WO2019053984A1 - Substance active d'électrode négative comprenant un matériau de silicium contenant de l'al - Google Patents

Substance active d'électrode négative comprenant un matériau de silicium contenant de l'al Download PDF

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WO2019053984A1
WO2019053984A1 PCT/JP2018/023077 JP2018023077W WO2019053984A1 WO 2019053984 A1 WO2019053984 A1 WO 2019053984A1 JP 2018023077 W JP2018023077 W JP 2018023077W WO 2019053984 A1 WO2019053984 A1 WO 2019053984A1
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negative electrode
containing silicon
silicon material
electrode active
active material
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PCT/JP2018/023077
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English (en)
Japanese (ja)
Inventor
有貴 前原
隆弘 杉岡
敬史 毛利
真平 宗
泰弘 山口
正則 原田
石川　英明
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株式会社豊田自動織機
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Priority claimed from JP2018023383A external-priority patent/JP6852689B2/ja
Application filed by 株式会社豊田自動織機 filed Critical 株式会社豊田自動織機
Publication of WO2019053984A1 publication Critical patent/WO2019053984A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/06—Metal silicides
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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 containing an Al-containing silicon material.
  • silicon materials containing silicon as a main component are used as components of semiconductors, solar cells, secondary batteries and the like, and in recent years, research on silicon materials has been actively conducted.
  • Patent Document 1 and Patent Document 2 describe a lithium ion secondary battery in which the negative electrode active material is silicon.
  • Patent Document 3 and Patent Document 4 describe lithium ion secondary batteries in which the negative electrode active material is SiO.
  • Patent Document 5 describes that CaSi 2 is reacted with an acid to synthesize a layered polysilane, and it is described that a lithium ion secondary battery having the layered polysilane as a negative electrode active material exhibits a suitable capacity. It is done.
  • Patent Document 6 CaSi 2 is reacted with an acid to synthesize a layered polysilane, and the layered polysilane is heated at 300 ° C. or higher to produce a nanosilicon material from which hydrogen is released, and the nanosilicon material It is described that the lithium ion secondary battery which comprises as a negative electrode active material shows a suitable capacity
  • the inventor of the present invention has intensively examined trial and error repeatedly to provide a new silicon material. Since silicon itself is a semiconductor, when using a silicon material as a negative electrode active material of a secondary battery, the inventor considered that it is preferable to increase the conductivity of the silicon material by some method. Therefore, when a silicon material was manufactured by adding a small amount of Al, and the resistance of the secondary battery provided with the silicon material was measured, the resistance was low compared to the secondary battery provided with the Al-free silicon material. It turned out that it was resistance. The present inventors have completed the present invention based on such findings.
  • the negative electrode active material of the present invention is an Al-containing silicon material in which Al mass% (W Al %) satisfies 0 ⁇ W Al ⁇ 1 and Si mass% (W Si %) satisfies 60 ⁇ W Si ⁇ 90. It is characterized by including.
  • a suitable secondary battery By employing the negative electrode active material of the present invention, a suitable secondary battery can be provided.
  • the numerical range “x to y” described in the present specification includes the lower limit x and the upper limit y within the range. Then, the upper limit value and the lower limit value, and the numerical values listed in the examples can be combined arbitrarily to constitute a numerical range. Further, numerical values arbitrarily selected from within the numerical value range can be used as upper limit and lower limit numerical values.
  • an Al-containing silicon material (Al mass% (W Al %) satisfies 0 ⁇ W Al ⁇ 1 and Si mass% (W Si %) satisfies 60 ⁇ W Si ⁇ 90 (
  • the present invention is characterized by including the Al-containing silicon material of the present invention.
  • the Al-containing silicon material of the present invention can be said to be useful as a negative electrode active material for a low resistance secondary battery because the conductivity is improved due to the presence of Al.
  • a silicon material having too high an Al mass% is not preferable as a negative electrode active material.
  • W Al % preferably satisfies 0 ⁇ W Al ⁇ 0.8, preferably 0.01 ⁇ W Al ⁇ 0.8, and 0.05 ⁇ It is more preferable to satisfy W Al ⁇ 0.6, it is further preferable to satisfy 0.1 ⁇ W Al ⁇ 0.5, and it is particularly preferable to satisfy 0.15 ⁇ W Al ⁇ 0.5.
  • the negative electrode active material is a silicon material containing silicon
  • the silicon of the silicon material is oxidized by oxygen contained in the SEI film to be degraded.
  • the Al-containing silicon material of the present invention contains Al, it is considered that the oxidative deterioration of silicon is suppressed. The reason is that Al is considered to bind preferentially and stably to oxygen since it has lower electronegativity than silicon, and that Al-O bond of Al and oxygen is more stable than Si-O bond.
  • oxygen having a stable Al—O bond can be said to be less likely to be involved in the oxidation of silicon which is more electronegative than Al. Therefore, a secondary battery including the Al-containing silicon material of the present invention as a negative electrode active material can be expected to have a long life.
  • a silicon material means a material containing silicon as a main component.
  • the Si mass% (W Si %) in the Al-containing silicon material of the present invention preferably satisfies 70 ⁇ W Si ⁇ 85, and more preferably 80 ⁇ W Si ⁇ 85. If the Si mass% is too low, the capacity per unit mass of the Al-containing silicon material of the present invention will be low, so the capacity as a negative electrode active material may be insufficient. If the Si mass% is too high, the degree of expansion and contraction of the Al-containing silicon material of the present invention during charge and discharge becomes too large, and there is a concern that the Al-containing silicon material of the present invention may be broken.
  • Al-containing silicon material of the present invention may be present in the Al-containing silicon material of the present invention without departing from the spirit of the present invention.
  • Other elements include those derived from raw materials and production processes. Specific examples of other elements include Fe, O, Ca, C and halogen.
  • Fe wt% in Al-containing silicon material of the present invention is preferably satisfies 0 ⁇ W Fe ⁇ 3, more preferably satisfies 0 ⁇ W Fe ⁇ 1, 0 ⁇ W Fe ⁇ It is more preferable to satisfy 0.5, particularly preferably to satisfy 0 ⁇ W Fe ⁇ 0.3, and most preferably to satisfy 0 ⁇ W Fe ⁇ 0.1.
  • Fe mass% (W 2 Fe %) in the Al-containing silicon material of the present invention is 0 ⁇ W 2 Fe .
  • the relationship of Al mass% (W Al %) and Fe mass% (W Fe %) satisfies W Al > W Fe, and more preferably W Al > 2 ⁇ W Fe .
  • O wt% in Al-containing silicon material of the present invention (W O%) is preferably satisfies 5 ⁇ W O ⁇ 30, more preferably satisfies 10 ⁇ W O ⁇ 25, 12 ⁇ W O ⁇ It is further preferable to satisfy 22, and it is particularly preferable to satisfy 13 ⁇ W o ⁇ 21.
  • the Al-containing silicon material of the present invention contains a certain degree of oxygen, the life of a secondary battery including the Al-containing silicon material of the present invention as a negative electrode active material is extended.
  • Ca mass% in Al-containing silicon material of the present invention is preferably satisfies 0 ⁇ W Ca ⁇ 3, more preferably satisfies 0 ⁇ W Ca ⁇ 1, 0 ⁇ W Ca ⁇ It is further preferable to satisfy 0.5, and it is particularly preferable to satisfy 0 ⁇ W Ca ⁇ 0.3. In view of the ease of incorporation and removal of Ca , it is assumed that Ca mass% (W Ca %) in the Al-containing silicon material of the present invention is 0 ⁇ W Ca.
  • the halogen mass% (W x %) in the Al-containing silicon material of the present invention preferably satisfies 0 ⁇ W x ⁇ 3, more preferably 0 ⁇ W x ⁇ 2, and 0 ⁇ W x ⁇ It is more preferable to satisfy 1 and particularly preferable to satisfy 0 ⁇ W x ⁇ 0.5. In view of easiness of mixing and removal of halogen, it is assumed that the mass% (W x %) of halogen in the Al-containing silicon material of the present invention is 0 ⁇ W x .
  • the Al-containing silicon material of the present invention When the Al-containing silicon material of the present invention is described in terms of structure, it is preferable to have a structure in which a plurality of plate-like silicon bodies are stacked in the thickness direction.
  • the plate-like silicon body has a thickness for efficient insertion and desorption reaction of charge carriers such as lithium ions. Is preferably in the range of 10 nm to 100 nm, and more preferably in the range of 20 nm to 50 nm.
  • the length of the plate-like silicon body in the long axis direction is preferably in the range of 0.1 ⁇ m to 50 ⁇ m.
  • the plate-like silicon body preferably has a (longitudinal direction length) / (thickness) in the range of 2 to 1,000.
  • the Al-containing silicon material of the present invention preferably contains amorphous silicon or silicon crystallites.
  • the size of the silicon crystallite is preferably nano-sized.
  • the silicon crystallite size is preferably in the range of 0.5 nm to 300 nm, more preferably in the range of 1 nm to 100 nm, still more preferably in the range of 1 nm to 50 nm, particularly preferably in the range of 1 nm to 10 nm preferable.
  • X-ray diffraction measurement X-ray diffraction measurement
  • the Scheller equation using the half value width of the diffraction peak of the Si (111) plane of the obtained XRD chart Calculated from
  • the Al-containing silicon material of the present invention is preferably in the form of particles.
  • the average particle diameter of the Al-containing silicon material of the present invention is preferably in the range of 1 to 30 ⁇ m, more preferably in the range of 2 to 20 ⁇ m, and still more preferably in the range of 3 to 10 ⁇ m.
  • the average particle size when measured in conventional laser diffraction particle size distribution measuring apparatus, means D 50.
  • One aspect of a method of producing a negative electrode active material containing the Al-containing silicon material of the present invention is a) cooling the molten metal containing Ca, Al and Si to solidify it; b) reacting the solid with an acid to obtain a precursor of an Al-containing silicon material, c) heating the precursor at 300 ° C. or higher, It is characterized by including.
  • the above manufacturing method is suitable for manufacturing the Al-containing silicon material of the present invention having a structure in which a plurality of plate-like silicon bodies are stacked in the thickness direction.
  • An example of the chemical change in the steps a), b) and c) of the above-mentioned production method is as follows, which is represented by an ideal reaction equation ignoring Al. a) Process: Ca + 2 Si ⁇ Ca Si 2 b) Process: 3CaSi 2 + 6HCl ⁇ Si 6 H 6 + 3CaCl 2 c) Process: Si 6 H 6 ⁇ 6 Si + 3 H 2 ⁇
  • the laminated structure of the Al-containing silicon material of the present invention having a structure in which a plurality of plate-like silicon bodies are laminated in the thickness direction is considered to be derived from the Si layer in CaSi 2 or Si 6 H 6 .
  • the process will be described.
  • Ca, Al and Si used at a process a an element single-piece
  • CaSi 2 may be used as part of the raw material.
  • the elemental composition ratio of Ca and Si in the molten metal is preferably in the range of 1: 1.5 to 1: 2.5, more preferably in the range of 1: 1.8 to 1: 2.2, and 1: 1.
  • the range of 9 to 1: 2.1 is more preferable.
  • the amount of Al in the molten metal may be appropriately determined according to the Al mass ratio in the Al-containing silicon material of the present invention to be produced. However, since Al can be dissolved in an acid, the amount of Al in the precursor may be reduced in step b) of the next step. Therefore, it is preferable to add a little more Al to the molten metal.
  • step a Al is substituted solid solution CaSi 2-x Al x obtained by replacing the Si of CaSi 2 is manufactured. Therefore, the phase diagram of the solid solution was calculated using thermodynamic equilibrium calculation software (FactSage, Computational Mechanics Research Center, Inc.). A state diagram is shown in FIG.
  • x is in the range of 0 ⁇ x ⁇ 0.16.
  • the amount of Al in the composition formula of the substitutional solid solution at ordinary temperature is extremely low.
  • less than 4.5% of the mass% of Al based on the total mass of Ca, Si and Al in the molten metal is preferably within the range of 0.01 to 3%, and more preferably within the range of 0.05 to 2%. Is more preferably in the range of 0.1 to 1%.
  • an excessive addition of Al it is considered that CaAl 2 Si 2 also generates, CaAl 2 Si 2 disappears by decomposition in the next step of b) step.
  • the molten metal temperature in the step a) may be a temperature at which a mixture of Ca, Al and Si can be a molten metal.
  • the molten metal means a liquid-like state of a mixture of Ca, Al and Si.
  • the temperature of the molten metal is preferably in the range of 1050 ° C. to 1800 ° C., more preferably in the range of 1100 ° C. to 1500 ° C., and still more preferably in the range of 1200 ° C. to 1400 ° C.
  • a heating device used at a) process a high frequency induction heating device, an electric furnace, and a gas furnace can be used, for example.
  • the step a) may be performed under pressure or reduced pressure conditions, or under an inert gas atmosphere such as argon, helium or nitrogen.
  • the melt it is preferable to cool the melt at a rate as fast as possible.
  • the formation of the interstitial solid solution can also be expected.
  • the molten metal may be poured into a predetermined mold and left at room temperature, but a cooling method using a rapid cooling device may be used.
  • the rapid cooling device described in the present specification does not include a device for leaving and cooling the molten metal, but means a device for forcibly cooling the molten metal.
  • a cooling means such as melt span method, strip casting method, or melt spinning method
  • a cooling method such as an atomizing method for spraying a fluid onto a molten metal
  • the cooling device using the means can be illustrated.
  • a gas atomizing method, a water atomizing method, a centrifugal atomizing method, and a plasma atomizing method can be exemplified.
  • Specific rapid cooling devices include liquid rapid solidification devices, rapid cooling thin plate production devices, in-liquid spinning devices, gas atomizing devices, water atomizing devices, rotating disk devices, rotating electrode method devices (Nisshin Giken Co., Ltd.), liquid A quenching apparatus and a gas atomizing apparatus (above, Makabe Giken Co., Ltd.) can be exemplified.
  • As a preferable cooling rate 1000 to 100,000 ° C./second can be exemplified.
  • an annealing step may be added in which heating is performed while maintaining the solid state obtained by cooling. From the phase diagram of FIG. 1, it is considered that the substitutional solid solution CaSi 2 -xAl x is most likely to be formed at around 900 ° C. Therefore, the heating temperature in the annealing step is preferably 800 to 1000 ° C., and more preferably 850 to 950 ° C. The heating time may be, for example, 1 to 50 hours or 5 to 30 hours. Naturally, the solid is cooled after the annealing step.
  • the solid obtained by cooling may be crushed or further classified.
  • Step b) is a step of reacting the solid obtained in step a) with an acid to obtain a precursor of an Al-containing silicon material.
  • Precursor of Al-containing silicon material because the basic skeleton of Si layer by CaSi 2-x Al x or CaSi 2 is maintained, forms a lamellar.
  • hydrofluoric acid hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, methanesulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluoro acid Arsenic acid, fluoroantimonic acid, hexafluorosilicic acid, hexafluorogermanic acid, hexafluorotin (IV) acid, trifluoroacetic acid, hexafluorotitanic acid, hexafluorozirconic acid, trifluoromethanesulfonic acid, fluorosulfonic acid are exemplified. Ru. These acids may be used alone or in combination.
  • the acid is preferably used in molar ratio in excess of Ca contained in the solid obtained in the step a).
  • the process may be carried out without a solvent, it is preferable to use water as a solvent from the viewpoint of separation of the target substance and removal of byproducts such as CaCl 2 and the like.
  • the reaction conditions in the same step are preferably reduced pressure conditions such as vacuum or under an inert gas atmosphere, and it is preferable to set temperature conditions below room temperature such as an ice bath. The reaction time of the same process may be set appropriately.
  • the step b) is preferably carried out in the presence of water, and Si 6 H 6 can be reacted with water. Therefore, in the step b), for example, the following reaction is considered to proceed. Si 6 H 6 + 3H 2 O ⁇ Si 6 H 3 (OH) 3 + 3H 2 ⁇
  • the precursor of the Al-containing silicon material may contain oxygen.
  • the element derived from the anion of the used acid may also be included.
  • the step c) is a step of heating the precursor of the Al-containing silicon material at 300 ° C. or higher to release hydrogen, water and the like to obtain the Al-containing silicon material.
  • the step c) is preferably carried out in a non-oxidizing atmosphere having a lower oxygen content than under normal atmosphere.
  • a non-oxidizing atmosphere a reduced pressure atmosphere including vacuum and an inert gas atmosphere can be exemplified.
  • the heating temperature is preferably in the range of 350 ° C. to 950 ° C., and more preferably in the range of 400 ° C. to 900 ° C. If the heating temperature is too low, hydrogen may not be sufficiently released, and if the heating temperature is too high, energy is wasted.
  • the heating time may be set appropriately according to the heating temperature. It is preferable to determine the heating time while measuring the amount of hydrogen and the like that escapes from the reaction system.
  • the heating temperature and the heating time By appropriately selecting the heating temperature and the heating time, the ratio of amorphous silicon and silicon crystallite contained in the Al-containing silicon material to be produced and the size of silicon crystallite can also be adjusted. By appropriately selecting the heating temperature and the heating time, it is also possible to prepare the shape of a nano-level thick layer including amorphous silicon and silicon crystallite contained in the Al-containing silicon material to be produced.
  • the obtained Al-containing silicon material may be crushed or further classified.
  • the Al-containing silicon material of the present invention can be used as a negative electrode active material of a storage battery such as a secondary battery such as a lithium ion secondary battery, an electric double layer capacitor, and a lithium ion capacitor.
  • a storage battery such as a secondary battery such as a lithium ion secondary battery, an electric double layer capacitor, and a lithium ion capacitor.
  • the Al-containing silicon material of the present invention can also be used as, for example, a material such as a CMOS, a semiconductor memory, and a solar cell, or as a photocatalytic material.
  • the lithium ion secondary battery of the present invention including the Al-containing silicon material of the present invention as a negative electrode active material will be described as a representative example of the power storage device.
  • the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode including the Al-containing silicon material of the present invention as a negative electrode active material, an electrolytic solution, and a separator.
  • the positive electrode has a current collector and a positive electrode active material layer bonded to the surface of the current collector.
  • the current collector refers to a chemically inert electron conductor for keeping current flowing to the electrode during discharge or charge of the lithium ion secondary battery.
  • As the current collector at least one selected from silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, stainless steel, etc. A metal material can be illustrated.
  • the current collector may be coated with a known protective layer. What processed the surface of a collector by a well-known method may be used as a collector.
  • the current collector can take the form of a foil, a sheet, a film, a line, a rod, a mesh or the like. Therefore, as the current collector, for example, metal foils such as copper foil, nickel foil, aluminum foil, and stainless steel foil can be suitably used.
  • the thickness is preferably in the range of 1 ⁇ m to 100 ⁇ m.
  • the positive electrode active material layer contains a positive electrode active material and, if necessary, a conductive aid and / or a binder.
  • a positive electrode active material spinel such as LiMn 2 O 4 and a solid solution composed of a mixture of spinel and layered compound, LiMPO 4 , LiMVO 4 or Li 2 MSiO 4 (M in the formula is Co, Ni, Mn, Polyanionic compounds represented by (at least one of Fe) and the like can be mentioned.
  • tavorite compound (the M a transition metal) LiMPO 4 F, such as LiFePO 4 F represented by, Limbo 3 such LiFeBO 3 (M is a transition metal) include borate-based compound represented by be able to.
  • any metal oxide used as a positive electrode active material may have the above composition formula as a basic composition, and one obtained by substituting a metal element contained in the basic composition with another metal element can also be used as a positive electrode active material .
  • a positive electrode active material a positive electrode active material containing no lithium ion contributing to charge and discharge, for example, a simple substance of sulfur, a compound of sulfur and carbon, a metal sulfide such as TiS 2 , V 2 O 5 , MnO Oxides such as 2 , polyaniline and anthraquinone, and compounds containing these aromatics in the chemical structure, conjugated materials such as conjugated diacetic acid organic substances, and other known materials can also be used.
  • a compound having a stable radical such as nitroxide, nitronyl nitroxide, galvinoxyl, phenoxyl or the like may be adopted as the positive electrode active material.
  • a positive electrode active material containing no lithium it is necessary to add ions to the positive electrode and / or the negative electrode by a known method.
  • a metal or a compound containing the ions may be used.
  • a conductive aid is added to enhance the conductivity of the electrode. Therefore, the conductive additive may be optionally added when the conductivity of the electrode is insufficient, and may not be added when the conductivity of the electrode is sufficiently excellent.
  • the conductive auxiliary agent may be any chemically active high electron conductor, and carbon black particles such as carbon black, graphite, acetylene black, ketjen black (registered trademark), vapor grown carbon fiber (vapor grown carbon) Fiber), and various metal particles are exemplified. These conductive assistants can be added to the active material layer singly or in combination of two or more.
  • the binder plays the role of anchoring the active material and the conductive aid to the surface of the current collector and maintaining the conductive network in the electrode.
  • the binder may, for example, be a fluorine-containing resin such as polyvinylidene fluoride, polytetrafluoroethylene or fluororubber, a thermoplastic resin such as polypropylene or polyethylene, an imide resin such as polyimide or polyamideimide, an alkoxysilyl group-containing resin, Examples of acrylic resins such as acrylic acid, styrene-butadiene rubber (SBR), alginates such as carboxymethylcellulose, sodium alginate and ammonium alginate, water-soluble cellulose ester cross-linked product, starch-acrylic acid graft polymer it can. These binders may be used alone or in combination.
  • a crosslinked polymer in which a carboxyl group-containing polymer such as polyacrylic acid or polymethacrylic acid as disclosed in WO 2016/063882 is crosslinked with a polyamine such as diamine may be used as a binder.
  • diamine used for the cross-linked polymer examples include alkylene diamines such as ethylene diamine, propylene diamine and hexamethylene diamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, isophorone diamine, bis (4-aminocyclohexyl) methane and the like.
  • Saturated carbocyclic ring diamine m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, bis (4-aminophenyl) sulfone, benzidine, o-tolidine, 2,4- Aromatic diamines such as tolylene diamine, 2,6-tolylene diamine, xylylene diamine and naphthalene diamine can be mentioned.
  • the blending ratio of the binder in the active material layer is, in mass ratio, preferably active material: binder 1: 0.001 to 1: 0.3, 1: 0.005 to 1: 0 It is more preferably 0.2, and more preferably 1: 0.01 to 1: 0.15.
  • the negative electrode includes a current collector and a negative electrode active material layer bonded to the surface of the current collector.
  • As the current collector one described for the positive electrode may be appropriately adopted appropriately.
  • the negative electrode active material layer contains a negative electrode active material and, if necessary, a conductive aid and / or a binder.
  • the negative electrode active material only the Al-containing silicon material of the present invention may be employed, or the Al-containing silicon material of the present invention may be used in combination with a known negative electrode active material. What coated Al content silicon material of the present invention with carbon may be used as a cathode active material.
  • C mass% (W C %) preferably satisfies 0 ⁇ W C ⁇ 30, 1 ⁇ W C ⁇ 20. Is more preferable, 2 ⁇ W c ⁇ 15 is more preferable, and 5 ⁇ W c ⁇ 10 is particularly preferable.
  • those described for the positive electrode may be appropriately adopted at the same mixing ratio.
  • an active material layer on the surface of a current collector current collection can be performed using conventionally known methods such as roll coating, die coating, dip coating, doctor blade method, spray coating, and curtain coating.
  • the active material may be applied to the surface of the body.
  • the active material, the solvent, and, if necessary, the binder and / or the conductive auxiliary agent are mixed to prepare a slurry.
  • the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone and water.
  • the slurry is applied to the surface of a current collector and then dried. The dried one may be compressed to increase the electrode density.
  • the electrolytic solution contains a non-aqueous solvent and an electrolyte dissolved in the non-aqueous solvent.
  • cyclic esters As the non-aqueous solvent, cyclic esters, linear esters, ethers and the like can be used.
  • examples of cyclic esters include ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, gamma-butyrolactone, vinylene carbonate, 2-methyl-gamma-butyrolactone, acetyl-gamma-butyrolactone and gamma-valerolactone.
  • chain ester examples include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, ethyl methyl carbonate, alkyl propionic acid ester, malonic acid dialkyl ester, acetic acid alkyl ester and the like.
  • ethers tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane can be exemplified.
  • non-aqueous solvent a compound in which part or all of hydrogens in the chemical structure of the above specific solvent is substituted with fluorine may be adopted.
  • Examples of the electrolyte include lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , and LiN (CF 3 SO 2 ) 2 .
  • lithium salts such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 and the like in a nonaqueous solvent such as fluoroethylene carbonate, ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate
  • a nonaqueous solvent such as fluoroethylene carbonate, ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate
  • the separator separates the positive electrode and the negative electrode, and allows lithium ions to pass while preventing a short circuit due to the contact of the both electrodes.
  • synthetic resins such as polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramid (Aromatic polyamide), polyester, polyacrylonitrile, etc., polysaccharides such as cellulose and amylose, natural substances such as fibroin, keratin, lignin and suberin Examples thereof include porous bodies, non-woven fabrics, and woven fabrics using one or more kinds of electrically insulating materials such as polymers and ceramics.
  • the separator may have a multilayer structure.
  • a separator is sandwiched between the positive electrode and the negative electrode as necessary to form an electrode body.
  • the electrode body may be any of a laminated type in which the positive electrode, the separator and the negative electrode are stacked, or a wound type in which the positive electrode, the separator and the negative electrode are wound.
  • the shape of the lithium ion secondary battery of the present invention is not particularly limited, and various shapes such as cylindrical, square, coin, and laminate types can be adopted.
  • the lithium ion secondary battery of the present invention may be mounted on a vehicle.
  • the vehicle may be a vehicle using electric energy from a lithium ion secondary battery for all or part of its power source, and may be, for example, an electric vehicle, a hybrid vehicle, or the like.
  • a lithium ion secondary battery is mounted on a vehicle, a plurality of lithium ion secondary batteries may be connected in series to form a battery pack.
  • various household appliances driven by a battery such as a personal computer and a mobile communication apparatus, as well as a vehicle, an office apparatus, an industrial apparatus and the like can be mentioned.
  • the lithium ion secondary battery of the present invention can be used in wind power generation, solar power generation, hydroelectric power generation, storage devices and power smoothing devices for electric power systems, power sources for power and / or accessories of ships, etc., aircraft, Power supply source for power of spacecraft and / or accessories, auxiliary power supply for vehicles not using electricity as power source, power supply for mobile home robots, power supply for system backup, power supply for uninterruptible power supply, You may use for the electrical storage apparatus which stores temporarily the electric power required for charge in the charge station etc. for electric vehicles.
  • Example 1 The Al-containing silicon material and lithium ion secondary battery of Example 1 were manufactured as follows.
  • Step Ca, Al and Si were weighed in a carbon crucible.
  • the elemental composition ratio of Ca and Si was 1: 2, and the amount of Al added was 1% with respect to the total mass of Ca, Al and Si.
  • a carbon crucible was heated at around 1300 ° C. in a high frequency induction heating apparatus under an argon gas atmosphere to obtain a molten metal containing Ca, Al and Si.
  • the molten metal is poured into a predetermined mold to cool and solidify.
  • the solid was pulverized into a powder and then subjected to the step b).
  • Example 1 Process The Al-containing silicon material of Example 1 was manufactured by heating the precursor of the Al-containing silicon material at 900 ° C. for 1 hour under a nitrogen gas atmosphere.
  • Example 1 Using the Al-containing silicon material of Example 1, the negative electrode of Example 1 and the lithium ion secondary battery of Example 1 were produced as follows.
  • a polyacrylic acid having a weight average molecular weight of 800,000 was dissolved in N-methyl-2-pyrrolidone to prepare a polyacrylic acid solution containing 10% by mass of polyacrylic acid.
  • a solution of 4,4'-diaminodiphenylmethane was prepared by dissolving 0.2 g (1.0 mmol) of 4,4'-diaminodiphenylmethane in 0.4 mL of N-methyl-2-pyrrolidone.
  • Example 1 72.5 parts by mass of the Al-containing silicon material of Example 1 as a negative electrode active material, 13.5 parts by mass of acetylene black as a conduction aid, and 14 parts by mass of a solid content as a binder And, an appropriate amount of N-methyl-2-pyrrolidone was mixed to prepare a slurry.
  • a copper foil was prepared as a current collector for the negative electrode.
  • the slurry was applied in the form of a film on the surface of the copper foil using a doctor blade.
  • the copper foil coated with the slurry was dried at 80 ° C. for 15 minutes to remove N-methyl-2-pyrrolidone. Thereafter, the resultant was pressed and heated at 180 ° C. for 30 minutes in a reduced pressure atmosphere using a vacuum pump to manufacture the negative electrode of Example 1 in which the negative electrode active material layer was formed.
  • a polyethylene porous membrane was prepared as a separator.
  • a solution in which LiPF 6 was dissolved at a concentration of 2 mol / L in a mixed solvent in which fluoroethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 19: 81 was used as an electrolytic solution.
  • Comparative example 1 In the step a), the silicon material of Comparative Example 1, the negative electrode of Comparative Example 1, and the lithium ion secondary battery of Comparative Example 1 were produced in the same manner as in Example 1 except that Al was not added.
  • Elemental analysis of the Al-containing silicon material of Example 1 and the silicon material of Comparative Example 1 was performed using an inductively coupled plasma atomic emission spectrometer (ICP-AES). As a result of elemental analysis, the Al mass% in the Al-containing silicon material of Example 1 is 0.25% and the Fe mass% is 0%, and the Al mass% in the silicon material of Comparative Example 1 is 0%, Fe mass% It was 0%.
  • ICP-AES inductively coupled plasma atomic emission spectrometer
  • the lithium ion secondary battery of Example 1 was adjusted to an SOC (State of Charge) of 15% in a thermostat of 25 ° C. Then, the lithium ion secondary battery was discharged for 10 seconds at a constant current of 1 C rate. The resistance was calculated by dividing the amount of change in voltage before and after discharge by the current value. The same test was performed on the lithium ion secondary battery of Comparative Example 1. The resistance of the lithium ion secondary battery of Example 1 was 3.3 ⁇ , and the resistance of the lithium ion secondary battery of Comparative Example 1 was 3.6 ⁇ . It was confirmed that the resistance of the lithium ion secondary battery is lowered by using the Al-containing silicon material.
  • SOC State of Charge
  • Example 2 The Al-containing silicon material, the negative electrode, and the lithium ion secondary battery of Example 2 were manufactured as follows.
  • Step Ca Al and Si were weighed in a carbon crucible.
  • the elemental composition ratio of Ca and Si was 1: 2, and the amount of Al added was 1% with respect to the total mass of Ca, Al and Si.
  • a carbon crucible was heated at around 1300 ° C. in a high frequency induction heating apparatus under an argon gas atmosphere to obtain a molten metal containing Ca, Al and Si.
  • the molten metal is poured into a predetermined mold and cooled to form a solid.
  • the solid was pulverized into a powder and then subjected to the step b).
  • Step 2 The Al-containing silicon material of Example 2 was manufactured by heating the precursor of the Al-containing silicon material at 900 ° C. for 1 hour in a nitrogen gas atmosphere.
  • Example 2 Using the Al-containing silicon material of Example 2, the negative electrode of Example 2 and the lithium ion secondary battery of Example 2 were manufactured as follows.
  • a polyacrylic acid having a weight average molecular weight of 800,000 was dissolved in N-methyl-2-pyrrolidone to prepare a polyacrylic acid solution containing 10% by mass of polyacrylic acid.
  • a solution of 4,4'-diaminodiphenylmethane was prepared by dissolving 0.2 g (1.0 mmol) of 4,4'-diaminodiphenylmethane in 0.4 mL of N-methyl-2-pyrrolidone.
  • Example 2 72.5 parts by mass of the Al-containing silicon material of Example 2 as a negative electrode active material, 13.5 parts by mass of acetylene black as a conduction aid, and 14 parts by mass of a solid content as a binder And, an appropriate amount of N-methyl-2-pyrrolidone was mixed to prepare a slurry.
  • a copper foil was prepared as a current collector for the negative electrode.
  • the slurry was applied in the form of a film on the surface of the copper foil using a doctor blade.
  • the copper foil coated with the slurry was dried at 80 ° C. for 15 minutes to remove N-methyl-2-pyrrolidone. After that, pressing was performed and heating was performed at 180 ° C. for 30 minutes in a reduced pressure atmosphere using a vacuum pump to manufacture the negative electrode of Example 2 in which the negative electrode active material layer was formed.
  • the negative electrode of Example 2 was cut to a diameter of 11 mm to obtain an evaluation electrode.
  • a metal lithium foil having a thickness of 500 ⁇ m was cut to a diameter of 13 mm and used as a counter electrode.
  • a glass filter (Hoechst Celanese) and celgard 2400 (Polypore Co., Ltd.) which is a single-layer polypropylene were prepared as a separator.
  • the volume ratio of ethylene carbonate and diethyl carbonate 1: LiPF 6 was prepared the electrolytic solution at a concentration 1 mol / L in a mixed solvent obtained by mixing 1.
  • the two types of separators were sandwiched between the counter electrode and the evaluation electrode in the order of the counter electrode, the glass filter, celgard 2400, and the evaluation electrode to form an electrode body.
  • the electrode body was housed in a coin-type battery case CR2032 (Housen Co., Ltd.), and an electrolyte was further injected to obtain a coin-type battery.
  • the resultant was used as a lithium ion secondary battery of Example 2.
  • Example 3 The following carbon coating process was added after the process c) with the point of increasing the production scale, and the carbon-coated Al-containing silicon material was used as the Al-containing silicon material of Example 3 and was used as a negative electrode active material.
  • the Al-containing silicon material, the negative electrode, and the lithium ion secondary battery of Example 3 were manufactured in the same manner as in Example 2 except for the point.
  • Step c) The Al-containing silicon material obtained in step c) is placed in a rotary kiln type reactor, and thermal CVD is performed at 880 ° C. for 60 minutes under aeration of propane-argon mixed gas, thereby carbon coating An Al-containing silicon material was obtained.
  • Example 4 Powdered CaSi 2 containing Al and Fe as impurities was prepared.
  • elemental analysis of the CaSi 2 was performed using ICP-AES, it was 38 mass% of Ca, 57 mass% of Si, 4 mass% of Fe, and 1 mass% of Al.
  • the Al-containing silicon material, the negative electrode, and the lithium ion secondary battery of Example 4 were manufactured in the same manner as in Example 3 except that step b) and the following steps were performed using the CaSi 2 .
  • Comparative example 2 The silicon material, the negative electrode, and the lithium ion secondary battery of Comparative Example 2 were manufactured in the same manner as in Example 2 except that Al was not added in the step a).
  • Comparative example 3 (Comparative example 3)
  • the silicon material, the negative electrode, and the lithium ion secondary battery of Comparative Example 3 were manufactured in the same manner as in Example 2 except that Al was not added and Fe was added.
  • Fe in the step a) was added in an amount of 4% with respect to the total mass of Ca, Fe and Si.
  • Elemental analysis was performed on the Al-containing silicon materials of Examples 2 to 4 and the silicon materials of Comparative Examples 2 and 3 using a fluorescent X-ray analyzer (XRF).
  • elemental analysis of oxygen was performed on the Al-containing silicon materials of Examples 2 to 4 and the silicon materials of Comparative Examples 2 and 3 using an oxygen / nitrogen / hydrogen analyzer.
  • elemental analysis for carbon was performed on the carbon-coated Al-containing silicon materials of Example 3 and Example 4 using a carbon / sulfur analyzer.
  • Example 2 The results of these elemental analyzes are shown in Table 1 as mass%.
  • the presence of a slight amount of Fe in Example 2, Example 3, and Comparative Example 2 is because Fe is contained as an impurity in the metal of the raw material.
  • O, Ca and Cl contained in all silicon materials are derived from the solvent (water) used in the production, the raw material, the anion of the acid and the like.
  • Initial efficiency (%) 100 ⁇ (initial charge capacity) / (initial discharge capacity)
  • Capacity retention rate (%) 100 ⁇ (charge capacity at each cycle) / (charge capacity at first cycle)
  • Example 5 The Al-containing silicon material, the negative electrode, and the lithium ion secondary battery of Example 5 were produced as follows.
  • Step Ca Al and Si were weighed in a carbon crucible.
  • the elemental composition ratio of Ca and Si was 1: 2, and the amount of Al added was 0.1% with respect to the total mass of Ca, Al and Si.
  • a carbon crucible was heated at around 1300 ° C. in a high frequency induction heating apparatus under an argon gas atmosphere to obtain a molten metal containing Ca, Al and Si.
  • the molten metal is poured into a predetermined mold and cooled to form a solid.
  • the solid was pulverized into a powder and then subjected to the step b).
  • Step 5 The Al-containing silicon material precursor of Example 5 was manufactured by heating the precursor of the Al-containing silicon material at 900 ° C. for 1 hour in a nitrogen gas atmosphere.
  • Example 5 The negative electrode of Example 5 and the lithium ion secondary battery of Example 5 were manufactured as follows using the Al-containing silicon material of Example 5.
  • a polyacrylic acid having a weight average molecular weight of 800,000 was dissolved in N-methyl-2-pyrrolidone to prepare a polyacrylic acid solution containing 10% by mass of polyacrylic acid.
  • a solution of 4,4'-diaminodiphenylmethane was prepared by dissolving 0.2 g (1.0 mmol) of 4,4'-diaminodiphenylmethane in 0.4 mL of N-methyl-2-pyrrolidone.
  • Example 5 72.5 parts by mass of the Al-containing silicon material of Example 5 as a negative electrode active material, 13.5 parts by mass of acetylene black as a conduction aid, and 14 parts by mass of solid content as a binder And, an appropriate amount of N-methyl-2-pyrrolidone was mixed to prepare a slurry.
  • a copper foil was prepared as a current collector for the negative electrode.
  • the slurry was applied in the form of a film on the surface of the copper foil using a doctor blade.
  • the copper foil coated with the slurry was dried at 80 ° C. for 15 minutes to remove N-methyl-2-pyrrolidone. After that, pressing was performed and heating was performed at 180 ° C. for 30 minutes in a reduced pressure atmosphere using a vacuum pump to manufacture the negative electrode of Example 5 in which the negative electrode active material layer was formed.
  • the negative electrode of Example 5 was cut to a diameter of 11 mm to obtain an evaluation electrode.
  • a metal lithium foil having a thickness of 500 ⁇ m was cut to a diameter of 13 mm and used as a counter electrode.
  • a glass filter (Hoechst Celanese) and celgard 2400 (Polypore Co., Ltd.) which is a single-layer polypropylene were prepared as a separator.
  • the volume ratio of ethylene carbonate and diethyl carbonate 1: LiPF 6 was prepared the electrolytic solution at a concentration 1 mol / L in a mixed solvent obtained by mixing 1.
  • the two types of separators were sandwiched between the counter electrode and the evaluation electrode in the order of the counter electrode, the glass filter, celgard 2400, and the evaluation electrode to form an electrode body.
  • the electrode body was housed in a coin-type battery case CR2032 (Housen Co., Ltd.), and an electrolyte was further injected to obtain a coin-type battery.
  • the resultant was used as a lithium ion secondary battery of Example 5.
  • Example 6 Al-containing silicon material of Example 6, negative electrode in the same manner as in Example 5 except that in the step a), the amount of Al added is 0.3% with respect to the total mass of Ca, Al and Si And a lithium ion secondary battery.
  • Example 7 Al-containing silicon material of Example 7, negative electrode in the same manner as in Example 5 except that in the step a), the amount of Al added is 0.5% with respect to the total mass of Ca, Al and Si And a lithium ion secondary battery.
  • Example 8 Al-containing silicon material, negative electrode and lithium of Example 8 in the same manner as in Example 5 except that in the step a), the amount of Al added is 1% with respect to the total mass of Ca, Al and Si An ion secondary battery was manufactured.
  • Example 9 The Al-containing silicon material, the negative electrode, and the lithium ion secondary battery of Example 9 were manufactured in the same manner as in Example 8 except that the following annealing step was added to the step a).
  • Elemental analysis of the Al-containing silicon materials of Examples 5 to 9 was performed in the same manner as in Evaluation Example 3. The results of these elemental analyzes are shown in Table 3 as mass%.
  • the reason why a small amount of Fe is present in the Al-containing silicon material of each example is that Fe is contained as an impurity in the metal of the raw material.
  • Cl, Ca, C and O contained in the Al-containing silicon material of each example are derived from the anion of the acid used in the production, the raw material, the carbon crucible, the solvent (water) and the like.
  • Example 7 The lithium ion secondary batteries of Example 5 to Example 9 were discharged to 0.01 V at a current of 0.2 mA and then charged to 1.0 V at a current of 0.2 mA. went. Furthermore, for the lithium ion secondary batteries of Example 5 to Example 9 after the initial charge and discharge, discharging to 0.01 V with a current of 0.5 mA and then charging to 1.0 V with a current of 0.5 mA The charge and discharge cycle of 50 cycles was performed. In addition, the lithium ion secondary batteries of Examples 5 to 9 were discharged to 0.01 V at a current of 0.2 mA, and then charged to 0.8 V at a current of 0.2 mA. Discharge was done.
  • Initial efficiency (%) 100 ⁇ (initial charge capacity) / (initial discharge capacity)
  • Capacity retention rate (%) 100 ⁇ (charge capacity at 50 cycles) / (charge capacity at first cycle)
  • the results of the initial discharge capacity, the initial charge capacity (1.0 V and 0.8 V), the initial efficiency (1.0 V and 0.8 V), and the capacity retention rate are shown in Tables 4 and 5 together with the results of Al mass%.
  • Example 10 The Al-containing silicon material of Example 10 was produced as follows.
  • Step Ca, Al and Si were weighed in a carbon crucible.
  • the elemental composition ratio of Ca and Si was 1: 2, and the amount of Al added was 1% with respect to the total mass of Ca, Al and Si.
  • a carbon crucible was heated at around 1300 ° C. in a high frequency induction heating apparatus under an argon gas atmosphere to obtain a molten metal containing Ca, Al and Si.
  • the molten metal is poured into a predetermined mold to cool and solidify.
  • the solid was pulverized into a powder and then subjected to the step b).
  • Step c) Step The precursor of the Al-containing silicon material was heated at 900 ° C. for 1 hour in a nitrogen gas atmosphere to produce an Al-containing silicon material.
  • Step c) The Al-containing silicon material obtained in step c) is placed in a rotary kiln type reactor, and thermal CVD is performed at 880 ° C. for 60 minutes under aeration of propane-argon mixed gas, thereby carbon coating An Al-containing silicon material was obtained. This carbon-coated Al-containing silicon material was used as the Al-containing silicon material of Example 10.
  • Example 10 The negative electrode of Example 10 and the lithium ion secondary battery of Example 10 were manufactured as follows using the Al-containing silicon material of Example 10.
  • Example 10 80.8 parts by mass of the Al-containing silicon material of Example 10 as a negative electrode active material, 10.2 parts by mass of acetylene black as a conduction aid, 9 parts by mass of polyamideimide as a binder, and an appropriate amount of N-methyl-2-
  • the pyrrolidone was mixed to produce a slurry.
  • a copper foil was prepared as a current collector for the negative electrode.
  • the slurry was applied in the form of a film on the surface of the copper foil using a doctor blade.
  • the copper foil coated with the slurry was dried at 80 ° C. for 15 minutes to remove N-methyl-2-pyrrolidone.
  • the negative electrode was pressed and heated at 180 ° C. for 30 minutes in a reduced pressure atmosphere using a vacuum pump to manufacture the negative electrode of Example 10 in which the negative electrode active material layer was formed.
  • a slurry was prepared by mixing 3 parts by mass of vinylidene and an appropriate amount of N-methyl-2-pyrrolidone.
  • An aluminum foil was prepared as a positive electrode current collector. The slurry was applied in the form of a film on the surface of the aluminum foil using a doctor blade. The N-methyl-2-pyrrolidone was removed by drying the slurry-coated aluminum foil at 80 ° C. for 20 minutes. Then, the resultant was pressed and heated at 120 ° C. for 6 hours in a reduced pressure atmosphere using a vacuum pump to manufacture a positive electrode having a positive electrode active material layer formed on the surface of the current collector.
  • a polyethylene porous membrane was prepared as a separator. Further, a solution in which LiPF 6 was dissolved at a concentration of 2 mol / L in a mixed solvent in which dimethyl carbonate and fluoroethylene carbonate were mixed at a volume ratio of 81:19 was used as an electrolytic solution.
  • Example 10 It laminated
  • the laminate and the electrolytic solution were housed in a laminate film bag, the bag was sealed, and the lithium ion secondary battery of Example 10 was manufactured.
  • the Al-containing silicon material of the present invention is excellent in thermal stability in a charged state due to the presence of Al.

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Abstract

L'invention concerne un nouveau matériau de silicium. L'invention concerne une substance active d'électrode négative caractérisée en ce qu'elle comprend un matériau de silicium contenant de l'Al, le pourcentage en masse d'Al (WAl%) satisfaisant à 0 < WAl < 1 et le pourcentage en masse de Si (WSi%) satisfaisant à 60 ≤ WSi ≤ 90.
PCT/JP2018/023077 2017-09-14 2018-06-18 Substance active d'électrode négative comprenant un matériau de silicium contenant de l'al WO2019053984A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015176674A (ja) * 2014-03-13 2015-10-05 山陽特殊製鋼株式会社 蓄電デバイスの負極材料
WO2015182120A1 (fr) * 2014-05-29 2015-12-03 株式会社豊田自動織機 Matériau de silicium contenant du cuivre, procédé de fabrication associé, substance active d'électrode négative et pile rechargeable
WO2016031146A1 (fr) * 2014-08-27 2016-03-03 株式会社豊田自動織機 Procédé permettant la production de matériau en silicium revêtu de carbone
JP2016062660A (ja) * 2014-09-16 2016-04-25 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
WO2017175518A1 (fr) * 2016-04-06 2017-10-12 株式会社豊田自動織機 Procédé de fabrication de matériau de silicium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015176674A (ja) * 2014-03-13 2015-10-05 山陽特殊製鋼株式会社 蓄電デバイスの負極材料
WO2015182120A1 (fr) * 2014-05-29 2015-12-03 株式会社豊田自動織機 Matériau de silicium contenant du cuivre, procédé de fabrication associé, substance active d'électrode négative et pile rechargeable
WO2016031146A1 (fr) * 2014-08-27 2016-03-03 株式会社豊田自動織機 Procédé permettant la production de matériau en silicium revêtu de carbone
JP2016062660A (ja) * 2014-09-16 2016-04-25 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
WO2017175518A1 (fr) * 2016-04-06 2017-10-12 株式会社豊田自動織機 Procédé de fabrication de matériau de silicium

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