WO2014073200A1 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
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- WO2014073200A1 WO2014073200A1 PCT/JP2013/006523 JP2013006523W WO2014073200A1 WO 2014073200 A1 WO2014073200 A1 WO 2014073200A1 JP 2013006523 W JP2013006523 W JP 2013006523W WO 2014073200 A1 WO2014073200 A1 WO 2014073200A1
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- current collector
- secondary battery
- electrolyte secondary
- aqueous electrolyte
- positive electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- 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
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a non-aqueous electrolyte secondary battery.
- a positive electrode current collector of a nonaqueous electrolyte secondary battery uses a metal such as Al that forms a stable passive film on the surface in order to withstand corrosion such as electrolytic salt.
- a metal such as Al that forms a stable passive film on the surface in order to withstand corrosion such as electrolytic salt.
- a passive film such as Al 2 O 3 or AlF 3 is formed on the surface of the Al current collector.
- the current collector of Al is less likely to be corroded by forming the passive film on the surface, and the current collecting function can be maintained.
- non-aqueous electrolyte secondary batteries can be used satisfactorily even in a high voltage use environment (in this specification, use at a voltage of 4.3 V or higher is defined as high voltage use).
- high voltage use in this specification, use at a voltage of 4.3 V or higher is defined as high voltage use.
- high voltage use in this specification, use at a voltage of 4.3 V or higher is defined as high voltage use.
- the Al current collector is likely to be gradually corroded in a high voltage environment, and the non-aqueous electrolyte secondary battery having the Al current collector may be deteriorated in cycle characteristics.
- LiPF 6 lithium hexafluorophosphate
- Al an electrolytic salt of a non-aqueous electrolyte secondary battery, but Al may be eluted in a high voltage use environment.
- Patent Document 1 Japanese Patent Laid-Open No. 2004-55247 discloses a protective film containing a compound selected from Al iodide, TiN, Ti 2 O 3 , SnO 2 , In 2 O 3 , RuO 2 and the like as a constituent component. The formed current collector is described.
- This protective film is made of an electrochemically stable compound even under a high voltage.
- Patent Document 1 describes only the capacity retention rate (%) and capacity recovery rate (%) of a battery after being left at 50 ° C. for 2 weeks, and the cycle characteristics (%) of the battery after a 300 cycle test at 50 ° C. The rate characteristics are not described.
- Patent Document 2 Japanese Patent Laid-Open No. 2011-96667
- the thickness of the passive film on the surface of the current collector made of aluminum or aluminum alloy is set to 3 nm or less, and a metal or metal carbide is formed on the passive film.
- a positive electrode current collector in which a conductive layer is formed is described.
- the battery capacity at each discharge rate is measured, and it is described that the battery capacity is improved by forming a conductive layer at a rate of 50 C or more.
- the cycle characteristics of the battery are not evaluated, and compared with the battery capacity of Test Example 1 in which an untreated aluminum foil is used as a current collector, an aluminum foil in which a conductive layer is formed. It is described that the battery capacities of Test Examples 2 to 7 in which 1 is used for the current collector are all low at the 1 / 3C, 1C, and 5C rates.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a non-aqueous electrolyte secondary battery having both excellent rate characteristics and cycle characteristics even under a high voltage use environment.
- the non-aqueous electrolyte secondary battery of the present invention is a non-aqueous electrolyte having a current collector body, and a film made of SnO 2 formed on the surface of the current collector body, a conductive carbon material, and a film binder. and electrolyte secondary battery positive electrode collector, and having a non-aqueous electrolyte containing LiPF 6 a (lithium hexafluorophosphate) as an electrolyte salt.
- LiPF 6 a lithium hexafluorophosphate
- the mixing ratio of SnO 2 and the conductive carbon material is preferably 75:25 to 25:75 by mass ratio.
- p, q, and r are in the ranges of 0 ⁇ p ⁇ 1, 0 ⁇ q ⁇ 1, and 0 ⁇ r ⁇ 1, respectively.
- the thickness of the coating is preferably 10 nm to 1 ⁇ m.
- the non-aqueous electrolyte secondary battery of the present invention uses a non-aqueous electrolyte containing LiPF 6 (lithium hexafluorophosphate) as an electrolytic salt, and has high oxidation resistance and high corrosion resistance on the surface of the current collector body. 2.
- LiPF 6 lithium hexafluorophosphate
- a non-aqueous electrolyte secondary battery that is excellent in both rate characteristics and cycle characteristics even when used in a high-voltage usage environment is formed because a film is formed of a conductive carbon material and a film binder. Can do.
- FIG. 6 is a graph showing rate characteristic measurement results of Examples 1 to 3 and Comparative Examples 1 to 3.
- 6 is a graph showing the cycle characteristic measurement results of Examples 1 to 3 and Comparative Examples 1 to 3.
- 1 current collector body
- 2 coating
- 3 positive electrode active material layer
- 4 current collector for positive electrode of non-aqueous electrolyte secondary battery.
- the non-aqueous electrolyte secondary battery of the present invention includes a current collector body, and a non-aqueous electrolyte battery having a film made of SnO 2 formed on the surface of the current collector body, a conductive carbon material, and a film binder. And a non-aqueous electrolyte containing LiPF 6 (lithium hexafluorophosphate) as an electrolytic salt.
- LiPF 6 lithium hexafluorophosphate
- the current collector body refers to a chemically inert electronic high conductor that keeps a current flowing through an electrode during discharging or charging of a nonaqueous electrolyte secondary battery. Since the current collector main body has a coating film formed on the surface of the current collector main body, the current collector main body can withstand the corrosion of electrolytic salts and the like. Therefore, examples of materials that can be used for the current collector main body include metal materials such as stainless steel, titanium, nickel, aluminum, and copper, and conductive resins.
- the current collector body can take the form of a foil, a sheet, a film and the like. Therefore, for example, a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector body.
- the current collector body preferably has a thickness of 10 ⁇ m to 100 ⁇ m.
- Al 2 O 3 formed by a natural reaction with oxygen in the atmosphere or AlF formed by a reaction with an electrolytic salt in an electrolytic solution is usually formed on the surface of the aluminum foil.
- a passive film such as 3 is formed. This passive film is an insulator, and the number of digits of the specific resistance ( ⁇ cm) is about 10 8 .
- the aluminum foil is protected from the electrolytic salt by the passive film, but since the passive film is a high resistance film, the electrode using the current collector having the passive film on the surface has high resistance, and the electrode was used. Batteries are said to have reduced output characteristics.
- the film is formed on the surface of the current collector main body, the passive film is hardly formed. Therefore, this coating can suppress the formation of the high resistance layer on the surface of the current collector body, and can protect the current collector body from corrosion such as electrolytic salt.
- the thickness of the coating is preferably 10 nm to 1 ⁇ m, more preferably 20 nm to 500 nm. If the thickness of the film is 10 nm or more, the surface of the current collector body can be protected by the film, and corrosion of the current collector body due to the electrolytic solution can be effectively suppressed. When the thickness of the coating is 1 ⁇ m or less, the volume occupied by the positive electrode current collector in the battery can be made appropriate. If the volume occupied by the positive electrode current collector in the battery becomes too large, the amount of the positive electrode active material and the like must be reduced, which leads to a decrease in battery capacity.
- the coating is composed of a SnO 2 and conductive carbon material and a coating binder.
- SnO 2 is resistant to oxygen, electrolytic solution and electrolytic salt in the atmosphere, and the resistance is exhibited even at a high voltage.
- SnO 2 is excellent in oxidation resistance and further excellent in corrosion resistance. Therefore, SnO 2 is effective in improving cycle characteristics.
- a powder having an average particle diameter of 10 nm to 100 nm can be used.
- the conductive carbon material is a material that imparts conductivity to the coating.
- As the conductive carbon material carbon black, graphite, acetylene black (AB), ketjen black (KB), vapor grown carbon fiber (Vapor Carbon Carbon Fiber: VGCF), etc. alone are used as the conductive carbon material. Or it can be used in combination of two or more.
- the coating binder serves to bind SnO 2 and the conductive carbon material to the current collector body.
- the same binder as that used to bind the positive electrode active material to the current collector body can be used.
- coating binders include fluorine-containing resins such as polyvinylidene fluoride, polytetrafluoroethylene and fluororubber, thermoplastic resins such as polypropylene, polyethylene and polyvinyl acetate resins, imide resins such as polyimide and polyamideimide, alkoxy Silyl group-containing resins and rubbers such as styrene butadiene rubber (SBR) can be used.
- fluorine-containing resins such as polyvinylidene fluoride, polytetrafluoroethylene and fluororubber
- thermoplastic resins such as polypropylene, polyethylene and polyvinyl acetate resins
- imide resins such as polyimide and polyamideimide
- the mixing ratio of SnO 2 and the conductive carbon material is preferably 75:25 to 25:75 by mass ratio.
- the content of the conductive carbon material is large, the rate characteristics of the nonaqueous electrolyte secondary battery are improved.
- the cycle characteristics of the nonaqueous electrolyte secondary battery and the SnO 2 content is often improved. Therefore, an optimal mixing ratio may be used according to the conditions for which the nonaqueous electrolyte secondary battery is desired to be used.
- the film formed on the surface of the current collector body functions as a resistance layer. For example, when a non-aqueous electrolyte secondary battery is short-circuited, current flow is limited by this coating.
- the method for forming the film on the current collector main body is not particularly limited, but can be formed by the following method.
- a paste-like mixture is prepared by dissolving SnO 2 powder, a conductive carbon material, and a coating binder in an organic solvent or water for viscosity adjustment, and the paste-like mixture is applied onto the current collector body and applied. Later dry.
- a coating method a conventionally known method such as a roll coating method, a dip coating method, a doctor blade method, a spray coating method, or a curtain coating method may be used.
- the organic solvent for viscosity adjustment ethanol, N-methyl-2-pyrrolidone (NMP), methanol, methyl isobutyl ketone (MIBK), etc. can be used.
- the water is preferably water from which impurities have been removed, such as distilled water or ion exchange water.
- a film can also be formed on the current collector body by the following method.
- the binder for coating is preferably a binder that can be dissolved in an organic solvent and solidifies when the organic solvent is volatilized.
- ethanol, NMP, methanol, MIBK or the like can be used as the organic solvent.
- the water is preferably water from which impurities have been removed, such as distilled water or ion exchange water.
- the nonaqueous electrolyte secondary battery of this invention has a positive electrode which has the said collector for nonaqueous electrolyte secondary battery positive electrodes.
- FIG. 1 is a schematic diagram illustrating a positive electrode for a nonaqueous electrolyte secondary battery according to this embodiment. As shown in FIG. 1, a film 2 is formed on the surface of the current collector body 1, and a positive electrode active material layer 3 is formed on the surface of the film 2.
- the current collector body 1 on which the coating 2 is formed is referred to as a non-aqueous electrolyte secondary battery positive electrode current collector 4.
- the positive electrode active material layer 3 may further contain a conductive additive.
- the positive electrode is prepared by forming a positive electrode active material layer-forming composition containing a positive electrode active material and a binder and, if necessary, a conductive additive, and further adding a suitable solvent to the composition to make a paste. It can be formed by applying to the surface of the coating film of the current collector for the positive electrode of the non-aqueous electrolyte secondary battery and drying it, and if necessary, compressing it to increase the electrode density.
- a conventionally known method such as a roll coating method, a dip coating method, a doctor blade method, a spray coating method, or a curtain coating method may be used.
- NMP N-methyl-2-pyrrolidone
- MIBK methyl isobutyl ketone
- a lithium-containing compound that can be used at a high voltage is suitable.
- lithium-containing metal composite oxides such as lithium cobalt composite oxide, lithium nickel composite oxide, and lithium manganese composite oxide can be used.
- Other metal compounds or polymer materials can also be used as the positive electrode active material.
- the other metal compound include oxides such as titanium oxide, vanadium oxide, and manganese dioxide, or disulfides such as titanium sulfide and molybdenum sulfide.
- the polymer material include conductive polymers such as polyaniline and polythiophene.
- p, q, and r are in the ranges of 0 ⁇ p ⁇ 1, 0 ⁇ q ⁇ 1, and 0 ⁇ r ⁇ 1, respectively. Since the composite metal oxide is excellent in thermal stability and low in cost, by using the composite metal oxide as a positive electrode active material, an inexpensive non-aqueous electrolyte secondary battery having good thermal stability is obtained. Can do.
- Examples of the composite metal oxide include LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiCoO 2 , LiNi 0.8 Co 0.2 O 2 , and LiCoMnO 2 can be used. Among these, LiCo 1/3 Ni 1/3 Mn 1/3 O 2 and LiNi 0.5 Co 0.2 Mn 0.3 O 2 are preferable in terms of thermal stability.
- the binder serves to bind the positive electrode active material and the conductive additive to the positive electrode current collector.
- the binder include fluorine-containing resins such as polyvinylidene fluoride, polytetrafluoroethylene and fluororubber, thermoplastic resins such as polypropylene, polyethylene and polyvinyl acetate resins, imide resins such as polyimide and polyamideimide, alkoxy Silyl group-containing resins and rubbers such as styrene butadiene rubber (SBR) can be used.
- fluorine-containing resins such as polyvinylidene fluoride, polytetrafluoroethylene and fluororubber
- thermoplastic resins such as polypropylene, polyethylene and polyvinyl acetate resins
- imide resins such as polyimide and polyamideimide
- alkoxy Silyl group-containing resins and rubbers such as styrene butadiene rubber (SBR)
- Conductive aid is added to increase the conductivity of the electrode.
- the conductive assistant for example, carbon black, graphite, acetylene black (AB), ketjen black (registered trademark) (KB), vapor grown carbon fiber (VGCF), etc., which are carbonaceous fine particles, are used alone or in combination of two or more. They can be added in combination.
- the amount of the conductive aid used is not particularly limited, but can be, for example, about 1 to 30 parts by mass with respect to 100 parts by mass of the active material contained in the positive electrode.
- Non-aqueous electrolyte secondary battery has an electrolyte that uses LiPF 6 as a negative electrode, a separator, and an electrolytic salt, in addition to the above-described positive electrode for a nonaqueous electrolyte secondary battery, as a battery component.
- the negative electrode has a current collector and a negative electrode active material layer bound to the surface of the current collector.
- a negative electrode active material layer contains a negative electrode active material and a binder, and contains a conductive support agent as needed.
- the current collector, the binder, and the conductive assistant are the same as the current collector main body, the binder, and the conductive assistant described in the positive electrode.
- a carbon-based material that can occlude and release lithium an element that can be alloyed with lithium, an elemental compound that has an element that can be alloyed with lithium, or a polymer material can be used.
- the carbon-based material examples include non-graphitizable carbon, artificial graphite, coke, graphite, glassy carbon, organic polymer compound fired body, carbon fiber, activated carbon, or carbon black.
- the organic polymer compound fired body refers to a material obtained by firing and carbonizing a polymer material such as phenols and furans at an appropriate temperature.
- Elements that can be alloyed with lithium are Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si, Ge, Sn. , Pb, Sb, Bi.
- silicon (Si) or tin (Sn) is preferable as an element that can be alloyed with lithium.
- Examples of elemental compounds having elements that can be alloyed with lithium include ZnLiAl, AlSb, SiB 4 , SiB 6 , Mg 2 Si, Mg 2 Sn, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2, CrSi 2, Cu 5 Si, FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3 N 4, Si 2 N 2 O, SiO v (0 ⁇ v ⁇ 2), SnO w (0 ⁇ w ⁇ 2), SnSiO 3 , LiSiO or LiSnO can be used.
- a silicon compound or a tin compound is preferable.
- the silicon compound SiO x (0.5 ⁇ x ⁇ 1.5) is preferable.
- the tin compound for example, a tin alloy (Cu—Sn alloy, Co—Sn alloy, etc.) can be used.
- polyacetylene polypyrrole, or the like can be used as the polymer material.
- the separator separates the positive electrode and the negative electrode and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes.
- a porous film made of synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene, or a porous film made of ceramics can be used.
- an electrolyte that can be used for a general non-aqueous electrolyte secondary battery can be used except that LiPF 6 is used as an electrolyte salt.
- the electrolyte includes a solvent and an electrolytic salt dissolved in the solvent.
- cyclic esters examples include ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone, and gamma valerolactone.
- chain esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl ethyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester.
- ethers examples include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane.
- LiPF 6 is used as the electrolytic salt. Since LiPF 6 has high electrical conductivity, a lithium ion secondary battery using LiPF 6 as an electrolytic salt can reduce internal resistance.
- a solution in which LiPF 6 is dissolved at a concentration of about 0.5 mol / l to 1.7 mol / l in a solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate, and diethyl carbonate can be used.
- a nonaqueous electrolyte secondary battery of the present invention Since having the above non-aqueous having a positive electrode for electrolytic secondary battery, and the electrolyte having a LiPF 6 as an electrolyte salt, a nonaqueous electrolyte secondary battery of the present invention has excellent rate characteristics and cycle characteristics.
- the non-aqueous electrolyte secondary battery can be mounted on a vehicle.
- the non-aqueous electrolyte secondary battery has a large charge / discharge capacity and can achieve both excellent rate characteristics and cycle characteristics. Therefore, vehicles equipped with the non-aqueous electrolyte secondary battery have high performance in terms of life and output. It becomes.
- the vehicle may be a vehicle that uses electric energy from a battery as a whole or a part of a power source.
- a vehicle that uses electric energy from a battery as a whole or a part of a power source.
- an electric vehicle a hybrid vehicle, a plug-in hybrid vehicle, a hybrid railway vehicle, an electric forklift, an electric wheelchair, and an electric assist.
- Bicycles and electric motorcycles are examples.
- PVDF Polyvinylidene fluoride as a film binder
- AB acetylene black
- NMP N-methyl-2-pyrrolidone
- a current collector B was prepared in the same manner as the current collector A, except that a second mixture in which the mass ratio of SnO 2 powder and AB was 50:50 was used instead of the first mixture.
- a current collector C was prepared in the same manner as the current collector A, except that a third mixture in which the mass ratio of SnO 2 powder and AB was 25:75 was used instead of the first mixture.
- a current collector D was prepared in the same manner as the current collector A except that only the SnO 2 powder was used instead of the first mixture.
- a current collector E was prepared in the same manner as the current collector A except that only AB was used in place of the first mixture.
- Current collector F was prepared in the same manner as current collector D, except that polytetrafluoroethylene (PTFE) was used instead of PVDF as a coating binder, and ion-exchanged water was used instead of NMP as a viscosity adjusting solvent. did.
- PTFE polytetrafluoroethylene
- Example 1 A laminated lithium ion secondary battery of Example 1 using the current collector A as a positive electrode current collector was produced as follows. First, LiNi 0.5 Co 0.2 Mn 0.3 O 2 as a positive electrode active material, acetylene black as a conductive additive, and polyvinylidene fluoride (PVDF) as a binder, respectively, 88 parts by mass, 6 parts by mass, The mixture was mixed as 6 parts by mass, and this mixture was dispersed in an appropriate amount of N-methyl-2-pyrrolidone (NMP) to prepare a slurry.
- NMP N-methyl-2-pyrrolidone
- the slurry was placed on the current collector A and applied to the current collector A using a doctor blade so that the slurry became a film.
- the obtained sheet was dried at 80 ° C. for 20 minutes to volatilize and remove NMP, and then the current collector A and the coated material on the current collector A were firmly and closely joined by a roll press. At this time, the electrode density was set to 2.3 g / cm 2 .
- the joined product was heated at 120 ° C. for 6 hours with a vacuum dryer, cut into a predetermined shape (rectangular shape of 25 mm ⁇ 30 mm), and the positive electrode 1 having a thickness of about 50 ⁇ m was obtained.
- the negative electrode was produced as follows. 97 parts by mass of graphite powder, 1 part by mass of acetylene black as a conductive auxiliary agent, 1 part by mass of styrene-butadiene rubber (SBR) and 1 part by mass of carboxymethyl cellulose (CMC) as a binder were mixed, and this mixture was mixed. A slurry was prepared by dispersing in an appropriate amount of ion-exchanged water. This slurry was applied to a copper foil having a thickness of 20 ⁇ m as a negative electrode current collector so as to form a film using a doctor blade, and the current collector coated with the slurry was dried and pressed. It was heated with a vacuum dryer for a time, cut into a predetermined shape (rectangular shape of 25 mm ⁇ 30 mm), and a negative electrode having a thickness of about 45 ⁇ m was obtained.
- SBR styrene-butadiene rubber
- CMC carboxymethyl cellulose
- EC ethylene carbonate
- DEC diethyl carbonate
- the laminated lithium ion secondary battery of Example 1 was produced through the above steps.
- Example 2 A laminated lithium ion secondary battery of Example 2 was produced in the same manner as in Example 1 except that the current collector B was used instead of the current collector A in Example 1.
- Example 3 A laminated lithium ion secondary battery of Example 3 was produced in the same manner as in Example 1 except that the current collector C was used instead of the current collector A in Example 1.
- Comparative Example 1 A laminated lithium ion secondary battery of Comparative Example 1 was produced in the same manner as in Example 1 except that the current collector D was used instead of the current collector A in Example 1.
- Comparative Example 2 A laminated lithium ion secondary battery of Comparative Example 2 was produced in the same manner as in Example 1 except that the current collector E was used instead of the current collector A in Example 1.
- Comparative Example 3 A laminated lithium ion secondary battery of Comparative Example 3 was produced in the same manner as in Example 1 except that the current collector F was used instead of the current collector A in Example 1.
- Capacity retention rate (%) (discharge capacity at each cycle / initial discharge capacity) x 100
- FIG. 3 shows the cycle characteristic results of the laminated lithium ion secondary batteries of Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3.
- LiPF 6 lithium hexafluorophosphate
- a non-aqueous electrolyte secondary battery excellent in rate characteristics and cycle characteristics can be obtained.
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Abstract
Description
本発明の非水電解質二次電池は、集電体本体と、集電体本体の表面に形成されたSnO2と導電性炭素材料と被膜用バインダーとからなる被膜と、を有する非水電解質二次電池正極用集電体と、LiPF6(六フッ化リン酸リチウム)を電解塩として含有する非水電解質と、を有することを特徴とする。
集電体本体は、非水電解質二次電池の放電または充電の間、電極に電流を流し続けるための化学的に不活性な電子高伝導体をいう。本発明の非水電解質二次電池正極用集電体は集電体本体の表面に被膜が形成されているため、集電体本体は電解塩等の腐食に耐えることができる。そのため、集電体本体に用いることのできる材料として、例えばステンレス鋼、チタン、ニッケル、アルミニウム、銅などの金属材料または導電性樹脂を挙げることができる。また集電体本体は、箔、シート、フィルムなどの形態をとることができる。そのため、集電体本体として、例えば銅箔、ニッケル箔、アルミニウム箔、ステンレス箔などの金属箔を好適に用いることができる。
本発明の非水電解質二次電池は、上記非水電解質二次電池正極用集電体を有する正極を有する。
本発明の非水電解質二次電池は、電池構成要素として、上記した非水電解質二次電池用正極に加えて、負極、セパレータ、電解塩としてLiPF6を用いる電解質を有する。
集電体として厚み20μmのアルミニウム箔を準備した。被膜用バインダーとしてポリフッ化ビニリデン(PVDF)、SnO2として平均粒径30nmのSnO2粉末、導電性炭素材料としてアセチレンブラック(AB)を準備した。また粘度調整溶媒としてN-メチル-2-ピロリドン(NMP)を準備した。
SnO2粉末とABとを質量比で75:25となるようにボールミル装置によって混合し、第1混合物とした。この第1混合物とPVDFとを質量比で3:1となるように混ぜて固形分率が20%となるようNMPに溶かし、第1スラリーを得た。アルミニウム箔に第1スラリーをドクターブレード法を用いて塗布し、120℃で乾燥し、厚みが100nmの被膜をアルミニウム箔上に形成した。これを集電体Aとする。
第1混合物に代えてSnO2粉末とABとを質量比で50:50とした第2混合物を用いた以外は集電体Aと同様にして集電体Bを作成した。
第1混合物に代えてSnO2粉末とABとを質量比で25:75とした第3混合物を用いた以外は集電体Aと同様にして集電体Cを作成した。
第1混合物に代えてSnO2粉末のみを用いた以外は集電体Aと同様にして集電体Dを作成した。
第1混合物に代えてABのみを用いた以外は集電体Aと同様にして集電体Eを作成した。
被膜用バインダーとしてPVDFに代えてポリテトラフルオロエチレン(PTFE)を用い、また粘度調整用溶媒としてNMPに代えてイオン交換水を用いた以外は集電体Dと同様にして集電体Fを作成した。
(実施例1)
集電体Aを正極用集電体として用いた実施例1のラミネート型リチウムイオン二次電池を次のようにして作製した。まず正極活物質としてLiNi0.5Co0.2Mn0.3O2と導電助剤としてアセチレンブラックと、結着剤としてポリフッ化ビニリデン(PVDF)とを、それぞれ88質量部、6質量部、6質量部として混合し、この混合物を適量のN-メチル-2-ピロリドン(NMP)に分散させて、スラリーを作製した。
実施例1における集電体Aの代わりに集電体Bを用いた以外は実施例1と同様にして実施例2のラミネート型リチウムイオン二次電池を作製した。
実施例1における集電体Aの代わりに集電体Cを用いた以外は実施例1と同様にして実施例3のラミネート型リチウムイオン二次電池を作製した。
実施例1における集電体Aの代わりに集電体Dを用いた以外は実施例1と同様にして比較例1のラミネート型リチウムイオン二次電池を作製した。
実施例1における集電体Aの代わりに集電体Eを用いた以外は実施例1と同様にして比較例2のラミネート型リチウムイオン二次電池を作製した。
実施例1における集電体Aの代わりに集電体Fを用いた以外は実施例1と同様にして比較例3のラミネート型リチウムイオン二次電池を作製した。
実施例1、実施例2、実施例3、比較例1、比較例2及び比較例3のラミネート型リチウムイオン二次電池の25℃でのレート特性を測定した。電圧範囲を4.5V-3.0Vとして1時間で放電する電流レートを1Cとする。電流レートが0.33C、1C、5Cの時の放電容量を測定した。電流レートが0.33Cの時の容量を基準とし、1C容量/0.33C容量、5C容量/0.33C容量の割合を%で表示した。結果を図2に示す。
実施例1、実施例2、実施例3、比較例1、比較例2及び比較例3のラミネート型リチウムイオン二次電池のサイクル特性を評価した。以下の条件で充放電を繰り返したサイクル試験を行い各サイクルの放電容量を測定した。充電の際は、25℃において1Cレート、電圧4.5VでCC充電(定電流充電)をした。放電の際は3.0V、1CレートでCC放電(定電流放電)を行った。この充放電を1サイクルとし、50サイクルまでサイクル試験を行った。初回サイクルの放電容量を基準とし、容量維持率を計算した。各サイクルにおける容量維持率は次に示す式にて求めた。
Claims (4)
- 集電体本体と、該集電体本体の表面に形成されたSnO2と導電性炭素材料と被膜用バインダーとからなる被膜と、を有する非水電解質二次電池正極用集電体と、
LiPF6(六フッ化リン酸リチウム)を電解塩として含有する非水電解質と、
を有する非水電解質二次電池。 - 前記SnO2と前記導電性炭素材料との混合比率は質量比で75:25~25:75である請求項1に記載の非水電解質二次電池。
- 一般式: LiCopNiqMnrDsO2 (Dはドープ成分であり、Al、Mg、Ti、Sn、Zn、W、Zr、Mo、Fe及びNaから選ばれる少なくとも1つであり、p+q+r+s=1、0≦p≦1、0≦q≦1、0≦r≦1、0≦s<1)で表される複合金属酸化物からなる正極活物質を有する請求項1または2に記載の非水電解質二次電池。
- 前記被膜の厚みは、10nm~1μmである請求項1~3のいずれかに記載の非水電解質二次電池。
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JP2020017422A (ja) * | 2018-07-26 | 2020-01-30 | トヨタ自動車株式会社 | 非水電解質二次電池 |
CN112510254A (zh) * | 2020-11-30 | 2021-03-16 | 北京理工大学 | 一种新型硫化物固态电解质及其制备方法和用途 |
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US11600825B2 (en) * | 2020-07-30 | 2023-03-07 | GM Global Technology Operations LLC | Positive electrode for secondary lithium metal battery and method of making |
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- 2013-11-05 US US14/440,384 patent/US20150280242A1/en not_active Abandoned
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