn as a constituent element and MA (note that MA is La, Ce, Pr, Nd, Mg, Si, Ca, Ga, Y, Zr, Nb, Ag, In) And a negative electrode including an alloy having a unit cell made of a composite layered structure having a layer including a layer including a constituent element as a constituent element selected from the group consisting of Hf and Pb.
  • This alloy is described as being obtained by cooling at a rate of 100 ° CZ seconds to 2000 ° CZ seconds, preferably 300 ° CZ seconds to 1300 ° CZ seconds, by a strip casting method.
  • the thickness of the resulting alloy is 10 ⁇ m or more and 50 ⁇ m or less.
  • Patent Document 2 Japanese Patent Laid-Open No. 2006-120324
  • Patent Document 3 includes a mixture of particles containing a carbon atom capable of inserting and desorbing lithium ions or a compound containing Z and tin atoms, and a vapor grown carbon fiber.
  • a negative electrode material has been proposed. This negative electrode material is an attempt to relieve the volume expansion of the particles by a composite with fibrous carbon.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-178922
  • Patent Document 4 there is a solid solution force formed in a non-equilibrium state between an element A alloying with an alkali metal or alkaline earth metal and an element B not alloying with an alkali metal or alkaline earth metal. It describes battery active materials that occlude and release alkali metals or alkaline earth metals.
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-075350
  • Patent Document 5 discloses a negative electrode material made of Si alloy powder containing Si and one or more of Cu, Ni and Co as constituent elements.
  • This Si alloy powder is synthesized by a single roll method or an atomizing method, and includes an intermetallic compound phase containing Si and at least one of the group consisting of Cu, Ni and Co as constituent elements.
  • S It is described that it has a eutectic phase including a phase i and a primary crystal phase of Si dispersed in the eutectic phase.
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-362895
  • An object of the present invention is to provide a lithium secondary battery negative electrode alloy having a large charge / discharge capacity and excellent cycle characteristics, a method for producing a lithium storage alloy, and a lithium secondary battery.
  • phase A containing as a main component and Phase B containing another element as a main component capable of occluding and releasing Li element, and the larger one of the above phases, phase A is a specific size
  • an alloy having a thickness is used as a negative electrode material for a lithium secondary battery, a large volume change does not occur, the generation of fine powder is almost eliminated, and a lithium secondary battery having a large charge / discharge capacity and excellent cycle characteristics can be obtained. I found out.
  • the present invention has been completed as a result of further studies based on this finding.
  • the present invention includes the following.
  • phase A containing an element capable of occluding and releasing Li element as a main constituent
  • phase B containing another element capable of occluding and releasing a Li element as a main constituent.
  • An alloy for negative electrodes of lithium secondary batteries in which the larger phase A of the above phases is 0.05 m to 20 m.
  • the mass ratio of the main constituent element of phase A to the main constituent element of phase B is 20/80
  • At least one of the phase containing Si element as the main constituent or the phase containing Sn element as the main constituent constitutes the dispersed phase and the other phase constitutes the continuous phase (5
  • Group force including B, C, N, 0, S, and P forces Further including at least one element selected from (4) to (8) For a lithium secondary battery negative electrode according to any one of (4) to (8) alloy.
  • a metal material containing a Sn element and a metal material containing a Si element are melted to obtain a molten metal, and the molten metal is obtained by a strip casting method for more than 2 ⁇ 10 3 ° CZ seconds and 10 4 ° CZ.
  • a method for producing a lithium storage alloy comprising a step of cooling and solidifying at a rate of seconds or less.
  • Average particle size (d50) The method according to any one of (12) to (19), further comprising a step of grinding and Z or classification so as to be within a range of 0.1 ⁇ to 50 / ⁇ m. Manufacturing method of lithium storage alloy.
  • boundary values X and y are included. “Less than ⁇ ” and “greater than y” indicate that the boundary values X and y are not included.
  • the boundary values X and y in the range indicated by “x to y” are included in the range.
  • the invention's effect [0019]
  • the lithium secondary battery negative electrode alloy of the present invention does not cause a large volume change even when lithium ions are occluded and Z or released, and hardly generates fine powder.
  • the powder of the lithium secondary battery negative electrode alloy of the present invention as a negative electrode material for a lithium secondary battery, a lithium secondary battery excellent in charge / discharge characteristics and cycle characteristics can be obtained.
  • FIG. 1 is a diagram showing an example of a cross-sectional structure of an alloy according to the present invention.
  • FIG. 2 is an enlarged view of FIG.
  • FIG. 3 is a top view schematically showing an example of a single roll rapid solidification method (strip casting method).
  • FIG. 4 is a side view of the apparatus shown in FIG.
  • FIG. 5 is a perspective view of the apparatus shown in FIG. 3.
  • the lithium secondary battery negative electrode alloy of the present invention is composed mainly of phase A containing an element capable of occluding and releasing Li element as a main component and another element capable of occluding and releasing Li element.
  • Phase B included as a component, and the larger phase A of the above phases has a size of 0.05 m to 20 ⁇ m.
  • Li occluding element An element capable of occluding and releasing Li element (hereinafter simply referred to as "Li occluding element”) is there. ) Include, for example, Sn, Si, Ge, Pb, Al, In and the like.
  • the present invention is characterized by having at least two phases containing this Li storage element as a main constituent.
  • a phase containing Si element as a main constituent a phase containing Sn element as a main constituent, a phase containing Si element as a main constituent, a phase containing A1 element as a main constituent, and a Si element as a main constituent
  • a phase containing Ge and a phase containing Ge As a main constituent.
  • a combination of a phase containing Si element as a main constituent and a phase containing Sn element as a main constituent is particularly suitable. That is, a lithium secondary battery negative alloy preferable in the present invention has a phase containing Si element as a main constituent and a phase containing Sn element as a main constituent, and the larger phase of the above phases.
  • A has a size of 0.05 m to 20 m.
  • Li When Li is occluded into an element that has the ability to occlude and release Li, it is represented by the chemical formula LiM (where M is the Li occlusion element) o X is The force that depends on the amount of Li stored In the present invention, when the maximum amount of Li is stored, X is greater than 0.01, more than 6 / J, and preferably less than 0.9 to 4.1. More preferably, it is more preferably a force of 0.24-0.5 1! / ,.
  • the alloy for the negative electrode of the lithium secondary battery is preferably one in which either phase A or phase B forms a dispersed phase and the other phase forms a continuous phase.
  • FIG. 1 and FIG. 2 show an example of an electron micrograph image of a flake of the alloy of the present invention having a phase A containing Si element as a main constituent and a phase B containing Sn element as a main constituent.
  • the central part in Fig. 1 and the right half in Fig. 2 are images of slice C.
  • the white part is phase B and the gray part is phase A.
  • the left end of the flake C shown in Fig. 1 and Fig. 2 is the solidified surface 6 formed by contact with the roll described later, and the right end of the flake shown in Fig. 1 is the free side on the opposite side of the roll contact surface Surface 9 is.
  • the lithium secondary battery negative electrode alloy of the present invention has a network, dendritic or marbling state around phase A (gray part) and phase B (white part).
  • the expanded phase structure has the relationship of phase A size> phase size.
  • the size of the larger phase A is 0.05 ⁇ m to 20 ⁇ m, preferably 0.2 ⁇ m to 8 m, more preferably 0.5 ⁇ m to 8 ⁇ m, particularly preferably 0. 8 ⁇ m to 2 ⁇ m. Big When the size of phase A is in this range, a lithium secondary battery having stable charge / discharge characteristics can be obtained.
  • phase A is larger in the electron micrograph of the alloy flakes as shown in Fig. 1 by dividing the line parallel to both sides of the flakes with 1Z4, 1/2, and Each of them is drawn at a position corresponding to 3Z4, and the number of phases B with the smaller size intersecting the line segment is obtained.
  • the length of the line segment is divided by the number of phase B, and the thickness of the flake is 1Z4, 1 It was expressed as the average value of the calculated values at positions corresponding to / 2, and 3Z4.
  • phase A is often included in a shape that is short in the direction parallel to the roll surface that is long in the thickness direction of the thin piece.
  • Phase A has a minor axis diameter of preferably 0.05 to 20 ⁇ m and a major axis diameter of preferably 0.05 to 300 ⁇ m.
  • minor axis diameter preferably 1 to 6 000, and more preferably 1 to 30.
  • the minor axis diameter of phase B is usually smaller than the minor axis diameter of phase A.
  • the mass ratio of the main constituent element of phase A to the main constituent element of phase B is not particularly limited. Preferably, it is 20 or 80 to 80/20, more preferably 30/70 ⁇ 70/30
  • the lithium secondary battery negative electrode alloy of the present invention may contain other elements in addition to an element capable of occluding and releasing Li elements.
  • Preferred elements that may be included include Ti, V, Co, Ni, Cu, Mo, Ru, Rh, Pd, Pt, Be, Nd, W, Au, Ag, Ga, etc. 1 type or 2 types or more may be contained. These elements are considered to play a role of connecting Phase A and Phase B described above.
  • elements that are inevitably included in the alloy manufacturing process may be included in the lithium secondary battery negative electrode alloy of the present invention.
  • examples include B, C, N, 0, S, P, and Al.
  • Al is used as the Li storage element, the A1 element is not included in the unavoidable element.
  • Al is used as the Li storage element, the Al element is included in the unavoidable element.
  • the lithium secondary battery negative electrode alloy of the present invention other elements than the element capable of occluding and releasing Li elements, that is, Ti, V, Co, Ni, Cu, Mo, Ru, Rh, Pd, At least one element selected from the group consisting of Pt, Be, Nd, W, Au, Ag, and Ga, and at least one element selected from the group force that also includes B, C, N, 0, S, and P forces.
  • the total amount is preferably 0.1% by mass or more and less than 35% by mass, more preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass. It is particularly preferred that it is less than or equal to%.
  • the lithium secondary battery negative electrode alloy of the present invention has an average particle size (d50) in order to increase the contact area with lithium ions to an appropriate size and to facilitate the formation of a negative electrode.
  • 0.1 m to 50 ⁇ m is preferable 1 m to: LO / zm is more preferable.
  • the average particle size (d50) is a 50% cumulative particle size in a volume-based particle size distribution. The average particle size can be measured with a laser diffraction particle size distribution analyzer.
  • the lithium secondary battery negative electrode alloy of the present invention is not particularly limited as long as it is a production method capable of forming the above phase structure. Alloy fabrication methods include strip casting with a single roll, ribbon production by ultra-quenching, centrifugal casting with molten metal droplets attached to the mold, rotating electrode method, water atomization method, gas atomization method, etc. Can be mentioned. However, according to previous studies by the present inventors, it has been found that an alloy for a lithium secondary battery negative electrode having the phase structure defined in the present invention can be obtained by the production method described below.
  • a method for producing a lithium storage alloy (lithium secondary battery negative electrode alloy) according to the present invention comprises obtaining a molten metal by melting two or more metal materials containing an element capable of inserting and extracting Li element, and stripping the molten metal. It includes a step of cooling and solidifying by a casting method at a rate exceeding 2 X 10 3 ° CZ seconds and not exceeding 10 4 ° CZ seconds.
  • the molten metal preparation step is an alloy raw material, that is, the above-mentioned Li storage element, for example, an element selected from the group consisting of Sn, Si, Ge, Pb, Al and In, preferably two metal materials containing Si element and Sn element.
  • the molten metal that contains two or more metallic materials containing Li storage elements contains Element, for example, Ti, V, Co, Ni, Cu, Mo, Ru, Rh, Pd, Pt, Be, Nd, W, Au, Ag, and Ga , C, N, 0, S and at least one element selected from the group force consisting of P and P may be melted.
  • Element for example, Ti, V, Co, Ni, Cu, Mo, Ru, Rh, Pd, Pt, Be, Nd, W, Au, Ag, and Ga , C, N, 0, S and at least one element selected from the group force consisting of P and P may be melted.
  • metal materials may be mixed in advance and melted in the melt, or one metal material may be melted and another metal material may be poured into the melt to melt.
  • the ratio of the Li storage element is not particularly limited, but the mass specific force between the main constituent element of phase A and the main constituent element of phase B is preferably 20 / 80-80 / 20, more preferably Is used at a rate of 30/70 to 70Z30.
  • the ratio of elements other than Li storage elements is preferably 0.1% by mass or more and less than 35% by mass of the whole alloy, more preferably 0.1% by mass or more and 10% by mass or less. It is particularly preferably 0.5% by mass or more and 5% by mass or less.
  • the metal material is melted by heating to a temperature equal to or higher than the melting point.
  • the heating temperature is usually 1200 ° C to 1800 ° C.
  • the inert gas include Ar and He.
  • Heating reduces impurities in the metal material, such as metal oxides, and increases the purity of the alloy. Therefore, if the heating temperature is too low, the above-described reduction reaction may not proceed sufficiently and the purity of the alloy may be lowered. On the other hand, if the heating temperature is too high, the amount of evaporation of the metal element increases, making it difficult to adjust to the desired composition.
  • the solidification step is a step in which the molten metal obtained in the previous molten metal preparation step is rapidly solidified to produce an alloy.
  • the rapid solidification method include a strip casting method, a new centrifugal forging method using a tundish that also has a rotating disk force, a centrifugal forging method, and the like, but the strip casting method is used in the production method of the present invention.
  • the cooling rate in the solidification step is at least 2 X 10 3 ° C / sec and at most 10 4 ° C / sec, preferably at least 3 X in the range from the temperature of the molten metal to 600 ° C. 10 3 ° C / second to 10 4 ° CZ second, more preferably 3 X 10 3 ° CZ second to 8 X 10 3 ° CZ second.
  • phase A By adjusting to such a cooling rate, it is possible to control the magnitude of the aforementioned phase A. it can. If the cooling rate is too slow, the size of phase A will be greater than 20 / zm. If the cooling rate is too fast, the size of phase A will be too small.
  • FIGS. 3 to 5 are diagrams for explaining the strip casting method
  • FIG. 3 is a top view of an example of an apparatus used for the strip casting method
  • FIG. 4 is a side view of the example of the apparatus shown in FIG.
  • FIG. 5 is a perspective view of the apparatus example shown in FIG.
  • the apparatus shown in the figure includes a crucible 1, a tundish 2, a cooling roll 3, and a collection container 4.
  • the alloy raw material is melted in the crucible 1 and a molten metal 5 is generated.
  • the generated molten metal 5 is poured through a tundish 2 onto a cylindrical cooling roll 3 that rotates in a predetermined direction (counterclockwise direction in the drawing).
  • the tundish 2 is a device including a rectifying mechanism and a slag removing mechanism.
  • the cooling roll 3 is a roll cooled by water cooling or the like.
  • the molten metal 5 in contact with the roll is rapidly solidified to produce an alloy.
  • the cooling speed of the molten metal 5 can be controlled by the peripheral speed of the cooling roll 3, the amount of molten metal poured onto the cooling roll 3, and the like.
  • the chill roll is usually made of a material that has good thermal conductivity and is easily available, such as copper or a copper alloy. Depending on the material of the cooling hole 3 and its surface condition, metal tends to adhere to the surface, so a cleaning device is installed if necessary.
  • the molten metal is preferably poured out from the slit-shaped mouth (rectifying mechanism) of the tundish 2 in a strip shape and brought into contact with the cooling roll.
  • the strip-shaped alloy flakes C are easily formed.
  • the produced alloy is peeled off from the cooling roll 3 by centrifugal force, jumps out in the direction of the arrow 8, becomes a flake C, and is collected in the collection container 4.
  • the thickness of the alloy flake C solidified material
  • the flakes C recovered in the recovery container 4 are taken out after being cooled to room temperature in the same container.
  • a cooling mechanism, a heat insulation mechanism, or the like in the recovery container 4 to control the cooling rate of the alloy flakes C in the container.
  • the particle size of the alloy is adjusted.
  • the particle size can be adjusted by a known pulverization method and / or classification method without particular limitation depending on the method.
  • the pulverizing means include a hammer mill, a jaw crusher, a collision type pulverizer, a ball mill, an attritor, and a jet mill.
  • the jet mill can be pulverized by colliding with the alloy itself coarsely pulverized with high-pressure nitrogen or high-pressure argon, so it can produce fine powder with very little contamination and high purity.
  • the structure is preferable because a powder with less acidity on the powder surface can be produced.
  • a composite of the alloy and carbon can be obtained by adding a carbon material such as graphite powder or carbon fiber.
  • This composite is suitable as a negative electrode material.
  • the classification method include an airflow classification method and a sieving method.
  • the alloy powder may oxidize and burn if left in air. Therefore, it is preferable to store the alloy powder in ethylene carbonate or propylene carbonate for safe storage.
  • the lithium secondary battery of the present invention uses the above-mentioned alloy for negative electrodes of lithium secondary batteries.
  • the lithium storage alloy powder is used as an active material for a negative electrode of a lithium secondary battery.
  • the lithium storage alloy powder preferably has an average particle size (d50) in the range of 0.1 / ⁇ ⁇ to 50 / ⁇ ⁇ , and an average particle size in the range of l to 10 / zm. Is more preferable, especially about 1 to 5 ⁇ m.
  • the negative electrode of a lithium secondary battery is usually obtained by laminating an active material and a conductive material on a current collector with a binder.
  • binder examples include polyvinylidene fluoride, polytetrafluoroethylene, and styrene butadiene.
  • a solvent such as N-methylpyrrolidone, xylene, or water, and is suitable for mixing with active materials.
  • the conductive material a carbon-based conductive aid is usually used.
  • the current collector is a foil, a punching metal, a net, or the like made of a known material such as copper, aluminum, stainless steel, nickel, or an alloy thereof. It is also possible to use a surface roughened by etching or the like.
  • a known method can be employed. For example, there is a method of kneading the lithium storage alloy, a conductive material, and a binder, preparing a slurry-like coating agent, applying the coating agent to a current collector, drying, and pressing.
  • Examples of means for kneading the alloy, the conductive material, and the binder include a ribbon mixer, a screw-type mixer, a planetary mixer, and a universal mixer.
  • Examples of means for applying the coating agent to the current collector include a doctor blade and a bar coater.
  • a roll press machine or the like is usually used for press force after coating.
  • a lithium secondary battery is obtained by placing the above-described negative electrode and positive electrode in a container containing an electrolyte so as to face each other with a separator interposed therebetween and sealing.
  • the positive electrode, separator, and electrolyte used in the lithium secondary battery of the present invention may be those normally used in lithium secondary batteries.
  • Examples of the positive electrode include those formed of lithium cobaltate, lithium nickelate, lithium manganate, and complex oxides or mixtures thereof.
  • Examples of the separator include a microporous film nonwoven fabric made of polyethylene or polypropylene.
  • electrolyte examples include known Li salts such as LiPF, LiBF, and Liimide salt. Electrolyte
  • the solvent for dissolving the electrolyte include known solvents such as jetyl carbonate, ethylene carbonate, and propylene carbonate.
  • the dissolution concentration of the electrolyte is not particularly limited, and is usually about 1 mol Z liter.
  • the alloy flakes were wet crushed with isopropanol using an attritor to obtain an alloy powder having an average particle size of 1.3 m.
  • the negative electrode material was punched into a disk shape having a diameter of 18 mm, pressed between super steel press plates, and dried again with a vacuum dryer at 120 ° C. for 12 hours to obtain a negative electrode.
  • a metal lithium foil was punched into a disk shape having a diameter of 18 mm to obtain a positive electrode.
  • a separator was obtained by punching a polypropylene microporous film into a disk with a diameter of 19 mm. It was.
  • a lithium secondary battery for charging was obtained.
  • a constant current charge was performed from the rest potential to 0.002 V, a current density of 0.2 mAZcm 2 , and then a constant voltage charge until the current value dropped to 25 A. Then, constant voltage discharge was performed at 0.2 mA / cm 2 and cut off at 1.5 V. This operation was one cycle, and a total of 50 cycles were performed.
  • Table 1 shows the capacity retention and capacity retention rate for one cycle at 50 cycles.
  • the obtained alloy lump was pulverized with an alumina mortar and subjected to X-ray diffraction measurement. Diffraction peaks corresponding to Sn metal and Si metal were observed. In addition, when the cross-section of the alloy was observed with a scanning electron microscope (Hitachi S-530), the structure of the alloy was observed using a backscattered electron image. Admitted. The larger phase A is 55 ⁇ m in size.
  • the alloy lump was wet pulverized with isopropanol using an attritor to obtain an alloy powder having an average particle size of 1.5 ⁇ m.
  • This comparative example was repeated three times.
  • the size of the phase A mainly containing Si element of the alloy obtained in the comparative example, the value of X, and the lithium secondary battery for evaluation obtained using the alloy in one cycle The capacity, the capacity at 50 cycles, and the capacity retention for one cycle at 50 cycles were determined in the same manner as in the example. The results are shown in Table 1.

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Abstract

Selon l'invention, on obtient une fonte en faisant fondre deux ou plusieurs matériaux métalliques comprenant un élément, tel que Si et Sn, pouvant absorber et désorber l'élément Li, ainsi qu'un autre matériau métallique comprenant Cu et analogue. La fonte ainsi obtenue est refroidie et solidifiée à une vitesse supérieure à 2 × 103 °C/s et n’étant pas supérieure à 104 °C/s par coulage de bandes, puis pulvérisée et classée, obtenant ainsi une poudre d'alliage ayant une taille granulaire moyenne de 0,1 à 50 µm. Une électrode négative destinée à des batteries secondaires est obtenue en disposant cette poudre d'alliage et un matériau conducteur sur un collecteur ayant la forme d'une couche en utilisant un liant. En utilisant une telle électrode négative, on peut obtenir une batterie secondaire au lithium ayant une capacité élevée de charge/décharge et d'excellentes caractéristiques de cycle.
PCT/JP2006/315281 2005-08-02 2006-08-02 Alliage pour une électrode négative de batterie secondaire au lithium WO2007015508A1 (fr)

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Application Number Priority Date Filing Date Title
JP2007529504A JPWO2007015508A1 (ja) 2005-08-02 2006-08-02 リチウム二次電池負極用合金
CN2006800282942A CN101233632B (zh) 2005-08-02 2006-08-02 用于锂二次电池负极的合金

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JP2005223759 2005-08-02
JP2005-223759 2005-08-02
US70555305P 2005-08-05 2005-08-05
US60/705,553 2005-08-05

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Cited By (15)

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JP2009187765A (ja) * 2008-02-06 2009-08-20 Tottori Univ リチウムイオン二次電池用合金負極、その製造方法及びそれを用いたリチウムイオン二次電池
WO2012063762A1 (fr) * 2010-11-08 2012-05-18 古河電気工業株式会社 Nanoparticules utilisées dans une électrode négative pour batterie secondaire au lithium-ion et procédé de fabrication s'y rapportant
JP2012102354A (ja) * 2010-11-08 2012-05-31 Furukawa Electric Co Ltd:The ナノサイズ粒子、ナノサイズ粒子を含むリチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極、リチウムイオン二次電池、ナノサイズ粒子の製造方法
JP2012101301A (ja) * 2010-11-08 2012-05-31 Furukawa Electric Co Ltd:The ナノサイズ粒子、ナノサイズ粒子を含むリチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極、リチウムイオン二次電池、ナノサイズ粒子の製造方法
JP2012101958A (ja) * 2010-11-08 2012-05-31 Furukawa Electric Co Ltd:The ナノサイズ粒子、ナノサイズ粒子を含むリチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極、リチウムイオン二次電池、ナノサイズ粒子の製造方法
WO2012160858A1 (fr) * 2011-05-25 2012-11-29 日産自動車株式会社 Matériau actif d'électrode négative pour dispositifs électriques
JP2013134906A (ja) * 2011-12-27 2013-07-08 Nissan Motor Co Ltd 電気デバイス用負極活物質
JP2015524988A (ja) * 2012-11-30 2015-08-27 エルジー・ケム・リミテッド リチウム二次電池用負極活物質及びそれを含むリチウム二次電池
JP2016183068A (ja) * 2015-03-26 2016-10-20 山陽特殊製鋼株式会社 フィラー用粉末
WO2017213147A1 (fr) * 2016-06-10 2017-12-14 新日鐵住金株式会社 Matériau de substance active de borne négative, borne négative, et batterie
US10290855B2 (en) 2012-11-22 2019-05-14 Nissan Motor Co., Ltd. Negative electrode for electrical device, and electrical device using the same
CN110085851A (zh) * 2019-05-20 2019-08-02 拓米(成都)应用技术研究院有限公司 一种锂电池含硅锡合金负极材料及其制备方法
US10476101B2 (en) 2014-01-24 2019-11-12 Nissan Motor Co., Ltd. Electrical device
US10535870B2 (en) 2014-01-24 2020-01-14 Nissan Motor Co., Ltd. Electrical device
US10566608B2 (en) 2012-11-22 2020-02-18 Nissan Motor Co., Ltd. Negative electrode for electric device and electric device using the same

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JP2001093524A (ja) * 1999-09-24 2001-04-06 Matsushita Electric Ind Co Ltd 非水電解質二次電池用負極活物質、その製造法および非水電解質二次電池
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009187765A (ja) * 2008-02-06 2009-08-20 Tottori Univ リチウムイオン二次電池用合金負極、その製造方法及びそれを用いたリチウムイオン二次電池
WO2012063762A1 (fr) * 2010-11-08 2012-05-18 古河電気工業株式会社 Nanoparticules utilisées dans une électrode négative pour batterie secondaire au lithium-ion et procédé de fabrication s'y rapportant
JP2012102354A (ja) * 2010-11-08 2012-05-31 Furukawa Electric Co Ltd:The ナノサイズ粒子、ナノサイズ粒子を含むリチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極、リチウムイオン二次電池、ナノサイズ粒子の製造方法
JP2012101301A (ja) * 2010-11-08 2012-05-31 Furukawa Electric Co Ltd:The ナノサイズ粒子、ナノサイズ粒子を含むリチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極、リチウムイオン二次電池、ナノサイズ粒子の製造方法
JP2012101958A (ja) * 2010-11-08 2012-05-31 Furukawa Electric Co Ltd:The ナノサイズ粒子、ナノサイズ粒子を含むリチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極、リチウムイオン二次電池、ナノサイズ粒子の製造方法
RU2540321C1 (ru) * 2011-05-25 2015-02-10 Ниссан Мотор Ко., Лтд. Активный материал отрицательного электрода для электрического устройства
WO2012160858A1 (fr) * 2011-05-25 2012-11-29 日産自動車株式会社 Matériau actif d'électrode négative pour dispositifs électriques
JP2012248286A (ja) * 2011-05-25 2012-12-13 Nissan Motor Co Ltd 電気デバイス用負極活物質
US10367198B2 (en) 2011-05-25 2019-07-30 Nissan Motor Co., Ltd. Negative electrode active material for electric device
JP2013134906A (ja) * 2011-12-27 2013-07-08 Nissan Motor Co Ltd 電気デバイス用負極活物質
US10566608B2 (en) 2012-11-22 2020-02-18 Nissan Motor Co., Ltd. Negative electrode for electric device and electric device using the same
US10290855B2 (en) 2012-11-22 2019-05-14 Nissan Motor Co., Ltd. Negative electrode for electrical device, and electrical device using the same
JP2015524988A (ja) * 2012-11-30 2015-08-27 エルジー・ケム・リミテッド リチウム二次電池用負極活物質及びそれを含むリチウム二次電池
US10476101B2 (en) 2014-01-24 2019-11-12 Nissan Motor Co., Ltd. Electrical device
US10535870B2 (en) 2014-01-24 2020-01-14 Nissan Motor Co., Ltd. Electrical device
JP2016183068A (ja) * 2015-03-26 2016-10-20 山陽特殊製鋼株式会社 フィラー用粉末
JPWO2017213147A1 (ja) * 2016-06-10 2019-04-18 新日鐵住金株式会社 負極活物質材料、負極及び電池
WO2017213147A1 (fr) * 2016-06-10 2017-12-14 新日鐵住金株式会社 Matériau de substance active de borne négative, borne négative, et batterie
CN110085851A (zh) * 2019-05-20 2019-08-02 拓米(成都)应用技术研究院有限公司 一种锂电池含硅锡合金负极材料及其制备方法

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