WO2013114946A1 - リチウム二次電池 - Google Patents
リチウム二次電池 Download PDFInfo
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- WO2013114946A1 WO2013114946A1 PCT/JP2013/050643 JP2013050643W WO2013114946A1 WO 2013114946 A1 WO2013114946 A1 WO 2013114946A1 JP 2013050643 W JP2013050643 W JP 2013050643W WO 2013114946 A1 WO2013114946 A1 WO 2013114946A1
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Definitions
- the present invention relates to a lithium secondary battery.
- Lithium secondary batteries are widely used in portable electronic devices, personal computers, and the like, and while miniaturization and weight reduction are required, increasing energy density is an important issue.
- a spinel compound in which a part of manganese is substituted with nickel or the like in lithium manganate, specifically, LiNi 0.5 Mn 1.5 O 4 shows a potential plateau in the region of 4.5 V or higher.
- a spinel compound as the positive electrode active material, a higher (5 V class) operating voltage can be realized.
- manganese exists in a tetravalent state, and the operation of the battery is performed by oxidation / reduction of Ni 2+ ⁇ ⁇ Ni 4+ instead of oxidation / reduction of Mn 3+ ⁇ ⁇ Mn 4+. Voltage is specified.
- LiNi 0.5 Mn 1.5 O 4 has a capacity of 130 mAh / g or more, an average operating voltage of 4.6 V or more with respect to metallic lithium, and a lithium storage capacity smaller than LiCoO 2, but its energy density is LiCoO 2. Higher than. For these reasons, spinel compounds such as LiNi 0.5 Mn 1.5 O 4 are promising as positive electrode materials.
- Patent Document 1 describes a problem that the charge / discharge cycle life is shortened when an electrolytic solution used so far is used for a battery having a voltage of 4 V or more.
- a specific organic fluorinated ether is described.
- An electrolyte for a lithium secondary battery containing a compound as a solvent is described.
- Patent Document 2 describes a specific fluorine-containing polyether that is useful as an ion conductor thin film material for a lithium battery and has excellent conductivity, film formability, and mechanical strength.
- Patent Document 3 describes a problem that load characteristics (capacity retention) decrease with an increase in charge / discharge cycle in a secondary battery using an organic solvent as a solvent of an electrolytic solution.
- a secondary battery using an organic electrolyte containing a fluorine-containing polymer ether is described.
- Patent Document 4 describes a problem that, when a high-viscosity electrolyte is used in a nonaqueous electrolyte secondary battery, the internal resistance of the battery increases due to the low mobility of lithium ions, and the output characteristics deteriorate.
- a specific glycol diether a compound in which at least one hydrogen atom is substituted with a fluorine atom
- Patent Document 5 has an object to provide a non-aqueous electrolyte secondary battery excellent in initial efficiency and low-temperature discharge characteristics and suppressed in the amount of gas generated after high-temperature storage.
- the use of non-aqueous electrolytes containing substituted ethers and monofluorophosphates and / or difluorophosphates is described.
- Patent Document 6 describes the problem of swelling and capacity reduction when left in a high temperature environment for a non-aqueous electrolyte secondary battery.
- an electrolyte containing a chain carbonate ester compound is used as a vinylene.
- carbonates and fluorinated chain ethers eg fluorinated diethers
- Patent Document 7 discloses that the surface of particles having a structure in which silicon microcrystals are dispersed in a silicon-based compound (silicon dioxide) is used as a negative electrode material for producing a non-aqueous electrolyte secondary battery with high cycleability.
- a silicon-based compound silicon dioxide
- Japanese Patent No. 3304187 Japanese Patent Laid-Open No. 08-183854 JP-A-10-112334 JP 2001-023691 A JP 2011-187234 A JP 2004-363301 A JP 2004-47404 A
- a higher operating voltage can be obtained than a battery using another positive electrode active material such as LiCoO 2 or LiMn 2 O 4.
- the decomposition reaction of the electrolyte solution is likely to proceed at the contact portion between the electrolyte solution and the electrolyte solution. Since gas is generated by this decomposition reaction, the internal pressure of the cell becomes high in the cycle operation, or the laminate cell swells, causing problems in practical use.
- the non-aqueous electrolyte As a solvent for the non-aqueous electrolyte, carbonate-based materials are mainly used. However, during the high-voltage operation or long-term operation at a high temperature of the battery using such a non-aqueous electrolyte, the above-mentioned is used. As described above, gas generation accompanying the decomposition of the electrolyte in the cell was remarkable.
- An object of the present invention is to provide a high energy density lithium secondary battery having excellent life characteristics.
- a lithium secondary battery including a positive electrode including a positive electrode active material capable of occluding and releasing lithium ions, a negative electrode including a negative electrode active material capable of occluding and releasing lithium ions, and a non-aqueous electrolyte.
- the positive electrode active material includes an active material capable of occluding or releasing lithium ions at a potential of 4.5 V or higher.
- the nonaqueous electrolytic solution has the following general formula (1):
- n1 to n5 are each independently a natural number of 1 to 5
- p, q and r are each independently 0 or a natural number and satisfy 1 ⁇ p + q + r ⁇ 3
- n1 to n5 each independently represent a natural number.
- the positive electrode includes a positive electrode active material capable of occluding or releasing lithium ions at a potential of 4.5 V or more with respect to lithium metal, and the non-aqueous electrolyte is the above general
- the specific fluorine-containing ether compound shown by Formula (1) is contained.
- an electrolytic solution containing such a fluorine-containing ether compound By using an electrolytic solution containing such a fluorine-containing ether compound, it is possible to provide a secondary battery with improved life characteristics while using a high potential positive electrode material. In particular, it is possible to suppress gas generation due to decomposition of the electrolytic solution due to the positive electrode material having a high potential, and it is possible to prevent problems due to an increase in the internal pressure of the cell and expansion of the cell due to gas generation. In addition, the low temperature characteristics can be improved.
- the fluorine-containing ether compound represented by the general formula (1) has two or more ether groups (1 ⁇ p + q + r).
- the total number of alkylene groups between ether bonds (that is, the number of alkylene ether units) is 3 or less (p + q + r ⁇ 3), and preferably 2 or less (p + q + r ⁇ 2).
- the number of alkylene groups is small, an increase in the viscosity of the electrolytic solution can be suppressed.
- the carbon number (m1, m5) of the alkyl group at the molecular end and the carbon number (m2, m3, m4) of the alkylene group between the ether bonds are each independently 1 or more and 5 or less. Preferably, it is 1 or more and 4 or less.
- the number of carbon atoms is 5 or less, the increase in the viscosity of the electrolytic solution is suppressed, and the electrolytic solution can easily penetrate into the pores in the electrode and the separator, and the ion conductivity is improved, and the battery is charged and discharged.
- the current value can be improved in characteristics.
- both the alkylene group between the ether bonds and the alkyl group at the molecular end have a fluorine atom (n1 to n5 are all natural numbers). Thereby, oxidation resistance can be improved and gas generation can be suppressed.
- These alkylene groups and the alkyl group at the molecular end preferably each have 2 or more fluorine atoms (n1 to n5 are 2 or more). When the fluorine atom content is large, the voltage resistance is further improved, and the generation of gas in the cell can be further suppressed.
- the number of fluorine atoms increases when the number of carbon atoms in the alkylene group is large, the number of carbon atoms (m2, m3, m4) in the alkylene group is preferably 3 or more.
- the content of the fluorine-containing ether compound of the general formula (1) contained in the non-aqueous electrolyte is not particularly limited, but the solvent constituting the non-aqueous electrolyte (the fluorine-containing compound represented by the formula (1)) 1 to 40% by volume is preferable.
- this content is 1% by volume or more, the withstand voltage can be increased, so that the gas generation suppressing effect is improved.
- the content is 40% by volume or less, the ionic conductivity of the nonaqueous electrolytic solution can be increased, so that the charge / discharge rate of the battery becomes better.
- the content is more preferably 2% by volume or more, further preferably 5% by volume or more, more preferably 30% by volume or less, and further preferably 20% by volume or less.
- Examples of the fluorine-containing ether compound represented by the general formula (1) include the following compounds: 2H-perfluoro-5-methyl-3,6-dioxanonane: CF 3 CHF—O— (CF 2 CF (CF 3 ) O) —C 3 F 7 ; 2H-perfluoro-5,8-dimethyl-3,6,9-trioxadodecane: CF 3 CHF—O— (CF 2 CF (CF 3 ) O) 2 —C 3 F 7 ; Perfluorodiglyme: CF 3 —O— (CF 2 CF 2 O) 2 —C 3 F 7 ; Perfluorotriglyme: CF 3 —O— (CF 2 CF 2 O) 3 —C 3 F 7 ; Is mentioned.
- n1 and n2 are preferably 2 or more, m1, m2 and m3 are preferably 4 or less, and particularly m2 is preferably 3 or 4.
- the compound represented by the formula (1) and further represented by the formula (2) is particularly 2H-perfluoro-5-methyl-3,6-dioxanonane (CF 3 CHF—O— (CF 2 CF (CF 3 ) O) —C 3 F 7 ), 2H-perfluoro-5,8-dimethyl-3,6,9-trioxadodecane (CF 3 CHF—O— (CF 2 CF (CF 3 ) O) 2 —C 3 F 7 ) preferable.
- the fluorine-containing ether compounds shown above can be used singly or in combination of two or more.
- the solvent component of the non-aqueous electrolyte it is preferable to further contain a fluorine-containing organic solvent such as a fluorine-containing phosphate compound.
- the content of the fluorine-containing organic solvent such as a fluorine-containing phosphate compound contained in the non-aqueous electrolyte is not particularly limited, but the solvent (shown by the formula (1)) constituting the non-aqueous electrolyte is not limited. 5% by volume or more, preferably 10% by volume or more, more preferably 20% by volume or more, more preferably 80% by volume or less, more preferably 70% by volume or less, and 60% by volume. % Or less is more preferable.
- a fluorine-containing organic solvent especially a fluorine-containing phosphate ester compound
- the oxidation resistance of the non-aqueous electrolyte can be increased, and the compatibility of the solvent components can be increased.
- a cyclic carbonate compound is further contained as a solvent component of the nonaqueous electrolytic solution. Since the cyclic carbonate compound has a large relative dielectric constant, the ion conductivity of the non-aqueous electrolyte can be increased by adding the cyclic carbonate compound.
- the content of the cyclic carbonate compound contained in the nonaqueous electrolytic solution is not particularly limited, but in the solvent (including the fluorine-containing ether compound represented by the formula (1)) constituting the nonaqueous electrolytic solution, 5 volume% or more is preferable, 10 volume% or more is more preferable, 20 volume% or more is more preferable, 60 volume% or less is preferable, 50 volume% or less is more preferable, and 40 volume% or less is further more preferable.
- the content of each of these components with respect to the total amount of the solvent containing them is preferably set as follows.
- the content of the cyclic carbonate compound is 5 to 60% by volume
- the content of the fluorine-containing organic solvent for example, fluorine-containing phosphate ester compound
- the content of the fluorine-containing ether compound represented by the formula (1) Is preferably set to 1 to 40% by volume
- the content of the cyclic carbonate compound is 10 to 60% by volume
- the content of the fluorine-containing organic solvent for example, a fluorine-containing phosphate ester compound
- the content of the fluorine-containing ether compound represented by the formula (1) is set to 5 to 30% by volume
- the content of the cyclic carbonate compound is 20 to 50% by volume
- the fluorine-containing organic solvent for example, The content of the fluorine-containing phosphate compound
- the content of the fluorine-containing ether compound represented by the formula (1) is 5 to 20 It can be set to the product%.
- the cyclic carbonate compound may be fluorinated. You may add the other solvent component mentioned later as needed.
- fluorine-containing organic solvent examples include a fluorine-containing phosphate compound, a fluorine-containing chain carbonate compound, and a fluorine-containing ether compound other than the fluorine-containing ether compound represented by the formula (1) (fluorine-containing chain ether compound, fluorine-containing compound).
- Cyclic ether compounds) and fluorine-containing carboxylic acid ester compounds fluorine-containing chain carboxylic acid ester compounds, fluorine-containing cyclic carboxylic acid ester compounds
- fluorine-containing phosphoric acid ester compounds are particularly preferred.
- solvent components include a chain carbonate compound, a chain ether compound, a cyclic ether compound, a chain carboxylic acid ester compound, a cyclic carboxylic acid ester compound, and a phosphoric acid ester compound that do not contain fluorine.
- the cyclic carbonate compound Since the cyclic carbonate compound has a large relative dielectric constant, the dissociation property of the supporting salt is improved and it becomes easy to obtain sufficient conductivity by containing it in the non-aqueous electrolyte. Furthermore, the viscosity of the non-aqueous electrolyte is lowered by using a cyclic carbonate compound in combination with other solvent components such as a chain carbonate compound (including fluorinated compounds), a fluorinated ether compound, and a fluorinated carboxylic acid ester compound. Therefore, the ion mobility in the non-aqueous electrolyte can be improved.
- cyclic carbonate compounds including fluorinated compounds, fluorinated chain carbonate compounds, fluorinated ether compounds, fluorinated carboxylic acid ester compounds, fluorinated carbonate compounds, and fluorine-containing phosphoric acid ester compounds have voltage resistance and electrical conductivity. Is high, it is suitable for combined use with the fluorine-containing ether compound represented by the general formula (1).
- a cyclic carbonate compound used as a solvent component of nonaqueous electrolyte For example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), or vinylene carbonate (VC And the like.
- the cyclic carbonate compound includes a fluorinated cyclic carbonate compound.
- the fluorinated cyclic carbonate compound for example, a compound in which some or all of hydrogen atoms such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), or vinylene carbonate (VC) are substituted with fluorine atoms. Etc.
- ethylene carbonate, propylene carbonate, or a compound obtained by fluorinating a part thereof is preferable from the viewpoint of voltage resistance and conductivity, and ethylene carbonate is more preferable.
- a cyclic carbonate compound can be used individually by 1 type or in combination of 2 or more types.
- the content of the cyclic carbonate compound is preferably 5 to 70% by volume in the solvent constituting the non-aqueous electrolyte from the viewpoint of increasing the degree of dissociation of the supporting salt and increasing the conductivity of the electrolytic solution. Volume% is more preferable, and 20 to 50 volume% is more preferable.
- the chain carbonate compound used as the solvent component of the non-aqueous electrolyte is not particularly limited, and examples thereof include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and dipropyl carbonate. (DPC).
- a fluorinated chain carbonate compound can be used as the chain carbonate compound.
- the fluorinated chain carbonate compound for example, a part or all of hydrogen atoms such as ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC) and the like are substituted with fluorine atoms. And the like.
- Examples thereof include bis (fluoroethyl) carbonate, 3-fluoropropyl methyl carbonate, and 3,3,3-trifluoropropyl methyl carbonate.
- dimethyl carbonate is preferable from the viewpoints of voltage resistance and conductivity.
- a chain carbonate compound can be used individually by 1 type or in combination of 2 or more types.
- the content of the chain carbonate compound is appropriately set in the range of 5 to 80% by volume in the solvent constituting the non-aqueous electrolyte from the viewpoints of reducing the viscosity of the non-aqueous electrolyte and increasing the dielectric constant. 10% by volume or more is more preferable from the viewpoint of obtaining a sufficient addition effect, 70% by volume or less is more preferable, and 60% by volume or less is more preferable from the viewpoint of obtaining a sufficient blending effect with another solvent.
- the carboxylic acid ester compound used as the solvent component of the non-aqueous electrolyte is not particularly limited.
- ethyl acetate, methyl propionate, ethyl formate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetate And methyl formate ethyl acetate, methyl propionate, ethyl formate, methyl butyrate, ethyl butyrate, methyl acetate And methyl formate.
- a fluorinated carboxylic acid ester can be used as the carboxylic acid ester compound.
- fluorinated carboxylic acid ester compound examples include ethyl acetate, methyl propionate, ethyl formate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetate, or part or all of hydrogen atoms of methyl formate replaced with fluorine atoms.
- the carboxylic acid ester compound has an effect of reducing the viscosity of the electrolytic solution, like the chain carbonate compound. Therefore, the carboxylic acid ester compound can be used in place of the chain carbonate compound, and can also be used in combination with the chain carbonate compound.
- the content of the carboxylic acid ester compound can be appropriately set in the range of 0.1 to 50% by volume in the solvent constituting the nonaqueous electrolytic solution, and is 0.2% by volume or more from the viewpoint of obtaining a sufficient addition effect. More preferably, it is more preferably 0.5% by volume or more, more preferably 20% by volume or less, and even more preferably 15% by volume or less from the viewpoint of obtaining a sufficient blending effect with other solvents.
- a carboxylic acid ester compound By including a carboxylic acid ester compound, the low temperature characteristics can be further improved, and the electrical conductivity can be further improved. Further, by suppressing the content of the carboxylic acid ester compound, it is possible to reduce an increase in vapor pressure when the battery is left at a high temperature.
- the chain ether compound used as the solvent component of the nonaqueous electrolytic solution is not particularly limited, and examples thereof include 1,2-ethoxyethane (DEE) and ethoxymethoxyethane (EME).
- DEE 1,2-ethoxyethane
- EME ethoxymethoxyethane
- a fluorinated chain ether compound obtained by substituting part of hydrogen of a chain ether compound with fluorine is suitable for a battery including a positive electrode that has high oxidation resistance and operates at a high potential.
- fluorinated chain ether compound examples include 2,2,3,3,3-pentafluoropropyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl 2, 2,2-trifluoroethyl ether, 1H, 1H, 2'H, 3H-decafluorodipropyl ether, 1,1,1,2,3,3-hexafluoropropyl-2,2-difluoroethyl ether, isopropyl 1,1,2,2-tetrafluoroethyl ether, propyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether 1H, 1H, 5H-perfluoropentyl-1,1,2,2-tetrafluoroethyl ether, 1H, 1H, 2′H-perfluorodip Pyrether, 1H
- the chain ether compound has an effect of reducing the viscosity of the electrolytic solution, like the chain carbonate compound. Therefore, for example, the chain ether compound can be used in place of the chain carbonate compound and the carboxylic acid ester compound, and can also be used in combination with the chain carbonate compound and the carboxylic acid ester compound.
- the content of the chain ether compound can be appropriately set in the range of 0.1 to 70% by volume in the solvent constituting the non-aqueous electrolyte, and is 0.2% by volume or more from the viewpoint of obtaining a sufficient addition effect. More preferably, it is more preferably 0.5% by volume or more, more preferably 60% by volume or less, and still more preferably 50% by volume or less from the viewpoint of obtaining a sufficient blending effect with another solvent.
- a chain ether compound By including a chain ether compound, the low temperature characteristics can be further improved, and the electrical conductivity can be further improved. Moreover, by suppressing the content of the chain ether compound, the compatibility of the electrolytic solution can be increased, and battery characteristics can be stably obtained.
- Examples of the phosphoric acid ester compound used as the solvent component of the non-aqueous electrolyte include trimethyl phosphate, triethyl phosphate, and tributyl phosphate.
- Examples of the fluorine-containing phosphate compound include 2,2,2-trifluoroethyldimethyl phosphate, bis (trifluoroethyl) methyl phosphate, bis (trifluoroethyl) ethyl phosphate, and trisphosphate (trifluoro).
- a fluorine-containing phosphate ester compound is preferable from the viewpoints of an inhibitory effect on electrolyte decomposition at a high potential, compatibility, and the like.
- O P (OR) 3 (In the formula, each R independently represents an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group, and at least one R is a fluoroalkyl group.)
- the fluorinated phosphate ester represented by is more preferable, and the following formula:
- O P (OCH 2 Ra) 3 (In the formula, Ra represents a fluoroalkyl group having 1 to 4 carbon atoms.)
- the fluorinated phosphate ester represented by is particularly preferable.
- the three Ras in the formula are preferably the same fluoroalkyl group.
- Ra in the formula preferably has 1 to 3 carbon atoms. Further, Ra preferably has at least one fluorine atom bonded to each carbon atom. Among these fluorine-containing phosphate ester compounds, tris phosphate (2,2,2-trifluoroethyl) is particularly preferable.
- the phosphoric acid ester compounds shown above can be used singly or in combination of two or more.
- the non-aqueous electrolyte may contain components other than those described above.
- examples of other components include ⁇ -lactones such as ⁇ -butyrolactone; cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran.
- aprotic organic solvents such as -2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethyl ether, 1,3-propane sultone, anisole, and N-methylpyrrolidone.
- the total content of the cyclic carbonate, the fluorine-containing organic solvent and the fluorine-containing ether compound represented by the formula (1) in the entire solvent is preferably 80% by volume or more, and more preferably 90% by volume or more.
- Examples of the supporting salt contained in the non-aqueous electrolyte include LiPF 6 , LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiB 10 Cl 10 and other lithium salts.
- Other supporting salts include lithium, lower aliphatic carboxylates, lithium chloroborane, lithium tetraphenylborate, LiBr, LiI, LiSCN, LiCl.
- the supporting salt can be used alone or in combination of two or more.
- An ion conductive polymer can be added to the non-aqueous electrolyte.
- the ion conductive polymer include polyethers such as polyethylene oxide and polypropylene oxide; polyolefins such as polyethylene and polypropylene; and polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl fluoride, polyvinyl chloride, Vinylidene chloride, polymethyl methacrylate, polymethyl acrylate, polyvinyl alcohol, polymethacrylonitrile, polyvinyl acetate, polyvinyl pyrrolidone, polycarbonate, polyethylene terephthalate, polyhexamethylene adipamide, polycaprolactam, polyurethane, polyethyleneimine, polybutadiene, polystyrene, or Mention may be made of polyisoprene or derivatives thereof.
- An ion conductive polymer can be used individually by 1 type or in combination of 2 or more types. Moreover, you may use
- the positive electrode of the lithium secondary battery according to the present embodiment includes a positive electrode active material that can occlude or release lithium ions at a potential of 4.5 V or more with respect to lithium metal from the viewpoint of obtaining a high energy density.
- this positive electrode active material a material having at least a part of the charge / discharge curve at least partially having a region of 4.5 V or more with respect to lithium metal can be used. That is, an active material having at least a region of 4.5 V or more with respect to lithium metal only in the charging curve, or at least a region of 4.5 V or more with respect to lithium metal in both the charging curve and discharging curve Can be used.
- the charge / discharge current can be set to 5 mA / g per mass of the positive electrode active material, the charge end voltage can be set to 5.2V, and the discharge end voltage can be set to 3V.
- positive electrode active materials examples include spinel materials, layered materials, and olivine materials.
- spinel materials include LiNi 0.5 Mn 1.5 O 4 , LiCoMnO 4 , LiCrMnO 4 , LiFeMnO 4 , LiCu 0.5 Mn 1.5 O 4, and the like that operate at a high potential of 4.5 V or higher; LiMn 2 O 4 LiM1 x Mn 2 -xy M2 y O 4 (M1 is at least one selected from Ni, Fe, Co, Cr, and Cu; 4 ⁇ x ⁇ 1.1, M2 is at least one selected from Li, Al, B, Mg, Si, and transition metals, 0 ⁇ y ⁇ 0.5); and one of oxygen in these materials And those in which the part is substituted with fluorine or chlorine.
- the spinel material a material represented by the following formula is particularly preferable.
- the layered material is represented by the general formula LiMO 2 , specifically, LiCoO 2 , LiNi 1-x M x O 2 (M is an element containing at least Co or Al, 0.05 ⁇ x ⁇ 0.3).
- Li (Ni x Co y Mn 2-xy) O 2 material expressed by (0.1 ⁇ x ⁇ 0.7,0 ⁇ y ⁇ 0.5) can be mentioned.
- Li (Li x M 1 -xz Mn z ) O 2 (0 ⁇ x ⁇ 0.3, 0.3 ⁇ ) can be obtained by charging lithium at a high potential of 4.5 V or higher.
- z ⁇ 0.7, M is at least one of Co and Ni), and this material is particularly preferable.
- X in the formula of this material is preferably 0 ⁇ x ⁇ 0.2.
- the olivine-based material is represented by a general formula LiMPO 4 , and specific examples include LiFePO 4 , LiMnPO 4 , LiCoPO 4 , and LiNiPO 4 . Those in which a part of these transition metals is replaced with another element or the oxygen part is replaced with fluorine can also be used. From the viewpoint of high energy density, a material represented by LiMPO 4 (M is at least one of Co and Ni) operating at a high potential is preferable.
- NASICON type lithium transition metal silicon composite oxide, and the like can be used.
- the positive electrode active material that operates at the above high potential may be used in combination with other normal positive electrode active materials, but the content of the above positive electrode active material that operates at a high potential in the entire positive electrode active material is 60% by mass or more. Is preferable, 80 mass% or more is more preferable, and 90 mass% or more is further preferable.
- the specific surface areas of the positive electrode active material is, for example, 0.01 ⁇ 5m 2 / g, preferably 0.05 ⁇ 4m 2 / g, more preferably 0.1 ⁇ 3m 2 / g, 0.2 ⁇ 2m 2 / g is more preferable.
- the contact area with the electrolytic solution can be adjusted to an appropriate range. That is, by setting the specific surface area to 0.01 m 2 / g or more, lithium ions can be easily inserted and desorbed smoothly, and the resistance can be further reduced.
- the specific surface area can be measured by a usual BET specific surface area measurement method.
- the center particle size of the positive electrode active material is preferably 0.01 to 50 ⁇ m, more preferably 0.02 to 40 ⁇ m. By setting the particle size to 0.02 ⁇ m or more, elution of constituent elements of the positive electrode active material can be further suppressed, and deterioration due to contact with the electrolytic solution can be further suppressed. In addition, when the particle size is 50 ⁇ m or less, lithium ions can be easily inserted and desorbed smoothly, and the resistance can be further reduced.
- the center particle diameter is 50% cumulative diameter D 50 (median diameter), and can be measured by a laser diffraction / scattering particle size distribution analyzer.
- the same negative electrode binder can be used.
- polyvinylidene fluoride is preferable from the viewpoint of versatility and low cost.
- 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 positive electrode active material from the viewpoints of binding force and energy density which are in a trade-off relationship.
- binders other than polyvinylidene fluoride (PVdF) vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, polytetrafluoroethylene, polypropylene,
- PVdF polyvinylidene fluoride
- Examples include polyethylene, polyimide, and polyamideimide.
- the positive electrode current collector for example, aluminum, nickel, silver, stainless steel (SUS), valve metal, or an alloy thereof can be used from the viewpoint of electrochemical stability.
- the shape include foil, flat plate, and mesh.
- an aluminum foil can be suitably used.
- a conductive auxiliary material may be added for the purpose of reducing impedance.
- the conductive auxiliary material include carbonaceous fine particles such as graphite, carbon black, and acetylene black.
- a slurry containing a positive electrode active material, a binder, and a solvent (and a conductive auxiliary material if necessary) is prepared, applied to the positive electrode current collector, dried, and pressurized as necessary.
- a positive electrode active material layer can be formed on the positive electrode current collector.
- a negative electrode will not be specifically limited if the negative electrode active material contains the material which can occlude and discharge
- the negative electrode active material is not particularly limited as long as it is a material capable of reversibly occluding and releasing lithium ions (a material capable of occluding and releasing lithium ions during charging and discharging during discharging).
- a material capable of occluding and releasing lithium ions during charging and discharging during discharging.
- carbon capable of occluding and releasing lithium ions examples thereof include a material (a), a metal (b) that can be alloyed with lithium, and a metal oxide (c) that can occlude and release lithium ions.
- carbon material (a) graphite, amorphous carbon, diamond-like carbon, carbon nanotube, or a composite thereof can be used.
- Highly crystalline graphite has high electrical conductivity, and excellent adhesion to a positive electrode current collector made of a metal such as copper and voltage flatness.
- 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 carbon material (a) can be used alone or in combination with other active materials, but when used in combination with other active materials, the content thereof ranges from 2% by mass to 80% by mass in the negative electrode active material. And can be set as appropriate, preferably in the range of 2% by mass to 30% by mass.
- the metal (b) Al, Si, Pb, Sn, Zn, Cd, Sb, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, La, or an alloy containing two or more thereof.
- an alloy of these metals or alloys and lithium can be used.
- silicon (Si) or a silicon-containing metal is preferable as the metal (b).
- the metal (b) can be used alone or in combination with other active materials, but when used in combination with other active materials, the content thereof is in the range of 5% by mass to 90% by mass in the negative electrode active material. It can set suitably, Preferably it can set in the range of 20 to 50 mass%.
- silicon oxide aluminum oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, or a composite containing two or more of these can be used.
- silicon oxide is preferably included as the metal oxide (c). This is because silicon oxide is relatively stable and hardly causes a reaction with other compounds.
- one or more elements selected from nitrogen, boron, and sulfur may be added to the metal oxide (c), for example, 0.1 to 5% by mass. By carrying out like this, the electrical conductivity of a metal oxide (c) can be improved.
- the metal oxide (c) can be used alone or in combination with other active materials, but when used in combination with other active materials, the content thereof is 5% by mass or more and 90% by mass or less in the negative electrode active material. It can set suitably in the range, Preferably it can set in the range of 40 to 70 mass%.
- metal oxide (c) examples include LiFe 2 O 3 , WO 2 , MoO 2 , SiO, SiO 2 , CuO, SnO, SnO 2 , Nb 3 O 5 , Li x Ti 2-x O 4 (1 ⁇ x ⁇ 4/3), PbO 2 , Pb 2 O 5 .
- Examples of other negative electrode active materials include metal sulfide (d) capable of occluding and releasing lithium ions.
- Examples of the metal sulfide (d) include SnS and FeS 2 .
- Other examples of the negative electrode active material include metallic lithium or lithium alloy, polyacene or polythiophene, or Li 5 (Li 3 N), Li 7 MnN 4 , Li 3 FeN 2 , Li 2.5 Co 0.5 N, or Li 3 Lithium nitride such as CoN can be mentioned.
- These negative electrode active materials can be used alone or in admixture of two or more.
- the carbon material (a), the metal (b), and the metal oxide (c) may be included.
- this negative electrode active material will be described.
- the amorphous metal oxide (c) can suppress the volume expansion of the carbon material (a) and the metal (b), and can suppress the decomposition of the electrolytic solution. This mechanism is presumed to have some influence on the film formation at the interface between the carbon material (a) and the electrolytic solution because the metal oxide (c) has an amorphous structure.
- the amorphous structure is considered to have relatively few elements due to non-uniformity such as crystal grain boundaries and defects.
- the metal oxide (c) does not have an amorphous structure, a peak specific to the metal oxide (c) is observed, but all or part of the metal oxide (c) is amorphous. In the case of having a structure, the intrinsic peak of the metal oxide (c) is broad and observed.
- the metal oxide (c) is preferably a metal oxide constituting the metal (b).
- the metal (b) and the metal oxide (c) are preferably silicon (Si) and silicon oxide (SiO), respectively.
- the metal (b) is preferably dispersed entirely or partially in the metal oxide (c).
- the metal (b) is preferably dispersed entirely or partially in the metal oxide (c).
- the volume expansion of the whole negative electrode can be further suppressed, and the decomposition of the electrolytic solution can also be suppressed.
- all or part of the metal (b) is dispersed in the metal oxide (c) because it is observed with a transmission electron microscope (general TEM observation) and energy dispersive X-ray spectroscopy (general). This can be confirmed by using a combination of a standard EDX measurement. Specifically, the cross section of a sample containing metal (b) particles is observed, the oxygen concentration of the particles dispersed in the metal oxide (c) is measured, and the metal constituting the particles is an oxide. It can be confirmed that it is not.
- each carbon material (a), metal (b), and metal oxide (c) with respect to the total of the carbon material (a), metal (b), and metal oxide (c) is as follows: It is preferable to set. 2 mass% or more and 80 mass% or less are preferable, and, as for content of a carbon material (a), 2 mass% or more and 30 mass% or less are more preferable. 5 mass% or more and 90 mass% or less are preferable, and, as for content of a metal (b), 20 mass% or more and 50 mass% or less are more preferable. 5 mass% or more and 90 mass% or less are preferable, and, as for content of a metal oxide (c), 40 mass% or more and 70 mass% or less are more preferable.
- a negative electrode active material in which all or part of the metal oxide (c) has an amorphous structure and all or part of the metal (b) is dispersed in the metal oxide (c) is disclosed in, for example, It can be produced by the method disclosed in Japanese Patent No. 47404.
- the metal oxide (c) is disproportionated at 900 to 1400 ° C. in an atmosphere containing an organic compound gas such as methane gas, and a thermal CVD process is performed.
- the metal element in metal oxide (c) can be nanoclustered as metal (b), and the composite body by which the surface was coat
- the negative electrode active material can be produced by mixing the carbon material (a), the metal (b), and the metal oxide (c) by mechanical milling.
- the carbon material (a), metal (b), and metal oxide (c) are not particularly limited, but particulate materials can be used.
- the average particle size of the metal (b) is preferably smaller than the average particle size of the carbon material (a) and the average particle size of the metal oxide (c). In this way, the metal (b) having a large volume change during charging and discharging has a relatively small particle size, and the carbon material (a) and the metal oxide (c) having a small volume change have a relatively large particle size.
- the average particle diameter of the metal (b) can be, for example, 20 ⁇ m or less, and is preferably 15 ⁇ m or less.
- the average particle diameter is a 50% cumulative diameter D 50 (median diameter) obtained by particle size distribution measurement by a laser diffraction scattering method.
- the average particle diameter of a metal oxide (c) is 1/2 or less of the average particle diameter of a carbon material (a), and the average particle diameter of a metal (b) is an average of a metal oxide (c). It is preferable that it is 1/2 or less of a particle diameter. Furthermore, the average particle diameter of the metal oxide (c) is 1 ⁇ 2 or less of the average particle diameter of the carbon material (a), and the average particle diameter of the metal (b) is the average particle diameter of the metal oxide (c). It is more preferable that it is 1/2 or less.
- the average particle diameter of the silicon oxide (c) is set to 1/2 or less of the average particle diameter of the graphite (a), and the average particle diameter of the silicon (b) is the average particle of the silicon oxide (c). It is preferable to make it 1/2 or less of the diameter.
- the average particle diameter of silicon (b) 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, but polyvinylidene fluoride (PVdF), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer.
- PVdF polyvinylidene fluoride
- Examples thereof include polymer rubber, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, and polyamideimide.
- the content of the negative electrode binder is preferably in the range of 1 to 30% by mass and more preferably 2 to 25% by mass with respect to the total amount of the negative electrode active material and the negative electrode binder.
- the content is preferably in the range of 1 to 30% by mass and more preferably 2 to 25% by mass with respect to the total amount of the negative electrode active material and the negative electrode binder.
- the negative electrode current collector is not particularly limited, but aluminum, nickel, copper, silver, and an alloy containing two or more of these are preferable from the viewpoint of electrochemical stability.
- Examples of the shape include foil, flat plate, and mesh.
- the negative electrode can be produced by forming a negative electrode active material layer containing a negative electrode active material and a negative electrode binder on a negative electrode current collector.
- the negative electrode active material layer can be formed by a general slurry coating method. Specifically, a negative electrode can be obtained by preparing a slurry containing a negative electrode active material, a binder, and a solvent, applying the slurry onto a negative electrode current collector, drying, and pressing as necessary. . Examples of the method for applying the negative electrode slurry include a doctor blade method, a die coater method, and a dip coating method. After the negative electrode active material layer is formed in advance, a negative electrode can be obtained by forming a thin film of aluminum, nickel, or an alloy thereof as a current collector by a method such as vapor deposition or sputtering.
- separator examples of the separator provided between the positive electrode and the negative electrode include a porous polymer film, a woven fabric, a nonwoven fabric, or an ion conductive polymer electrolyte made of a polyolefin such as polyethylene or polypropylene, a fluorine resin such as polyimide or polyvinylidene fluoride, and the like.
- a membrane is mentioned. These can be used alone or in combination.
- Examples of the shape of the battery include a cylindrical shape, a square shape, a coin shape, a button shape, and a laminate shape.
- the electrodes and the separator are laminated in a planar shape, and there is no portion with a small R (region close to the winding core of the wound structure or region corresponding to the folded portion of the flat wound structure). Therefore, when an active material having a large volume change associated with charging / discharging is used, it is less likely to be adversely affected by the volume change of the electrode associated with charging / discharging than a battery having a wound structure.
- the battery outer package examples include stainless steel, iron, aluminum, titanium, alloys thereof, and plated products thereof.
- the plating for example, nickel plating can be used.
- a laminate film is preferable as the outer package.
- Examples of the metal foil layer on the resin base layer of the laminate film include aluminum, aluminum alloy, and titanium foil.
- Examples of the material for the heat-welded layer of the laminate film include thermoplastic polymer materials such as polyethylene, polypropylene, and polyethylene terephthalate.
- the resin base material layer and the metal foil layer of the laminate film are not limited to one layer, but may be two or more layers. From the viewpoint of versatility and cost, an aluminum laminate film is preferable.
- the lithium secondary battery according to the present embodiment includes a positive electrode current collector 3 made of a metal such as an aluminum foil, and a positive electrode active material layer 1 containing a positive electrode active material provided thereon. And a negative electrode current collector 4 made of a metal such as copper foil and a negative electrode active material layer 2 containing a negative electrode active material provided thereon.
- the positive electrode and the negative electrode are laminated via a separator 5 made of a nonwoven fabric or a polypropylene microporous film so that the positive electrode active material layer 1 and the negative electrode active material layer 2 face each other.
- This electrode pair is accommodated in a container formed of exterior bodies 6 and 7 such as an aluminum laminate film.
- a positive electrode tab 9 is connected to the positive electrode current collector 3, and a negative electrode tab 8 is connected to the negative electrode current collector 4, and these tabs are drawn out of the container.
- An electrolytic solution is injected into the container and sealed. It can also be set as the structure where the electrode group by which the several electrode pair was laminated
- a secondary battery having the structure shown in FIG. 1 according to the following examples and comparative examples was produced and evaluated.
- Example 1 LiNi 0.5 Mn 1.5 O 4 (90 parts by mass) as a positive electrode active material, polyvinylidene fluoride (5 parts by mass) as a binder, and carbon black (5 parts by mass) as a conductive agent are mixed to form a positive electrode A mixture was prepared. This positive electrode mixture was dispersed in N-methyl-2-pyrrolidone to prepare a positive electrode slurry. This positive electrode slurry was uniformly applied to one side of an aluminum current collector having a thickness of 20 ⁇ m. The thickness of the coating film was adjusted so that the initial charge capacity per unit area was 2.5 mAh / cm 2 . After drying, compression molding was performed with a roll press to obtain a positive electrode.
- Artificial graphite was used as the negative electrode active material. This artificial graphite was dispersed in a solution of PVDF dissolved in N-methylpyrrolidone to prepare a negative electrode slurry. The mass ratio of the negative electrode active material to the binder was 90/10 (active material / binder). This negative electrode slurry was uniformly coated on a 10 ⁇ m thick Cu current collector. The thickness of the coating film was adjusted so that the initial charge capacity was 3.0 mAh / cm 2 . After drying, compression molding was performed with a roll press to obtain a negative electrode.
- the positive electrode and the negative electrode cut out to 3 cm ⁇ 3 cm were laminated so as to face each other with a separator interposed therebetween.
- a separator a microporous polypropylene film having a thickness of 25 ⁇ m was used.
- EC ethylene carbonate
- TTFEP tris (2,2,2-trifluoroethyl) phosphate
- 2H— a fluorine-containing ether compound
- EC ethylene carbonate
- TTFEP tris (2,2,2-trifluoroethyl) phosphate
- 2H— a fluorine-containing ether compound
- the electrode pair with the separator interposed therebetween was covered with an aluminum laminate film, and a nonaqueous electrolyte was injected and sealed to obtain a lithium secondary battery.
- tabs were connected to the positive electrode and the negative electrode, and were electrically connected to the outside of the outer container made of an aluminum laminate film.
- volume (initial volume) was measured before charge and discharge.
- the volume was measured by the Archimedes method.
- the volume increase rate was calculated according to the following formula.
- Volume increase rate (%) 100 ⁇ (volume after charge / discharge ⁇ initial volume) / initial volume.
- This lithium secondary battery was charged at 20 mA, and after the upper limit voltage reached 4.8 V, it was charged at a constant voltage until the total charging time reached 2.5 hours. Thereafter, the battery was discharged at a constant current at 20 mA until the lower limit voltage was 3V. This charging / discharging was repeated 50 times. This charging / discharging was implemented in a 45 degreeC thermostat. When 50 cycles of charging and discharging were performed, the volume of the lithium secondary battery was measured by the same method as that before charging and discharging. The measurement results are shown in Table 1.
- Example 2 As a fluorine-containing ether compound, instead of ET7, 2H-perfluoro-5,8-dimethyl-3,6,9-trioxadodecane (CF 3 CHF—O— (CF 2 CF (CF 3 ) O) 2 — A lithium secondary battery was produced in the same manner as in Example 1 except that C 3 F 7 (hereinafter referred to as “ET8”) was used, and its volume was measured. The measurement results are shown in Table 1.
- Example 1 A lithium secondary battery was produced in the same manner as in Example 1 except that the following mixed solvent containing no fluorine-containing ether compound and TTFEP was used instead of the mixed solvent used in Example 1, and the volume was measured. Went. The measurement results are shown in Table 1. Composition of mixed solvent: EC and diethyl carbonate (DEC) were mixed at a volume ratio of 3/7 (EC / DEC).
- Example 1 A lithium secondary battery was produced in the same manner as in Example 1 except that the following mixed solvent not containing a fluorine-containing ether compound was used instead of the mixed solvent used in Example 1, and the volume was measured. It was. The measurement results are shown in Table 1. Composition of mixed solvent: EC and TTFEP were mixed at a volume ratio of 3/7 (EC / TTFEP).
- Example 3 A lithium secondary battery was produced in the same manner as in Example 1 except that the following mixed solvent not containing a fluorine-containing ether compound was used instead of the mixed solvent used in Example 1, and the volume was measured. It was. The measurement results are shown in Table 1.
- Composition of mixed solvent: EC, TTFEP and diethylene glycol dimethyl ether (hereinafter referred to as “ET2”) were mixed at a volume ratio of 3/6/1 (EC / TTFEP / ET2).
- Example 4 A lithium secondary battery was produced in the same manner as in Example 1 except that the following mixed solvent not containing a fluorine-containing ether compound was used instead of the mixed solvent used in Example 1, and the volume was measured. It was. The measurement results are shown in Table 1.
- Composition of mixed solvent: EC, TTFEP and triethylene glycol dimethyl ether (hereinafter referred to as “ET3”) were mixed at a volume ratio of 3/6/1 (EC / TTFEP / ET3).
- Example 5 A lithium secondary battery was produced in the same manner as in Example 1 except that the following mixed solvent not containing a fluorine-containing ether compound was used instead of the mixed solvent used in Example 1, and the volume was measured. It was. The measurement results are shown in Table 1.
- Composition of mixed solvent EC, TTFEP and n-butyl-1,1,2,2-tetrafluoroethyl ether (hereinafter referred to as “ET4”) mixed at a volume ratio of 3/6/1 (EC / TTFEP / ET4) .
- Example 6 A lithium secondary battery was produced in the same manner as in Example 1 except that the following mixed solvent not containing a fluorine-containing ether compound was used instead of the mixed solvent used in Example 1, and the volume was measured. It was. The measurement results are shown in Table 1.
- Composition of mixed solvent: EC, TTFEP and methyl-1H, 1H-heptafluorobutyl ether (hereinafter referred to as “ET5”) were mixed at a volume ratio of 3/6/1 (EC / TTFEP / ET5).
- Example 7 A lithium secondary battery was produced in the same manner as in Example 1 except that the following mixed solvent not containing a fluorine-containing ether compound was used instead of the mixed solvent used in Example 1, and the volume was measured. It was. The measurement results are shown in Table 1.
- Composition of mixed solvent: EC, TTFEP and fluoromethyl-2,2,3,3-tetrafluoropropyl ether (hereinafter referred to as “ET6”) were mixed at a volume ratio of 3/6/1 (EC / TTFEP / ET6).
- Example 3 A lithium secondary battery was produced in the same manner as in Example 1 except that Li (Li 0.15 Ni 0.2 Co 0.1 Mn 0.55 ) O 2 was used as the positive electrode active material, and its volume was measured. The measurement results are shown in Table 2.
- Example 4 A lithium secondary battery was produced in the same manner as in Example 1 except that LiCoPO 4 was used as the positive electrode active material and the charging voltage (upper limit voltage) was 5.0 V, and the volume was measured. The measurement results are shown in Table 2.
- Example 8 A lithium secondary battery was produced in the same manner as in Example 3 except that the following mixed solvent containing no fluorine-containing ether compound was used instead of the mixed solvent used in Example 3, and the volume was measured. It was. The measurement results are shown in Table 2. Composition of mixed solvent: EC and TTFEP were mixed at a volume ratio of 3/7 (EC / TTFEP).
- Example 9 A lithium secondary battery was produced in the same manner as in Example 4 except that the following mixed solvent containing no fluorine-containing ether compound was used instead of the mixed solvent used in Example 4, and the volume was measured. It was. The measurement results are shown in Table 2. Composition of mixed solvent: EC and TTFEP were mixed at a volume ratio of 3/7 (EC / TTFEP).
- Example 2 the charge / discharge characteristics in a low temperature environment (0 ° C.) were evaluated.
- Charging was performed at a current value of 20 mA, and after reaching the upper limit voltage of 4.8 V, charging was performed by controlling the current value with a constant voltage until the total charging time reached 10 hours. Thereafter, the battery was discharged at a constant current until the lower limit voltage was 3 V at 20 mA, left for 5 minutes (the voltage increased when left), and discharged at a constant current until the lower limit voltage was 3 V at 4 mA.
- the ratio (CH) of the capacity value (CH) at the time of discharge at 20 mA to the sum (CT) of the capacity value (CH) at the time of discharge at 20 mA and the capacity value (CL) at the time of discharge at 4 mA at this time (CH) / CT) was evaluated as a discharge capacity ratio (%). The results are shown in Table 3.
- the amount of gas generated inside the battery can be reduced even when operated at a high voltage (around 5 V) in a high temperature environment (about 45 ° C.). Therefore, according to this embodiment, it is possible to provide a high energy density lithium secondary battery having excellent life characteristics. In addition, the operating characteristics of the lithium secondary battery at low temperatures can be improved.
- Laminated batteries that are packaged and sealed with an aluminum laminate film have the advantage of being lightweight. However, when gas is generated inside the battery, external deformation such as swelling is likely to occur, and the internal electrode laminate structure also has an adverse effect. There is an easy problem. According to the present embodiment, since gas generation can be suppressed, it is particularly effective for a laminate-type battery covered with a laminate film.
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Abstract
Description
前記正極活物質は、4.5V以上の電位でリチウムイオンを吸蔵又は放出可能な活物質を含み、
前記非水電解液は、下記一般式(1):
2H-パーフルオロ-5-メチル-3,6-ジオキサノナン:
CF3CHF-O-(CF2CF(CF3)O)-C3F7;
2H-パーフルオロ-5,8-ジメチル-3,6,9-トリオキサドデカン:
CF3CHF-O-(CF2CF(CF3)O)2-C3F7;
パーフルオロジグライム:
CF3-O-(CF2CF2O)2-C3F7;
パーフルオロトリグライム:
CF3-O-(CF2CF2O)3-C3F7;
が挙げられる。
で表される化合物が好ましい。式(2)において、n1及びn2は2以上が好ましく、m1、m2及びm3は4以下が好ましく、特にm2は3又は4であることが好ましい。式(1)さらに式(2)で表される化合物として、特に2H-パーフルオロ-5-メチル-3,6-ジオキサノナン(CF3CHF-O-(CF2CF(CF3)O)-C3F7)、2H-パーフルオロ-5,8-ジメチル-3,6,9-トリオキサドデカン(CF3CHF-O-(CF2CF(CF3)O)2-C3F7)が好ましい。
O=P(OR)3
(式中、Rはそれぞれ独立に炭素数1~5のアルキル基又はフルオロアルキル基を示し、少なくとも一つのRがフルオロアルキル基である。)
で示されるフッ素化リン酸エステルがより好ましく、さらに下記式:
O=P(OCH2Ra)3
(式中、Raは炭素数1~4のフルオロアルキル基を示す。)
で示されるフッ素化リン酸エステルが特に好ましい。式中の三つのRaは同じフルオロアルキル基であることが好ましい。式中のRaは炭素数が1~3であることが好ましい。またRaは、各炭素原子にフッ素原子が少なくとも一つ結合していることが好ましい。これらのフッ素含有リン酸エステル化合物の中でもリン酸トリス(2,2,2-トリフルオロエチル)が特に好ましい。
本実施形態によるリチウム二次電池の正極は、高エネルギー密度を得る観点から、リチウム金属に対して4.5V以上の電位でリチウムイオンを吸蔵又は放出可能な正極活物質を含む。
(式中、0≦x≦1.2、0≦y、x+y<2、0≦a≦1.2、0≦w≦1であり、MはCo、Ni、Fe、Cr、Cuから選ばれる少なくとも一種であり、YはLi、B、Na、Al、Mg、Ti、Si、K、Caから選ばれる少なくとも一種であり、ZはF及びClの少なくとも一方である。)
負極は、負極活物質として、リチウムを吸蔵及び放出し得る材料を含むものであれば特に限定されない。
正極と負極との間に設けられるセパレータとしては、例えば、ポリエチレンやポリプロピレンなどのポリオレフィン、ポリイミド、ポリフッ化ビニリデン等のフッ素樹脂等からなる多孔質ポリマー膜や織布、不織布、あるいはイオン伝導性ポリマー電解質膜が挙げられる。これらは単独または組み合わせで使用することができる。
電池の形状としては、例えば、円筒形、角形、コイン型、ボタン型、ラミネート型が挙げられる。
本実施形態によるラミネート型のリチウム二次電池の断面図を図1に示す。図1に示すように、本実施形態によるリチウム二次電池は、アルミニウム箔等の金属からなる正極集電体3と、その上に設けられた正極活物質を含有する正極活物質層1とからなる正極、及び銅箔等の金属からなる負極集電体4と、その上に設けられた負極活物質を含有する負極活物質層2とからなる負極を有する。正極および負極は、正極活物質層1と負極活物質層2とが対向するように、不織布やポリプロピレン微多孔膜などからなるセパレータ5を介して積層されている。この電極対は、アルミニウムラミネートフィルム等の外装体6、7で形成された容器内に収容されている。正極集電体3には正極タブ9が接続けられ、負極集電体4には負極タブ8が接続され、これらのタブは容器の外に引き出されている。容器内には電解液が注入され封止される。複数の電極対が積層された電極群が容器内に収容された構造とすることもできる。
正極活物質としてのLiNi0.5Mn1.5O4(90質量部)と、結着剤としてのポリフッ化ビニリデン(5質量部)と、導電剤としてカーボンブラック(5質量部)と、を混合して正極合剤を調製した。この正極合剤をN-メチル-2-ピロリドンに分散させることにより、正極用スラリーを調製した。この正極用スラリーを厚さ20μmのアルミニウム製集電体の片面に、均一に塗布した。単位面積当たりの初回充電容量が2.5mAh/cm2となるように塗布膜の厚さを調整した。乾燥させた後、ロールプレスで圧縮成形して正極を得た。
フッ素含有エーテル化合物として、ET7に代えて、2H-パーフルオロ-5,8-ジメチル-3,6,9-トリオキサドデカン(CF3CHF-O-(CF2CF(CF3)O)2-C3F7、以下「ET8」という)を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物およびTTFEPを含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとジエチルカーボネート(DEC)を3/7の体積比(EC/DEC)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPを3/7の体積比(EC/TTFEP)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとジプロピルエーテル(以下「ET1」という)を3/6/1の体積比(EC/TTFEP/ET1)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとジエチレングリコールジメチルエーテル(以下「ET2」という)を3/6/1の体積比(EC/TTFEP/ET2)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとトリエチレングリコールジメチルエーテル(以下「ET3」という)を3/6/1の体積比(EC/TTFEP/ET3)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとn-ブチル-1,1,2,2-テトラフルオロエチルエーテル(以下「ET4」という)を3/6/1の体積比(EC/TTFEP/ET4)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとメチル-1H,1H-ヘプタフルオロブチルエーテル(以下「ET5」という)を3/6/1の体積比(EC/TTFEP/ET5)で混合。
実施例1で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表1に示す。
混合溶媒の組成:ECとTTFEPとフルオロメチル-2,2,3,3-テトラフルオロプロピルエーテル(以下「ET6」という)を3/6/1の体積比(EC/TTFEP/ET6)で混合。
正極活物質として、Li(Li0.15Ni0.2Co0.1Mn0.55)O2を用いた以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表2に示す。
正極活物質として、LiCoPO4を用い、充電電圧(上限電圧)を5.0Vにした以外は、実施例1と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表2に示す。
実施例3で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例3と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表2に示す。
混合溶媒の組成:ECとTTFEPを3/7の体積比(EC/TTFEP)で混合。
実施例4で用いた混合溶媒に代えて、フッ素含有エーテル化合物を含まない以下の混合溶媒を用いた以外は、実施例4と同様にしてリチウム二次電池を作製し、その体積の測定を行った。測定結果を表2に示す。
混合溶媒の組成:ECとTTFEPを3/7の体積比(EC/TTFEP)で混合。
2 負極活物質層
3 正極集電体
4 負極集電体
5 セパレータ
6 ラミネート外装体
7 ラミネート外装体
8 負極タブ
9 正極タブ
Claims (16)
- 一般式(1)において、n1~n5は2以上である、請求項1に記載のリチウム二次電池。
- 一般式(1)において、n2=2m2、n3=2m3、n4=2m4である、請求項1に記載のリチウム二次電池。
- 一般式(1)において、m2、m3、m4は3以上である、請求項3に記載のリチウム二次電池。
- 一般式(1)において、1≦p+q+r≦2を満たす、請求項1から4のいずれか一項に記載のリチウム二次電池。
- 前記フッ素含有エーテル化合物は、
CF3CHF-O-(CF2CF(CF3)O)-C3F7及び
CF3CHF-O-(CF2CF(CF3)O)2-C3F7
の少なくとも一方である、請求項1に記載のリチウム二次電池。 - 前記非水電解液の溶媒(前記フッ素含有エーテル化合物を含む)中の前記フッ素含有エーテル化合物の含有量は、1体積%以上40体積%以下の範囲にある、請求項1から6のいずれか一項に記載のリチウム二次電池。
- 前記非水電解液は、溶媒成分としてフッ素含有リン酸エステル化合物を含有する、請求項1から7のいずれか一項に記載のリチウム二次電池。
- 前記非水電解液の溶媒(前記フッ素含有エーテル化合物を含む)中の前記フッ素含有リン酸エステル化合物の含有量は、5体積%以上80体積%以下の範囲にある、請求項8に記載のリチウム二次電池。
- 前記フッ素含有リン酸エステル化合物は、下記式:
O=P(OR)3
(式中、Rはそれぞれ独立に炭素数1~5のアルキル基又はフルオロアルキル基を示し、少なくとも一つのRがフルオロアルキル基である。)
で示される化合物である、請求項8又は9に記載のリチウム二次電池。 - 前記非水電解液は、溶媒成分として環状カーボネート化合物を含有する、請求項1から10のいずれか一項に記載のリチウム二次電池。
- 前記非水電解液の溶媒(前記フッ素含有エーテル化合物を含む)中の前記環状カーボネート化合物の含有量は、5体積%以上60体積%以下の範囲にある、請求項11に記載のリチウム二次電池。
- 前記非水電解液は、さらにフッ素含有有機溶媒及び環状カーボネート化合物を含有する、請求項1から7のいずれか一項に記載のリチウム二次電池。
- 前記フッ素含有有機溶媒は、フッ素含有リン酸エステル化合物、フッ素含有鎖状カーボネート化合物、フッ素含有エーテル化合物、フッ素含有カルボン酸エステル化合物から選ばれる、請求項13に記載のリチウム二次電池。
- セパレータを含み、該セパレータを介して前記正極と前記負極が対向配置され、これらを内包するラミネートフィルム外装体を含む、請求項1から14のいずれか一項に記載のリチウム二次電池。
- 前記正極活物質は、4.5V以上の電位でリチウムイオンを吸蔵又は放出可能な前記活物質として、下記式(3)、(4)及び(5)のいずれかで表される活物質を含む、請求項1から15のいずれか一項に記載のリチウム二次電池。
Lia(MxMn2-x-yYy)(O4-wZw) (3)
(式中、0≦x≦1.2、0≦y、x+y<2、0≦a≦1.2、0≦w≦1であり、MはCo、Ni、Fe、Cr、Cuから選ばれる少なくとも一種であり、YはLi、B、Na、Al、Mg、Ti、Si、K、Caから選ばれる少なくとも一種であり、ZはF及びClの少なくとも一方である。)
LiMPO4 (4)
(式中、MはCo及びNiの少なくとも一方である。)
Li(LixM1-x-zMnz)O2 (5)
(式中、0≦x<0.3、0.3≦z≦0.7であり、MはCo及びNiの少なくとも一方である。)
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US10003100B2 (en) | 2018-06-19 |
US20150010831A1 (en) | 2015-01-08 |
JPWO2013114946A1 (ja) | 2015-05-11 |
JP6123682B2 (ja) | 2017-05-10 |
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