WO2016006381A1 - 非水電解液及びリチウムイオン二次電池 - Google Patents
非水電解液及びリチウムイオン二次電池 Download PDFInfo
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- WO2016006381A1 WO2016006381A1 PCT/JP2015/066861 JP2015066861W WO2016006381A1 WO 2016006381 A1 WO2016006381 A1 WO 2016006381A1 JP 2015066861 W JP2015066861 W JP 2015066861W WO 2016006381 A1 WO2016006381 A1 WO 2016006381A1
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- 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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- 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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- 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
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Definitions
- the present invention relates to a non-aqueous electrolyte and a lithium ion secondary battery.
- Lithium ion secondary batteries are attracting attention as power sources for mobile phones and laptop computers because they can achieve high energy density. Recently, lithium ion secondary batteries are also attracting attention as power sources for driving motors of hybrid vehicles (HEV) due to improved output characteristics and long-term reliability such as storage characteristics. In these applications, higher energy density is required. In order to improve the energy density, it is necessary to increase the operating voltage of the lithium ion secondary voltage, and a nonaqueous electrolytic solution that does not undergo oxidative decomposition even at a high potential is required.
- a method for improving the oxidation resistance of the nonaqueous electrolytic solution for example, use of an oxidation resistant solvent or an oxidation resistance improving additive, a positive electrode surface treatment, or the like can be considered. There is also known a method of suppressing oxidative decomposition of a nonaqueous electrolytic solution by forming a film on a positive electrode or a negative electrode.
- Non-Patent Document 1 discloses a technique for adding thiophene to a non-aqueous electrolyte.
- Thiophene is said to form a film by oxidative polymerization on the positive electrode, and the film can suppress decomposition of the solvent.
- Non-Patent Document 2 discloses a technique for suppressing the reaction of the nonaqueous electrolytic solution by inactivating the positive electrode with a phosphite.
- Non-Patent Document 3 discloses a technique for forming a film on a positive electrode with a benzene derivative.
- Non-Patent Document 4 discloses a technique for forming a film with a phosphate ester.
- an object of the present invention is to provide a non-aqueous electrolyte that can provide a secondary battery that suppresses gas generation and has an excellent capacity retention rate even when high-voltage charge / discharge is performed.
- One embodiment of the present invention is a nonaqueous electrolytic solution containing a phosphinoamine-based compound represented by the following formula (1).
- R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted.
- R 3 and R 4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, substituted or unsubstituted It represents a substituted heterocyclic group, a substituted or unsubstituted alkoxy group, or a hydroxy group.
- R 1 and R 2 may be bonded via a single bond, an ether bond, or a hydrocarbon chain having 1 to 4 carbon atoms.
- R 3 and R 4 may be bonded via a single bond, an ether bond, or a hydrocarbon chain having 1 to 4 carbon atoms. ].
- One embodiment of the present invention is a lithium ion secondary battery including the above non-aqueous electrolyte.
- a nonaqueous electrolytic solution capable of obtaining a secondary battery that suppresses gas generation and has an excellent capacity retention rate even when high-voltage charge / discharge is performed. Further, according to one embodiment of the present invention, it is possible to provide a lithium ion secondary battery in which gas generation is suppressed and the capacity retention rate is excellent even when high-voltage charge / discharge is performed.
- Negative electrode ⁇ Negative electrode active material layer> The negative electrode is formed, for example, by binding a negative electrode active material to a negative electrode current collector with a negative electrode binder. As long as the negative electrode active material in this embodiment can occlude and release lithium, any material can be used as long as the effects of the present invention are not significantly impaired.
- the negative electrode active material is not particularly limited as long as it is a material capable of occluding and releasing lithium ions, and a known negative electrode active material can be arbitrarily used.
- a known negative electrode active material can be arbitrarily used.
- carbonaceous materials such as coke, acetylene black, mesophase micro beads, and graphite; lithium metal; lithium alloys such as lithium-silicon and lithium-tin, lithium titanate, and the like can be used.
- a carbonaceous material in that the cycle characteristics and safety are good and the continuous charge characteristics are also excellent.
- a negative electrode active material may be used individually by 1 type, and may be used in combination of 2 or more type.
- the average particle diameter (D 50 ) of the negative electrode active material is not particularly limited, but is preferably 1 ⁇ m or more from the viewpoint of battery characteristics such as initial efficiency, rate characteristics, cycle characteristics, More preferably, it is 15 ⁇ m or more, preferably 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
- D 50 average particle diameter
- organic substances used for coating include coal tar pitch from soft pitch to hard pitch; coal heavy oil such as dry distillation liquefied oil; straight heavy oil such as atmospheric residual oil and vacuum residual oil; crude oil And petroleum heavy oils such as cracked heavy oil (for example, ethylene heavy end) produced as a by-product during thermal decomposition of naphtha and the like.
- a solid residue obtained by distilling these heavy oils at 200 to 400 ° C. and pulverized to 1 to 100 ⁇ m can be used.
- a vinyl chloride resin, a phenol resin, an imide resin, etc. can also be used.
- the negative electrode active material layer can be formed into a sheet electrode by roll molding the negative electrode active material described above, or a pellet electrode by compression molding.
- the negative electrode active material, the binder, and, if necessary, various auxiliary agents and the like can be produced by applying a coating solution obtained by slurrying with a solvent onto a current collector and drying it. it can.
- Examples of the negative electrode active material containing silicon include silicon and silicon compounds.
- Examples of silicon include simple silicon.
- Examples of the silicon compound include silicon oxide, silicate, a compound of transition metal such as nickel silicide and cobalt silicide and silicon, and the like.
- the silicon compound has a role of relaxing expansion and contraction due to repeated charge / discharge of the negative electrode active material itself, and is preferably used from the viewpoint of charge / discharge cycle characteristics. Furthermore, depending on the type of silicon compound, it also has a role of ensuring conduction between silicons. From this point of view, silicon oxide is preferably used as the silicon compound.
- the silicon oxide is not particularly limited, but is represented by, for example, SiO x (0 ⁇ x ⁇ 2).
- the silicon oxide may contain Li, and the silicon oxide containing Li is represented by, for example, SiLi y O z (y> 0, 2>z> 0). Further, the silicon oxide may contain a trace amount of a metal element or a nonmetal element. The silicon oxide can contain, for example, 0.1 to 5% by mass of one or more elements selected from nitrogen, boron and sulfur. By containing a trace amount of a metal element or a nonmetal element, the electrical conductivity of the silicon oxide can be improved. Further, the silicon oxide may be crystalline or amorphous.
- the negative electrode active material preferably contains a carbon material capable of inserting and extracting lithium ions in addition to silicon or silicon oxide. The carbon material can also be contained in a composite state with silicon or silicon oxide.
- the carbon material Similar to silicon oxide, the carbon material has the role of relaxing expansion and contraction due to repeated charge and discharge of the negative electrode active material itself and ensuring conduction between silicon as the negative electrode active material. Therefore, better cycle characteristics can be obtained by the coexistence of silicon, silicon oxide, and carbon material.
- the carbon material for example, graphite, amorphous carbon, diamond-like carbon, carbon nanotube, or a composite thereof can be used.
- graphite with high crystallinity has high electrical conductivity, and is excellent in adhesiveness and voltage flatness with a positive electrode current collector made of a metal such as copper.
- amorphous carbon having low crystallinity has a relatively small volume expansion, it has a high effect of relaxing the volume expansion of the entire negative electrode, and deterioration due to non-uniformity such as crystal grain boundaries and defects hardly occurs.
- the content of the carbon material in the negative electrode active material is preferably 2% by mass or more and 50% by mass or less, and more preferably 2% by mass or more and 30% by mass or less.
- a method for producing a negative electrode active material containing silicon and a silicon compound when silicon oxide is used as the silicon compound, for example, a method of mixing simple silicon and silicon oxide and sintering under high temperature and reduced pressure Is mentioned. Further, when a compound of transition metal and silicon is used as the silicon compound, for example, a method of mixing and melting simple silicon and the transition metal, and a method of coating the transition metal on the surface of the simple silicon by vapor deposition or the like can be mentioned. .
- a method of introducing a mixed sintered product of simple silicon and silicon compound into a gas atmosphere of an organic compound in a high temperature non-oxygen atmosphere, or a mixed sintered product of single silicon and silicon oxide and carbon in a high temperature non-oxygen atmosphere By the method of mixing the precursor resins, a coating layer made of carbon can be formed around the cores of simple silicon and silicon oxide. Thereby, the suppression of volume expansion with respect to charging / discharging and the further improvement effect of cycling characteristics are acquired.
- silicon When silicon is used as the negative electrode active material in the present embodiment, it is preferably made of a composite containing silicon, silicon oxide and carbon material (hereinafter also referred to as Si / SiO / C composite). Furthermore, it is preferable that all or part of the silicon oxide has an amorphous structure.
- the silicon oxide having an amorphous structure can suppress the volume expansion of a carbon material or silicon which is another negative electrode active material. Although this mechanism is not clear, it is presumed that the formation of a film on the interface between the carbon material and the electrolytic solution has some influence due to the amorphous structure of silicon oxide.
- the amorphous structure is considered to have relatively few elements due to non-uniformity such as crystal grain boundaries and defects.
- the Si / SiO / C composite it is preferable that all or part of silicon is dispersed in silicon oxide.
- silicon oxide By dispersing at least a part of silicon in silicon oxide, volume expansion as a whole of the negative electrode can be further suppressed, and decomposition of the electrolytic solution can also be suppressed.
- all or part of silicon is dispersed in the silicon oxide because transmission electron microscope observation (general TEM observation) and energy dispersive X-ray spectroscopy measurement (general EDX measurement). It can confirm by using together. Specifically, the cross section of the sample is observed, the oxygen concentration of the silicon portion dispersed in the silicon oxide is measured, and it can be confirmed that the sample is not an oxide.
- the Si / SiO / C composite for example, all or part of silicon oxide has an amorphous structure, and all or part of silicon is dispersed in silicon oxide.
- a Si / SiO / C composite can be produced, for example, by a method disclosed in Patent Document 3 (Japanese Patent Laid-Open No. 2004-47404). That is, the Si / SiO / C composite can be obtained, for example, by performing a CVD process on silicon oxide in an atmosphere containing an organic gas such as methane gas.
- the Si / SiO / C composite obtained by such a method has a form in which the surface of particles made of silicon oxide containing silicon is coated with carbon. Silicon is nanoclustered in silicon oxide.
- the ratio of silicon, silicon oxide and carbon material is not particularly limited.
- Silicon is preferably 5% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 50% by mass or less with respect to the Si / SiO / C composite.
- the silicon oxide is preferably 5% by mass or more and 90% by mass or less, and more preferably 40% by mass or more and 70% by mass or less with respect to the Si / SiO / C composite.
- the carbon material is preferably 2% by mass or more and 50% by mass or less, and more preferably 2% by mass or more and 30% by mass or less with respect to the Si / SiO / C composite.
- the Si / SiO / C composite can be composed of a mixture of simple silicon, silicon oxide and carbon material, and can also be produced by mixing simple silicon, silicon oxide and carbon material by mechanical milling. it can.
- the Si / SiO / C composite can be obtained by mixing particulate silicon, silicon oxide and carbon materials.
- the average particle diameter of simple silicon can be made smaller than the average particle diameter of the carbon material and the average particle diameter of the silicon oxide. In this way, simple silicon with a small volume change during charge / discharge has a relatively small particle size, and carbon materials and silicon oxides with a large volume change have a relatively large particle size. Is more effectively suppressed.
- the average particle diameter of the single silicon can be set to 20 ⁇ m or less, for example, and preferably 15 ⁇ m or less.
- the average particle diameter of silicon oxide is preferably 1/2 or less of the average particle diameter of the carbon material, and the average particle diameter of simple silicon is 1/2 or less of the average particle diameter of silicon oxide. preferable.
- the average particle diameter of the silicon oxide is 1/2 or less of the average particle diameter of the carbon material, and the average particle diameter of the simple silicon is 1/2 or less of the average particle diameter of the silicon oxide.
- the average particle diameter of silicon oxide is 1 ⁇ 2 or less of the average particle diameter of graphite, and the average particle diameter of simple silicon is 1 ⁇ 2 or less of the average particle diameter of silicon oxide.
- the average particle diameter of the single silicon can be, for example, 20 ⁇ m or less, and is preferably 15 ⁇ m or less.
- the binder for the negative electrode is not particularly limited.
- polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, polytetrafluoroethylene, Polypropylene, polyethylene, polyimide, polyamideimide, various polyurethanes and the like can be used. Among these, polyimide and polyamideimide are preferable because of their high binding properties.
- An aqueous binder can also be used.
- the aqueous binder is not particularly limited, but usually, a water-dispersible polymer is used in the form of a latex or an emulsion.
- an acrylic resin emulsion, a styrene resin emulsion, a vinyl acetate polymer emulsion, a urethane resin emulsion, or the like can be used.
- a water-dispersible synthetic rubber latex or emulsion is preferable from the viewpoint of viscoelastic properties.
- the water-dispersible synthetic rubber latex (emulsion) include polybutadiene rubber latex, styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, (meth) acrylic acid ester-butadiene rubber latex, chloroprene rubber latex, and the like.
- Styrene-butadiene rubber latex is preferred from the viewpoint of resistance to the electrolytic solution.
- These binders can be used alone or in combination of two or more.
- the amount of the binder for the negative electrode to be used is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. .
- a thickener in order to facilitate the production of the negative electrode slurry, a thickener can also be used.
- Such thickeners include carboxymethylcellulose (including alkali neutralized lithium, sodium and potassium salts), polyethylene oxide, polypropylene oxide, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylhydroxyethylcellulose, polyvinyl alcohol. , Polyacrylamide, hydroxyethyl polyacrylate, ammonium polyacrylate, polyacrylic acid (including lithium salt, sodium salt and potassium salt neutralized with alkali).
- These thickeners can be used alone or in combination of two or more.
- the proportion of the thickener in the negative electrode active material layer is preferably 0.1 to 5% by mass.
- a nonionic surfactant can also be used for the purpose of improving the dispersibility of the carbon particles in the slurry.
- Polyoxyalkylene alkyl ether can be used preferably.
- the polyoxyalkylene alkyl ether is represented by the general formula: R—O— (AO) n H (wherein R represents an alkyl group, A represents an alkylene group, and n represents a natural number).
- the carbon number of the alkyl group represented by the symbol R, the carbon number of the alkylene group represented by the symbol A, and the degree of polymerization of the alkyleneoxy group (AO) represented by n are not particularly limited.
- the polyoxyalkylene alkyl ether is different in at least one of the number of carbon atoms of the alkyl group represented by the symbol R, the number of carbon atoms of the alkylene group represented by the symbol A, and the degree of polymerization of the alkyleneoxy group (AO) represented by the symbol n.
- a mixture of polyoxyalkylene alkyl ethers may be used.
- a material of the current collector for the negative electrode a known material can be arbitrarily used.
- a metal material such as copper, nickel, or SUS is used.
- copper is particularly preferable from the viewpoint of ease of processing and cost.
- the current collector is preferably subjected to a roughening treatment in advance.
- the shape of the current collector is also arbitrary, and examples thereof include a foil shape, a flat plate shape, and a mesh shape.
- a perforated current collector such as expanded metal or punching metal can be used.
- the preferable thickness and shape when using a thin film as the current collector are also arbitrary.
- the negative electrode is produced by forming a negative electrode active material layer containing a negative electrode active material, a negative electrode binder, a negative electrode thickener, a surfactant, and the like on a negative electrode current collector.
- a negative electrode active material layer containing a negative electrode active material, a negative electrode binder, a negative electrode thickener, a surfactant, and the like on a negative electrode current collector.
- the method for forming the negative electrode active material layer include a doctor blade method, a die coater method, a CVD method, and a sputtering method.
- a thin film of aluminum, nickel, or an alloy thereof may be formed by a method such as vapor deposition or sputtering to form a negative electrode current collector.
- a method of preparing a slurry by mixing a negative electrode active material, a negative electrode binder, a negative electrode thickener, a surfactant and the like in a dispersion solvent, applying the slurry onto a current collector, and then drying by heating is inexpensive. It is preferable because it can be manufactured.
- the heating and drying temperature is preferably 50 ° C. or higher and 140 ° C. or lower, more preferably 80 ° C. or higher and 120 ° C. or lower.
- the dispersion solvent is preferably N-methylpyrrolidone (NMP) or water.
- an active material that operates at a potential of 4.5 V or higher with respect to lithium hereinafter also referred to as a 5 V class active material
- gas generation is likely to occur due to decomposition of the components of the non-aqueous electrolyte, but by using the non-aqueous electrolyte of this embodiment, gas generation can be suppressed and cycle characteristics can be improved.
- the positive electrode active material that operates at a potential of 4.5 V or higher with respect to lithium can be selected, for example, by the following method.
- a positive electrode containing a positive electrode active material and Li metal are placed in a state of facing each other with a separator interposed therebetween, and an electrolytic solution is injected to produce a battery.
- a charge / discharge capacity of 10 mAh / g or more per mass of active material is a potential of 4.5 V or more with respect to lithium.
- the charge / discharge capacity per active material mass at a potential of 4.5 V or higher with respect to lithium is 20 mAh / g or higher. It is preferable that it is 50 mAh / g or more, and it is further more preferable that it is 100 mAh / g or more.
- the shape of the battery can be, for example, a coin type.
- the positive electrode preferably includes a 5V class active material composed of a compound represented by the composition formula Li a M1 b O d or Li a M1 b M2 c O d (a, b, c, and d indicating a composition ratio are: 1.2 ⁇ a ⁇ 2, 0 ⁇ b, c ⁇ 2, and 2 ⁇ d ⁇ 4.
- M1 and M2 are Co, Ni, Mn, Fe, Al, Sn, Mg And any one element selected from the group consisting of Ge, Si and P.
- M1 and M2 are different elements.
- a is more preferably 1.2 ⁇ a ⁇ 1.7.
- M1 and M2 are preferably selected from Mn, Ni, Co, Fe, P, Mg, Si, Sn, and Al, preferably Mn, Ni, Co, Al, P, or Fe. More preferably it is.
- Preferable specific examples of the compound represented by the composition formula Li a M1 b O d or Li a M1 b M2 c O d include Li 1.3 Mn 2 O 4 , Li 1.2 CoO 2 , Li 1.2 NiO. 2 , Li 1.3 Co 0.15 Ni 0.8 Al 0.05 O 2 , Li 1.3 Mn 1.5 Ni 0.5 O 4 and the like. However, it is not limited to these.
- a lithium manganese composite oxide represented by the following formula (A) can be used as the 5V class active material.
- M is Co, Ni, Fe, Cr.
- Y is at least one selected from the group consisting of Li, B, Na, Mg, Al, Ti, Si, K and Ca, and Z is F and Cl. At least one selected from the group consisting of:
- a spinel compound represented by the following formula (B) is preferably used among such metal complex oxides from the viewpoint of obtaining a sufficient capacity and extending the life.
- LiNi x Mn 2-xy A y O 4 (B) (In the formula (B), 0.4 ⁇ x ⁇ 0.6, 0 ⁇ y ⁇ 0.3, A is at least one selected from the group consisting of Li, B, Na, Mg, Al, Ti and Si. is there.).
- an olivine-type positive electrode active material As an active material that operates at a potential of 4.5 V or higher with respect to lithium, an olivine-type positive electrode active material can be given.
- the olivine-type 5V active material include LiCoPO 4 and LiNiPO 4 .
- Si composite oxide As an active material that operates at a potential of 4.5 V or more with respect to lithium, Si composite oxide can be given.
- Si complex oxide the compound shown by a following formula (C) is mentioned, for example.
- Li 2 MSiO 4 (C) (In the formula (C), M is at least one selected from the group consisting of Mn, Fe and Co).
- the active material that operates at a potential of 4.5 V or more with respect to lithium may have a layered structure.
- a 5V class active material containing a layered structure the compound shown by following formula (D) is mentioned, for example.
- M1 is at least one selected from the group consisting of Ni, Co, and Fe.
- M2 is at least one selected from the group consisting of Li, Mg, and Al. 0.1 ⁇ x ⁇ 0.5, 0.05 ⁇ y ⁇ 0.3).
- lithium metal composite oxides represented by the following (E) to (G) can be preferably used.
- LiMPO 4 (E) (In formula (E), M is at least one selected from the group consisting of Co and Ni).
- Li (M y Mn z ) O 2 (F) (In Formula (F), 0.1 ⁇ y ⁇ 0.5, 0.7 ⁇ z ⁇ 0.33, and M is at least one selected from the group consisting of Li, Co, and Ni.) .
- Li (Li x M y Mn z ) O 2 (G) (In Formula (G), 0.3> x ⁇ 0.1, 0.1 ⁇ y ⁇ 0.4, 0.7 ⁇ z ⁇ 0.33, and M is composed of Li, Co, and Ni. At least one selected from the group).
- a conductive auxiliary material may be added for the purpose of reducing the impedance of the positive electrode active material.
- the conductive auxiliary material carbonaceous fine particles such as graphite, carbon black, and acetylene black can be used.
- the binder for the positive electrode is not particularly limited.
- polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer Rubber, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide and the like can be used.
- polyimide, polyamideimide, polyacrylic acid (including lithium salt, sodium salt and potassium salt neutralized with alkali), carboxymethylcellulose (lithium salt neutralized with alkali) due to its strong binding properties , Sodium salts and potassium salts) are preferred.
- the amount of the positive electrode binder used is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material from the viewpoints of “sufficient binding force” and “higher energy” which are in a trade-off relationship. .
- the positive electrode current collector may be any material that supports the positive electrode active material layer including the positive electrode active material integrated by the binder and has conductivity that enables conduction with the external terminal.
- the same negative electrode current collector as described above can be used.
- the method for producing the positive electrode is not particularly limited. For example, only the surface-treated Mn-based positive electrode powder, or the surface-treated Mn-based positive electrode powder and the lithium nickel composite oxide powder, After mixing with a binder and an appropriate dispersion medium that can dissolve the binder (slurry method), apply it on a current collector such as an aluminum foil, dry the solvent, and then compress it with a press or the like. Form a film.
- a conductive support material Usually used things, such as carbon black, acetylene black, natural graphite, artificial graphite, carbon fiber, can be used.
- Non-aqueous electrolyte contains a phosphinoamine-based compound represented by the following formula (1).
- the phosphinoamine compound is presumed to function as a film forming agent for forming a film on the electrode. More specifically, by adding a phosphinoamine-based compound to the non-aqueous electrolyte, a stable film can be formed on the positive electrode during the first charge / discharge.
- the coating can suppress oxidative decomposition of components (particularly non-aqueous electrolytic solvent) in the non-aqueous electrolyte during charging / discharging (especially during high-voltage charging / discharging) and suppress gas generation.
- the maintenance rate can be improved.
- the above mechanism is speculation and does not limit the present invention.
- R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted.
- R 3 and R 4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, substituted or unsubstituted It represents a substituted heterocyclic group, a substituted or unsubstituted alkoxy group, or a hydroxy group.
- R 1 and R 2 may be bonded via a single bond, an ether bond, or a hydrocarbon chain having 1 to 4 carbon atoms.
- R 3 and R 4 may be bonded via a single bond, an ether bond, or a hydrocarbon chain having 1 to 4 carbon atoms. ].
- the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.
- the alkenyl group has preferably 2 to 6 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 2 to 4 carbon atoms.
- the alkyl group and alkenyl group may be linear or branched.
- the cycloalkyl group preferably has 4 to 7 carbon atoms, and more preferably 5 to 6 carbon atoms.
- the aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- the number of carbon atoms of the heterocyclic group is preferably 2 to 12, more preferably 2 to 10, and further preferably 2 to 8.
- the hetero atom of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- the alkoxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.
- the alkoxy group may be linear or branched.
- R 1 and R 2 may be bonded via a single bond, an ether bond, or a hydrocarbon chain having 1 to 4 carbon atoms to form a ring structure.
- the hydrocarbon chain is preferably a methylene chain having 1 to 3 repeats.
- the hydrocarbon chain may be branched.
- both R 1 and R 2 are substituted or unsubstituted phenyl groups, and these phenyl groups are bonded via a single bond or an ether bond to form a hetero 5-membered ring or hetero 6-membered ring.
- R 1 and R 2 are both substituted or unsubstituted alkoxy groups, and the alkoxy groups are bonded to each other through a single bond to form a hetero 5-membered ring or a hetero 6-membered ring. Can be mentioned.
- the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.
- the alkenyl group has preferably 2 to 6 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 2 to 4 carbon atoms.
- the alkyl group and alkenyl group may be linear or branched.
- the cycloalkyl group preferably has 4 to 7 carbon atoms, and more preferably 5 to 6 carbon atoms.
- the aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- the number of carbon atoms of the heterocyclic group is preferably 2 to 12, more preferably 2 to 10, and further preferably 2 to 8.
- the hetero atom of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- the alkoxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.
- the alkoxy group may be linear or branched.
- R 3 and R 4 may be bonded via a single bond, an ether bond, or a hydrocarbon chain having 1 to 4 carbon atoms to form a ring structure.
- the hydrocarbon chain is preferably a methylene chain having 1 to 3 repeats.
- the hydrocarbon chain may be linear or branched.
- examples of the substituents for R 1 to R 4 are each independently an optionally branched alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group).
- Group, butyl group optionally branched halogen-substituted alkyl group having 1 to 4 carbon atoms (for example, perfluoromethyl group, perfluoroethyl group), and optionally branched alkoxy group having 1 to 4 carbon atoms.
- the halogen-substituted alkyl group represents a substituted alkyl group having a structure in which at least one hydrogen atom of the unsubstituted alkyl group is substituted with a halogen atom (for example, fluorine atom, chlorine atom, bromine atom).
- a halogen atom for example, fluorine atom, chlorine atom, bromine atom.
- the halogen-substituted alkyl group is preferably a fluorine-substituted alkyl group.
- the fluorine-substituted alkyl group represents a substituted alkyl group having a structure in which at least one hydrogen atom in the unsubstituted alkyl group is substituted with a fluorine atom.
- the heterocyclic group is preferably a thiophene group from the viewpoint of oxidation resistance.
- phosphinoamine-based compound one kind may be used alone, or two or more kinds may be used in combination.
- the content of the phosphinoamine compound in the non-aqueous electrolyte is preferably 0.001% by mass or more and 5.0% by mass or less, and 0.01% by mass or more and 2.0% by mass or less. More preferably, the content is 0.01% by mass or more and 0.3% by mass or less.
- the content of the phosphinoamine compound is in the above range, it is easy to form a film only on the electrode surface, and it is possible to suppress the film from becoming too thick. As a result, an increase in internal resistance of the electrode is suppressed, ion conductivity and electron conductivity in the electrode are improved, and battery characteristics are improved.
- Preferred examples of the phosphinoamine compound include the following compounds (PN-1) to (PN-8). Of these, the compound (PN-1) is more preferable. In addition, the phosphinoamine-type compound in this embodiment is not limited to these examples.
- nonaqueous electrolytic solvent contained in the nonaqueous electrolytic solution examples include cyclic carbonates, chain carbonates, aliphatic carboxylic acid esters, ⁇ -lactones, cyclic ethers, chain ethers, and fluorine derivatives thereof, One or more solvents selected from the group consisting of: Specific examples of the nonaqueous electrolytic solvent include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl.
- PC propylene carbonate
- EC ethylene carbonate
- BC butylene carbonate
- DMC dimethyl carbonate
- DEC diethyl carbonate
- ethyl ethyl
- Chain carbonates such as methyl carbonate (EMC) and dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate, ⁇ -lactones such as ⁇ -butyrolactone, 1, 2 -Chain ethers such as diethoxyethane (DEE) and ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylform Amide, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetrahydro
- the nonaqueous electrolytic solution can contain a lithium salt as an electrolyte salt.
- the lithium salt include lithium imide salt, LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiClO 4 , LiAlCl 4 , LiN (CnF 2n + 1 SO 2 ) (CmF 2m + 1 SO 2 ) (n and m are natural numbers), etc. Is mentioned. These can be used individually by 1 type or in mixture of 2 or more types. In particular, it is preferable to use LiPF 6 or LiBF 4 . By using these, the electrical conductivity of the lithium salt can be increased, and the cycle characteristics of the secondary battery can be further improved.
- the separator is not particularly limited, and a porous film such as polypropylene or polyethylene or a nonwoven fabric can be used. Moreover, what laminated
- Exterior Body is not particularly limited, and for example, a laminate film can be used.
- the laminate film can be appropriately selected as long as it is stable to the electrolytic solution and has a sufficient water vapor barrier property.
- the distortion of the electrode element is greatly increased when gas is generated, compared to a secondary battery using a metal can as the outer package. This is because the laminate film is more easily deformed by the internal pressure of the secondary battery than the metal can. Furthermore, when sealing a secondary battery using a laminate film as an exterior body, the internal pressure of the battery is usually lower than the atmospheric pressure, so there is no extra space inside, and if gas is generated, it is immediately It may lead to battery volume changes and electrode element deformation.
- gas generation is suppressed even when high-voltage charge / discharge is performed, so that the above problem can be overcome.
- the laminate film for example, a laminate film made of polypropylene, polyethylene or the like coated with aluminum, silica, or alumina can be used as the outer package.
- an aluminum laminate film is preferable from the viewpoint of suppressing volume expansion.
- a typical layer structure of a laminate film the structure by which the metal thin film layer and the heat-fusible resin layer were laminated
- a protective layer made of a film of polyester such as polyethylene terephthalate or nylon is further laminated on the surface of the metal thin film layer opposite to the heat fusion resin layer. The structure which was made is mentioned.
- the battery element When sealing the battery element, the battery element is surrounded with the heat-fusible resin layer facing each other.
- the metal thin film layer for example, a foil of Al, Ti, Ti alloy, Fe, stainless steel, Mg alloy or the like having a thickness of 10 to 100 ⁇ m is used.
- the resin used for the heat-fusible resin layer is not particularly limited as long as it can be heat-sealed.
- An ionomer resin bonded between molecules is used as the heat-fusible resin layer.
- the thickness of the heat-fusible resin layer is preferably 10 to 200 ⁇ m, more preferably 30 to 100 ⁇ m.
- FIG. 1 is a schematic cross-sectional view showing the structure of a laminated laminate type secondary battery 10.
- a plurality of positive electrodes 1 and a plurality of negative electrodes 3 having a planar structure are alternately stacked with a separator 2 interposed therebetween to form an electrode assembly (also referred to as an electrode element).
- the positive electrode current collector 1b of each positive electrode 1 is welded and electrically connected to each other at an end portion not covered with the positive electrode active material layer 1a, and the positive electrode terminal 4 is welded to the welded portion.
- the negative electrode current collector 3b included in each negative electrode 3 is welded and electrically connected to each other at an end portion not covered with the negative electrode active material layer 3a, and the negative electrode terminal 6 is welded to the welded portion. Further, the positive electrode terminal 4 is welded to the positive electrode tab 5, and the negative electrode terminal 6 is welded to the negative electrode tab 7.
- the electrode element having such a planar laminated structure does not have a portion with a small R (a region close to the winding core of the wound structure), the electrode element associated with charge / discharge is compared with an electrode element having a wound structure.
- an electrode element having a wound structure since the electrode is curved, the structure is easily distorted when a volume change occurs.
- a negative electrode active material having a large volume change due to charge / discharge such as silicon oxide
- a secondary battery using an electrode element having a wound structure has a large capacity reduction due to charge / discharge.
- the electrode assembly is enclosed in the exterior body 9 together with the non-aqueous electrolyte 8, and the positive electrode tab 5 and the negative electrode tab 7 are led out from the exterior body 9.
- the electrode element having a planar laminated structure has a problem that when the gas is generated between the electrodes, the generated gas tends to stay between the electrodes. This is because, in the case of an electrode element having a wound structure, the distance between the electrodes is difficult to widen because tension is applied to the electrodes, whereas in the case of an electrode element having a laminated structure, the distance between the electrodes is widened. This is because it is easy. This problem is particularly noticeable when the outer package is an aluminum laminate film.
- the above problem can be solved by forming a film on the positive electrode with a film forming agent.
- the secondary battery according to the present embodiment includes a laminated laminate having an electrode assembly in which a positive electrode and a negative electrode are arranged to face each other, a non-aqueous electrolyte, and an outer package containing the electrode assembly and the non-aqueous electrolyte.
- the present invention relates to a type secondary battery.
- the positive electrode has a positive electrode active material layer containing a positive electrode active material and a positive electrode binder, and a film made of the film forming agent is formed on the positive electrode active material layer.
- Example 1 [Production of negative electrode] Silicon having an average particle diameter of 5 ⁇ m, amorphous silicon oxide (SiO x , 0 ⁇ x ⁇ 2) having an average particle diameter of 13 ⁇ m, and graphite having an average particle diameter of 30 ⁇ m were weighed in a mass ratio of 29:61:10. . These materials were mixed for 24 hours by so-called mechanical milling to obtain a negative electrode active material (Si / SiO / C composite). In this negative electrode active material, silicon is dispersed in silicon oxide (SiO x , 0 ⁇ x ⁇ 2).
- a negative electrode slurry 80 parts by mass of a Si / SiO / C composite, 15 parts by mass of polyimide, and 5 parts by mass of a carbon-based conductive additive were mixed, and the mixture was dispersed in N-methylpyrrolidone (NMP) to prepare a negative electrode slurry. . Thereafter, a negative electrode slurry was applied to a copper foil as a negative electrode current collector so that the thickness after drying was 50 ⁇ m, dried, and punched to a size of 23 mm ⁇ 25 mm to produce a negative electrode.
- NMP N-methylpyrrolidone
- Positive electrode 92 parts by mass of a mixture of lithium nickel manganese cobalt composite oxide and lithium manganese spinel (5V class active material), 4 parts by mass of a carbon-based conductive agent, and 4 parts by mass of polyvinylidene fluoride are mixed, and the mixture is made into NMP.
- the positive electrode slurry was prepared by dispersing. Thereafter, a positive electrode slurry was applied to an aluminum foil as a positive electrode current collector so that the thickness after drying was 170 ⁇ m, dried, and punched out to a size of 22 mm ⁇ 24 mm to produce a positive electrode.
- non-aqueous electrolyte The content of the compound (PN-1) is 0.1% by mass in an ethylene carbonate / diethyl carbonate mixed solution (mixing ratio (volume basis) 3: 7) containing 1.0 mol / L LiPF 6 as an electrolyte salt.
- a non-aqueous electrolyte was prepared.
- the negative electrode, the polypropylene porous film separator, and the positive electrode were laminated in this order to obtain an electrode assembly.
- the electrode assembly was wrapped with an aluminum laminate film, and the nonaqueous electrolyte was injected into the film, followed by vacuum sealing to produce a sheet-like lithium ion secondary battery.
- volume expansion coefficient The amount of gas generation was measured by measuring the mass difference of the lithium ion secondary battery before and after the cycle test in water and dividing the mass difference by the specific gravity of water.
- the volume expansion rate was the ratio (%) of the gas generation amount in the secondary battery produced in Example 1 to the gas generation amount in the secondary battery produced in Comparative Example 1 described later.
- a lithium ion secondary battery was prepared and evaluated in the same manner as in Example 1 except that the non-aqueous electrolyte was prepared without adding the compound (PN-1).
- This embodiment can be used in, for example, all industrial fields that require a power source and industrial fields related to the transport, storage, and supply of electrical energy.
- power supplies for mobile devices such as mobile phones and notebook computers
- power supplies for transportation and transportation media such as trains, satellites, and submarines, including electric vehicles such as electric cars, hybrid cars, electric bikes, and electric assist bicycles
- a backup power source such as a UPS
- a power storage facility for storing power generated by solar power generation, wind power generation, etc .
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Abstract
Description
<負極活物質層>
負極は、例えば負極活物質が負極用結着剤によって負極集電体に結着されてなる。本実施形態における負極活物質は、リチウムの吸蔵及び放出が可能なものであれば、本発明の効果を著しく損なわない限り任意のものを用いることができる。
負極用結着剤としては、特に制限されるものではないが、例えば、ポリフッ化ビニリデン、ビニリデンフルオライド-ヘキサフルオロプロピレン共重合体、ビニリデンフルオライド-テトラフルオロエチレン共重合体、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、ポリイミド、ポリアミドイミド、各種ポリウレタン等を用いることができる。これらの中でも、結着性が強いことから、ポリイミド、ポリアミドイミドが好ましい。また、水性バインダーも使用することができる。水性バインダーは特に制限されるものではないが、通常、水分散性ポリマーがラテックス又はエマルジョンの形態で使用される。例えば、アクリル系樹脂エマルジョン、スチレン系樹脂エマルジョン、酢酸ビニル系重合体エマルジョン、ウレタン系樹脂エマルジョン等を用いることができる。これらの中でも、粘弾特性の点から、水分散性の合成ゴムラテックス又はエマルジョンが好ましい。水分散性の合成ゴムラテックス(エマルジョン)としては、例えば、ポリブタジエンゴムラテックス、スチレン-ブタジエンゴムラテックス、アクリロニトリル-ブタジエンゴムラテックス、(メタ)アクリル酸エステル-ブタジエンゴムラテックス、クロロプレンゴムラテックスなどが挙げられる。電解液に対する耐性の点から、スチレン-ブタジエンゴムラテックス(SBRラテックス)が好ましい。これらの結着剤は、1種を単独で又は2種類以上混合して用いることもできる。使用する負極用結着剤の量は、トレードオフの関係にある「十分な結着力」と「高エネルギー化」の観点から、負極活物質100質量部に対して、2~10質量部が好ましい。
負極スラリーを作製しやすくするために、増粘剤を用いることもできる。このような増粘剤としては、カルボキシメチルセルロース(アルカリで中和されたリチウム塩、ナトリウム塩、カリウム塩を含む)、ポリエチレンオキシド、ポリプロピレンオキシド、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルヒドロキシエチルセルロース、ポリビニルアルコール、ポリアクリルアミド、ポリアクリル酸ヒドロキシエチル、ポリアクリル酸アンモニウム、ポリアクリル酸(アルカリで中和されたリチウム塩、ナトリウム塩、カリウム塩を含む)等が挙げられる。これらの増粘剤は、1種を単独でまたは2種類以上混合して用いることもできる。負極活物質層中の増粘剤の割合としては、0.1~5質量%が好ましい。
分散溶媒に水を用いる場合、スラリー中の炭素粒子の分散性を向上させる目的で、ノニオン系界面活性剤を用いることもできる。ノニオン系界面活性剤としては、特に限定されないが、ポリオキシアルキレンアルキルエーテルを好ましく使用できる。ポリオキシアルキレンアルキルエーテルは、一般式:R-O-(AO)nH(式中、Rはアルキル基を示す。Aはアルキレン基を示す。nは自然数を示す。)で表される。ここで、符号Rで示されるアルキル基の炭素数及び符号Aで示されるアルキレン基の炭素数、並びにnで示されるアルキレンオキシ基(AO)の重合度は特に限定されない。ポリオキシアルキレンアルキルエーテルは、符号Rで示されるアルキル基の炭素数、符号Aで示されるアルキレン基の炭素数及び符号nで示されるアルキレンオキシ基(AO)の重合度の少なくとも1種が異なる複数のポリオキシアルキレンアルキルエーテルの混合物であってもよい。
負極用集電体の材質としては、公知のものを任意に用いることができるが、例えば、銅、ニッケル、SUS等の金属材料が用いられる。中でも加工し易さとコストの点から特に銅が好ましい。また、集電体は予め粗面化処理しておくのが好ましい。さらに、集電体の形状も任意であり、箔状、平板状、メッシュ状等が挙げられる。また、エキスパンドメタルやパンチングメタルのような穴あきタイプの集電体を使用することもできる。また、集電体として薄膜を使用する場合の好ましい厚さ、形状も任意である。
負極の作製方法としては、例えば、負極集電体上に、負極活物質、負極用結着剤、負極用増粘剤、界面活性剤などを含む負極活物質層を形成することで作製することができる。負極活物質層の形成方法としては、例えば、ドクターブレード法、ダイコーター法、CVD法、スパッタリング法などが挙げられる。予め負極活物質層を形成した後に、蒸着、スパッタ等の方法でアルミニウム、ニッケルまたはそれらの合金の薄膜を形成して、負極集電体としてもよい。中でも、負極活物質、負極用結着剤、負極用増粘剤、界面活性剤などを分散溶媒に混合してスラリーを作製し、集電体上に塗布した後、加熱乾燥する方法が、安価に製造できるため好ましい。加熱乾燥温度は50℃以上140℃以下、さらには80℃以上120℃以下が好ましい。分散溶媒には、N-メチルピロリドン(NMP)または水が好ましい。
<正極活物質層>
正極活物質としては、高電圧が得られるという観点から、リチウムに対して4.5V以上の電位で動作する活物質(以下、5V級活物質とも称す)を用いることが好ましい。5V級活物質を用いた場合、非水電解液の成分の分解によるガス発生が起こり易いが、本実施形態の非水電解液を用いることにより、ガス発生を抑制でき、サイクル特性を改善できる。リチウムに対して4.5V以上の電位で動作する正極活物質は、例えば、以下のような方法によって選択することができる。まず、正極活物質を含む正極とLi金属とをセパレータを挟んで対向させた状態で電池内に配置させ、電解液を注液し、電池を作製する。そして、正極内の正極活物質質量あたり例えば5mAh/gとなる定電流で充放電を行った場合に、活物質質量あたり10mAh/g以上の充放電容量をリチウムに対して4.5V以上の電位で持つものを、リチウムに対して4.5V以上の電位で動作する正極活物質とすることができる。また、正極内の正極活物質質量あたり5mAh/gとなる定電流で充放電を行った場合に、リチウムに対して4.5V以上の電位における活物質質量あたりの充放電容量が20mAh/g以上であることが好ましく、50mAh/g以上であることがより好ましく、100mAh/g以上であることがさらに好ましい。電池の形状としては例えばコイン型とすることができる。
(式(B)中、0.4<x<0.6、0≦y<0.3、Aは、Li、B、Na、Mg、Al、Ti及びSiからなる群より選ばれる少なくとも一種である。)。
(式(C)中、Mは、Mn、Fe及びCoからなる群より選ばれる少なくとも一種である)。
(式(D)中、M1は、Ni、Co及びFeからなる群より選ばれる少なくとも一種である。M2は、Li、Mg及びAlからなる群より選ばれる少なくとも一種である。0.1<x<0.5、0.05<y<0.3)。
(式(E)中、Mは、Co及びNiからなる群より選ばれる少なくとも一種である。)。
(式(F)中、0.1≦y≦0.5、0.7≧z≧0.33であって、Mは、Li、Co及びNiからなる群より選ばれる少なくとも一種である。)。
(式(G)中、0.3>x≧0.1、0.1≦y≦0.4、0.7≧z≧0.33であって、Mは、Li、Co及びNiからなる群より選ばれる少なくとも一種である。)。
正極用結着剤としては、特に制限されるものではないが、例えば、ポリフッ化ビニリデン、ビニリデンフルオライド-ヘキサフルオロプロピレン共重合体、ビニリデンフルオライド-テトラフルオロエチレン共重合体、スチレン-ブタジエン共重合ゴム、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、ポリイミド、ポリアミドイミド等を用いることができる。これらの中でも、結着性が強いことから、ポリイミド、ポリアミドイミド、ポリアクリル酸(アルカリで中和されたリチウム塩、ナトリウム塩、カリウム塩を含む)、カルボキシメチルセルロース(アルカリで中和されたリチウム塩、ナトリウム塩、カリウム塩を含む)が好ましい。使用する正極用結着剤の量は、トレードオフの関係にある「十分な結着力」と「高エネルギー化」の観点から、負極活物質100質量部に対して、2~10質量部が好ましい。
正極用集電体は、結着剤により一体化される正極活物質を含む正極活物質層を支持し、外部端子との導通を可能とする導電性を有するものであればよく、具体的には、上記負極集電体と同様のものを用いることができる。
正極電極の製造方法としては、特に制限はないが例えば、表面処理Mn系正極の粉体のみ、あるいは、表面処理Mn系正極の粉体とリチウムニッケル複合酸化物の粉体を、導電補助材および結着剤と共に、結着剤を溶解しうる適当な分散媒で混合(スラリー法)した上で、アルミ箔等の集電体上に塗布し、溶剤を乾燥した後、プレス等により圧縮して成膜する。尚、導電補助材としては特に制限は無く、カーボンブラック、アセチレンブラック、天然黒鉛、人工黒鉛、炭素繊維等の通常用いられるものを用いることができる。
本実施形態の非水電解液は、下記式(1)で表わされるホスフィノアミン系化合物を含む。該ホスフィノアミン系化合物は、電極上に皮膜を形成する皮膜形成剤として機能すると推測されている。より具体的には、ホスフィノアミン系化合物を非水電解液中に添加することにより、初回充放電時に正極上に安定な皮膜を形成することができる。該皮膜は、充放電時(特に高電圧充放電時)における非水電解液中の成分(特に非水電解溶媒)の酸化分解を抑制し、ガス発生を抑制することができ、その結果、容量維持率を向上することができる。以上のメカニズムは推測であり、本願発明を制限するものではない。
セパレータとしては、特に制限されるものではないが、ポリプロピレン、ポリエチレン等の多孔質フィルムや不織布を用いることができる。また、セパレータとしては、それらを積層したものを用いることもできる。
外装体としては、特に制限されるものではないが、例えば、ラミネートフィルムを用いることができる。ラミネートフィルムとしては、電解液に安定でかつ十分な水蒸気バリア性を持つものであれば、適宜選択することができる。
また、ラミネートフィルムの代表的な層構成としては、金属薄膜層と熱融着性樹脂層とが積層された構成が挙げられる。また、ラミネートフィルムの代表的な層構成としては、その他にも、金属薄膜層の熱融着樹脂層と反対側の面に、さらにポリエチレンテレフタレートなどのポリエステルやナイロン等のフィルムからなる保護層が積層された構成が挙げられる。電池要素を封止する場合、熱融着性樹脂層を対向させて電池要素が包囲される。金属薄膜層としては、例えば、厚さ10~100μmの、Al、Ti、Ti合金、Fe、ステンレス、Mg合金などの箔が用いられる。熱融着性樹脂層に用いられる樹脂は、熱融着が可能な樹脂であれば特に制限はない。例えば、ポリプロピレン、ポリエチレン、これらの酸変成物、ポリフェニレンサルファイド、ポリエチレンテレフタレートなどのポリエステル、ポリアミド、エチレン-酢酸ビニル共重合体、エチレン-メタクリル酸共重合体やエチレン-アクリル酸共重合体を金属イオンで分子間結合させたアイオノマー樹脂などが、熱融着性樹脂層として用いられる。熱融着性樹脂層の厚さは10~200μmが好ましく、より好ましくは30~100μmである。
二次電池の構成は、特に制限されるものではないが、例えば、正極および負極が対向配置された電極集積体と、電解液と、が外装体に内包されている積層ラミネート型とすることができる。図1は、積層ラミネート型の二次電池10の構造を示す模式的断面図である。この二次電池10は、平面構造を有する正極1の複数および負極3の複数が、セパレータ2を挟みつつ交互に積み重ねられて電極集積体(電極素子ともいう)を構成している。各正極1が有する正極集電体1bは、正極活物質層1aに覆われていない端部で互いに溶接されて電気的に接続され、さらにその溶接箇所に正極端子4が溶接されている。各負極3が有する負極集電体3bは、負極活物質層3aに覆われていない端部で互いに溶接されて電気的に接続され、さらにその溶接箇所に負極端子6が溶接されている。さらに、正極端子4は正極タブ5に、負極端子6は負極タブ7に溶接されている。このような平面的な積層構造を有する電極素子は、Rの小さい部分(捲回構造の巻き芯に近い領域)がないため、捲回構造を持つ電極素子に比べて、充放電に伴う電極の体積変化に対する悪影響を受けにくいという利点がある。すなわち、体積膨張を起こしやすい活物質を用いた電極集積体として有効である。一方で、捲回構造を持つ電極素子では電極が湾曲しているため、体積変化が生じた場合にその構造が歪みやすい。特に、ケイ素酸化物のように充放電に伴う体積変化が大きい負極活物質を用いた場合、捲回構造を持つ電極素子を用いた二次電池では、充放電に伴う容量低下が大きい。電極集積体は非水電解液8と共に外装体9に内包されており、正極タブ5及び負極タブ7が外装体9から外部に導出されている。
[負極の作製]
平均粒径5μmのシリコンと、平均粒径13μmの非晶質酸化シリコン(SiOx、0<x≦2)と、平均粒径30μmの黒鉛とを、29:61:10の質量比で計量した。そして、これら材料をいわゆるメカニカルミリングで24時間混合して、負極活物質(Si/SiO/C複合体)を得た。なお、この負極活物質において、シリコンは、酸化シリコン(SiOx、0<x≦2)中に分散している。
リチウムニッケルマンガンコバルト複合酸化物とリチウムマンガンスピネルの混合物(5V級活物質)92質量部と、カーボン系導電剤4質量部と、ポリフッ化ビニリデン4質量部と、を混合し、該混合物をNMPに分散させ、正極スラリーを調製した。その後、正極集電体としてのアルミニウム箔に、乾燥後の厚さが170μmになるように正極スラリーを塗布し、乾燥させ、22mm×24mmの寸法に打ち抜いて正極を作製した。
電解質塩として1.0mol/LのLiPF6を含むエチレンカーボネート/ジエチルカーボネート混合溶液(混合比(体積基準)3:7)に、化合物(PN-1)を含有量が0.1質量%となるように添加し、非水電解液を調製した。
上記負極と、ポリプロピレン多孔質フィルムセパレーターと、上記正極と、をこの順に積層し、電極集積体を得た。この電極集積体をアルミニウムラミネートフィルムで包み込み、該フィルム内部に上記非水電解液を注入した後で真空封止し、シート状のリチウムイオン二次電池を作製した。
<サイクル試験>
作製したリチウムイオン二次電池について、20℃の恒温槽中で、1.5Vから4.5Vの電圧範囲で10回充放電を繰り返し、放電容量(初回、10サイクル後)を測定した。容量維持率は、初回放電容量に対する10サイクル後の放電容量の割合(%)とした。なお、放電容量とは、正極活物質の単位質量あたりの値である。測定した容量維持率の結果を表1に示す。
ガス発生量は、サイクル試験前後のリチウムイオン二次電池の質量差を水中で測定し、その質量差を水の比重で割ることによって測定した。体積膨張率は、後述の比較例1で作製した二次電池におけるガス発生量に対する実施例1で作製した二次電池におけるガス発生量の割合(%)とした。
この出願は、2014年7月9日に出願された日本出願特願2014-141488を基礎とする優先権を主張し、その開示の全てをここに取り込む。
1b 正極集電体
2 セパレータ
3a 負極活物質層
3b 負極集電体
4 正極端子
5 正極タブ
6 負極端子
7 負極タブ
8 非水電解液
9 外装体
10 二次電池
Claims (8)
- 下記一般式(1)で表されるホスフィノアミン系化合物を含むことを特徴とする非水電解液。
- 前記ホスフィノアミン系化合物の前記非水電解液中の含有量が、0.001質量%以上、5.0質量%以下である請求項1又は2に記載の非水電解液。
- さらに、電解質塩及び非水電解溶媒を含む請求項1乃至3のいずれか一項に記載の非水電解液。
- 請求項1乃至4のいずれか一項に記載の非水電解液を備えるリチウムイオン二次電池。
- 正極および負極がセパレータを介して対向配置された電極集積体と、該電極集積体及び前記非水電解液を内包する外装体と、を有する請求項5に記載のリチウムイオン二次電池。
- 前記正極が、リチウムに対して4.5V以上の電位で動作する正極活物質を含む請求項5又は6に記載のリチウムイオン二次電池。
- 前記外装体がラミネートフィルムである請求項5乃至7のいずれか一項に記載のリチウムイオン二次電池。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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JP2016532506A JP6624055B2 (ja) | 2014-07-09 | 2015-06-11 | 非水電解液及びリチウムイオン二次電池 |
US15/324,453 US10128538B2 (en) | 2014-07-09 | 2015-06-11 | Non-aqueous electrolytic solution and lithium ion secondary battery |
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Publication number | Priority date | Publication date | Assignee | Title |
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US10886564B2 (en) | 2016-09-02 | 2021-01-05 | Samsung Electronics Co., Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery including the electrolyte |
WO2022047628A1 (zh) * | 2020-09-01 | 2022-03-10 | 宁德新能源科技有限公司 | 电解液、电化学装置及电子装置 |
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US11600861B2 (en) | 2019-06-20 | 2023-03-07 | Samsung Sdi Co., Ltd. | Additive, electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same |
PL3796450T3 (pl) | 2019-09-18 | 2024-05-13 | Samsung Sdi Co., Ltd. | Dodatek, elektrolit do akumulatora litowego i akumulator litowy go zawierający |
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JP2014170689A (ja) * | 2013-03-04 | 2014-09-18 | Mitsui Chemicals Inc | 非水電解液及びリチウム二次電池 |
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KR100634772B1 (ko) | 2002-03-19 | 2006-10-16 | 가부시키가이샤 브리지스톤 | 리튬 1차 전지용 양극 및 그 제조방법, 그리고 리튬 1차전지 |
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JPH06228172A (ja) * | 1985-03-06 | 1994-08-16 | Hoechst Ag | 燐酸化剤 |
JPS61208758A (ja) * | 1985-03-12 | 1986-09-17 | Hitachi Maxell Ltd | 有機電解質電池 |
JP2003272643A (ja) * | 2002-03-20 | 2003-09-26 | Bridgestone Corp | リチウム1次電池 |
JP2008137979A (ja) * | 2006-12-05 | 2008-06-19 | Toyota Motor Corp | リチウム塩およびその製造方法 |
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JP2014170689A (ja) * | 2013-03-04 | 2014-09-18 | Mitsui Chemicals Inc | 非水電解液及びリチウム二次電池 |
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US10886564B2 (en) | 2016-09-02 | 2021-01-05 | Samsung Electronics Co., Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery including the electrolyte |
WO2022047628A1 (zh) * | 2020-09-01 | 2022-03-10 | 宁德新能源科技有限公司 | 电解液、电化学装置及电子装置 |
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JP6624055B2 (ja) | 2019-12-25 |
US10128538B2 (en) | 2018-11-13 |
US20180183099A1 (en) | 2018-06-28 |
JPWO2016006381A1 (ja) | 2017-04-27 |
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