Classifications

• • 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
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0569—Liquid materials characterised by the solvents
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/46—Metal oxides
• • 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
  • H01G11/54—Electrolytes
  • H01G11/58—Liquid electrolytes
• • 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
  • H01G11/54—Electrolytes
  • H01G11/58—Liquid electrolytes
  • H01G11/64—Liquid electrolytes characterised by additives
• • 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
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
• • 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
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
• • 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
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
• • 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
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• • 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
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0025—Organic electrolyte
• • 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 non-aqueous electrolyte solution and a non-aqueous electrolyte battery, and more particularly, a non-aqueous electrolyte solution containing a specific amount of a specific compound and a specific amount of ions of a specific metal element, and a non-aqueous electrolyte solution using the non-aqueous electrolyte solution.
• a non-aqueous electrolyte solution containing a specific amount of a specific compound and a specific amount of ions of a specific metal element
• a non-aqueous electrolyte solution using the non-aqueous electrolyte solution Regarding water-based electrolyte batteries.
• non-aqueous electrolyte batteries such as lithium secondary batteries have been put into practical use in applications of in-vehicle power supplies for driving such as for electric vehicles.
• Patent Document 1 contains at least one fluorosulfonate represented by M (FSO 3 ) x for the purpose of improving the initial charge capacity and input / output characteristics of a non-aqueous electrolyte secondary battery.
• a nonaqueous electrolyte further adding to LiPF 6, and the nonaqueous electrolyte and a nonaqueous electrolyte secondary battery according to a specific range of ratio between the fluorosulfonic acid salt and LiPF 6 is disclosed.
• Patent Document 2 provides a non-aqueous electrolyte solution capable of improving electrochemical properties in a wide temperature range, and a non-aqueous electrolyte solution in which an electrolyte salt is dissolved in a non-aqueous solvent for the purpose of providing a storage device using the non-aqueous electrolyte solution.
• a non-aqueous electrolytic solution containing 0.001 to 5% by mass of a specific acyclic lithium salt in the non-aqueous electrolytic solution, and a power storage device using the non-aqueous electrolytic solution.
• Patent Document 3 aims to provide a non-aqueous electrolyte secondary battery in which a stable film is formed on the surface of a negative electrode active material (graphite material) and can exhibit higher battery performance.
• a non-aqueous electrolyte secondary battery comprising an electrode body containing, and a non-aqueous electrolyte solution; the negative electrode includes a negative electrode active material layer mainly composed of a graphite material, and the amount of acidic functional groups of the graphite material. Is 1 ⁇ eq / m 2 or more, and a film containing a sulfur (S) atom and a charge carrier is formed on the surface of the graphite material, and the non-aqueous electrolyte secondary battery is disclosed. Has been done.
• Patent Document 4 provides a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and a non-aqueous electrolyte for the purpose of providing a lithium ion secondary battery having excellent durability.
• a lithium ion secondary battery is disclosed in which tungsten is present on the surface of the substance and lithium fluorosulfonate is added to the non-aqueous electrolyte. According to the document, due to the above configuration, even if the battery is used for a long period of time, the metal element attached to the surface of the positive electrode does not elute into the non-aqueous electrolyte, and a low reaction resistance is maintained for a long period of time. It is stated that it is possible to provide a lithium ion battery having excellent durability.
• the present invention is excellent in a non-aqueous electrolyte solution and a high-temperature environment, which can improve the charge storage characteristics of the non-aqueous electrolyte battery in a high-temperature environment, even though it is a non-aqueous electrolyte solution containing FSO 3 Li.
• a non-aqueous electrolyte battery having a charge storage property.
• the present inventor has further obtained nickel ions (a), cobalt ions (b), copper ions (c), and manganese ions (c) for non-aqueous electrolyte solutions containing FSO 3 Li. It contains at least one metal ion selected from the group consisting of d) and aluminum ion (e), and the content of any of the metal ions (a) to (e) is within a specific range. As a result, they have found that the charge storage characteristics of a non-aqueous electrolyte battery in a high temperature environment can be improved, and have reached the present invention.
• the concentration of (a) is 1 mass ppm or more and 500 mass ppm or less (ii)
• the concentration of (b) is 1 mass ppm or more and 500 mass ppm or less (iii)
• the concentration of (c) is 1 mass ppm or more 500 mass ppm or less (iv)
• Concentration of the above (d) is 1 mass ppm or more and 100 mass ppm or less (v)
• Concentration of the above (e) is 1 mass ppm or more and 100 mass ppm or less [2]
• At least nickel ion (a) The non-aqueous electrolyte solution according to [1].
• a non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of occluding and releasing metal ions and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution contains (1a) FSO 3 Li.
• (1b) Contains at least one metal ion selected from the group consisting of nickel ion (a), cobalt ion (b), copper ion (c), manganese ion (d) and aluminum ion (e), and (1c).
• a non-aqueous electrolyte battery which is a non-aqueous electrolyte that satisfies at least one of the following conditions (i) to (v).
• the concentration of (a) is 1 mass ppm or more and 500 mass ppm or less (ii)
• the concentration of (b) is 1 mass ppm or more and 500 mass ppm or less (iii)
• the concentration of (c) is 1 mass ppm or more 500 mass ppm or less (iv)
• the concentration of (d) is 1 mass ppm or more and 100 mass ppm or less (v)
• the concentration of (e) is 1 mass ppm or more and 100 mass ppm or less [7]
• the positive electrode is a current collector and
• the non-aqueous electrolyte battery according to [6] which has a positive electrode active material layer provided on the current collector, and the positive positive active material is a metal oxide represented by the following composition formula (1).
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector, and the positive electrode active material is a metal oxide represented by the following composition formula (2). 7] The non-aqueous electrolyte battery. Li a2 Ni b2 Co c2 M d2 O 2 ...
• the present inventor has made that the electrolytic solution containing FSO 3 Li further contains nickel ions and the nickel ion content is within a specific range.
• the charge storage characteristics of a non-aqueous electrolyte battery in a high temperature environment can be improved by using a liquid, and have reached aspect A of the present invention.
• the aspect A of the present invention provides the specific aspects shown in the following [A1] to [A8].
• [A1] A non-aqueous electrolyte solution containing FSO 3 Li and containing nickel ions of 1 mass ppm or more and 500 mass ppm or less.
• [A2] The non-aqueous electrolyte solution according to [A1], wherein the content of FSO 3 Li is 0.001% by mass or more and 10.0% by mass or less.
• a non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of occluding and releasing metal ions and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution contains FSO 3 Li and contains 1 mass ppm or more of nickel ions.
• a non-aqueous electrolyte battery which is a non-aqueous electrolyte containing 500 mass ppm or less.
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector, and the positive electrode active material is a metal oxide represented by the following composition formula (1).
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector, and the positive electrode active material is a metal oxide represented by the following composition formula (2).
• [A7] The non-aqueous electrolyte battery according to [A3], [A5] or [A6], wherein the positive electrode is an NMC positive electrode, and the content of nickel element in the NMC positive electrode is 40 mol% or more.
• [A8] The non-aqueous electrolyte battery according to any one of [A3] to [A7], wherein the content of FSO 3 Li in the non-aqueous electrolyte is 0.001% by mass or more and 10.0% by mass or less. ..
• the present inventor has made that the non-aqueous electrolyte solution containing FSO 3 Li further contains cobalt ions and the cobalt ion content is within a specific range.
• the charge storage characteristics of a non-aqueous electrolyte battery in a high temperature environment can be improved by using an aqueous electrolyte, and have reached aspect B of the present invention.
• the aspect B of the present invention provides the specific aspects shown in the following [B1] to [B8].
• [B1] A non-aqueous electrolyte solution containing FSO 3 Li and containing cobalt ions of 1 mass ppm or more and 500 mass ppm or less.
• [B2] The non-aqueous electrolyte solution according to [B1], wherein the content of FSO 3 Li is 0.001% by mass or more and 10.0% by mass or less.
• a non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of occluding and releasing metal ions and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution contains FSO 3 Li and contains 1 mass ppm or more of cobalt ions.
• a non-aqueous electrolyte battery which is a non-aqueous electrolyte containing 500 mass ppm or less.
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector, and the positive electrode active material is a metal oxide represented by the following composition formula (1). B3]. The non-aqueous electrolyte battery.
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector, and the positive electrode active material is a metal oxide represented by the following composition formula (2). B3].
• the non-aqueous electrolyte battery Li a2 Ni b2 Co c2 M d2 O 2 ...
• the present inventor has found that the non-aqueous electrolyte solution containing FSO 3 Li further contains copper ions and the copper ion content is within a specific range.
• the charge storage characteristics of a non-aqueous electrolyte battery in a high temperature environment can be improved by using an aqueous electrolyte, and have reached aspect C of the present invention.
• the aspect C of the present invention provides the specific aspects shown in the following [C1] to [C8].
• [C1] A non-aqueous electrolyte solution containing FSO 3 Li and containing copper ions of 1 mass ppm or more and 500 mass ppm or less.
• [C2] The non-aqueous electrolyte solution according to [C1], wherein the content of FSO 3 Li is 0.001% by mass or more and 10.0% by mass or less.
• a non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of occluding and releasing metal ions and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution contains FSO 3 Li and contains 1 mass ppm or more of copper ions.
• a non-aqueous electrolyte battery which is a non-aqueous electrolyte containing 500 mass ppm or less.
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector, and the positive electrode active material is a metal oxide represented by the following composition formula (1). C3].
• the non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of occluding and releasing metal ions and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution contains FSO 3 Li and contains 1 mass ppm or more of copper ions.
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector, and the positive electrode active material is a metal oxide represented by the following composition formula (2). C3].
• the non-aqueous electrolyte battery Li a2 Ni b2 Co c2 M d2 O 2 ...
• the present inventor has made that the non-aqueous electrolyte solution containing FSO 3 Li further contains manganese ions and the manganese ion content is within a specific range.
• the charge storage characteristics of a non-aqueous electrolyte battery in a high temperature environment can be improved by using an aqueous electrolyte, and have reached aspect D of the present invention.
• the aspect D of the present invention provides the specific aspects shown in the following [D1] to [D8].
• [D1] A non-aqueous electrolyte solution containing FSO 3 Li and containing manganese ions of 1 mass ppm or more and 100 mass ppm or less.
• [D2] The non-aqueous electrolyte solution according to [D1], wherein the content of FSO 3 Li is 0.001% by mass or more and 10.0% by mass or less.
• a non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of occluding and releasing metal ions and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution contains FSO 3 Li and contains manganese ions in an amount of 1 mass ppm or more.
• a non-aqueous electrolyte battery which is a non-aqueous electrolyte containing 100% by mass or less.
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector, and the positive electrode active material is a metal oxide represented by the following composition formula (1). D3].
• the non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of occluding and releasing metal ions and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution contains FSO 3 Li and contains manganese ions in an amount of 1 mass ppm or
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector, and the positive electrode active material is a metal oxide represented by the following composition formula (2). D3].
• the non-aqueous electrolyte battery Li a2 Ni b2 Co c2 M d2 O 2 ...
• [D7] The non-aqueous electrolyte battery according to [D3], [D5] or [D6], wherein the positive electrode is an NMC positive electrode, and the content of nickel element in the NMC positive electrode is 40 mol% or more.
• [D8] The non-aqueous electrolyte battery according to any one of [D3] to [D7], wherein the content of FSO 3 Li in the non-aqueous electrolyte is 0.001% by mass or more and 10.0% by mass or less. ..
• the present inventor has determined that the non-aqueous electrolyte solution containing FSO 3 Li further contains aluminum ions and the content of aluminum ions is within a specific range. As a result, it was found that the charge storage characteristics of the non-aqueous electrolyte battery in a high temperature environment can be improved, and the aspect E of the present invention was reached.
• the aspect E of the present invention provides the specific aspects shown in the following [E1] to [E8].
• [E1] A non-aqueous electrolyte solution containing FSO 3 Li and containing aluminum ions in an amount of 1 mass ppm or more and 100 mass ppm or less.
• [E2] The non-aqueous electrolyte solution according to [E1], wherein the content of FSO 3 Li is 0.001% by mass or more and 10.0% by mass or less.
• a non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of occluding and releasing metal ions and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution contains FSO 3 Li and contains 1 mass ppm or more of aluminum ions.
• a non-aqueous electrolyte battery which is a non-aqueous electrolyte containing 100% by mass or less.
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector, and the positive electrode active material is a metal oxide represented by the following composition formula (1).
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector, and the positive electrode active material is a metal oxide represented by the following composition formula (2).
• non-aqueous electrolyte solution of the present invention it is possible to obtain a non-aqueous electrolyte battery having improved charge storage characteristics in a high temperature environment.
• Non-aqueous electrolyte solution contains FSO 3 Li and contains ions of a specific metal element in an amount in a specific range.
• the non-aqueous electrolyte solution according to the embodiment of the present invention will be described in detail. The description of each item of the present specification is applicable to all aspects except the description regarding ions of a specific metal element.
• the non-aqueous electrolyte solution of this embodiment contains FSO 3 Li.
• the content of FSO 3 Li is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.010% by mass or more, and particularly preferably 0.10% by mass in the non-aqueous electrolyte solution.
• % Or more while the upper limit is not particularly limited, but is preferably 10.0% by mass or less, more preferably 7.0% by mass or less, still more preferably 5.0% by mass or less, and particularly still more preferable. Is 4.0% by mass or less, particularly preferably 3.0% by mass or less.
• FSO 3 Li When the content of FSO 3 Li is 10.0% by mass or less in the non-aqueous electrolyte solution, the negative electrode reduction reaction does not increase as the internal resistance of the non-aqueous electrolyte battery increases, which is preferable. When it is 0.001% by mass or more, it is preferable because the effect of the present application of containing FSO 3 Li is produced. Therefore, within the above range, the charge storage characteristics in a high temperature environment can be improved by suppressing the negative electrode reduction reaction in a high temperature environment.
• FSO 3 Li may be synthesized and used by a known method, or a commercially available product may be obtained and used.
• detection method suppressor with conductivity detection method (12.5mM H 2 SO 4)
• detects a SO 4 2-ions separated by, FSO 3 - ions of SO 4 2-ions from the calibration curve, the molar sensitivity ratio [k (SO 4 2-) / k (FSO 3 -)] 2.0 in terms as FSO 3 - can be quantified ions.
• FSO 3 - can be regarded as the amount of ions to the amount of FSO 3 Li.
• a compound containing FSO 3 - ion can be used as a specific metal ion source.
• Al (FSO 3 ) 3 may be used as the aluminum ion source.
• the amount of FSO 3 Li may be obtained by subtracting the amount of FSO 3 ⁇ ions derived from Al (FSO 3 ) 3 from the total amount of FSO 3 ⁇ ions in the non-aqueous electrolyte solution.
• FSO 3 nonaqueous electrolytic solution - the amount of ions may be regarded as the amount of FSO 3 Li.
• the non-aqueous electrolyte solution according to one embodiment of the present invention is selected from the group consisting of nickel ions (a), cobalt ions (b), copper ions (c), manganese ions (d), and aluminum ions (e). It contains at least one metal ion and satisfies at least one of the following conditions (i) to (v).
• the concentration of (a) is 1 mass ppm or more and 500 mass ppm or less (ii)
• the concentration of (b) is 1 mass ppm or more and 500 mass ppm or less (iii)
• the concentration of (c) is 1 mass ppm or more and 500 mass ppm or less below (iv)
• the concentration of (d) is 1 mass ppm or more and 100 mass ppm or less (v)
• the concentration of (e) is 1 mass ppm or more and 100 mass ppm or less
• the specific ion (a) in the non-aqueous electrolyte solution )-(E) is the concentration of the ion of a specific metal element in the non-aqueous electrolyte solution (100% by mass).
• the valence of the ions of a specific metal element may be any valence, or may be a combination of metal ions having different valences. Further, it may contain a plurality of types of metal ions.
• a member containing the non-aqueous electrolyte can be taken out from the non-aqueous electrolyte battery, and the non-aqueous electrolyte can be extracted and measured.
• the non-aqueous electrolyte solution can be extracted by a centrifuge, or the non-aqueous electrolyte solution can be extracted using an organic solvent.
• Metal elements ie metal ions
• ICP-AES inductively coupled high frequency plasma emission spectroscopy
• iCAP 7600duo inductively coupled high frequency plasma emission spectroscopy
• the non-aqueous electrolyte solution according to the embodiment of the present invention contains nickel ions in an amount of 1 mass ppm or more and 500 mass ppm or less.
• the content of nickel ions in the non-aqueous electrolyte solution is the concentration of nickel element ions in the non-aqueous electrolyte solution.
• the valence of nickel ions contained in the non-aqueous electrolyte solution is not particularly limited, and may be divalent or trivalent. Further, the non-aqueous electrolyte solution according to the embodiment of the present invention may contain both divalent nickel ions (Ni 2+ ) and trivalent nickel ions (Ni 3+ ) in an arbitrary ratio.
• the content of nickel ions in the non-aqueous electrolyte solution is usually 1 mass ppm or more, preferably 2 mass ppm or more, more preferably 3 mass ppm or more, still more preferably 5 mass ppm or more, and particularly preferably 10 mass ppm or more. It is ppm or more, particularly preferably 25 mass ppm or more, while the upper limit is usually 500 mass ppm or less, preferably 400 mass ppm or less, more preferably 350 mass ppm or less, still more preferably 300 mass ppm or less, particularly still more preferable. Is 220 mass ppm or less, particularly preferably 150 mass ppm or less.
• the compound serving as a nickel ion source one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• Examples of the ligand include elements constituting the battery, such as cyclic carbonates such as ethylene carbonate, propylene carbonate and fluoroethylene carbonate, dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate, which are used as non-aqueous solvents.
• examples thereof include chain carbonates, carboxylic acid esters such as methyl acetate, ether compounds, and organic solvents such as sulfone compounds.
• Examples thereof include nickel halides such as Ni (CH 3 COO) 2 , Ni (OH) 2 , NiO, NiCO 3 , NiSO 4 , and nickel chloride.
• the nickel ions may be those eluted from the constituent elements of the battery, such as a positive electrode active material, a negative electrode active material, a positive electrode current collector, a negative electrode current collector or an exterior body, which may contain a nickel element.
• Nickel ions usually form a salt with a counter anion in a non-aqueous electrolyte solution.
• counter anions other than FSO 3 - ion may be coordinated with nickel ions to form a complex, or a salt may be formed with one or more counter anions.
• the counter anion include preferably elements constituting the battery, e.g., PF 6 from LiPF 6 - ions, LiPO 2 F 2 from the PO 2 F 2 - and ion-fluoro phosphate ion, from FSO 3 Li
• FSO 3 - ion fluoride ion, carbonate ion, carboxylate ion, sulfonate ion, sulfonylimide ion, (oxalate) borate ion and the like, and more preferably, PF 6 - ion, FSO 3 - ion or foot.
• Examples include compound ions.
• FSO 3 - ion is particularly preferable because it has a higher coordinating power to nickel ion than PF 6 - ion.
• FSO 3 - ions are coordinated or interact with nickel ions to withstand reduction of nickel ions. It is presumed that the charge storage characteristics in a high temperature environment can be improved by improving the properties and suppressing the negative electrode reduction reaction in a high temperature environment.
• the non-aqueous electrolyte solution according to the embodiment of the present invention contains cobalt ions of 1 mass ppm or more and 500 mass ppm or less.
• the content of cobalt ions in the non-aqueous electrolyte solution is the concentration of cobalt element ions in the non-aqueous electrolyte solution.
• the valence of the cobalt ion contained in the non-aqueous electrolyte solution is not particularly limited, and may be divalent or trivalent.
• the non-aqueous electrolyte solution according to the embodiment of the present invention may contain both divalent cobalt ions (Co 2+ ) and trivalent cobalt ions (Co 3+ ) in an arbitrary ratio.
• the content of cobalt ions in the non-aqueous electrolyte solution is usually 1 mass ppm or more, preferably 2 mass ppm or more, more preferably 3 mass ppm or more, still more preferably 5 mass ppm or more, and particularly preferably 10 mass ppm or more.
• ppm or more is usually 500 mass ppm or less, preferably 400 mass ppm or less, more preferably 350 mass ppm or less, still more preferably 300 mass ppm or less, particularly still more preferable.
• the compound serving as a cobalt ion source one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• the ligand include elements constituting the battery, such as cyclic carbonates such as ethylene carbonate, propylene carbonate and fluoroethylene carbonate, dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate, which are used as non-aqueous solvents.
• Examples thereof include chain carbonates, carboxylic acid esters such as methyl acetate, ether compounds, and organic solvents such as sulfone compounds.
• cobalt halides such as cobalt fluoride (II), cobalt fluoride (III), cobalt bromide (II) and cobalt chloride (II).
• the cobalt ion may be one eluted from a battery component such as a positive electrode active material, a negative electrode active material, a positive electrode current collector, a negative electrode current collector or an exterior body, which may contain a cobalt element.
• Cobalt ions usually form salts with counter anions in non-aqueous electrolytes.
• counter anions other than FSO 3 - ion may coordinate with cobalt ions to form a complex, or may form a salt with one or more counter anions.
• the counter anion include preferably elements constituting the battery, e.g., PF 6 from LiPF 6 - ions, LiPO 2 F 2 from the PO 2 F 2 - and ion-fluoro phosphate ion, from FSO 3 Li
• FSO 3 - ion fluoride ion, carbonate ion, carboxylate ion, sulfonate ion, sulfonylimide ion, (oxalate) borate ion and the like, and more preferably, PF 6 - ion, FSO 3 - ion or foot.
• Examples include compound ions.
• FSO 3 - ion is particularly preferable because it has a higher coordinating power to cobalt ion than PF 6 - ion.
• FSO 3 - ion coordinates or interacts with cobalt ion, thereby reducing the reduction of cobalt ion. It is presumed that the charge storage characteristics in a high temperature environment can be improved by improving the properties and suppressing the negative electrode reduction reaction in a high temperature environment.
• the non-aqueous electrolyte solution according to the embodiment of the present invention contains copper ions in an amount of 1 mass ppm or more and 500 mass ppm or less.
• the content of copper ions in the non-aqueous electrolyte solution is the concentration of copper element ions in the non-aqueous electrolyte solution.
• the valence of copper ions contained in the non-aqueous electrolyte solution is not particularly limited, and may be monovalent or divalent. Further, the non-aqueous electrolyte solution according to the embodiment of the present invention may contain both monovalent copper ions (Cu + ) and divalent copper ions (Cu 2+ ) in an arbitrary ratio.
• the content of copper ions in the non-aqueous electrolyte solution is usually 1 mass ppm or more, preferably 2 mass ppm or more, more preferably 3 mass ppm or more, still more preferably 5 mass ppm or more, and particularly preferably 10 mass ppm or more. It is ppm or more, particularly preferably 25 mass ppm or more, while the upper limit is usually 500 mass ppm or less, preferably 400 mass ppm or less, more preferably 350 mass ppm or less, still more preferably 300 mass ppm or less, particularly still more preferable. Is 220 mass ppm or less, particularly preferably 150 mass ppm or less.
• the compound serving as a copper ion source one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• the ligand examples include elements constituting the battery, such as cyclic carbonates such as ethylene carbonate, propylene carbonate and fluoroethylene carbonate, dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate, which are used as non-aqueous solvents.
• cyclic carbonates such as ethylene carbonate, propylene carbonate and fluoroethylene carbonate
• dimethyl carbonate ethyl methyl carbonate and diethyl carbonate
• non-aqueous solvents examples include chain carbonates, carboxylic acid esters such as methyl acetate, ether compounds, and organic solvents such as sulfone compounds.
• the copper ions may be those eluted from the constituent elements of the battery, such as a positive electrode active material, a negative electrode active material, a positive electrode current collector, a negative electrode current collector or an exterior body, which may contain a copper element. Copper ions usually form salts with counter anions in non-aqueous electrolytes.
• counter anions other than FSO 3 - ion may be coordinated with copper ions to form a complex, or a salt may be formed with one or more counter anions.
• the counter anion include preferably elements constituting the battery, e.g., PF 6 from LiPF 6 - ions, LiPO 2 F 2 from the PO 2 F 2 - and ion-fluoro phosphate ion, from FSO 3 Li Examples thereof include FSO 3 - ion, fluoride ion, carbonate ion, carboxylate ion, sulfonate ion, sulfonylimide ion, (oxalate) borate ion and the like, and more preferably, PF 6 - ion, FSO 3 - ion or foot.
• Examples include compound ions.
• FSO 3 - ion is particularly preferable because it has a higher coordination force with copper ion than PF 6 - ion.
• FSO 3 - ions fluorosulfonic acid ions
• the reduction resistance of copper ions is improved and the negative electrode reduction reaction in a high temperature environment is suppressed, so that the charge storage characteristics in a high temperature environment can be improved.
• the non-aqueous electrolyte solution according to the embodiment of the present invention contains manganese ions in an amount of 1 mass ppm or more and 100 mass ppm or less.
• the content of manganese ions in the non-aqueous electrolyte solution is the concentration of manganese element ions in the non-aqueous electrolyte solution.
• the valence of manganese ions contained in the non-aqueous electrolyte solution is not particularly limited, and may be divalent or trivalent.
• the non-aqueous electrolyte solution according to the embodiment of the present invention may contain both divalent manganese ions (Mn 2+ ) and trivalent manganese ions (Mn 3+ ) in an arbitrary ratio.
• the content of manganese ions in the non-aqueous electrolyte solution is usually 1 mass ppm or more, preferably 2 mass ppm or more, more preferably 3 mass ppm or more, still more preferably 5 mass ppm or more, and particularly preferably 10 mass ppm or more.
• ppm or more is ppm or more, particularly preferably 25 mass ppm or more, while the upper limit is usually 100 mass ppm or less, preferably 95 mass ppm or less, more preferably 90 mass ppm or less, still more preferably 85 mass ppm or less, particularly still more preferable.
• the compound serving as a manganese ion source one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• the ligand include elements constituting the battery, such as cyclic carbonates such as ethylene carbonate, propylene carbonate and fluoroethylene carbonate, dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate, which are used as non-aqueous solvents.
• Examples thereof include chain carbonates, carboxylic acid esters such as methyl acetate, ether compounds, and organic solvents such as sulfone compounds.
• the manganese ion may be eluted from a battery component such as a positive electrode active material, a negative electrode active material, a positive electrode current collector, a negative electrode current collector or an exterior body which may contain a manganese element.
• a battery component such as a positive electrode active material, a negative electrode active material, a positive electrode current collector, a negative electrode current collector or an exterior body which may contain a manganese element.
• Manganese ions usually form salts with counter anions in non-aqueous electrolytes.
• counter anions other than FSO 3 - ion may be coordinated with manganese ions to form a complex, or a salt may be formed with one or more counter anions.
• the counter anion include preferably elements constituting the battery, e.g., PF 6 from LiPF 6 - ions, LiPO 2 F 2 from the PO 2 F 2 - and ion-fluoro phosphate ion, from FSO 3 Li
• FSO 3 - ion fluoride ion, carbonate ion, carboxylate ion, sulfonate ion, sulfonylimide ion, (oxalate) borate ion and the like, and more preferably, PF 6 - ion, FSO 3 - ion or foot.
• Examples include compound ions.
• FSO 3 - ion is particularly preferable because it has a higher coordination force with manganese ion than PF 6 - ion.
• FSO 3 - ion coordinates or interacts with manganese ion, thereby reducing reduction of manganese ion. It is presumed that the charge storage characteristics in a high temperature environment can be improved by improving the properties and suppressing the negative electrode reduction reaction in a high temperature environment.
• the non-aqueous electrolyte solution according to the embodiment of the present invention contains aluminum ions in an amount of 1 mass ppm or more and 100 mass ppm or less.
• the content of aluminum ions in the non-aqueous electrolyte solution is the concentration of aluminum element ions in the non-aqueous electrolyte solution.
• the content of aluminum ions in the non-aqueous electrolyte solution is usually 1 mass ppm or more, preferably 2 mass ppm or more, more preferably 3 mass ppm or more, still more preferably 5 mass ppm or more, and particularly preferably 10 mass ppm or more.
• ppm or more is ppm or more, particularly preferably 25 mass ppm or more, while the upper limit is usually 100 mass ppm or less, preferably 90 mass ppm or less, more preferably 80 mass ppm or less, still more preferably 70 mass ppm or less, particularly preferably. It is 60 mass ppm or less.
• the content of aluminum ions is higher than 100 mass ppm, the internal resistance of the non-aqueous electrolyte battery increases due to the increase in the negative electrode reduction reaction, while when the content is lower than 1 mass ppm, aluminum ions are contained. The effect is low because the difference from the case without it is small.
• the compound serving as an aluminum ion source one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• the ligand elements constituting the battery are preferably mentioned, and for example, cyclic carbonates such as ethylene carbonate, propylene carbonate and fluoroethylene carbonate used as non-aqueous solvents; dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and the like.
• Examples thereof include organic solvents such as chain carbonates; carboxylic acid esters such as methyl acetate; ether compounds; and sulfone compounds ;.
• the compounds that serve as aluminum ion sources include Al (FSO 3 ) 3 ; Al (CH 3 COO) 3 ; Al (CF 3 COO) 3 ; Al (CF 3 SO 3 ) 3 ; Tris (2,4-pentangio).
• Aluminum alkoxides such as aluminum, aluminum ethoxydo, aluminum isopropoxide, aluminum-n-butoxide; alkylaluminum such as trimethylaluminum; Al halides such as aluminum chloride; and other aluminum salts can also be mentioned.
• the aluminum ion may be eluted from a battery component such as a positive electrode active material, a negative electrode active material, a positive electrode current collector, a negative electrode current collector or an exterior body, which may contain an aluminum element.
• a battery component such as a positive electrode active material, a negative electrode active material, a positive electrode current collector, a negative electrode current collector or an exterior body, which may contain an aluminum element.
• Aluminum ions usually form a salt with a counter anion in a non-aqueous electrolyte solution.
• FSO 3 - counter anion other than ion is coordinated to the aluminum ion may form a complex, and aluminum ions and one or more counter anions may form a salt ..
• the counter anion, elements constituting the battery also preferably mentioned, for example, LiPF 6 from the PF 6 - ions, LiPO 2 F 2 from the PO 2 F 2 - and ion-fluoro phosphate ions, derived from FSO 3 Li
• LiPF 6 from the PF 6 - ions LiPO 2 F 2 from the PO 2 F 2 - and ion-fluoro phosphate ions, derived from FSO 3 Li
• FSO 3 - ion, fluoride ion, carbonate ion, carboxylic acid ion, sulfonate ion, sulfonylimide ion, (oxalate) borate ion and the like and more preferably, PF 6 - ion and FSO 3 - and ion or fluoride ion.
• FSO 3 - ion is particularly preferable because it has a higher coordinating power to aluminum ion than PF 6 - ion.
• FSO 3 - ions coordinate or interact with the aluminum ions to withstand reduction of the aluminum ions. It is presumed that the charge storage characteristics in a high temperature environment can be improved by improving the properties and suppressing the negative electrode reduction reaction in a high temperature environment.
• a member containing the non-aqueous electrolyte can be taken out from the non-aqueous electrolyte battery, and the non-aqueous electrolyte can be extracted and measured.
• the non-aqueous electrolyte solution can be extracted by a centrifuge, or the non-aqueous electrolyte solution can be extracted by using an organic solvent.
• the extracted non-aqueous electrolyte solution is used to quantify Li and acid concentration matching calibration curves for Li and acid concentration matching calibration curves by inductively coupled high frequency plasma emission spectroscopy (ICP-AES, eg Thermo Fisher Scientific, iCAP 7600duo).
• ICP-AES inductively coupled high frequency plasma emission spectroscopy
• the non-aqueous electrolyte solution contains at least one metal ion selected from the group consisting of nickel ion, cobalt ion, copper ion, manganese ion, and aluminum ion, the total of the metal ions.
• the content is usually 1 mass ppm or more, preferably 2 mass ppm or more, more preferably 3 mass ppm or more, still more preferably 5 mass ppm or more, and particularly still more preferably 10 mass ppm or more in the non-aqueous electrolyte solution.
• the non-aqueous electrolyte solution according to the embodiment of the present invention contains at least nickel ions, and preferably contains nickel ions in an amount of 30% by mass or more, more preferably 40% by mass or more, based on the total amount of the above five types of metal ions. Including.
• non-aqueous electrolyte solution contains a plurality of metal ions selected from the group consisting of nickel ions, cobalt ions, copper ions, manganese ions, and aluminum ions, at least the following It is preferable to include a combination of metal ions shown in.
• each metal ion in the above particularly preferred combination is as follows.
• Nickel ion and cobalt ion; nickel ion is usually 1 mass ppm or more, preferably 10 mass ppm or more, more preferably 20 mass ppm or more, further preferably 25 mass ppm or more, and usually 300 mass ppm or less, preferably 220 mass ppm or more. It is ppm or less, more preferably 150 mass ppm or less, and cobalt ions are usually 1 mass ppm or more, preferably 5 mass ppm or more, more preferably 10 mass ppm or more, usually 300 mass ppm or less, preferably 220 mass ppm or less. Hereinafter, it is more preferably 150 mass ppm or less.
• Nickel ion and copper ion are usually 1 mass ppm or more, preferably 10 mass ppm or more, more preferably 20 mass ppm or more, usually 300 mass ppm or less, preferably 220 mass ppm or less, more preferably 150 mass ppm or more. It is usually 1 mass ppm or less, and the copper ion is usually 1 mass ppm or more, preferably 10 mass ppm or more, more preferably 25 mass ppm or more, usually 300 mass ppm or less, preferably 220 mass ppm or less, more preferably 150 mass ppm or less. It is as follows.
• Nickel ion and manganese ion are usually 1 mass ppm or more, preferably 10 mass ppm or more, preferably 25 mass ppm or more, usually 300 mass ppm or less, preferably 220 mass ppm or less, more preferably 150 mass ppm or more.
• the manganese ion is usually 1 mass ppm or more, preferably 2 mass ppm or more, usually 100 mass ppm or less, preferably 80 mass ppm or less, and more preferably 75 mass ppm or less.
• Is 150 mass ppm or less, and cobalt ions are usually 1 mass ppm or more, preferably 5 mass ppm or more, more preferably 10 mass ppm or more, usually 300 mass ppm or less, preferably 220 mass ppm or less, more preferably.
• the manganese ion is preferably 1 mass ppm or more, usually 100 mass ppm or less, preferably 80 mass ppm or less, and more preferably 75 mass ppm or less.
• Nickel ion, copper ion and manganese ion; nickel ion is usually 1 mass ppm or more, preferably 5 mass ppm or more, more preferably 10 mass ppm or more, usually 300 mass ppm or less, preferably 220 mass ppm or less, more preferably.
• Is 150 mass ppm or less, copper ions are usually 1 mass ppm or more, preferably 10 mass ppm or more, usually 300 mass ppm or less, preferably 220 mass ppm or less, preferably 150 mass ppm or less, and manganese ions.
• Copper ions are usually 1 mass ppm or more, preferably 5 mass ppm or more, more preferably 10 mass ppm or more, usually 300 mass ppm or less, preferably 220 mass ppm or less, preferably 150 mass ppm or less, and manganese ions. Is preferably 1 mass ppm or more, usually 100 mass ppm or less, preferably 80 mass ppm or less, and more preferably 75 mass ppm or less.
• the non-aqueous electrolyte solution of the present embodiment usually contains an electrolyte as a component thereof, like a general non-aqueous electrolyte solution.
• the electrolyte used in the non-aqueous electrolyte solution of the present embodiment is not particularly limited, and known electrolytes can be used. Hereinafter, specific examples of the electrolyte will be described in detail.
• the lithium salt is not particularly limited as long as it is known to be used for this purpose, and any one or more lithium salts can be used, and specific examples thereof include the following.
• lithium fluoroborate salts such as LiBF 4 ; Lithium fluorophosphates such as LiPF 6 and LiPO 2 F 2 ; Lithium tungstic acid salts such as LiWOF 5 ; Lithium carboxylic acid salts such as CF 3 CO 2 Li; Lithium sulfonic acid salts such as CH 3 SO 3 Li; Lithium imide salts such as LiN (FSO 2 ) 2 and LiN (CF 3 SO 2 ) 2 ; Licymethide salts such as LiC (FSO 2 ) 3 ; Lithium oxalate salts such as lithium difluorooxalate borate; In addition, fluorine-containing organic lithium salts such as LiPF 4 (CF 3 ) 2 ; And so on.
• Lithium fluoroborate salts, lithium fluorophosphate salts, lithium sulfonate salts from the viewpoint of further enhancing the effect of improving charge / discharge rate characteristics and impedance characteristics in addition to the effect of improving charge storage characteristics in a high temperature environment obtained by the present invention.
• the total concentration of these electrolytes in the non-aqueous electrolyte solution is not particularly limited, but is usually 8% by mass or more, preferably 8.5% by mass or more, more preferably 9% by mass, based on the total amount of the non-aqueous electrolyte solution. % Or more.
• the upper limit thereof is usually 18% by mass or less, preferably 17% by mass or less, and more preferably 16% by mass or less.
• the non-aqueous electrolyte solution of the present embodiment usually contains a non-aqueous solvent that dissolves the above-mentioned electrolyte as its main component.
• the non-aqueous solvent used here is not particularly limited, and a known organic solvent can be used.
• the organic solvent include saturated cyclic carbonates, chain carbonates, carboxylic acid esters, ether compounds, sulfone compounds and the like. Although not particularly limited to these, a saturated cyclic carbonate, a chain carbonate or a carboxylic acid ester is preferable, and a saturated cyclic carbonate or a chain carbonate is more preferable.
• a combination of two or more non-aqueous solvents a combination of two or more selected from the group consisting of saturated cyclic carbonate, chain carbonate, and carboxylic acid ester is preferable, and a combination of saturated cyclic carbonate or chain carbonate is more preferable. ..
• saturated cyclic carbonate usually include those having an alkylene group having 2 to 4 carbon atoms, and a saturated cyclic carbonate having 2 to 3 carbon atoms is preferably used from the viewpoint of improving battery characteristics resulting from an improvement in the degree of lithium ion dissociation. .. Further, the saturated cyclic carbonate may be a cyclic carbonate having a fluorine atom such as monofluoroethylene carbonate.
• saturated cyclic carbonate examples include ethylene carbonate, propylene carbonate, butylene carbonate and the like. Of these, ethylene carbonate and propylene carbonate are preferable, and ethylene carbonate, which is difficult to be oxidized and reduced, is more preferable.
• saturated cyclic carbonate one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• the content of the saturated cyclic carbonate is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired, but the lower limit is usually 3% by volume or more, preferably 5 by volume, based on the total amount of the solvent of the non-aqueous electrolyte solution. It is more than% by volume. By setting this range, the decrease in electrical conductivity due to the decrease in the dielectric constant of the non-aqueous electrolyte solution is avoided, and the large current discharge characteristics, stability with respect to the negative electrode, and cycle characteristics of the non-aqueous electrolyte battery are in a good range. It becomes easy to do.
• the upper limit is usually 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less.
• the volume% in the present invention means the volume at 25 ° C. and 1 atm.
• Chain carbonate As the chain carbonate, one having 3 to 7 carbon atoms is usually used, and in order to adjust the viscosity of the electrolytic solution in an appropriate range, a chain carbonate having 3 to 5 carbon atoms is preferably used.
• chain carbonate dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, n-propylisopropyl carbonate, ethylmethyl carbonate, methyl-n-propyl carbonate, n-butylmethyl carbonate, etc.
• examples thereof include isobutylmethyl carbonate, t-butylmethyl carbonate, ethyl-n-propyl carbonate, n-butylethyl carbonate, isobutylethyl carbonate, t-butylethyl carbonate and the like.
• dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, n-propylisopropyl carbonate, ethylmethyl carbonate and methyl-n-propyl carbonate are preferable, and dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate are particularly preferable. is there.
• chain carbonates having a fluorine atom can also be preferably used.
• the number of fluorine atoms contained in the fluorinated chain carbonate is not particularly limited as long as it is 1 or more, but is usually 6 or less, preferably 4 or less.
• the fluorinated chain carbonate has a plurality of fluorine atoms, they may be bonded to the same carbon or different carbons.
• the fluorinated chain carbonate include a fluorinated dimethyl carbonate derivative, a fluorinated ethyl methyl carbonate derivative, and a fluorinated diethyl carbonate derivative.
• fluorinated dimethyl carbonate derivative examples include fluoromethylmethyl carbonate, difluoromethylmethyl carbonate, trifluoromethylmethyl carbonate, bis (fluoromethyl) carbonate, bis (difluoro) methyl carbonate, bis (trifluoromethyl) carbonate and the like.
• fluorinated ethyl methyl carbonate derivative examples include 2-fluoroethyl methyl carbonate, ethyl fluoromethyl carbonate, 2,2-difluoroethyl methyl carbonate, 2-fluoroethyl fluoromethyl carbonate, ethyl difluoromethyl carbonate, and 2,2,2-tri.
• fluorinated diethyl carbonate derivative examples include ethyl- (2-fluoroethyl) carbonate, ethyl- (2,2-difluoroethyl) carbonate, bis (2-fluoroethyl) carbonate, and ethyl- (2,2,2-trifluoro).
• Ethyl) carbonate 2,2-difluoroethyl-2'-fluoroethyl carbonate, bis (2,2-difluoroethyl) carbonate, 2,2,2-trifluoroethyl-2'-fluoroethyl carbonate, 2,2 Examples thereof include 2-trifluoroethyl-2', 2'-difluoroethyl carbonate and bis (2,2,2-trifluoroethyl) carbonate.
• chain carbonate one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• the content of the chain carbonate is not particularly limited, but is usually 15% by volume or more, preferably 20% by volume or more, and more preferably 25% by volume or more with respect to the total amount of the solvent of the non-aqueous electrolyte solution. Further, it is usually 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less.
• the battery performance can be significantly improved.
• the content of ethylene carbonate is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired, but the non-aqueous electrolyte solution It is usually 15% by volume or more, preferably 20% by volume, and usually 45% by volume or less, preferably 40% by volume or less with respect to the total amount of the solvent, and the content of dimethyl carbonate is based on the total amount of the solvent of the non-aqueous electrolyte solution.
• ethylmethyl carbonate It is usually 20% by volume or more, preferably 30% by volume or more, and usually 50% by volume or less, preferably 45% by volume or less, and the content of ethylmethyl carbonate is usually 20% by volume or more, preferably 30% by volume or more. In addition, it is usually 50% by volume or less, preferably 45% by volume or less.
• Ether compounds a chain ether having 3 to 10 carbon atoms and a cyclic ether having 3 to 6 carbon atoms are preferable.
• the ether compound one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• the content of the ether compound is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1% by volume or more, preferably 2% by volume or more, more preferably in 100% by volume of the non-aqueous solvent. Is 3% by volume or more, and usually 30% by volume or less, preferably 25% by volume or less, and more preferably 20% by volume or less.
• the total amount of the ether compounds may satisfy the above range.
• the content of the ether-based compound is within the above-mentioned preferable range, it is easy to secure the effect of improving the lithium ion dissociation degree of the chain ether and improving the ionic conductivity due to the decrease in viscosity. Further, when the negative electrode active material is a carbonaceous material, the phenomenon that the chain ether is co-inserted together with the lithium ions can be suppressed, so that the input / output characteristics and the charge / discharge rate characteristics can be set in an appropriate range.
• the sulfone compound is not particularly limited even if it is a cyclic sulfone or a chain sulfone, but in the case of a cyclic sulfone, the number of carbon atoms is usually 3 to 6, preferably 3 to 5, and in the case of a chain sulfone. , Usually, a compound having 2 to 6 carbon atoms, preferably 2 to 5 carbon atoms is preferable. The number of sulfonyl groups in one molecule of the sulfone compound is not particularly limited, but is usually 1 or 2.
• cyclic sulfone examples include trimethylene sulfones, tetramethylene sulfones, hexamethylene sulfones, which are monosulfone compounds; trimethylene disulfones, tetramethylene disulfones, hexamethylene disulfones, etc., which are disulfone compounds.
• trimethylene sulfones, tetramethylene disulfones, hexamethylene sulfones and hexamethylene disulfones are more preferable, and tetramethylene sulfones (sulfolanes) are particularly preferable.
• sulfolanes As the sulfolanes, sulfolanes or sulfolane derivatives (hereinafter, sulfolanes may be abbreviated as "sulfolanes") are preferable.
• the sulfolane derivative is preferably one in which one or more hydrogen atoms bonded on the carbon atom constituting the sulfolane ring are substituted with a fluorine atom or an alkyl group.
• the sulfone compound one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• the content of the sulfone compound is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3% by volume or more, preferably 0. It is 5% by volume or more, more preferably 1% by volume or more, and usually 40% by volume or less, preferably 35% by volume or less, more preferably 30% by volume or less.
• the total amount of the sulfone compounds may satisfy the above range.
• an electrolytic solution having excellent high temperature storage stability tends to be obtained.
• the carboxylic acid ester is preferably a chain carboxylic acid ester, and more preferably a saturated chain carboxylic acid ester.
• the total carbon number of the carboxylic acid ester is usually 3 to 7, and a carboxylic acid ester of 3 to 5 is preferably used from the viewpoint of improving the battery characteristics resulting from the improvement of the output characteristics.
• carboxylic acid ester examples include saturated chain carboxylic acid esters such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl pivalate, and ethyl pivalate, methyl acrylate, ethyl acrylate, methyl methacrylate, and methacrylic acid.
• saturated chain carboxylic acid esters such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl pivalate, and ethyl pivalate, methyl acrylate, ethyl acrylate, methyl methacrylate, and methacrylic acid.
• unsaturated chain carboxylic acid esters such as ethyl.
• methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl pivalate, and ethyl pivalate are preferable, and methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate are more preferable from the viewpoint of improving output characteristics.
• the carboxylic acid ester one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• the content of the carboxylic acid ester is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired, but the lower limit is usually 3% by volume or more, preferably 5 by volume, based on the total amount of the solvent of the non-aqueous electrolyte solution. It is more than% by volume. By setting this range, the decrease in electrical conductivity due to the decrease in the dielectric constant of the non-aqueous electrolyte solution is avoided, and the large current discharge characteristics, stability with respect to the negative electrode, and cycle characteristics of the non-aqueous electrolyte battery are in a good range. It becomes easy to do.
• the upper limit is usually 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less.
• the volume% in the present invention means the volume at 25 ° C. and 1 atm.
• Fluorosulfates other than FSO 3 Li The counter cation of a fluorosulfonate (hereinafter, simply referred to as "fluorosulfonate”) other than FSO 3 Li is not particularly limited, but sodium, potassium, rubidium, cesium, magnesium, calcium, barium, and NR 13 Examples thereof include ammonium represented by R 14 R 15 R 16 (in the formula, R 13 to R 16 each independently represent a hydrogen atom or an organic group having 1 to 12 carbon atoms).
• fluorosulfonates include Examples thereof include sodium fluorosulfonate, potassium fluorosulfonate, rubidium fluorosulfonate, and cesium fluorosulfonate.
• the fluorosulfonate one type may be used alone, or two or more types may be used in combination in any combination and ratio.
• the total content of fluorosulfonate and FSO 3 Li with respect to the entire non-aqueous electrolyte solution of the present embodiment is usually 0.001% by mass or more, preferably 0.01% by mass, based on 100% by mass of the non-aqueous electrolyte solution.
• it is particularly preferably 1% by mass or less.
• the total amount of FSO 3 Li and fluorosulfonate may satisfy the above range. Within this range, swelling of the non-aqueous electrolyte battery due to charging / discharging can be suitably suppressed.
• the non-aqueous electrolyte solution of the present embodiment may contain the following auxiliaries as long as the effects of the present invention are exhibited.
• Unsaturated cyclic carbonates such as vinylene carbonate, vinylethylene carbonate or ethynylethylene carbonate; Carbonate compounds such as methoxyethyl-methyl carbonate; Spiro compounds such as methyl-2-propynyl oxalate; Sulfur-containing compounds such as ethylene sulfite;
• Isocyanate compounds such as diisocyanates having a cycloalkylene group such as 1,3-bis (isocyanatomethyl) cyclohexane; Nitrogen-containing compounds such as 1-methyl-2-pyrrolidinone; Hydrocarbon compounds such as cycloheptane; Fluoro-containing aromatic compounds such as fluorobenzene; Silane compounds such as tris borate (trimethylsilyl); Ester compounds such as 2-propynyl 2- (methane
• the content of the auxiliary agent is not particularly limited and is arbitrary as long as the effect of the present invention is not significantly impaired.
• the content of the auxiliary agent is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and usually 5% by mass, based on the total amount of the non-aqueous electrolyte solution. It is mass% or less, preferably 3 mass% or less, and more preferably 1 mass% or less. Within this range, the effect of the auxiliary agent is likely to be sufficiently exhibited, and the high temperature storage stability tends to be improved. When two or more kinds of auxiliary agents are used in combination, the total amount of auxiliary agents may satisfy the above range.
• Non-aqueous electrolyte battery is a non-aqueous electrolyte battery including a positive electrode and a negative electrode capable of occluding and releasing metal ions and a non-aqueous electrolyte, and is one of the above-mentioned inventions.
• the non-aqueous electrolyte solution according to the embodiment is provided. More specifically, the non-aqueous electrolyte battery according to the embodiment of the present invention has a current collector and a positive electrode active material layer provided on the current collector, and has a positive electrode capable of storing and releasing metal ions.
• a negative electrode having a current collector and a negative electrode active material layer provided on the current collector and capable of storing and releasing metal ions, and FSO 3 Li, nickel ions (a) and cobalt ions (b). ), Copper ion (c), manganese ion (d), and at least one metal ion selected from the group consisting of aluminum ion (e), and at least one of the following conditions (i) to (v). It is provided with a non-aqueous electrolyte solution to be filled.
• the concentration of (a) is 1 mass ppm or more and 500 mass ppm or less (ii)
• the concentration of (b) is 1 mass ppm or more and 500 mass ppm or less (iii)
• the concentration of (c) is 1 mass ppm or more 500 mass ppm or less (iv)
• Concentration of the above (d) is 1 mass ppm or more and 100 mass ppm or less (v)
• Concentration of the above (e) is 1 mass ppm or more and 100 mass ppm or less
• the aqueous electrolyte battery is provided on the current collector and the positive electrode having a positive electrode active material layer provided on the current collector and capable of storing and releasing metal ions, and on the current collector and the current collector.
• the non-aqueous electrolyte battery according to the aspect B of the present invention has a current collector, a positive electrode having a positive electrode active material layer provided on the current collector, and a positive electrode capable of storing and releasing metal ions, and collecting current.
• the non-aqueous electrolyte battery of the present embodiment has the same configuration as the conventionally known non-aqueous electrolyte battery except for the above-mentioned non-aqueous electrolyte battery.
• the positive electrode and the negative electrode are laminated via a porous film (separator) impregnated with the non-aqueous electrolyte solution, and these are housed in a case (exterior body). Therefore, the shape of the non-aqueous electrolyte battery of the present embodiment is not particularly limited, and may be any of a cylindrical type, a square type, a laminated type, a coin type, a large size, and the like.
• Non-aqueous electrolyte As the non-aqueous electrolyte solution, the non-aqueous electrolyte solution according to the above-described embodiment of the present invention is used. It is also possible to mix and use other non-aqueous electrolyte solutions with the above non-aqueous electrolyte solution as long as the gist of the present invention is not deviated.
• the positive electrode has a current collector and a positive electrode active material layer provided on the current collector.
• the positive electrode used in the non-aqueous electrolyte battery of the present embodiment will be described in detail below.
• the positive electrode active material used for the positive electrode will be described below.
• the positive electrode active material is a transition metal oxide containing lithium cobaltate or at least Ni and Co, and 50 mol% or more of the transition metal is Ni and Co, and is an electrochemically metal ion.
• the positive electrode active material is a transition metal oxide containing lithium cobaltate or at least Ni and Co, and 50 mol% or more of the transition metal is Ni and Co, and is an electrochemically metal ion.
• a transition metal oxide in which% or more is Ni and Co is preferable. This is because Ni and Co have a redox potential suitable for use as a positive electrode material for a secondary battery and are suitable for high-capacity applications.
• the metal component of the lithium transition metal oxide contains at least Ni or Co as an essential transition metal element, but Mn, V, Ti, Cr, Fe, Cu, Al, Mg, Zr, Er as other metal elements. Etc., and Mn, Ti, Fe, Al, Mg, Zr and the like are preferable.
• Specific examples of the lithium transition metal oxide include LiCoO 2 , LiNi 0.85 Co 0.10 Al 0.05 O 2 , LiNi 0.80 Co 0.15 Al 0.05 O 2 , and LiNi 0.33.
• Co 0.33 Mn 0.33 O 2 Li 1.05 Ni 0.33 Mn 0.33 Co 0.33 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , Li 1.05 Ni Examples thereof include 0.50 Mn 0.29 Co 0.21 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 .
• the positive electrode active material is a transition metal oxide represented by the following composition formula (1).
• M is Mn, Al, Mg, Zr. Represents at least one element selected from the group consisting of Fe, Ti and Er.
• composition ratio of Ni and Co and the composition ratio of other metal species are within a specific range, it is difficult for the transition metal to elute from the positive electrode, and even if it elutes, Ni and Co can be contained in the non-aqueous secondary battery. This is because the adverse effect of
• the positive electrode active material is a transition metal oxide represented by the following composition formula (2).
• M is Mn, Al, Mg. , Zr, Fe, Ti and Er represents at least one element selected from the group.
• the positive electrode active material is a transition metal oxide represented by the following composition formula (3).
• Li a3 Ni b3 Co c3 M d3 O 2 ... (3) (In the formula (3), the numerical values of 0.90 ⁇ a3 ⁇ 1.10, 0.50 ⁇ b3 ⁇ 0.94, 0.05 ⁇ c3 ⁇ 0.2, and 0.01 ⁇ d3 ⁇ 0.3 are shown.
• B3 + c3 + d3 1.
• M represents at least one element selected from the group consisting of Mn, Al, Mg, Zr, Fe, Ti and Er.)
• two or more of the above positive electrode active materials may be mixed and used. Similarly, at least one of the above positive electrode active materials may be mixed with another positive electrode active material.
• positive electrode active materials include transition metal oxides, transition metal phosphoric acid compounds, transition metal silicic acid compounds, and transition metal boric acid compounds not listed above.
• a lithium manganese composite oxide having a spinel-type structure and a lithium-containing transition metal phosphoric acid compound having an olivine-type structure are preferable.
• Specific examples of the lithium manganese composite oxide having a spinel-type structure include LiMn 2 O 4 , LiMn 1.8 Al 0.2 O 4 , Limn 1.5 Ni 0.5 O 4, and the like.
• the transition metal of the lithium-containing transition metal phosphoric acid compound is preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu or the like, and specific examples thereof include LiFePO 4 and Li 3 Fe 2 (PO 4). ) 3 , Iron phosphates such as LiFeP 2 O 7 , cobalt phosphates such as LiCoPO 4 , manganese phosphates such as LiMnPO 4 , and some of the transition metal atoms that are the main constituents of these lithium transition metal phosphoric acid compounds are Al and Ti.
• the lithium-containing transition metal phosphoric acid compounds the lithium iron phosphoric acid compound is preferable. This is because iron is an extremely inexpensive metal with abundant resources and is less harmful. That is, among the above specific examples, LiFePO 4 can be mentioned as a more preferable specific example.
• the positive electrode is an NMC positive electrode
• the nickel element content in the NMC positive electrode is preferably 30 mol% or more, and 40 mol% or more is a non-aqueous electrolyte battery. It is more preferable from the viewpoint of increasing the capacity.
• a substance having a composition different from that of the substance constituting the main positive electrode active material may be used on the surface of the positive electrode active material.
• surface adhering substances include oxides such as aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, and bismuth oxide; lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, etc. Sulfates such as calcium sulfate and aluminum sulfate; carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate; carbon; and the like can be mentioned.
• These surface-adhering substances are, for example, dissolved or suspended in a solvent, impregnated and added to the positive electrode active material, and then dried.
• the surface-adhering substance precursor is dissolved or suspended in the solvent and impregnated and added to the positive electrode active material. After that, it can be adhered to the surface of the positive electrode active material by a method of reacting by heating or the like, a method of adding to the positive electrode active material precursor and firing at the same time, or the like.
• a method of mechanically attaching carbonaceous material later in the form of activated carbon or the like can also be used.
• the mass of the surface-adhering substance adhering to the surface of the positive electrode active material is preferably 0.1 ppm or more, more preferably 1 ppm or more, still more preferably 10 ppm or more, based on the mass of the positive electrode active material. Further, it is preferably 20% or less, more preferably 10% or less, still more preferably 5% or less.
• the surface-adhering substance can suppress the oxidation reaction of the non-aqueous electrolyte solution on the surface of the positive electrode active material, and can improve the battery life. Further, when the amount of adhesion is within the above range, the effect can be sufficiently exhibited, and the resistance is less likely to increase without inhibiting the inflow and outflow of lithium ions.
• the positive electrode active material may have a particle form.
• As the shape of the positive electrode active material particles a lump, a polyhedron, a spherical shape, an elliptical spherical shape, a plate shape, a needle shape, a columnar shape, or the like, which are conventionally used, are used. Further, the primary particles may be aggregated to form secondary particles, and the shape of the secondary particles may be spherical or elliptical spherical.
• the method for producing the positive electrode active material is not particularly limited as long as it does not exceed the gist of the present invention, but some methods are mentioned and are general as a method for producing an inorganic compound.
• the method is used.
• various methods can be considered for producing spherical or elliptical spherical active materials.
• transition metal raw materials such as transition metal nitrate and sulfate, and raw materials of other elements as necessary.
• a solvent such as water
• the pH is adjusted while stirring to prepare and recover a spherical precursor, which is dried as necessary, and then LiOH, Li 2 CO 3 , Li NO.
• Examples thereof include a method of adding a Li source such as 3 and firing at a high temperature to obtain an active material.
• a transition metal raw material such as transition metal nitrate, sulfate, hydroxide, or oxide and, if necessary, a raw material of another element are dissolved or pulverized and dispersed in a solvent such as water. Then, it is dried and molded with a spray dryer or the like to obtain a spherical or elliptical spherical precursor, to which a Li source such as LiOH, Li 2 CO 3 or LiNO 3 is added and fired at a high temperature to obtain an active material.
• a Li source such as LiOH, Li 2 CO 3 or LiNO 3
• a transition metal raw material such as a transition metal nitrate, a sulfate, a hydroxide, an oxide, a Li source such as LiOH, Li 2 CO 3 , LiNO 3 , and other elements as required.
• a method of dissolving or pulverizing and dispersing the raw material of the above in a solvent such as water, drying and molding it with a spray dryer or the like to obtain a spherical or elliptical spherical precursor, and firing this at a high temperature to obtain an active material. can be mentioned.
• the positive electrode is produced by forming a positive electrode active material layer containing positive electrode active material particles and a binder on a current collector.
• the positive electrode using the positive electrode active material may be produced by any known method. For example, a positive electrode active material and a binder, and if necessary, a conductive material and a thickener are mixed in a dry manner to form a sheet, which is then pressure-bonded to the positive electrode current collector, or these materials are applied to a liquid medium.
• a positive electrode can be obtained by forming a positive electrode active material layer on the current collector by applying the slurry as a slurry to the positive electrode current collector and drying the slurry.
• the content of the positive electrode active material in the positive electrode active material layer is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and preferably 99.9% by mass or less. Yes, 99% by mass or less is more preferable.
• the content of the positive electrode active material is within the above range, the electric capacity of the non-aqueous electrolyte battery can be sufficiently secured. Further, the strength of the positive electrode is also sufficient.
• one type of positive electrode active material powder (particles) may be used alone, or two or more types having different compositions or different powder physical properties may be used in combination in any combination and ratio.
• the composite oxide containing lithium and manganese is an expensive metal with a small amount of resources, and is not preferable in terms of cost because the amount of active material used is large in a large battery that requires a high capacity such as for automobiles. Therefore, in a large battery, it is desirable to use manganese as a main component as a cheaper transition metal for the positive electrode active material.
• a known conductive material can be arbitrarily used. Specific examples include metal materials such as copper and nickel; graphite (graphite) such as natural graphite and artificial graphite; carbon black such as acetylene black; and carbonaceous materials such as amorphous carbon such as needle coke. It should be noted that one of these may be used alone, or two or more thereof may be used in any combination and ratio.
• the content of the conductive material in the positive electrode active material layer is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, and preferably 50% by mass or less. It is more preferably 30% by mass or less, and further preferably 15% by mass or less. When the content is within the above range, sufficient conductivity can be ensured. Furthermore, it is easy to prevent a decrease in battery capacity.
• the binder used in the production of the positive electrode active material layer is not particularly limited as long as it is a material stable to the non-aqueous electrolyte solution and the solvent used in the production of the electrode.
• the material is not particularly limited as long as it is a material that is dissolved or dispersed in the liquid medium used at the time of electrode production, but specific examples thereof include polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, and cellulose.
• Resin-based polymer such as nitrocellulose; rubber-like polymer such as SBR (styrene / butadiene rubber), NBR (acrylonitrile / butadiene rubber), fluororubber, isoprene rubber, butadiene rubber, ethylene / propylene rubber; styrene / butadiene / Styrene block copolymer or hydrogen additive thereof, EPDM (ethylene / propylene / diene ternary copolymer), styrene / ethylene / butadiene / ethylene copolymer, styrene / isoprene / styrene block copolymer or hydrogen additive thereof
• Thermoplastic elastomeric polymers such as syndiotactic-1,2-polybutadiene, polyvinylacetate, ethylene / vinyl acetate copolymer, soft resinous polymer such as propylene / ⁇ -olefin
• the content of the binder in the positive electrode active material layer is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and preferably 80% by mass or less. Yes, 60% by mass or less is more preferable, 40% by mass or less is further preferable, and 10% by mass or less is particularly preferable.
• the ratio of the binder is within the above range, the positive electrode active material can be sufficiently retained and the mechanical strength of the positive electrode can be ensured, so that the battery performance such as cycle characteristics is improved. Further, it also leads to avoiding a decrease in battery capacity and conductivity.
• the liquid medium used for preparing the slurry for forming the positive electrode active material layer can be dissolved or dispersed.
• the type thereof is not particularly limited, and either an aqueous solvent or an organic solvent may be used.
• the aqueous solvent include water and a mixed solvent of alcohol and water.
• organic solvents examples include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene and methylnaphthalene; heterocyclic compounds such as quinoline and pyridine; ketones such as acetone, methylethylketone and cyclohexanone.
• esters such as methyl acetate and methyl acrylate
• amines such as diethylenetriamine, N, N-dimethylaminopropylamine
• ethers such as diethyl ether and tetrahydrofuran (THF); N-methylpyrrolidone (NMP), dimethylformamide
• Amides such as dimethylacetamide
• aprotic polar solvents such as hexamethylphosphalamide and dimethylsulfoxide can be mentioned. It should be noted that one of these may be used alone, or two or more thereof may be used in any combination and ratio.
• ⁇ Thickener> When an aqueous solvent is used as the liquid medium for forming the slurry, it is preferable to use a thickener and a latex such as styrene-butadiene rubber (SBR) to form the slurry. Thickeners are commonly used to adjust the viscosity of the slurry.
• the thickener is not limited as long as the effect of the present invention is not significantly limited, but specifically, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and salts thereof. And so on. These may be used alone or in any combination and ratio of two or more.
• the ratio of the thickener to the positive electrode active material is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 0.6% by mass or more. It is preferable, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less. Within the above range, the coatability is good, and the ratio of the active material to the positive electrode active material layer is sufficient, so that the problem of a decrease in battery capacity and an increase in resistance between the positive electrode active materials increase. It makes it easier to avoid problems.
• the positive electrode active material layer obtained by applying the slurry to the current collector and drying is preferably consolidated by a hand press, a roller press, or the like in order to increase the packing density of the positive electrode active material.
• the density of the positive electrode active material layer is preferably 1 g ⁇ cm -3 or more, more preferably 1.5 g ⁇ cm -3 or more, particularly preferably 2 g ⁇ cm -3 or more, and preferably 4 g ⁇ cm -3 or less. 3.5 g ⁇ cm -3 or less is more preferable, and 3 g ⁇ cm -3 or less is particularly preferable.
• the density of the positive electrode active material layer is within the above range, the permeability of the non-aqueous electrolyte solution to the vicinity of the current collector / active material interface does not decrease, and the charge / discharge characteristics are particularly good at a high current density. Become. Further, the conductivity between the active materials is less likely to decrease, and the battery resistance is less likely to increase.
• the material of the positive electrode current collector is not particularly limited, and any known material can be used. Specific examples include metal materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum; and carbonaceous materials such as carbon cloth and carbon paper. Of these, metal materials, especially aluminum, are preferable.
• Examples of the shape of the current collector include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, foamed metal, etc. in the case of metal material, and carbon plate in the case of carbonaceous material. Examples include a carbon thin film and a carbon column. Of these, a metal thin film is preferable. The thin film may be formed in a mesh shape as appropriate.
• the thickness of the current collector is arbitrary, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, further preferably 5 ⁇ m or more, and preferably 1 mm or less, more preferably 100 ⁇ m or less, further preferably 50 ⁇ m or less. preferable. When the thickness of the current collector is within the above range, sufficient strength required for the current collector can be secured. Further, the handleability is also good.
• the ratio of the thickness of the current collector to the positive electrode active material layer is not particularly limited, but (thickness of the active material layer on one side immediately before injection of the non-aqueous electrolyte solution) / (thickness of the current collector) is preferable. It is 150 or less, more preferably 20 or less, particularly preferably 10 or less, and preferably 0.1 or more, more preferably 0.4 or more, and particularly preferably 1 or more.
• the ratio of the thickness of the current collector to the positive electrode active material layer is within the above range, the current collector is less likely to generate heat due to Joule heat during high current density charging / discharging. Further, the volume ratio of the current collector to the positive electrode active material is unlikely to increase, and a decrease in battery capacity can be prevented.
• the area of the positive electrode active material layer is preferably large with respect to the outer surface area of the battery outer case.
• the total area of the electrode areas of the positive electrode with respect to the surface area of the exterior of the non-aqueous electrolyte battery is preferably 20 times or more, and more preferably 40 times or more in terms of area ratio.
• the outer surface area of the outer case means the total area calculated from the vertical, horizontal, and thickness dimensions of the case part filled with the power generation element excluding the protruding part of the terminal in the case of the bottomed square shape. ..
• the geometric surface area approximates the case portion filled with the power generation element excluding the protruding portion of the terminal as a cylinder.
• the total electrode area of the positive electrode is the geometric surface area of the positive electrode mixture layer facing the mixture layer containing the negative electrode active material, and in a structure in which the positive electrode mixture layer is formed on both sides via a current collector foil. , Refers to the sum of the areas calculated separately for each surface.
• the positive electrode plate has a fully charged discharge capacity, preferably 3 Ah (ampere hour) or more, more preferably 4 Ah or more, preferably 100 Ah or less, more preferably 70 Ah or less, and particularly preferably. Design to be 50 Ah or less.
• the voltage drop due to the electrode reaction resistance does not become too large when a large current is taken out, and deterioration of power efficiency can be prevented. Furthermore, the temperature distribution due to internal heat generation of the battery during pulse charging / discharging does not become too large, the durability of repeated charging / discharging is inferior, and the heat dissipation efficiency is also poor against sudden heat generation at the time of abnormalities such as overcharging and internal short circuit. It is possible to avoid the phenomenon of becoming.
• the thickness of the positive electrode plate is not particularly limited, but from the viewpoint of high capacity, high output, and high rate characteristics, the thickness of the positive electrode active material layer obtained by subtracting the thickness of the current collector is the thickness of the positive electrode active material layer with respect to one side of the current collector. 10 ⁇ m or more is preferable, 20 ⁇ m or more is more preferable, 200 ⁇ m or less is preferable, and 100 ⁇ m or less is more preferable.
• the negative electrode has a current collector and a negative electrode active material layer provided on the current collector.
• the negative electrode active material used for the negative electrode will be described below.
• the negative electrode active material is not particularly limited as long as it can store and release metal ions electrochemically. Specific examples include those having carbon as a constituent element of carbonaceous materials, alloy-based materials, and the like. One of these may be used alone, or two or more thereof may be arbitrarily combined and used in combination.
• Negative electrode active material examples include carbonaceous materials, alloy-based materials and the like as described above.
• Examples of the carbonaceous material include (1) natural graphite, (2) artificial graphite, (3) amorphous carbon, (4) carbon-coated graphite, (5) graphite-coated graphite, and (6) resin-coated graphite. Be done.
• Examples of natural graphite include scaly graphite, scaly graphite, soil graphite and / or graphite particles obtained by subjecting these graphites to a treatment such as spheroidization or densification.
• a treatment such as spheroidization or densification.
• spherical or ellipsoidal graphite that has been subjected to a spheroidizing treatment is particularly preferable from the viewpoint of particle packing property and charge / discharge rate characteristics.
• the device used for the spheroidizing process for example, a device that repeatedly applies mechanical actions such as compression, friction, and shearing force including the interaction of particles mainly with impact force to the particles can be used.
• a rotor with a large number of blades installed inside the casing, and by rotating the rotor at high speed, impact compression, friction, and shearing force are applied to the raw material of natural graphite (1) introduced inside.
• a device that gives a mechanical action such as, etc. to perform the spheroidizing process is preferable.
• an apparatus having a mechanism for repeatedly giving a mechanical action by circulating a raw material is preferable.
• the peripheral speed of the rotating rotor is preferably set to 30 to 100 m / sec, more preferably 40 to 100 m / sec, and 50 to 100 m / sec. It is even more preferable to set it to seconds.
• the spheroidizing treatment can be performed by simply passing the raw material through the device, but it is preferable to circulate or retain the inside of the device for 30 seconds or more, and to circulate or stay in the device for 1 minute or more. Is more preferable.
• a silicon-containing compound, a boron-containing compound, or the like can also be used as a graphitization catalyst.
• artificial graphite obtained by graphitizing mesocarbon microbeads separated in a pitch heat treatment process can be mentioned.
• artificial graphite of granulated particles composed of primary particles can also be mentioned.
• mesocarbon microbeads, graphitizable carbon material powder such as coke, graphitizable binder such as tar and pitch, and graphitization catalyst are mixed, graphitized, and pulverized if necessary. Examples thereof include graphite particles obtained by assembling or bonding a plurality of flat particles so that the orientation planes are non-parallel.
• an amorphous carbon which uses an easily graphitizable carbon precursor such as tar or pitch as a raw material and is heat-treated at least once in a temperature range (range of 400 to 2200 ° C.) where graphitization does not occur.
• Examples thereof include amorphous carbon particles that have been heat-treated using particles or a non-graphitizable carbon precursor such as a resin as a raw material.
• Examples of carbon-coated graphite include those obtained as follows. Natural graphite and / or artificial graphite is mixed with a carbon precursor which is an organic compound such as tar, pitch or resin, and heat-treated at least once in the range of 400 to 2300 ° C. Natural graphite and / or artificial graphite after heat treatment is used as nuclear graphite, and this is coated with amorphous carbon to obtain a carbon graphite composite. This carbon-graphite composite is mentioned as carbon-coated graphite (4).
• a carbon precursor which is an organic compound such as tar, pitch or resin
• the composite form is a form in which a plurality of primary particles are composited using carbon derived from the carbon precursor as a binder even when the entire surface or a part of the surface of nuclear graphite is coated with amorphous carbon. You may. It is also possible to react natural graphite and / or artificial graphite with hydrocarbon gases such as benzene, toluene, methane, propane, and aromatic volatiles at high temperatures to deposit carbon on the graphite surface (CVD). The carbon graphite composite can be obtained.
• hydrocarbon gases such as benzene, toluene, methane, propane, and aromatic volatiles
• Natural graphite and / or artificial graphite is mixed with a carbon precursor of an easily graphitizable organic compound such as tar, pitch or resin, and heat-treated at least once in a temperature range of about 2400 to 3200 ° C. Natural graphite and / or artificial graphite after the heat treatment is used as nuclear graphite, and the entire surface or a part of the surface of the nuclear graphite is coated with graphite to obtain graphite-coated graphite (5).
• the resin-coated graphite for example, natural graphite and / or artificial graphite obtained by mixing natural graphite and / or artificial graphite with a resin or the like and drying at a temperature of less than 400 ° C. is used as nuclear graphite, and the resin or the like is used. It is obtained by coating the nuclear graphite with.
• carbonaceous materials of (1) to (6) described above one kind may be used alone, or two or more kinds may be used in any combination and ratio.
• Examples of the organic compounds such as tar, pitch and resin used for the carbonaceous materials (2) to (5) above include coal-based heavy oil, DC-based heavy oil, cracked petroleum heavy oil, and aromatic hydrocarbons. , N-ring compounds, S-ring compounds, polyphenylenes, synthetic organic polymers, natural polymers, thermoplastic resins, thermosetting resins and the like, which are carbonizable organic compounds selected from the group. Further, the raw material organic compound may be used by being dissolved in a low molecular weight organic solvent in order to adjust the viscosity at the time of mixing.
• natural graphite and / or artificial graphite which is a raw material of nuclear graphite
• spheroidized natural graphite is preferable.
• the alloy-based material used as the negative electrode active material is lithium alone, a single metal and alloy forming a lithium alloy, or oxides, carbides, nitrides thereof, if lithium ions can be occluded and released. It may be any of compounds such as silicides, sulfides and phosphors, and is not particularly limited.
• the elemental metals and alloys forming the lithium alloy are preferably materials containing group 13 and group 14 metal / semi-metal elements (that is, excluding carbon), more preferably elemental metals of aluminum, silicon and tin, and these.
• an alloy or compound containing an atom more preferably a simple substance metal of silicon and tin, and an alloy or compound containing these atoms, which has silicon or tin as a constituent element.
• One of these may be used alone, or two or more thereof may be used in any combination and ratio.
• Metal particles that can be alloyed with Li When a single metal and alloy forming a lithium alloy or a compound such as an oxide, carbide, nitride, silicide, sulfide or phosphide thereof is used as a negative electrode active material, the metal that can be alloyed with Li is It is a particle form. Techniques for confirming that the metal particles are metal particles that can be alloyed with Li include identification of the metal particle phase by X-ray diffraction, observation of the particle structure by an electron microscope, EDX elemental analysis, and fluorescent X-ray. Elemental analysis and the like can be mentioned.
• the metal particles that can be alloyed with Li any conventionally known metal particles can be used, but from the viewpoint of the capacity and cycle life of the non-aqueous electrolyte battery, the metal particles are, for example, Fe, Co, Sb. , Bi, Pb, Ni, Ag, Si, Sn, Al, Zr, Cr, P, S, V, Mn, As, Nb, Mo, Cu, Zn, Ge, In, Ti and W. It is preferably a metal or a compound thereof. Further, the metal particles may be alloy particles formed by two or more kinds of metal elements. Among these, a metal selected from the group consisting of Si, Sn, As, Sb, Al, Zn and W or a metal compound thereof is preferable.
• metal compound examples include metal oxides, metal nitrides, metal carbides and the like. Further, an alloy composed of two or more kinds of metals may be used.
• the Si metal compound is preferably a Si metal oxide.
• Si or Si metal compounds are collectively referred to as Si compounds.
• the Si compound is preferably a Si metal oxide, and the Si metal oxide is SiO x in the general formula.
• This general formula SiO x is obtained by using silicon dioxide (SiO 2 ) and metal Si (Si) as raw materials, and the value of x is usually 0 ⁇ x ⁇ 2.
• SiO x has a larger theoretical capacity than graphite, and amorphous Si or nano-sized Si crystals allow alkaline ions such as lithium ions to enter and exit easily, making it possible to obtain a high-capacity battery. ..
• the Si metal oxide is specifically represented as SiO x , where x is 0 ⁇ x ⁇ 2, more preferably 0.2 or more and 1.8 or less, still more preferably 0. It is 4 or more and 1.6 or less, particularly preferably 0.6 or more and 1.4 or less. Within this range, the battery has a high capacity, and at the same time, the irreversible capacity due to the combination of Li and oxygen can be reduced.
• the oxygen content of the metal particles that can be alloyed with Li is not particularly limited, but is usually 0.01% by mass or more and 8% by mass or less, and preferably 0.05% by mass or more and 5% by mass or less.
• the oxygen distribution state in the particle may be present near the surface, inside the particle, or uniformly present in the particle, but it is particularly preferable that the oxygen is present near the surface.
• the amount of oxygen contained in the metal particles that can be alloyed with Li is within the above range, the strong bond between the metal particles and O (oxygen atom) suppresses the volume expansion due to the secondary charge / discharge of the non-aqueous electrolyte battery.
• the negative electrode active material may contain metal particles that can be alloyed with Li and graphite particles.
• the negative electrode active material may be a mixture in which Li and alloyable metal particles and graphite particles are mixed in the state of mutually independent particles, or Li and alloyable metal particles are mixed on the surface of the graphite particles and the graphite particles. / Or it may be a complex existing inside.
• the composite of the metal particles that can be alloyed with Li and the graphite particles is particularly limited as long as the particles contain the metal particles that can be alloyed with Li and the graphite particles.
• the metal particles and graphite particles that can be alloyed with Li are integrated by physical and / or chemical bonding.
• metal particles and graphite particles that can be alloyed with Li are present in the particles in a dispersed manner so that at least the surface of the composite particles and the inside of the bulk are present. It is in the form in which graphite particles are present in order to unite them by physical and / or chemical bonding.
• a more specific preferred form is a composite material composed of at least Li and alloyable metal particles and graphite particles, in which graphite particles, preferably natural graphite, have a curved structure and have a folded structure.
• it is a composite material (negative electrode active material) characterized in that metal particles that can be alloyed with Li are present in the gaps in the structure.
• the gap may be a void, and a substance such as amorphous carbon, a graphitic material, or a resin that buffers the expansion and contraction of metal particles that can be alloyed with Li exists in the gap. You may.
• the content ratio of the metal particles that can be alloyed with Li to the total of the metal particles that can be alloyed with Li and the metal particles that can be alloyed with Li is usually 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1. It is 0% by mass or more, more preferably 2.0% by mass or more. Further, it is usually 99% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20% by mass or less, particularly. It is preferably 15% by mass or less, and most preferably 10% by mass or less.
• the content ratio of the metal particles that can be alloyed with Li is within this range, it is possible to control the side reaction on the Si surface, and it is possible to obtain a sufficient capacity in the non-aqueous electrolyte battery. preferable.
• the negative electrode active material may be coated with a carbonaceous material or a graphite material.
• coating with an amorphous carbonaceous material is preferable from the viewpoint of lithium ion acceptability.
• This coverage is usually 0.5% or more and 30% or less, preferably 1% or more and 25% or less, and more preferably 2% or more and 20% or less.
• the upper limit of the coverage is from the viewpoint of reversible capacity when the battery is assembled, and the lower limit of the coverage is from the viewpoint that the core carbonaceous material is uniformly coated with amorphous carbon to achieve strong granulation. From the viewpoint of the particle size of the particles obtained when pulverized after firing, the above range is preferable.
• the coating rate (content rate) of the carbide derived from the organic compound of the negative electrode active material finally obtained is the amount of the negative electrode active material, the amount of the organic compound, and the balance measured by the micro method based on JIS K2270. It can be calculated by the following formula from the coal ratio.
• the internal pore space of the negative electrode active material is usually 1% or more, preferably 3% or more, more preferably 5% or more, still more preferably 7% or more. Further, it is usually less than 50%, preferably 40% or less, more preferably 30% or less, still more preferably 20% or less. If this internal pore space ratio is too small, the amount of liquid in the particles of the negative electrode active material tends to decrease in the non-aqueous electrolyte battery. On the other hand, if the internal pore space is too large, the interparticle gap tends to decrease when the electrode is used.
• the lower limit of the internal pore space is preferably in the above range from the viewpoint of charge / discharge characteristics, and the upper limit is preferably set to the above range from the viewpoint of diffusion of the non-aqueous electrolyte solution.
• the gap may be a void, and a substance such as amorphous carbon, a graphitic material, or a resin that buffers the expansion and contraction of metal particles that can be alloyed with Li is a gap. The presence or gap in it may be filled with these.
• Negative electrode configuration and manufacturing method Any known method can be used for producing the negative electrode as long as the effects of the present invention are not significantly impaired. For example, it is formed by adding a binder, a solvent, and if necessary, a thickener, a conductive material, a filler, etc. to a negative electrode active material to form a slurry, which is applied to a current collector, dried, and then pressed. can do.
• the alloy-based material negative electrode can be manufactured by any known method.
• a method for manufacturing a negative electrode for example, a method in which a binder, a conductive material, or the like is added to the above-mentioned negative electrode active material is directly rolled to form a sheet electrode, or a pellet electrode is compression-molded.
• the above-mentioned negative electrode is used by a coating method, a vapor deposition method, a sputtering method, a plating method, or the like on a current collector for a negative electrode (hereinafter, may be referred to as a “negative electrode current collector”).
• a method of forming a thin film layer (negative electrode active material layer) containing an active material is used.
• a binder, a thickener, a conductive material, a solvent, etc. are added to the above-mentioned negative electrode active material to form a slurry, which is applied to the negative electrode current collector, dried, and then pressed to increase the density.
• a negative electrode active material layer is formed on the negative electrode current collector.
• Examples of the material of the negative electrode current collector include steel, copper, copper alloy, nickel, nickel alloy, stainless steel and the like. Of these, copper is preferable, and copper foil is preferable, from the viewpoint of easy processing into a thin film and cost.
• the thickness of the negative electrode current collector is usually 1 ⁇ m or more, preferably 5 ⁇ m or more, and usually 100 ⁇ m or less, preferably 50 ⁇ m or less. If the thickness of the negative electrode current collector is too thick, the capacity of the entire non-aqueous electrolyte battery may be reduced too much, and conversely, if it is too thin, handling may be difficult.
• the surface of these negative electrode current collectors be roughened in advance in order to improve the binding effect with the negative electrode active material layer formed on the surface.
• Surface roughening methods include blasting, rolling with a rough surface roll, polishing cloth with abrasive particles fixed, a grindstone, emeri buff, a wire brush equipped with a steel wire, etc. to polish the surface of the current collector. Specific polishing method, electrolytic polishing method, chemical polishing method and the like can be mentioned.
• a perforated type negative electrode current collector such as expanded metal or punching metal can also be used.
• the mass of this type of negative electrode current collector can be freely changed by changing the aperture ratio.
• the negative electrode active material layers are formed on both sides of this type of negative electrode current collector, the negative electrode active material layer is less likely to be peeled off due to the rivet effect through the holes.
• the aperture ratio becomes too high, the contact area between the negative electrode active material layer and the negative electrode current collector becomes small, so that the adhesive strength may be rather low.
• the slurry for forming the negative electrode active material layer is usually prepared by adding a binder, a thickener, etc. to the negative electrode material.
• the term "negative electrode material” as used herein refers to a material in which the negative electrode active material and the conductive material are combined.
• the content of the negative electrode active material in the negative electrode material is usually 70% by mass or more, particularly 75% by mass or more, and usually 97% by mass or less, particularly preferably 95% by mass or less. If the content of the negative electrode active material is too small, the capacity of the secondary battery using the obtained negative electrode tends to be insufficient, and if it is too large, the content of the conductive material is relatively insufficient, resulting in electricity as the negative electrode. It tends to be difficult to secure conductivity. When two or more negative electrode active materials are used in combination, the total amount of the negative electrode active materials may satisfy the above range.
• the conductive material used for the negative electrode examples include metal materials such as copper and nickel; carbon materials such as graphite and carbon black. One of these may be used alone, or two or more thereof may be used in any combination and ratio. In particular, it is preferable to use a carbon material as the conductive material because the carbon material also acts as an active material.
• the content of the conductive material in the negative electrode material is usually 3% by mass or more, preferably 5% by mass or more, and usually 30% by mass or less, preferably 25% by mass or less. If the content of the conductive material is too small, the conductivity tends to be insufficient, and if it is too large, the content of the negative electrode active material or the like is relatively insufficient, so that the battery capacity and strength tend to decrease. When two or more conductive materials are used in combination, the total amount of the conductive materials may satisfy the above range.
• any binder can be used as long as it is a material stable to the solvent and electrolytic solution used in electrode manufacturing.
• examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, isoprene rubber, butadiene rubber, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer and the like. One of these may be used alone, or two or more thereof may be used in any combination and ratio.
• the content of the binder is usually 0.5 parts by mass or more, preferably 1 part by mass or more, usually 10 parts by mass or less, and preferably 8 parts by mass or less with respect to 100 parts by mass of the negative electrode material. .. If the content of the binder is too small, the strength of the obtained negative electrode tends to be insufficient, and if it is too large, the content of the negative electrode active material or the like is relatively insufficient, so that the battery capacity and conductivity tend to be insufficient. It becomes. When two or more binders are used in combination, the total amount of the binders may satisfy the above range.
• Examples of the thickener used for the negative electrode include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and the like. One of these may be used alone, or two or more thereof may be used in any combination and ratio.
• the thickener may be used as needed, but when used, the content of the thickener in the negative electrode active material layer is usually in the range of 0.5% by mass or more and 5% by mass or less. Is preferable.
• the slurry for forming the negative electrode active material layer is prepared by mixing the negative electrode active material with a conductive material, a binder, and a thickener as necessary, and using an aqueous solvent or an organic solvent as a dispersion medium.
• aqueous solvent usually used as the aqueous solvent, but alcohols such as ethanol and organic solvents such as cyclic amides such as N-methylpyrrolidone are used in combination with water in a range of 30% by mass or less. You can also.
• organic solvent examples include cyclic amides such as N-methylpyrrolidone; linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as anisole, toluene and xylene.
• Alcohols such as butanol and cyclohexanol; among them, cyclic amides such as N-methylpyrrolidone; linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide are preferable. Any one of these may be used alone, or two or more thereof may be used in any combination and ratio.
• the obtained slurry is applied onto the above-mentioned negative electrode current collector, dried, and then pressed to form a negative electrode active material layer, and a negative electrode is obtained.
• the method of application is not particularly limited, and a method known per se can be used.
• the drying method is not particularly limited, and known methods such as natural drying, heat drying, and vacuum drying can be used.
• the electrode structure when the negative electrode active material is converted into an electrode is not particularly limited, but the density of the negative electrode active material existing on the current collector is preferably 1 g ⁇ cm -3 or more, and 1.2 g ⁇ cm -3 or more. Is more preferable, 1.3 g ⁇ cm -3 or more is particularly preferable, 2.2 g ⁇ cm -3 or less is preferable, 2.1 g ⁇ cm -3 or less is more preferable, and 2.0 g ⁇ cm -3 or less is more preferable. More preferably, 1.9 g ⁇ cm -3 or less is particularly preferable.
• the density of the negative electrode active material existing on the current collector exceeds the above range, the negative electrode active material particles are destroyed, the initial irreversible capacity of the non-aqueous electrolyte battery increases, and the current collector / negative electrode active material High current density charge / discharge characteristics may deteriorate due to a decrease in the permeability of the non-aqueous electrolyte solution near the interface. Further, when the density of the negative electrode active material is lower than the above range, the conductivity between the negative electrode active materials may decrease, the battery resistance may increase, and the capacity per unit volume may decrease.
• a separator is usually interposed between the positive electrode and the negative electrode to prevent a short circuit.
• the non-aqueous electrolyte solution of the present invention is usually used by impregnating this separator.
• the material and shape of the separator are not particularly limited, and any known separator can be used as long as the effect of the present invention is not significantly impaired.
• resins, glass fibers, inorganic substances and the like formed of a material stable to the non-aqueous electrolytic solution of the present invention are preferably used, and a porous sheet or a non-woven fabric-like material having excellent liquid retention is used. Is preferable.
• polyolefins such as polyethylene and polypropylene, polytetrafluoroethylene, polyether sulfone, glass filter and the like can be used.
• glass filters and polyolefins are preferable, and polyolefins are more preferable.
• One of these materials may be used alone, or two or more of these materials may be used in any combination and ratio.
• the thickness of the separator is arbitrary, but is usually 1 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and usually 50 ⁇ m or less, preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less. If the separator is too thin than the above range, the insulating property and mechanical strength may decrease. Further, if it is too thick than the above range, not only the battery performance such as rate characteristics may be deteriorated, but also the energy density of the non-aqueous electrolyte battery as a whole may be lowered.
• the porosity of the separator is arbitrary, but is usually 20% or more, preferably 35% or more, more preferably 45% or more. Further, it is usually 90% or less, preferably 85% or less, and more preferably 75% or less. If the porosity is too small than the above range, the film resistance tends to increase and the rate characteristics tend to deteriorate. On the other hand, if it is larger than the above range, the mechanical strength of the separator tends to decrease and the insulating property tends to decrease.
• the average pore size of the separator is also arbitrary, but is usually 0.5 ⁇ m or less, preferably 0.2 ⁇ m or less, and usually 0.05 ⁇ m or more. If the average pore diameter exceeds the above range, a short circuit is likely to occur. Further, if it falls below the above range, the film resistance may increase and the rate characteristics may deteriorate.
• oxides such as alumina and silicon dioxide
• nitrides such as aluminum nitride and silicon nitride
• sulfates such as barium sulfate and calcium sulfate are used.
• a thin film such as a non-woven fabric, a woven fabric, or a microporous film is used.
• a thin film shape a thin film having a pore diameter of 0.01 to 1 ⁇ m and a thickness of 5 to 50 ⁇ m is preferably used.
• a separator formed by forming a composite porous layer containing a particle-shaped or fiber-shaped inorganic substance using a resin binder on the surface layer of the positive electrode and / or the negative electrode can be used. ..
• a porous layer containing alumina particles having a 90% particle size of less than 1 ⁇ m may be formed on both sides of the positive electrode using a fluororesin as a binder.
• the electrode group has a laminated structure in which the above-mentioned positive electrode plate and the negative electrode plate are formed by the above-mentioned separator, and a structure in which the above-mentioned positive electrode plate and the negative electrode plate are spirally wound through the above-mentioned separator. Either may be used.
• the ratio of the volume of the electrode group to the internal volume of the battery (hereinafter referred to as the electrode group occupancy rate) is usually 40% or more, preferably 50% or more, and usually 90% or less, 80% or less. preferable.
• the lower limit of the electrode group occupancy rate is preferably in the above range from the viewpoint of battery capacity.
• the upper limit of the electrode group occupancy rate is to secure a gap space from the viewpoint of various characteristics such as charge / discharge repetition performance as a battery and high temperature storage characteristics, and from the viewpoint of avoiding the operation of the gas discharge valve that releases the internal pressure to the outside. It is preferable to set the above range. If the gap space is too small, the temperature of the battery will increase, causing the members to expand and the vapor pressure of the liquid component of the electrolyte to increase, resulting in an increase in internal pressure, resulting in repeated charging / discharging performance and high-temperature storage characteristics of the battery. In some cases, the gas release valve that releases the internal pressure to the outside may operate.
• the current collecting structure is not particularly limited, but in order to more effectively improve the discharge characteristics of the non-aqueous electrolyte solution, it is preferable to use a structure that reduces the resistance of the wiring portion and the joint portion. .. When the internal resistance is reduced in this way, the effect of using the above-mentioned non-aqueous electrolyte solution is particularly well exhibited.
• the electrode group has the above-mentioned laminated structure
• a structure formed by bundling the metal core portions of each electrode layer and welding them to the terminals is preferably used.
• the area of one electrode becomes large, the internal resistance becomes large. Therefore, it is also preferably used to reduce the resistance by providing a plurality of terminals in the electrode.
• the electrode group has the above-mentioned wound structure, the internal resistance can be reduced by providing a plurality of lead structures on the positive electrode and the negative electrode and bundling them in the terminals.
• a protective element As a protective element, a PTC element (Positive Temperature Coafficient) element whose resistance increases when abnormal heat generation or excessive current flows, a thermal fuse, a thermistor, and a current flowing in a circuit due to a sudden rise in battery internal pressure or internal temperature during abnormal heat generation. (Current cutoff valve) and the like. It is preferable to select the protective element under conditions that do not operate under normal use of high current, and from the viewpoint of high output, it is more preferable to design the protective element so as not to cause abnormal heat generation or thermal runaway even without the protective element.
• the non-aqueous electrolyte battery of the present embodiment is usually configured by storing the above-mentioned non-aqueous electrolyte, negative electrode, positive electrode, separator and the like in an exterior body (exterior case).
• an exterior body exterior body
• a known one can be arbitrarily adopted as long as the effect of the present invention is not significantly impaired.
• the material of the outer case is not particularly limited as long as it is a substance stable to the non-aqueous electrolyte solution used. Specifically, a nickel-plated steel plate, stainless steel, aluminum or aluminum alloy, magnesium alloy, metals such as nickel and titanium, or a laminated film (laminated film) of resin and aluminum foil is preferably used.
• the metals are welded together by laser welding, resistance welding, or ultrasonic welding to form a sealed and sealed structure, or the above metals are used to caulk the structure via a resin gasket.
• the outer case using the above-mentioned laminated film include a case in which resin layers are heat-sealed to form a sealed and sealed structure.
• a resin different from the resin used for the laminate film may be interposed between the resin layers.
• a resin having a polar group or a modification in which a polar group is introduced as an intervening resin is introduced. Resin is preferably used.
• the shape of the exterior body is also arbitrary, and may be any of, for example, a cylindrical type, a square type, a laminated type, a coin type, and a large size.
• Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2 85 parts by mass as the positive electrode active material, 10 parts by mass of acetylene black as the conductive material, and 5 parts by mass of polyvinylidene fluoride (PVdF) as the binder.
• PVdF polyvinylidene fluoride
• Preparation of negative electrode 98 parts by mass of natural graphite, 1 part by mass of aqueous dispersion of sodium carboxymethyl cellulose (concentration of sodium carboxymethyl cellulose 1% by mass) and aqueous dispersion of styrene-butadiene rubber (styrene-butadiene rubber) as a thickener and binder 1 part by mass was added and mixed with a disperser to form a slurry. The obtained slurry was applied to one side of a copper foil having a thickness of 10 ⁇ m, dried, and then pressed to obtain a negative electrode.
• aqueous dispersion of sodium carboxymethyl cellulose concentration of sodium carboxymethyl cellulose 1% by mass
• styrene-butadiene rubber styrene-butadiene rubber
• FSO 3 Li was added to the Ni (PF 6 ) 2- containing non-aqueous electrolyte solution or reference electrolyte solution A1 prepared above to prepare the non-aqueous electrolyte solution shown in Table 1 below.
• Comparative Example A1-1 is the reference electrolyte A1 itself.
• the content of FSO 3 Li indicates the amount of addition
• the content of nickel element (nickel ion) is a value obtained based on the measurement results of inductively coupled high frequency plasma emission spectroscopy (ICP-AES) described later. ..
• the “content (mass%)" and “content (mass ppm)" in the table are the contents when the reference electrolytic solution A1 is 100% by mass.
• the non-aqueous electrolyte secondary battery after the charge storage test was again CC-CV charged at 1 / 6C to 4.2 V, and then stored at a high temperature at 60 ° C. for 336 hours.
• the discharge capacity when the non-aqueous electrolyte secondary battery was discharged to 2.5 V at 1/6 C at 25 ° C. was determined, and this was defined as "residual capacity (2 weeks)".
• Table 1 below shows the values of the remaining capacity when the remaining capacity (2 weeks) of Comparative Example A1-1 is set to 100.
• Comparative Example A1-1 From the comparison between Comparative Example A1-1 and Comparative Example A1-2, it was shown that the residual capacity of the battery was increased by containing FSO 3 Li in the electrolytic solution. On the other hand, from Comparative Examples A1-1 to A1-3, it was shown that even if the electrolytic solution contains FSO 3 Li, the residual volume decreases when the nickel ion exceeds a predetermined amount. Further, from Comparative Examples A1-4 to A1-7, when the electrolytic solution contained about 50 mass ppm of nickel ions (Comparative Example A1-6), the residual capacity was improved, but the amount of nickel was less or more than that. In the case of containing ions, a decrease in residual capacity was shown.
• Examples A2-1 to A2-3, Comparative Examples A2-1 to A2-3> [Preparation of positive electrode] A positive electrode was prepared in the same manner as in Example A1-1.
• a negative electrode was prepared in the same manner as in Example A1-1.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example A1-1 except that the above non-aqueous electrolyte was used.
• Example A1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• Initial conditioning and charge storage tests were performed in the same manner as in Example A1-1.
• the remaining capacity was determined by the same method as in Example A1-1.
• Table 2 below shows the remaining capacity (1 week) of Examples A2-1 to A2-3 and Comparative Examples A2-1 to A2-3 when the remaining capacity (1 week) of Comparative Example A1-1 is set to 100. The value of is shown together with the results of Comparative Examples A1-1 and A1-5.
• Example A2-1 showed a remarkable effect that the remaining capacity was improved as compared with Comparative Example A1-5 and Comparative Example A2-1, and further, the remaining capacity was improved as compared with Comparative Example A1-1. .. Further, from the comparison between Example A2-2 and Comparative Example A2-2 and the comparison between Example A2-3 and Comparative Example A2-3, the electrolytic solution contained FSO 3 Li and a predetermined amount of nickel ions. The inclusion has a remarkable effect of improving the remaining capacity of the non-aqueous electrolyte secondary battery, that is, improving the charge storage characteristics of the non-aqueous electrolyte secondary battery in a high temperature environment.
• Examples A3-1 to A3-2, Comparative Examples A3-1 to A3-5> [Preparation of positive electrode] 90 parts by mass of Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2 as a positive electrode active material, 7 parts by mass of acetylene black as a conductive material, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder. was mixed with a disperser in an N-methylpyrrolidone solvent to form a slurry. This was uniformly applied to one side of an aluminum foil having a thickness of 15 ⁇ m, dried, and then pressed to obtain a positive electrode.
• PVdF polyvinylidene fluoride
• a negative electrode was prepared in the same manner as in Example A1-1 except that a slurry containing the negative electrode active material was applied to both surfaces of the copper foil.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example A1-1 except that the above-mentioned positive electrode, negative electrode and non-aqueous electrolyte were used.
• Example A1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• Initial conditioning and charge storage tests were performed in the same manner as in Example A1-1.
• the remaining capacity (1 week) and the remaining capacity (2 weeks) were determined by the same method as in Example A1-1.
• Table 3 below shows the values of the remaining capacity when the remaining capacity (1 week) of Comparative Example A3-1 is 100, and the remaining capacity when the remaining capacity (2 weeks) of Comparative Example A3-1 is 100. 2 weeks) is shown.
• the electrolytic solution containing 5 mass ppm of nickel ions improves the remaining capacity of the non-aqueous electrolyte battery, while the amount of nickel ions is 515 mass by mass. It can be seen that when the amount is as large as ppm, the remaining capacity is reduced.
• examples A3-1, when Examples A3-2 and Comparative Examples A3-2, the electrolytic solution comprising nickel ions of a predetermined amount, and including FSO 3 Li comprises FSO 3 Li alone It was shown that the remaining capacity increased more than in the case.
• the storage period of the battery is usually about 200 days for a vehicle manufacturer, for example. Since the difference in the remaining capacity after storage for 1 week or 2 weeks increases with time, it can be said that the longer the storage period, the more remarkable the effect of the present invention becomes.
• Examples B1-1 to B1-4, Comparative Examples B1-1 to B1-6> [Preparation of EC solution containing Co (PF 6 ) 2 ]
• 0.30 g (2.3 mmol) of CoCl 2 was weighed in a 50 mL beaker and suspended in acetonitrile (AN). While stirring this, 1.168 g (4.6 mmol) of AgPF 6 was added slowly in small portions, and then stirred at room temperature for 3 hours. As the reaction proceeded, a white solid of AgCl was produced.
• a positive electrode was prepared in the same manner as in Example A1-1.
• a negative electrode was prepared in the same manner as in Example A1-1.
• a non-aqueous electrolyte solution containing no Co (PF 6 ) 2 is referred to as a reference electrolyte solution B1.
• FSO 3 Li was added to the Co (PF 6 ) 2- containing non-aqueous electrolyte solution or reference electrolyte solution B1 prepared above to prepare the non-aqueous electrolyte solution shown in Table 4 below.
• Comparative Example B1-1 is the reference electrolyte B1 itself.
• the content of FSO 3 Li indicates the amount added, and the content of cobalt element (cobalt ion) is a value obtained based on the measurement results of inductively coupled high frequency plasma emission spectroscopy (ICP-AES) described later. ..
• the “content (mass%)" and “content (mass ppm)” in the table are the contents when the reference electrolytic solution B1 is 100% by mass.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example A1-1 except that the above non-aqueous electrolyte was used.
• Example A1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• Initial conditioning and charge storage tests were performed in the same manner as in Example A1-1.
• the remaining capacity was determined by the same method as in Example A1-1.
• Table 4 below shows the values of the remaining capacity when the remaining capacity (1 week) of Comparative Example B1-1 is 100.
• Table 4 below shows the values of the remaining capacity when the remaining capacity (2 weeks) of Comparative Example B1-1 is set to 100.
• Example B2-1 to B2-3, Comparative Examples B2-1 to B2-3> [Preparation of positive electrode] A positive electrode was prepared in the same manner as in Example B1-1.
• a negative electrode was prepared in the same manner as in Example B1-1.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example B1-1 except that the above non-aqueous electrolyte was used.
• Example B1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• Initial conditioning and charge storage tests were performed in the same manner as in Example B1-1.
• the remaining capacity was determined by the same method as in Example B1-1.
• Table 5 below shows the remaining capacity (1 week) of Examples B2-1 to B2-3 and Comparative Examples B2-1 to B2-3 when the remaining capacity (1 week) of Comparative Example B1-1 is set to 100. The value of is shown together with the results of Comparative Examples B1-1 and B1-4.
• the non-aqueous electrolyte solution containing 78 mass ppm of cobalt ions without containing FSO 3 Li is more non-aqueous electrolyte solution than the non-aqueous electrolyte solution containing cobalt ions. It has been shown to reduce the remaining capacity of the next battery. Further, from Comparative Examples B2-1 and B2-2, even when the non-aqueous electrolyte solution contains FSO 3 Li, if the content is too small, the remaining capacity of the non-aqueous electrolyte secondary battery is improved. Instead of doing, it was shown to decline.
• Example B2-1 has a lower residual capacity than that of Comparative Example B1-4 and Comparative Example B2-1.
• Example B2-1 showed a remarkable effect that the remaining capacity was improved as compared with Comparative Example B1-4 and Comparative Example B2-1, and further, the remaining capacity was improved as compared with Comparative Example B1-1. ..
• the non-aqueous electrolyte solution was FSO 3 Li and a predetermined amount of cobalt. It was shown that the inclusion of ions has a remarkable effect of improving the remaining capacity of the non-aqueous electrolyte secondary battery, that is, improving the charge storage characteristics of the non-aqueous electrolyte secondary battery in a high temperature environment.
• Examples B3-1 to B3-3, Comparative Examples B3-1 to B3-6> [Preparation of positive electrode] A positive electrode was prepared in the same manner as in Example A3-1.
• a negative electrode was prepared in the same manner as in Example A3-1.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example B1-1 except that the positive electrode, the negative electrode and the non-aqueous electrolyte were used.
• Example B1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• the remaining capacity (1 week) and the remaining capacity (2 weeks) were determined by the same method as in Example B1-1.
• Table 6 below shows the values of the remaining capacity (1 week) when the remaining capacity (1 week) of Comparative Example B3-1 is 100, and the remaining capacity (2 weeks) of Comparative Example B3-1 is 100. The value of the remaining capacity (2 weeks) of is shown.
• the non-aqueous electrolyte solution containing 4 mass ppm of cobalt ions improves the remaining capacity of the non-aqueous electrolyte secondary battery, while the amount of cobalt ions.
• the residual capacity after high temperature storage for 168 hours (1 week) is lowered, and it is shown that the residual capacity after high temperature storage for 336 hours (2 weeks) is equivalent to the case where cobalt ions are not contained.
• the residual capacity of the non-aqueous electrolyte secondary battery after high temperature storage increases compared to the case where ions are contained alone, especially after 168 hours (1 week) high temperature storage and 336 hours (2 weeks) high temperature storage. From the comparison of the capacity ratios, it was shown that the deterioration of the non-aqueous electrolyte secondary battery due to aging is remarkably suppressed, and the charge storage characteristics of the non-aqueous electrolyte secondary battery in a high temperature environment are improved.
• the storage period of the battery is usually about 200 days for a vehicle manufacturer, for example. Since the difference in the remaining capacity after storage for 1 week or 2 weeks increases with time, it can be said that the longer the storage period, the more remarkable the effect of the present invention becomes.
• a positive electrode was prepared in the same manner as in Example A1-1.
• a negative electrode was prepared in the same manner as in Example A1-1.
• FSO 3 Li was added to the Cu (PF 6 ) 2- containing non-aqueous electrolyte solution or reference electrolyte C1 prepared above to prepare the non-aqueous electrolyte solution shown in Table 7 below.
• Comparative Example C1-1 is the reference electrolyte C1 itself.
• the content of FSO 3 Li indicates the amount of addition
• the content of copper element (copper ion) is a value obtained based on the measurement result of inductively coupled high frequency plasma emission spectroscopy (ICP-AES) described later. ..
• the "content (mass%)" and “content (mass ppm)" in the table are the contents when the reference electrolytic solution C1 is 100% by mass.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example A1-1 except that the above non-aqueous electrolyte was used.
• Example A1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• Initial conditioning and charge storage tests were performed in the same manner as in Example A1-1.
• the remaining capacity was determined by the same method as in Example A1-1.
• Table 7 below shows the values of the remaining capacity (1 week) when the remaining capacity of Comparative Example C1-1 is 100.
• Table 7 below shows the values of the remaining capacity when the remaining capacity (2 weeks) of Comparative Example C1-1 is set to 100.
• Comparative Example C1-1 From the comparison between Comparative Example C1-1 and Comparative Example C1-2, it was shown that the residual capacity of the battery was increased by containing FSO 3 Li in the electrolytic solution. On the other hand, from Comparative Examples C1-1 to C1-3, even if the electrolytic solution contains FSO 3 Li, the residual capacity does not change when the copper ion exceeds a predetermined amount, and the effect of containing FSO 3 Li does not change. It was shown that it does not exert. Further, from Comparative Examples C1-4 to C1-7, when the electrolytic solution contains 5 mass ppm of copper ions, the residual capacity is the same as when it does not contain copper ions, and when it contains about 60 mass ppm, the residual capacity is improved.
• Example C1-2 of a non-aqueous electrolyte battery containing the same amount of copper ions and FSO 3 Li the ratio of residual capacity was improved after high temperature storage at 60 ° C. for 168 hours, and 60 ° C. for 336 hours. It was shown that the ratio of residual capacity was further improved after high temperature storage under the conditions of. That is, it was shown that when the non-aqueous electrolyte solution contains a predetermined amount of copper ions and contains FSO 3 Li, deterioration of the non-aqueous electrolyte battery due to aging is remarkably suppressed.
• a negative electrode was prepared in the same manner as in Example C1-1.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example C1-1 except that the above non-aqueous electrolyte was used.
• Example C1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• Initial conditioning and charge storage tests were performed in the same manner as in Example C1-1.
• the remaining capacity (1 week) was determined by the same method as in Example C1-1.
• Table 8 below shows the remaining capacities (1 week) of Examples C2-1 to C2-3 and Comparative Examples C2-1 to C2-3 when the remaining capacity (1 week) of Comparative Example C1-1 is set to 100. The value of is shown together with the results of Comparative Examples C1-1 and C1-5.
• the non-aqueous electrolyte battery of Example C2-1 is remarkably improved in residual capacity as compared with Comparative Example C1-5 and Comparative Example C2-1, and further improved as compared with Comparative Example C1-1.
• the effect was shown.
• the non-aqueous electrolyte battery of Example C2-2 has a remarkable remaining capacity higher than that of Comparative Example C1-5 and Comparative Example C2-2, and further improved as compared with Comparative Example C1-1.
• the effect was shown.
• the residual capacity of the non-aqueous electrolyte secondary battery is improved by containing FSO 3 Li and a predetermined amount of copper ions in the electrolytic solution, that is, non-aqueous electrolytic solution. The remarkable effect of improving the charge storage characteristics of the liquid secondary battery in a high temperature environment was shown.
• Examples C3-1 to C3-2, Comparative Examples C3-1 to C3-5> [Preparation of positive electrode] A positive electrode was prepared in the same manner as in Example A3-1.
• a negative electrode was prepared in the same manner as in Example A3-1.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example C1-1 except that the positive electrode, the negative electrode and the non-aqueous electrolyte were used.
• Example C1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• the remaining capacity (1 week) and the remaining capacity (2 weeks) were determined by the same method as in Example C1-1.
• Table 9 below shows the values of the remaining capacity (1 week) when the remaining capacity (1 week) of Comparative Example C3-1 is 100, and the remaining capacity (2 weeks) of Comparative Example C3-1 is 100. The value of the remaining capacity (2 weeks) of is shown.
• the non-aqueous electrolyte solution contains a predetermined amount of copper ions and contains FSO 3 Li, whereby FSO 3 Li or The residual capacity after high temperature storage for 168 hours (1 week) is higher than that when copper ions are contained alone, and the residual capacity after 168 hours (1 week) high temperature storage and 336 hours (2 weeks) high temperature storage. It was shown that the deterioration of the non-aqueous electrolyte secondary battery due to aging is remarkably suppressed. That is, it was shown that when the non-aqueous electrolyte solution contains FSO 3 Li and a predetermined amount of copper ions, the charge storage characteristics of the non-aqueous electrolyte secondary battery in a high temperature environment are improved.
• the storage period of the battery is usually about 200 days for a vehicle manufacturer, for example. Since the difference in the remaining capacity after storage for 1 week or 2 weeks increases with time, it can be said that the longer the storage period, the more remarkable the effect of the present invention becomes.
• a positive electrode was prepared in the same manner as in Example A1-1.
• a negative electrode was prepared in the same manner as in Example A1-1.
• a non-aqueous electrolytic solution containing no Mn (PF 6 ) 2 is referred to as a reference electrolytic solution D1.
• FSO 3 Li was added to the Mn (PF 6 ) 2- containing non-aqueous electrolyte solution or reference electrolyte D1 prepared above to prepare the non-aqueous electrolyte solution shown in Table 10 below.
• Comparative Example D1-1 is the reference electrolyte D1 itself.
• the content of FSO 3 Li indicates the amount of addition
• the content of manganese element (manganese ion) is a value obtained based on the measurement results of inductively coupled high frequency plasma emission spectroscopy (ICP-AES) described later. ..
• the “content (mass%)" and “content (mass ppm)” in the table are the contents when the reference electrolytic solution D1 is 100% by mass.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example A1-1 except that the above non-aqueous electrolyte was used.
• Example A1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery> [Initial conditioning] Initial conditioning and charge storage tests were performed in the same manner as in Example A1-1. The remaining capacity was determined by the same method as in Example A1-1. Table 10 below shows the values of the remaining capacity (1 week) when the remaining capacity (1 week) of Comparative Example D1-1 is 100. Table 10 below shows the values of the remaining capacity when the remaining capacity (2 weeks) of Comparative Example D1-1 is 100.
• the non-aqueous electrolyte solution contains FSO 3 Li and a predetermined amount of manganese ions, the deterioration of the non-aqueous electrolyte secondary battery due to aging is remarkably suppressed, and the high temperature environment of the non-aqueous electrolyte secondary battery. It was shown that the charge storage characteristics underneath were improved.
• Example D2-1 to D2-3, Comparative Examples D2-1 to D2-3> [Preparation of positive electrode] A positive electrode was prepared in the same manner as in Example D1-1.
• a negative electrode was prepared in the same manner as in Example D1-1.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example D1-1 except that the above non-aqueous electrolyte was used.
• Example D1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• Initial conditioning and charge storage tests were performed in the same manner as in Example D1-1.
• the remaining capacity was determined by the same method as in Example D1-1.
• Table 11 shows the remaining capacities (1 week) of Examples D2-1 to D2-3 and Comparative Examples D2-1 to D2-3 when the remaining capacity (1 week) of Comparative Example D1-1 is set to 100. The value of is shown together with the results of Comparative Examples D1-1 and D1-4.
• Example D2-1 has a lower residual capacity than that of Comparative Example D1-4 and Comparative Example D2-1.
• Example D2-1 showed a remarkable effect that the remaining capacity was improved as compared with Comparative Example D1-4 and Comparative Example D2-1, and further, the remaining capacity was improved as compared with Comparative Example D1-1. ..
• the non-aqueous electrolyte solution was FSO 3 Li and a predetermined amount of manganese.
• the inclusion of ions has a remarkable effect of improving the residual capacity of the non-aqueous electrolyte secondary battery after high temperature storage, that is, improving the charge storage characteristics of the non-aqueous electrolyte secondary battery in a high temperature environment. Shown.
• Examples D3-1 to D3-3, Comparative Examples D3-1 to D3-6> [Preparation of positive electrode] A positive electrode was prepared in the same manner as in Example A3-1.
• a negative electrode was prepared in the same manner as in Example A3-1.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example D1-1 except that the above-mentioned positive electrode, negative electrode and non-aqueous electrolyte were used.
• Example D1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• the remaining capacity (1 week) and the remaining capacity (2 weeks) were determined by the same method as in Example D1-1.
• Table 12 below shows the values of the remaining capacity when the remaining capacity of Comparative Example D3-1 is 100, and the remaining capacity (2 weeks) when the remaining capacity of Comparative Example D3-1 is 100. Indicates the value.
• the non-aqueous electrolyte solution containing 10% by mass or more of manganese ions was used as a non-aqueous electrolyte secondary battery after high temperature storage for 168 hours (1 week). It can be seen that while reducing the residual capacity, the residual capacity after high temperature storage for 336 hours (2 weeks) is improved as compared with the case where manganese ions are not contained. Further, from Examples D3-1 to D3-3, since the non-aqueous electrolyte solution contains a predetermined amount of manganese ions and contains FSO 3 Li, it takes 168 hours as compared with the case where FSO 3 Li or manganese ions are contained alone.
• the storage period of the battery is usually about 200 days for a vehicle manufacturer, for example. Since the difference in the remaining capacity after storage for 1 week or 2 weeks increases with time, it can be said that the longer the storage period, the more remarkable the effect of the present invention becomes.
• Examples E1-1 to E1-7, Comparative Examples E1-1 to E1-10> [Preparation of positive electrode] A positive electrode was prepared in the same manner as in Example A3-1.
• a negative electrode was prepared in the same manner as in Example A3-1.
• Table 13 shows the aluminum ion concentrations of tris (2,4-pentanedionato) aluminum (Al (acac) 3 ) or aluminum fluorosulfonate (Al (FSO 3 ) 3 ) in a mixed solvent under a dry argon atmosphere. And so that the solvent composition is ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) in a volume ratio of 3: 4: 3, dissolved in EC, EMC, and DMC.
• the fully dried LiPF 6 was dissolved at 1 mol / L (12.3% by mass, as a concentration in the non-aqueous electrolyte solution).
• a non-aqueous electrolyte solution containing neither Al (acac) 3 nor Al (FSO 3 ) 3 is called a reference electrolyte solution E1.
• FSO 3 Li was added to the non-aqueous electrolyte solution or reference electrolyte solution E1 prepared above, and the non-aqueous electrolyte solutions of Examples E1-1 to E1-7 shown in Table 13 below, Comparative Example E1 -The non-aqueous electrolyte solution of Comparative Example E1-3 was prepared.
• Comparative Example E1-1 is the reference electrolyte E1 itself. Further, those to which FSO 3 Li was not added were used as non-aqueous electrolyte solutions of Comparative Examples E1-4 to E1-10.
• the content of FSO 3 Li indicates the amount added, and the content of the aluminum element (aluminum ion) is a value obtained based on the measurement results of inductively coupled high frequency plasma emission spectroscopy (ICP-AES) described later. ..
• the “content (mass%)” and “content (mass ppm)” in the table are the contents when the reference electrolytic solution E1 is 100% by mass.
• Al (FSO 3 ) 3 was synthesized according to the method described in Polyhedron, 1983, Volume 2, Issue 11, Pages 1209-1210.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example A1-1 except that the above non-aqueous electrolyte was used.
• Example A1-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• Initial conditioning and charge storage tests were performed in the same manner as in Example A1-1.
• the remaining capacity was determined by the same method as in Example A1-1.
• Table 13 below shows the residual capacity of Examples E1-1 to E1-7 and Comparative Examples E1-1 to E1-10 when the remaining capacity (1 week) of Comparative Example E1-1 is set to 100. The value of (1 week) is shown.
• Table 13 below shows the residual capacity of Examples E1-1 to E1-7 and Comparative Examples E1-1 to E1-10 when the remaining capacity (2 weeks) of Comparative Example E1-1 is set to 100. The value of (2 weeks) is shown.
• the electrolytic solution contains a specific amount of aluminum ions and FSO 3 Li, deterioration of the non-aqueous electrolyte battery due to aging is suppressed, that is, non-aque. It was shown that the charge storage characteristics of the water-based electrolyte secondary battery in a high temperature environment are improved. From Examples E1-1 to E1-7, the non-aqueous electrolyte solution contains FSO 3 Li and a specific amount of aluminum ions regardless of the type of counter anion of the aluminum ion, so that the non-aqueous electrolyte solution secondary It was shown that the charge storage characteristics of the battery in a high temperature environment are improved.
• the storage period of a battery is usually about 200 days for a vehicle manufacturer, for example. Since the difference in the remaining capacity after storage for 1 week or 2 weeks increases with time, it can be said that the longer the storage period, the more remarkable the effect of the present invention becomes.
• Example E2-1 to Example E2-3, Comparative Example E2-1 to Comparative Example E2-3> [Preparation of positive electrode] A positive electrode was prepared in the same manner as in Example E1-1.
• a negative electrode was prepared in the same manner as in Example E1-1.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example E1-4 except that the above non-aqueous electrolyte was used.
• Example E1-4 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• the remaining capacity (1 week) was determined by the same method as in Example E1-4.
• Table 14 below shows the remaining capacities of Examples E2-1 to E2-3 and Comparative Examples E2-1 to E2-3 when the remaining capacity (1 week) of Comparative Example E1-1 is set to 100.
• the value of (remaining capacity) is shown together with the results of Comparative Example E1-1 and Comparative Example E1-7.
• Comparative Example E1-7 the electrolytic solution not containing FSO 3 Li and containing a specific amount of aluminum ions (Comparative Example E1-7) is an electrolytic solution not containing aluminum ions (comparative). From Example E1-1), it was shown that the remaining capacity of the non-aqueous electrolyte battery was reduced. Further, from Comparative Example E2-1 and Comparative Example E2-2, even when the electrolytic solution contains FSO 3 Li, if the content is too small, the remaining capacity of the battery is reduced rather than improved. It has been shown. From these results, it is expected that the battery of Example E2-1 has a lower remaining capacity than that of Comparative Example E1-7 and Comparative Example E2-1.
• Example E2-1 showed a remarkable effect that the remaining capacity was improved as compared with Comparative Example E1-7 and Comparative Example E2-1, and further, the remaining capacity was improved as compared with Comparative Example E1-1. .. Further, from the comparison between Example E2-2 and Comparative Example E2-2, and the comparison between Example E2-3 and Comparative Example E2-3, the non-aqueous electrolyte solution was FSO 3 Li and a specific amount of aluminum. It was shown that the inclusion of ions has a remarkable effect of improving the remaining capacity of the non-aqueous electrolyte secondary battery, that is, improving the charge storage characteristics of the non-aqueous electrolyte secondary battery in a high temperature environment.
• Examples F1-1 to F1-17, Comparative Examples F1-1 to F1-19> [Preparation of positive electrode] A positive electrode was prepared in the same manner as in Example A3-1.
• a negative electrode was prepared in the same manner as in Example A3-1.
• the metal ion-containing non-aqueous electrolyte solutions of Examples F1-1 to F1-17 were used in the same manner as in Example A3 except that the contents of FSO 3 Li and metal ions were changed as shown in Table 15 below.
• the reference electrolyte F1 is an electrolyte prepared by dissolving 1 mol / L (as a concentration in a non-aqueous electrolyte) of LiPF 6 in a mixture having a volume ratio of EC: EMC: DMC of 3: 4: 3. Is.
• FSO 3 Li was added to the reference electrolyte F1 as shown in the table below to prepare a non-aqueous electrolyte of Comparative Example F1-2. Further, those in which specific metal ions were added and FSO 3 Li was not added were used as non-aqueous electrolyte solutions of Comparative Examples F1-3 to F1-19.
• a laminated non-aqueous electrolyte secondary battery was produced in the same manner as in Example A3-1 except that the above non-aqueous electrolyte was used.
• Example A3-1 ⁇ Evaluation of non-aqueous electrolyte secondary battery>
• the remaining capacity (1 week) was determined by the same method as in Example A3-1.
• the value of capacity is shown.
• the remaining capacity of Example F1-1 to Example F1-17 and Comparative Example F1-1 to Comparative Example F1-19 when the remaining capacity (2 weeks) of Comparative Example F1-1 is set to 100 ( 2 weeks) is shown.
• Comparative Examples F1-3 to F1-19 used an electrolytic solution containing specific metal ions and not containing FSO 3 Li.
• Comparative Example F1-3 Comparative Example F1-5, Comparative Example F1-7, Comparative Example F1-8, Comparative Example F1-12, Comparative Example F1-14, and Comparative Example F1-16, specific metal ions are also FSO. It showed a tendency that the remaining capacity of the battery was lower than that of Comparative Example F1-1 which did not contain 3 Li.
• Comparative Example F1-4, Comparative Example F1-9, Comparative Example F1-10, and Comparative Example F1-15 had the same residual capacity after 1 week as Comparative Example F1-1, but remained after 2 weeks. The capacity has decreased.
• Comparative Example F1-6, Comparative Example F1-11, Comparative Example F1-13, Comparative Example F1-17, Comparative Example F1-18, and Comparative Example F1-19 have residual volumes after one week as compared with Comparative Example F1-1. However, the remaining capacity after 2 weeks was inferior to that of Comparative Example F1-1. From these results, it can be seen that even if a non-aqueous electrolyte solution containing a plurality of specific metal ions is used, the remaining capacity of the battery is not always improved, and it is often deteriorated due to aging. On the other hand, from Examples F1-1 to F1-17, when the electrolytic solution contains both specific metal ions and FSO 3 Li, the same amount of metal ions as in Comparative Examples F1-3 to F1-19.
• the present invention it is possible to realize a non-aqueous electrolyte battery having excellent charge storage characteristics in a high temperature environment, which is useful. Further, the non-aqueous electrolyte solution and the non-aqueous electrolyte battery of the present invention can be used in various known applications in which the non-aqueous electrolyte solution or the non-aqueous electrolyte battery is used. Specific examples include, for example, laptop computers, pen input computers, mobile computers, electronic book players, mobile phones, mobile fax machines, mobile copies, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, and mini discs.
• Transceivers electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, bikes, motorized bicycles, bicycles, lighting fixtures, toys, game consoles, watches, power tools, strobes, cameras, household backups
• Examples include a power source, a backup power source for business establishments, a power source for load leveling, a natural energy storage power source, and a lithium ion capacitor.

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