WO2022059340A1 - 二次電池用負極活物質、二次電池用負極および二次電池 - Google Patents

二次電池用負極活物質、二次電池用負極および二次電池 Download PDF

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WO2022059340A1
WO2022059340A1 PCT/JP2021/027134 JP2021027134W WO2022059340A1 WO 2022059340 A1 WO2022059340 A1 WO 2022059340A1 JP 2021027134 W JP2021027134 W JP 2021027134W WO 2022059340 A1 WO2022059340 A1 WO 2022059340A1
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lithium
negative electrode
silicon
magnesium
active material
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French (fr)
Japanese (ja)
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琴 斯
大輔 伊藤
泰大 池田
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2022550388A priority Critical patent/JPWO2022059340A1/ja
Priority to CN202180063716.4A priority patent/CN116235310A/zh
Publication of WO2022059340A1 publication Critical patent/WO2022059340A1/ja
Priority to US18/122,211 priority patent/US20230223522A1/en
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

  • This technology relates to negative electrode active materials for secondary batteries, negative electrodes for secondary batteries, and secondary batteries.
  • This secondary battery includes an electrolyte together with a positive electrode and a negative electrode, and the negative electrode contains a negative electrode active material involved in a charge / discharge reaction.
  • a silicon oxide composite containing silicon, silicon oxide (SiO x (0 ⁇ x ⁇ 2)), and an oxide of silicon and an element M (element M is Mg or the like) is used as a negative electrode active material.
  • silicon oxide (SiO x (0 ⁇ x ⁇ 2)) in which metal atoms such as magnesium are uniformly dispersed is used as a negative electrode active material (see, for example, Patent Document 2).
  • a negative electrode active material for a secondary battery a negative electrode for a secondary battery, and a secondary battery capable of obtaining excellent cycle characteristics are desired.
  • the negative electrode active material for a secondary battery contains lithium and silicon as constituent elements and a lithium silicon-containing oxide in which magnesium is present on the surface layer.
  • the lithium silicon-containing oxide includes a silicon-containing phase and a phase containing at least one of lithium silicate represented by the formula (1).
  • the range in which magnesium is present is within a range of 10 nm or more and 3000 nm or less in the depth direction from the surface.
  • Magnesium forms at least one of magnesium silicate represented by the formula (2).
  • the ratio of the number of moles of magnesium to the number of moles of lithium is 0.1 mol% or more and 20 mol% or less.
  • the negative electrode for a secondary battery according to an embodiment of the present technology contains a negative electrode active material, and the negative electrode active material has the same configuration as the negative electrode active material for a secondary battery according to the above-described embodiment of the present technology. Is.
  • the secondary battery of one embodiment of the present technology includes a positive electrode, a negative electrode, and an electrolytic solution, and the negative electrode has the same configuration as the negative electrode for a secondary battery of the above-described embodiment of the present technology. ..
  • lithium silicon-containing oxide is an oxide containing lithium and silicon as constituent elements as described above, and has a so-called Li—Si—O bond.
  • ratio (number of moles of magnesium / number of moles of lithium) x 100.
  • the negative electrode active material for a secondary battery contains lithium and silicon as constituent elements and magnesium is on the surface layer. Since it contains the existing lithium silicon-containing oxide, and the above conditions are satisfied for each of the phase composition of the lithium silicon-containing oxide, the existence range of magnesium, the bonding state of magnesium, and the content of magnesium. Excellent cycle characteristics can be obtained.
  • the effect of the present technology is not necessarily limited to the effect described here, and may be any effect of a series of effects related to the present technology described later.
  • FIG. 1 It is a figure which shows typically the structure of the negative electrode active material for a secondary battery in one Embodiment of this technique. It is a perspective view which shows the structure of the secondary battery (including the negative electrode for a secondary battery) in one Embodiment of this technique. It is sectional drawing which shows the structure of the battery element shown in FIG. It is a block diagram which shows the structure of the application example of a secondary battery. It is sectional drawing which shows the structure of the secondary battery for a test.
  • Negative electrode active material for secondary batteries 1-1. Configuration 1-2. Manufacturing method 1-3. Action and effect 2. Secondary battery (negative electrode for secondary battery) 2-1. Configuration 2-2. Operation 2-3. Manufacturing method 2-4. Action and effect 3. Modification example 4. Applications for secondary batteries
  • Negative electrode active material for secondary batteries > First, a negative electrode active material for a secondary battery according to an embodiment of the present technology will be described.
  • the negative electrode active material for a secondary battery described here (hereinafter, simply referred to as “negative electrode active material”) is a substance that absorbs and releases an electrode reactant, and is used as a negative electrode of a secondary battery for advancing the electrode reaction. Be done.
  • the type of electrode reactant is not particularly limited, but specifically, it is a light metal such as an alkali metal and an alkaline earth metal.
  • Alkali metals are lithium, sodium and potassium and the like, and alkaline earth metals are beryllium, magnesium and calcium and the like.
  • the electrode reactant is lithium
  • the negative electrode active material is a substance that occludes and releases lithium as an electrode reactant, and in the negative electrode active material, lithium is occluded and released in an ionic state.
  • the negative electrode active material contains lithium and silicon as constituent elements and also contains a lithium silicon-containing oxide in which magnesium is present on the surface layer. That is, since the negative electrode active material is a so-called surface-doped lithium silicic acid-containing oxide, magnesium is dispersed in a part (surface layer) of the lithium silicon-containing oxide in the negative electrode active material.
  • lithium-silicon-containing oxide is an oxide containing lithium and silicon as constituent elements, and has a so-called Li—Si—O bond.
  • the composition of the lithium silicon-containing oxide is not particularly limited as long as it is any one or more of the oxides containing lithium and silicon as constituent elements.
  • the negative electrode active material is an oxide that contains lithium and silicon as constituent elements as a whole and magnesium as a constituent element in a part (surface layer).
  • magnesium does not exist in the center of the lithium silicon-containing oxide but exists only in the surface layer, and more specifically, it exists locally only on the surface of the lithium silicon-containing oxide and its vicinity. is doing. That is, when the lithium silicon-containing oxide is in the form of particles, magnesium is present only within the range from the surface of the particulate lithium silicon-containing oxide to a predetermined depth.
  • FIG. 1 schematically shows the composition of the negative electrode active material.
  • FIG. 1 schematically shows the internal structure of the negative electrode active material in order to make the composition of the negative electrode active material easy to understand.
  • the negative electrode active material is a particulate substance containing the central portion 100 and the surface layer portion 200.
  • the shape of the negative electrode active material is not particularly limited as long as it is in the form of so-called particles.
  • FIG. 1 shows a case where the shape of the negative electrode active material is spherical.
  • the central portion 100 contains a lithium silicon-containing oxide, and the lithium silicon-containing oxide contains a silicon phase 110 and a lithium silicate phase 120.
  • the silicon phase 110 is a phase containing silicon
  • the lithium silicate phase 120 is a phase containing any one or more of lithium silicate represented by the formula (1). be.
  • the silicon phase 110 is heavily shaded, whereas the lithium silicate phase 120 is lightly shaded.
  • Lithium silicate is so-called lithium-doped silicon oxide, which serves as a solid electrolyte in the negative electrode active material.
  • the composition of lithium silicate is not particularly limited, but specifically, Li 2 SiO 3 , Li 2 Si 2 O 5 , Li 4 SiO 4 , Li 6 Si 2 O 7 , and the like. This is because lithium silicate fully serves as a solid electrolyte.
  • the lithium silicate may be of only one type of Li 2 SiO 3 or the like, or may be two or more types of the Li 2 SiO 3 or the like.
  • the dispersed state of lithium silicate in the lithium silicate phase 120 is not particularly limited. Specifically, any one or more of Li 2 SiO 3 , Li 2 Si 2 O 5 and Li 6 Si 2 O 7 may be dispersed in Li 4 SiO 4 .
  • the central portion 100 contains the silicon phase 110 because lithium is stably occluded and released in the silicon phase 110. Further, the reason why the central portion 100 contains the lithium silicate phase 120 is that lithium silicate plays a role as a solid electrolyte, so that lithium is more easily occluded and released in the central portion 100.
  • the central portion 100 contains a plurality of silicon phases 110, and the plurality of silicon phases 110 are dispersed in the lithium silicate phase 120. This is because lithium is sufficiently easily occluded and released in the central portion 100.
  • the central portion 100 may be analyzed by using an analysis method such as X-ray diffractometry (XRD).
  • the surface layer portion 200 contains magnesium together with the above-mentioned lithium silicon-containing oxide.
  • the surface layer 200 contains magnesium when the negative electrode active material containing the lithium silicon-containing oxide is charged into the aqueous solvent, as compared with the case where the surface layer 200 does not contain magnesium. This is because the lithium in the negative electrode active material is less likely to elute into the aqueous solvent. As a result, lithium hydroxide (LiOH) is less likely to be generated in the aqueous solvent, so that the alkalinity of the aqueous solvent is suppressed. In FIG. 1, the surface layer portion 200 is darkly shaded.
  • a boundary line (broken line) is shown between the central portion 100 and the surface layer portion 200 in order to make the composition of the negative electrode active material easy to understand.
  • magnesium is present only in the surface layer (surface layer portion 200) of the lithium silicon-containing oxide, so that an interface exists between the central portion 100 and the surface layer portion 200. do not have. That is, the central portion 100 and the surface layer portion 200 are not separated from each other but integrated with each other. Therefore, in FIG. 1, since the central portion 100 and the surface layer portion 200 are continuous with each other, the above-mentioned boundary line is drawn in order to show that an interface does not exist between the central portion 100 and the surface layer portion 200. It is shown by a broken line.
  • the range in which magnesium is present in the lithium silicon-containing oxide is in the range of 10 nm to 3000 nm in the depth direction from the surface of the lithium silicon-containing oxide. This is because the existence range R is optimized, so that lithium in the negative electrode active material is not sufficiently eluted in the aqueous solvent.
  • This existence range R is a range in the depth direction from the surface of the lithium silicon-containing oxide, and is the thickness of the so-called surface layer portion 200.
  • the surface layer (surface layer portion 200) of the negative electrode active material may be analyzed by using an analysis method such as X-ray photoelectron spectroscopy (XPS).
  • the existence range R is preferably 50 nm to 3000 nm. This is because lithium in the negative electrode active material is less likely to elute in the aqueous solvent.
  • magnesium is bonded to silicon and oxygen in the lithium silicon-containing oxide, so that it forms a compound having a so-called Mg—Si—O bond. This is because lithium in the negative electrode active material is less likely to elute into the aqueous solvent.
  • magnesium forms any one or more of magnesium silicate represented by the formula (2).
  • the composition of magnesium silicate is not particularly limited, but specifically, it is MgSiO 3 and Mg 2 SiO 4 . This is because lithium in the negative electrode active material is not sufficiently eluted in the aqueous solvent.
  • the magnesium silicate may be only one kind of MgSiO 3 or the like, or two or more kinds of the MgSiO 3 or the like.
  • the surface layer portion 200 may be analyzed by using an analysis method such as XRD.
  • the ratio of the number of moles of magnesium M2 to the number of moles of lithium M1 (molar ratio M) is 0.1 mol% to 20 mol%. This is because the relationship between the amount of lithium and the amount of magnesium is optimized, so that the amount of lithium stored and released is secured, and the amount of lithium in the negative electrode active material is less likely to elute into the aqueous solvent.
  • this negative electrode active material includes a silicon-containing oxide forming step, a silicon silicon-containing oxide forming step (a lithium predoping step for a silicon-containing oxide), and a negative electrode active material forming step (a negative electrode active material forming step). It is produced by performing the surface doping step of magnesium with respect to the lithium silicon-containing oxide) in this order.
  • Step of forming silicon-containing oxide A mixture is obtained by mixing powdered silicon (Si) and powdered silicon dioxide (SiO 2 ) with each other.
  • the mixing ratio (weight ratio) of silicon and silicon dioxide can be arbitrarily set according to the composition of the lithium silicate phase 120 (lithium silicate) and the like.
  • the mixture is reduced and calcined at a high temperature to form a powdery silicon-containing oxide (SiO x (0 ⁇ x ⁇ 2)).
  • the firing temperature at the time of high-temperature reduction firing is not particularly limited, but specifically, it is 1400 ° C. or higher.
  • a lithium-containing solution is prepared by adding an additive to the solvent together with the lithium metal.
  • the form (shape) of the lithium metal is not particularly limited, but specifically, it is a lithium metal piece, a lithium metal foil, or the like.
  • the solvent is one or more of organic solvents such as ether, and specific examples of the ether are N-butyl methyl ether, tetrahydrofuran, dimethyl ether, diethyl ether, dibutyl ether, ethyl vinyl ether, and propyl vinyl ether.
  • the additive is any one or more of the polycyclic aromatic compounds and the like, and specific examples of the polycyclic aromatic compounds are naphthalene, anthracene and the like. However, the additive may be a compound other than the polycyclic aromatic compound.
  • the silicon-containing oxide is reacted with lithium in the lithium-containing solution.
  • lithium is pre-doped into the silicon-containing oxide, so that a powdery lithium-doped product of the silicon-containing oxide is formed.
  • the lithium-doped product of the silicon-containing oxide is dried.
  • the lithium-doped product of the silicon-containing oxide is calcined to form a powdered lithium silicon-containing oxide containing the above-mentioned silicon phase 110 and lithium silicate phase 120.
  • the firing temperature at the time of firing is not particularly limited, but specifically, it is 300 ° C. to 600 ° C., preferably 400 ° C. to 600 ° C.
  • the firing time at the time of firing is not particularly limited, but specifically, it is 10 minutes to 180 minutes.
  • the composition of the lithium silicate phase 120 (lithium silicate) can be controlled because the bonding state of lithium in the lithium silicon-containing oxide changes by adjusting the conditions such as the firing temperature and the firing time. Is.
  • the lithium silicon-containing oxide is washed with a cleaning solvent.
  • the type of the cleaning solvent is not particularly limited, but is any one or more of pure water and an organic solvent.
  • Formation step of negative electrode active material surface doping step of magnesium for lithium silicon-containing oxide
  • a mixture is obtained by mixing the powdered lithium silicon-containing oxide and the powdered magnesium with each other.
  • the mixing ratio weight ratio
  • the molar ratio M is 0.1 mol% to 20 mol%.
  • the firing temperature at the time of firing is not particularly limited, but specifically, it is 300 ° C. to 600 ° C., preferably 400 ° C. to 600 ° C.
  • the firing time at the time of firing is not particularly limited, but specifically, it is 10 minutes to 180 minutes.
  • magnesium is surface-doped into the lithium silicon-containing oxide to form magnesium silicate in the lithium silicon-containing oxide, so that the negative electrode active material (central portion 100 and surface layer portion 200) is completed. ..
  • the existence range R can be controlled because the diffusion amount (surface doping amount) of magnesium with respect to the lithium silicon-containing oxide changes by adjusting the conditions such as the firing temperature and the firing time.
  • lithium and silicon are contained as constituent elements and magnesium is contained in the surface layer of the lithium silicon-containing oxide, and the phase composition of the lithium silicon-containing oxide, the range of magnesium present, and magnesium. The above-mentioned conditions are satisfied with respect to each of the binding state and the magnesium content of.
  • the lithium silicon-containing oxide contains a silicon phase 110 and a lithium silicate phase 120.
  • the existence range R is 10 nm to 3000 nm.
  • Magnesium forms magnesium silicate.
  • the molar ratio M is 0.1 mol% to 20 mol%.
  • the lithium silicon-containing oxide contains the silicon phase 110, lithium is stably occluded and released in the silicon phase 110, and the lithium silicon silicate phase 120 in which the lithium silicon-containing oxide functions as a solid electrolyte is used. This is because, because it is contained, lithium is more easily occluded and released by utilizing the lithium silicate phase 120.
  • the relationship between the amount of lithium and the amount of magnesium is optimized, the amount of lithium stored and released is guaranteed, and the amount of lithium in the negative electrode active material is less likely to elute in the aqueous solvent.
  • lithium silicate contains Li 2 SiO 3 or the like, the lithium silicate sufficiently plays a role as a solid electrolyte, so that a higher effect can be obtained.
  • magnesium silicate contains MgSiO 3 or the like, lithium in the negative electrode active material is not sufficiently eluted in the aqueous solvent, so that a higher effect can be obtained.
  • lithium in the negative electrode active material is not sufficiently eluted in the aqueous solvent, so that a higher effect can be obtained.
  • the secondary battery described here is a secondary battery whose battery capacity can be obtained by utilizing the storage and release of an electrode reactant, and includes an electrolytic solution which is a liquid electrolyte together with a positive electrode and a negative electrode.
  • the charge capacity of the negative electrode is larger than the discharge capacity of the positive electrode in order to prevent the electrode reactant from precipitating on the surface of the negative electrode during charging. That is, the electrochemical capacity per unit area of the negative electrode is set to be larger than the electrochemical capacity per unit area of the positive electrode.
  • a secondary battery whose battery capacity can be obtained by utilizing the occlusion and release of lithium is a so-called lithium ion secondary battery.
  • FIG. 2 shows the perspective configuration of the secondary battery
  • FIG. 3 shows the cross-sectional configuration of the battery element 20 shown in FIG.
  • FIG. 2 shows a state in which the exterior film 10 and the battery element 20 are separated from each other
  • FIG. 3 shows only a part of the battery element 20.
  • this secondary battery includes an exterior film 10, a battery element 20, a positive electrode lead 31 and a negative electrode lead 32, and sealing films 41 and 42.
  • the secondary battery described here is a laminated film type secondary battery using a flexible (or flexible) exterior film 10 as an exterior member for accommodating the battery element 20.
  • the exterior film 10 is a flexible exterior member that houses the battery element 20, and has a bag-like structure in which the battery element 20 is housed inside. is doing. Therefore, the exterior film 10 stores the electrolytic solution together with the positive electrode 21 and the negative electrode 22 which will be described later.
  • the three-dimensional shape of the exterior film 10 is not particularly limited, but specifically, it corresponds to the three-dimensional shape of the battery element 20.
  • the three-dimensional shape of the exterior film 10 is a flat rectangular parallelepiped according to the three-dimensional shape of the flat battery element 20 described later.
  • the configuration (material, number of layers, etc.) of the exterior film 10 is not particularly limited, it may be a single-layer film or a multilayer film.
  • the exterior film 10 is a single film and can be folded in the direction of the arrow F (dashed-dotted line).
  • the exterior film 10 is provided with a recessed portion 10U (so-called deep drawing portion) for accommodating the battery element 20.
  • the exterior film 10 is a three-layer multilayer film (laminated film) in which a fusion layer, a metal layer, and a surface protective layer are laminated in this order from the inside.
  • a fusion layer In the folded state of the exterior film 10, the outer peripheral edges of the fused layers facing each other are joined to each other.
  • the fused layer contains a polymer compound such as polypropylene.
  • the metal layer contains a metallic material such as aluminum.
  • the surface protective layer contains a polymer compound such as nylon.
  • the sealing film 41 is inserted between the exterior film 10 and the positive electrode lead 31, and the sealing film 42 is inserted between the exterior film 10 and the negative electrode lead 32.
  • the sealing films 41 and 42 may be omitted.
  • the sealing film 41 is a sealing member that prevents outside air and the like from entering the inside of the exterior film 10. Further, the sealing film 41 contains a polymer compound such as a polyolefin having adhesion to the positive electrode lead 31, and a specific example of the polyolefin is polypropylene or the like.
  • the structure of the sealing film 42 is the same as that of the sealing film 41, except that it is a sealing member having adhesion to the negative electrode lead 32. That is, the sealing film 42 contains a polymer compound such as polyolefin having adhesion to the negative electrode lead 32.
  • the battery element 20 is housed inside the exterior film 10, and includes a positive electrode 21, a negative electrode 22, a separator 23, and an electrolytic solution (not shown). There is.
  • This battery element 20 is a so-called wound electrode body. That is, in the battery element 20, the positive electrode 21 and the negative electrode 22 are laminated with each other via the separator 23, and the positive electrode 21, the negative electrode 22 and the separator are centered on the winding shaft P which is a virtual axis extending in the Y-axis direction. 23 is wound. Therefore, the positive electrode 21 and the negative electrode 22 are wound while facing each other via the separator 23.
  • the three-dimensional shape of the battery element 20 is a flat, substantially cylindrical body. That is, the shape of the cross section (cross section along the XZ plane) of the battery element 20 intersecting the winding axis P is a flat shape defined by the long axis J1 and the short axis J2, and more specifically, it is flat. It is almost oval.
  • the long axis J1 is a virtual axis extending in the X-axis direction and having a relatively large length
  • the short axis J2 extends in the Z-axis direction intersecting the X-axis direction and is relative. It is a virtual axis with a small length.
  • the positive electrode 21 includes a positive electrode current collector 21A and a positive electrode active material layer 21B.
  • the positive electrode current collector 21A has a pair of surfaces on which the positive electrode active material layer 21B is provided.
  • the positive electrode current collector 21A contains a conductive material such as a metal material, and the metal material is aluminum or the like.
  • the positive electrode active material layer 21B is provided on both sides of the positive electrode current collector 21A, and contains any one or more of the positive electrode active materials that occlude and release lithium.
  • the positive electrode active material layer 21B may be provided on only one side of the positive electrode current collector 21A on the side where the positive electrode 21 faces the negative electrode 22.
  • the positive electrode active material layer 21B may further contain a positive electrode binder, a positive electrode conductive agent, and the like.
  • the method for forming the positive electrode active material layer 21B is not particularly limited, but specifically, it is a coating method or the like.
  • the positive electrode active material contains a lithium compound.
  • This lithium compound is a compound containing lithium as a constituent element, and more specifically, a compound containing one or more kinds of transition metal elements as a constituent element together with lithium. This is because a high energy density can be obtained.
  • the lithium compound may further contain any one or more of other elements (elements other than lithium and transition metal elements).
  • the type of the lithium compound is not particularly limited, and specific examples thereof include oxides, phosphoric acid compounds, silicic acid compounds and boric acid compounds. Specific examples of oxides are LiNiO 2 , LiCoO 2 and LiMn 2 O 4 , and specific examples of phosphoric acid compounds are LiFePO 4 and LiMnPO 4 .
  • the positive electrode binder contains any one or more of synthetic rubber and polymer compounds.
  • the synthetic rubber is styrene-butadiene rubber or the like, and the polymer compound is polyvinylidene fluoride or the like.
  • the positive electrode conductive agent contains any one or more of the conductive materials such as carbon material, and the carbon material is graphite, carbon black, acetylene black, ketjen black and the like.
  • the conductive material may be a metal material, a polymer compound, or the like.
  • the negative electrode 22 includes a negative electrode current collector 22A and a negative electrode active material layer 22B.
  • the negative electrode current collector 22A has a pair of surfaces on which the negative electrode active material layer 22B is provided.
  • the negative electrode current collector 22A contains a conductive material such as a metal material, and the metal material is copper or the like.
  • the negative electrode active material layer 22B is provided on both sides of the negative electrode current collector 22A and contains the above-mentioned negative electrode active material.
  • the negative electrode active material layer 22B may be provided on only one side of the negative electrode current collector 22A on the side where the negative electrode 22 faces the positive electrode 21.
  • the negative electrode active material layer 22B may further contain a negative electrode binder, a negative electrode conductive agent, and the like.
  • the method for forming the negative electrode active material layer 22B is not particularly limited, but specifically, any one of a coating method, a gas phase method, a liquid phase method, a thermal spraying method, a firing method (sintering method), and the like, or There are two or more types.
  • each of the negative electrode binder and the negative electrode conductive agent are the same as the details regarding each of the positive electrode binder and the positive electrode conductive agent.
  • the negative electrode active material layer 22B may further contain any one or more of the other negative electrode active materials that occlude and release lithium.
  • Other negative electrode active materials are one or both of carbon materials and metal-based materials. This is because a high energy density can be obtained.
  • Carbon materials include graphitizable carbon, non-graphitizable carbon and graphite (natural graphite and artificial graphite).
  • the metal-based material is a material containing one or more of metal elements and semi-metal elements capable of forming an alloy with lithium as constituent elements, and the metal elements and semi-metal elements are silicon and semi-metal elements. One or both of the tin.
  • the metal-based material may be a simple substance, an alloy, a compound, a mixture of two or more of them, or a material containing two or more of these phases.
  • Specific examples of the metallic material are TiSi 2 and SiO x (0 ⁇ x ⁇ 2 or 0.2 ⁇ x ⁇ 1.4).
  • the above-mentioned negative electrode active material is excluded from the metal-based materials described here.
  • the separator 23 is an insulating porous film interposed between the positive electrode 21 and the negative electrode 22, and while preventing contact (short circuit) between the positive electrode 21 and the negative electrode 22. Allows lithium ions to pass through.
  • the separator 23 contains a polymer compound such as polyethylene.
  • Electrolytic solution The electrolytic solution is impregnated in each of the positive electrode 21, the negative electrode 22, and the separator 23, and contains a solvent and an electrolyte salt.
  • the solvent contains any one or more of non-aqueous solvents (organic solvents) such as carbonic acid ester compounds, carboxylic acid ester compounds and lactone compounds, and contains the non-aqueous solvent.
  • the electrolytic solution is a so-called non-aqueous electrolytic solution.
  • the electrolyte salt contains any one or more of light metal salts such as lithium salts.
  • the positive electrode lead 31 is a positive electrode terminal connected to the battery element 20 (positive electrode 21), and more specifically, is connected to the positive electrode current collector 21A.
  • the positive electrode lead 31 is led out to the outside of the exterior film 10 and contains a conductive material such as aluminum.
  • the shape of the positive electrode lead 31 is not particularly limited, but specifically, it is one of a thin plate shape and a mesh shape.
  • the negative electrode lead 32 is a negative electrode terminal connected to the battery element 20 (negative electrode 22), and more specifically, is connected to the negative electrode current collector 22A.
  • the negative electrode lead 32 is led out to the outside of the exterior film 10 and contains a conductive material such as copper.
  • the lead-out direction of the negative electrode lead 32 is the same as the lead-out direction of the positive electrode lead 31.
  • the details regarding the shape of the negative electrode lead 32 are the same as the details regarding the shape of the positive electrode lead 31.
  • the positive electrode active material, the positive electrode binder and the positive electrode conductive agent are mixed with each other to obtain a positive electrode mixture.
  • the positive electrode mixture is added to the solvent to prepare a paste-like positive electrode mixture slurry.
  • the type of the solvent is not particularly limited, but specifically, it may be an aqueous solvent or a non-aqueous solvent (organic solvent).
  • the aqueous solvent is pure water or the like, and the details regarding the types of the aqueous solvent described here will be the same thereafter.
  • the positive electrode active material layer 21B is formed by applying the positive electrode mixture slurry on both sides of the positive electrode current collector 21A.
  • the positive electrode active material layer 21B may be compression-molded using a roll press machine or the like. In this case, the positive electrode active material layer 21B may be heated, or compression molding may be repeated a plurality of times. As a result, the positive electrode 21 is manufactured.
  • the negative electrode active material layers 22B are formed on both sides of the negative electrode current collector 22A by the same procedure as the procedure for manufacturing the positive electrode 21. Specifically, a negative electrode active material, a negative electrode binder, and a negative electrode conductive agent are mixed with each other to form a negative electrode mixture, and then a negative electrode mixture is added to a solvent (aqueous solvent) to form a paste-like negative electrode. Prepare a mixture slurry. Subsequently, the negative electrode mixture layer 22B is formed by applying the negative electrode mixture slurry on both sides of the negative electrode current collector 22A. After that, the negative electrode active material layer 22B may be compression-molded. As a result, the negative electrode 22 is manufactured.
  • the positive electrode lead 31 is connected to the positive electrode 21 (positive electrode current collector 21A) and the negative electrode lead 32 is connected to the negative electrode 22 (negative electrode current collector 22A) by using a welding method or the like.
  • the positive electrode 21 and the negative electrode 22 are laminated with each other via the separator 23, and then the positive electrode 21, the negative electrode 22 and the separator 23 are wound to produce a wound body (not shown).
  • This winding body has the same configuration as that of the battery element 20 except that the positive electrode 21, the negative electrode 22, and the separator 23 are not impregnated with the electrolytic solution.
  • the winding body is molded into a flat shape by pressing the winding body using a press machine or the like.
  • the exterior films 10 (fused layer / metal layer / surface protection layer) are folded so that the exterior films 10 face each other. Subsequently, by joining the outer peripheral edges of the two sides of the exterior films 10 (fused layers) facing each other to each other by using a heat fusion method or the like, the film is wound inside the bag-shaped exterior film 10. Store your body.
  • the outer peripheral edges of the remaining one side of the exterior film 10 are joined to each other by a heat fusion method or the like.
  • the sealing film 41 is inserted between the exterior film 10 and the positive electrode lead 31, and the sealing film 42 is inserted between the exterior film 10 and the negative electrode lead 32.
  • the wound body is impregnated with the electrolytic solution, so that the battery element 20 which is a wound electrode body is manufactured, and the battery element 20 is enclosed inside the bag-shaped exterior film 10, so that it is secondary. Batteries are assembled.
  • the negative electrode 22 contains the above-mentioned negative electrode active material.
  • the negative electrode mixture slurry is prepared using an aqueous solvent as the solvent, so that the alkalinity of the negative electrode mixture slurry is suppressed, so that the negative electrode binder is polymerized (aggregated) in the negative electrode mixture slurry. ) It becomes difficult. As a result, the negative electrode binder is easily dispersed in the negative electrode mixture slurry, so that the adhesion strength (peeling strength) of the negative electrode active material layer 22B to the negative electrode current collector 22A increases. Therefore, the negative electrode active material layer 22B is less likely to collapse, and the negative electrode active material layer 22B is less likely to fall off from the negative electrode current collector 22A.
  • lithium is easily occluded and released in the negative electrode 22 (negative electrode active material layer 22B), so that the amount of lithium stored and released is guaranteed.
  • the secondary battery is a lithium-ion secondary battery
  • a sufficient battery capacity can be stably obtained by utilizing the occlusion and release of lithium, so that a higher effect can be obtained.
  • the negative electrode active material layer 22B is in close contact with the negative electrode current collector 22A while the amount of lithium stored and released is secured. Be maintained. Therefore, excellent cycle characteristics can be obtained in the secondary battery using the negative electrode 22.
  • the other actions and effects of the secondary battery and the negative electrode 22 are the same as the other actions and effects of the negative electrode active material described above.
  • the laminated separator includes a porous membrane having a pair of faces and a polymer compound layer arranged on one or both sides of the porous membrane. This is because the adhesion of the separator to each of the positive electrode 21 and the negative electrode 22 is improved, so that the position shift (winding shift) of the battery element 20 is less likely to occur. As a result, even if a decomposition reaction of the electrolytic solution occurs, the secondary battery is less likely to swell.
  • the polymer compound layer contains a polymer compound such as polyvinylidene fluoride. This is because polyvinylidene fluoride and the like have excellent physical strength and are electrochemically stable.
  • one or both of the porous membrane and the polymer compound layer may contain any one or more of the plurality of insulating particles. This is because a plurality of insulating particles dissipate heat when the secondary battery generates heat, so that the safety (heat resistance) of the secondary battery is improved.
  • Insulating particles include inorganic particles and resin particles. Specific examples of the inorganic particles are particles such as aluminum oxide, aluminum nitride, boehmite, silicon oxide, titanium oxide, magnesium oxide and zirconium oxide. Specific examples of the resin particles are particles such as acrylic resin and styrene resin.
  • a precursor solution containing a polymer compound, an organic solvent, etc. When producing a laminated separator, prepare a precursor solution containing a polymer compound, an organic solvent, etc., and then apply the precursor solution to one or both sides of the porous membrane. In this case, a plurality of insulating particles may be added to the precursor solution as needed.
  • lithium ions can move between the positive electrode 21 and the negative electrode 22, so that the same effect can be obtained.
  • the positive electrode 21 and the negative electrode 22 are laminated with each other via the separator 23 and the electrolyte layer, and the positive electrode 21, the negative electrode 22, the separator 23 and the electrolyte layer are wound around the battery element 20.
  • This electrolyte layer is interposed between the positive electrode 21 and the separator 23, and is interposed between the negative electrode 22 and the separator 23.
  • the electrolyte layer contains a polymer compound together with the electrolytic solution, and the electrolytic solution is held by the polymer compound. This is because leakage of the electrolytic solution is prevented.
  • the structure of the electrolytic solution is as described above.
  • the polymer compound contains polyvinylidene fluoride and the like.
  • the application (application example) of the secondary battery is not particularly limited.
  • the secondary battery used as a power source may be a main power source for electronic devices and electric vehicles, or may be an auxiliary power source.
  • the main power source is a power source that is preferentially used regardless of the presence or absence of another power source.
  • the auxiliary power supply is a power supply used in place of the main power supply or a power supply that can be switched from the main power supply.
  • secondary batteries Specific examples of applications for secondary batteries are as follows.
  • Electronic devices including portable electronic devices
  • a storage device such as a backup power supply and a memory card.
  • Power tools such as electric drills and saws.
  • It is a battery pack installed in electronic devices.
  • Medical electronic devices such as pacemakers and hearing aids.
  • It is an electric vehicle such as an electric vehicle (including a hybrid vehicle).
  • It is a power storage system such as a household or industrial battery system that stores power in case of an emergency.
  • one secondary battery may be used, or a plurality of secondary batteries may be used.
  • the battery pack may use a single battery or an assembled battery.
  • the electric vehicle is a vehicle that operates (runs) using a secondary battery as a drive power source, and may be a hybrid vehicle that also has a drive source other than the secondary battery as described above.
  • household electric products and the like can be used by using the power stored in a secondary battery which is a power storage source.
  • FIG. 4 shows the block configuration of the battery pack.
  • the battery pack described here is a battery pack (so-called soft pack) using one secondary battery, and is mounted on an electronic device represented by a smartphone.
  • this battery pack includes a power supply 51 and a circuit board 52.
  • the circuit board 52 is connected to the power supply 51 and includes a positive electrode terminal 53, a negative electrode terminal 54, and a temperature detection terminal 55.
  • the power supply 51 includes one secondary battery.
  • the positive electrode lead is connected to the positive electrode terminal 53
  • the negative electrode lead is connected to the negative electrode terminal 54. Since the power supply 51 can be connected to the outside via the positive electrode terminal 53 and the negative electrode terminal 54, it can be charged and discharged.
  • the circuit board 52 includes a control unit 56, a switch 57, a heat-sensitive resistance element (PTC element) 58, and a temperature detection unit 59. However, the PTC element 58 may be omitted.
  • the control unit 56 includes a central processing unit (CPU), a memory, and the like, and controls the operation of the entire battery pack.
  • the control unit 56 detects and controls the usage state of the power supply 51 as needed.
  • the overcharge detection voltage is not particularly limited, but specifically, it is 4.2 V ⁇ 0.05 V.
  • the over-discharge detection voltage is not particularly limited, but is specifically 2.4 V ⁇ 0.1 V.
  • the switch 57 includes a charge control switch, a discharge control switch, a charging diode, a discharging diode, and the like, and switches whether or not the power supply 51 is connected to an external device according to an instruction from the control unit 56.
  • the switch 57 includes a field effect transistor (MOSFET) using a metal oxide semiconductor, and the charge / discharge current is detected based on the ON resistance of the switch 57.
  • MOSFET field effect transistor
  • the temperature detection unit 59 includes a temperature detection element such as a thermistor, measures the temperature of the power supply 51 using the temperature detection terminal 55, and outputs the measurement result of the temperature to the control unit 56.
  • the temperature measurement result measured by the temperature detection unit 59 is used when the control unit 56 performs charge / discharge control when abnormal heat generation occurs, or when the control unit 56 performs correction processing when calculating the remaining capacity.
  • FIG. 5 shows a cross-sectional configuration of a secondary battery (coin type) for testing.
  • a secondary battery coin type
  • the test pole 61 is housed inside the outer cup 64, and the counter electrode 63 is housed inside the outer can 62.
  • the test pole 61 and the counter electrode 63 are laminated to each other via the separator 65, and the outer can 62 and the outer cup 64 are crimped to each other via the gasket 66.
  • the electrolytic solution is impregnated in each of the test electrode 61, the counter electrode 63 and the separator 65.
  • the negative electrode active material was produced by the procedure described below.
  • a mixed powder was obtained by mixing the silicon powder and the silicon dioxide powder with each other.
  • the silicon-containing oxide powder was put into the lithium-containing solution, the silicon-containing oxide was reacted with the lithium-containing solution by stirring the lithium-containing solution.
  • the input amount of the silicon-containing oxide powder was set to 70% by weight.
  • the lithium-doped powder of the silicon-containing oxide was recovered from the lithium-containing aqueous solution, and then the lithium-doped powder of the silicon-containing oxide was dried.
  • three types of lithium silicon-containing oxides were formed by setting three types of firing temperatures. Specifically, the lithium silicon-containing oxide (LiSiOA) was formed by setting the firing temperature to 580 ° C. Further, by setting the firing temperature to 500 ° C., a lithium silicon-containing oxide (LiSiOB) was formed. Further, by setting the firing temperature to 400 ° C., a lithium silicon-containing oxide (LiSiOC) was formed. Subsequently, the lithium silicon-containing oxide powder was washed with a cleaning solvent (dimethyl carbonate), and then the lithium silicon-containing oxide powder was washed with another cleaning solvent (pure water).
  • a cleaning solvent dimethyl carbonate
  • the lithium silicon-containing oxide When the lithium silicon-containing oxide was analyzed using XRD, the lithium silicon-containing oxide contained a silicon phase 110 and a lithium silicate phase 120.
  • the lithium silicate phase 120 contained Li 2 SiO 3 , Li 2 Si 2 O 5 , Li 4 SiO 4 and Li 6 Si 2 O 7 , as shown in Tables 1 and 2.
  • the lithium silicon-containing oxide powder and the magnesium powder were mixed with each other to obtain a mixed powder.
  • the molar ratio M (mol%) was adjusted as shown in Tables 1 and 2 by changing the mixing ratio (weight ratio) of the lithium silicon-containing oxide powder and the magnesium powder.
  • the "Surface Dope" column shown in each of Tables 1 and 2 indicates whether or not the lithium silicon-containing oxide was surface-doped with magnesium.
  • the lithium silicon-containing oxide is surface-doped with magnesium, it is indicated as "Mg" in the "surface-doped” column.
  • the mixed powder was fired.
  • the calcination is present by changing the calcination temperature in the range of 300 ° C. to 600 ° C. and the calcination time in the range of 10 minutes to 180 minutes.
  • the range R (nm) was adjusted.
  • magnesium silicate contained MgSiO 3 and Mg2 SiO 4 , as shown in Tables 1 and 2 .
  • test pole 61 the test pole 61, the counter electrode 63 and the separator 65 were enclosed inside the outer cup 64 and the outer can 62, so that a coin-shaped secondary battery was assembled.
  • 0.2C is a current value that can completely discharge the battery capacity (theoretical capacity) in 5 hours
  • 0.025C is a current value that can completely discharge the battery capacity in 40 hours.
  • the discharge capacity discharge capacity in the first cycle
  • the discharge capacity discharge capacity at the 100th cycle
  • the charging / discharging conditions were the same as the charging / discharging conditions at the time of stabilization of the secondary battery described above, except that the charging current and the discharging current were each changed to 0.7C.
  • 0.7C is a current value that can completely discharge the battery capacity in 10/7 hours.
  • the negative electrode mixture slurry was prepared by the above procedure, and then the state of the negative electrode mixture slurry was visually confirmed. As a result, it was investigated whether or not the negative electrode mixture slurry was gelled due to the polymerization (aggregation) of the negative electrode binder.
  • the amount of lithium hydroxide generated (%) that affects the pH of the negative electrode mixture slurry was examined.
  • elution amount (%) (weight of precipitate / weight of dispersion solution) ⁇ 100.
  • the existence range R is in the appropriate range, and the molar ratio M is also in the appropriate range (Examples 1 to 14), the negative electrode mixture is prepared.
  • the slurry did not gel, the amount of elution decreased, and the capacity retention rate increased.
  • the existence range R is 50 nm to 3000 nm, the capacity retention rate is further increased.
  • the negative electrode active material contains lithium and silicon as constituent elements and magnesium is contained in the surface layer of the lithium silicon-containing oxide, and the phase composition of the lithium silicon-containing oxide is contained.
  • the capacity retention rate increased when the above conditions were met for each of the magnesium abundance range, magnesium binding state and magnesium content. Therefore, excellent cycle characteristics were obtained in the secondary battery.
  • the battery structure of the secondary battery is a laminated film type has been described, but the battery structure is not particularly limited. Specifically, the battery structure may be cylindrical, square, coin-shaped, button-shaped, or the like.
  • the element structure of the battery element is not particularly limited.
  • the element structure may be a laminated type in which electrodes (positive electrode and negative electrode) are laminated, or a zigzag folded type in which the electrodes are folded in a zigzag manner.
  • the electrode reactant is not particularly limited. Specifically, as described above, the electrode reactant may be another alkali metal such as sodium and potassium, or an alkaline earth metal such as beryllium, magnesium and calcium. In addition, the electrode reactant may be another light metal such as aluminum.
  • the negative electrode active material for a secondary battery and the negative electrode for a secondary battery are not limited to the secondary battery, they may be applied to other electrochemical devices such as capacitors.

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