ABSTRACT
Abstract
To provide a non-aqueous electrolyte solution, a non-aqueous secondary battery, a cell pack, and a hybrid power system, capable of improving desired battery performance in an acetonitrile electrolyte solution, the non-aqueous electrolyte solution contains a non-aqueous solvent, PO2F2 anions, and cyclic acid anhydride.
Description
FIELD OF THE INVENTION
The present invention relates to a non-aqueous electrolyte solution, a non-aqueous secondary battery, a cell pack, and a hybrid power system.
BACKGROUND OF THE INVENTION
A non-aqueous secondary battery such as a lithium ion battery (LIB) is characterized in a light weight, high energy, and a long service life, and is widely used as a power source of various portable electronic devices. In recent years, applications of the non-aqueous secondary batteries are widened to an industrial field represented by a power tool such as an electric tool, an in-vehicle device in an electric bicycle, or the like. Furthermore, attention is also focused in the field of a power storage field such as a home energy storage system.
Patent Document 1 discusses a non-aqueous electrolyte solution of a lithium ion battery. In the technique of Patent Document 1, durability is evaluation by measuring a capacity after a predetermined cycle through a high-temperature cycle test or the like.
Patent Document 2 discusses a non-aqueous electrolyte solution for a lithium secondary battery, capable of improving an initial capacity and an output power characteristic at a room temperature and a low temperature. In the technique of Patent Document 2, the non-aqueous electrolyte solution contains an organic solvent, lithium salt, and a phosphorus compound.
Patent Document 3 discusses a battery technique capable of improving a service life and a rate characteristic by modifying a positive electrode material of the secondary battery.
CITATION LIST
Patent Documents
Patent Document 1: Japanese Unexamined Patent Application Publication No. 2014-194930
Patent Document 2: Japanese Translation of PCT International Application Publication No. 2016-531388
Patent Document 3: Japanese Unexamined Patent Application Publication No. 10-208742
SUMMARY OF THE INVENTION
However, it is known that an acetonitrile-based electrolyte solution is required to form a film on a surface of a negative electrode in order to suppress reductive electrolysis, and a film formation agent used in the prior art is insufficient.
From the discussion described above, it is known that, if a film that can withstand the acetonitrile electrolyte solution is not sufficiently formed, reductive decomposition proceeds at the time of initial charging or each test under a high-temperature environment to cause gas generation, capacity reduction, or the like.
Meanwhile, if a highly durable film is formed, insertion or dissociation of lithium ions to or from the negative electrode is inhibited, so that it is difficult to exhibit high ion conductivity which is the characteristic of the acetonitrile.
In this regard, in order to address the problems of the prior art, the present invention provides a non-aqueous electrolyte solution, a non-aqueous secondary battery, a cell pack, and a hybrid power system, particularly, capable of improving desired battery performance in an acetonitrile electrolyte solution.
According to the present invention, there is provided a non-aqueous electrolyte solution containing a non-aqueous solvent, PO 2 F 2 anions, and cyclic acid anhydride.
In the present invention, it is preferable that a content of the PO 2 F 2 anions is 0.001 mass % or more and 1 mass % or less with respect to the non-aqueous electrolyte solution.
In the present invention, it is preferable that the PO 2 F 2 anions are obtained by dissociating LiPO 2 F 2 .
In the present invention, it is preferable that the cyclic acid anhydride includes at least one of succinic anhydride, maleic anhydride, and phthalic anhydride.
In the present invention, it is preferable that the cyclic acid anhydride includes at least succinic anhydride.
In the present invention, it is preferable that a content of the cyclic acid anhydride is 0.01 mass % or more and 1 mass % or less with respect to the non-aqueous electrolyte solution.
In the present invention, it is preferable that the non-aqueous solvent contains at least acetonitrile.
In the present invention, it is preferable that the non-aqueous electrolyte solution further contains PF 6 anions.
In the present invention, it is preferable that the PF 6 anions are obtained by dissociating LiPF 6 .
In the present invention, it is preferable that the non-aqueous electrolyte solution further contains linear carbonate.
In the present invention, it is preferable that the linear carbonate is at least one selected from a group consisting of diethyl carbonate, ethyl methyl carbonate, and dimethyl carbonate.
In the present invention, it is preferable that the non-aqueous solvent contains acetonitrile, and a molar mixing ratio of the linear carbonate relative to the acetonitrile is 0.15 or higher and 2 or lower.
In the present invention, it is preferable that the non-aqueous solvent contains acetonitrile, and a molar mixing ratio of the linear carbonate relative to the acetonitrile is 0.25 or higher and 2 or lower.
In the present invention, it is preferable that the non-aqueous solvent contains acetonitrile, and a molar mixing ratio of the linear carbonate relative to the acetonitrile is 0.4 or higher and 2 or lower.
In the present invention, it is preferable that the non-aqueous electrolyte solution further contains imide salt.
In the present invention, it is preferable that the imide salt includes at least one selected from a group consisting of LiN(SO 2 F) 2 and LiN(SO 2 CF 3 ) 2 .
In the present invention, it is preferable that a main component of the lithium salt is the imide salt, or the imide salt and the lithium salt other than the imide salt are contained as the main component in the same amount.
In the present invention, it is preferable that the imide salt is contained in a molarity relationship of âLiPF 6 â¤imide saltâ.
In the present invention, it is preferable that a content of the imide salt is 0.5 mol or more and 3.0 mol or less with respect to a non-aqueous solvent of 1 L.
In the present invention, it is preferable that the non-aqueous solvent contains acetonitrile, and a molar mixing ratio of PF 6 anions relative to the acetonitrile is 0.01 or higher and lower than 0.08.
In the present invention, it is preferable that the non-aqueous electrolyte solution further contains cyclic carbonate without saturated secondary carbon.
In the present invention, it is preferable that the cyclic carbonate without saturated secondary carbon includes at least one selected from a group consisting of ethylene carbonate and vinylene carbonate.
In the present invention, it is preferable that the cyclic carbonate without saturated secondary carbon is vinylene carbonate, and a content of vinylene carbonate of 4 volume % or less is contained in the non-aqueous electrolyte solution.
In the present invention, it is preferable that a â30° C. ionic conductivity of the non-aqueous electrolyte solution is 3 mS/cm or higher.
In the present invention, it is preferable that a 0° C. ionic conductivity of the non-aqueous electrolyte solution is 10 mS/cm or higher.
In the present invention, it is preferable that a 20° C. ionic conductivity of the non-aqueous electrolyte solution is 15 mS/cm or higher.
According to the present invention, there is provided a non-aqueous electrolyte solution containing a non-aqueous solvent and lithium salt, wherein activation energy in ion conduction is 15 kJ/mol or lower at a temperature of â20 to 0° C.
In the present invention, it is preferable that activation energy in the ion conduction is 15 kJ/mol or lower at a temperature of 0 to 20° C.
In the present invention, it is preferable that the non-aqueous electrolyte solution further contains a compound expressed as the following Formula (1).
[Chemical Formula 1]
âNâFormula (1)
In the present invention, it is preferable that the compound is a nitrogen-containing cyclic compound.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution contains acetonitrile and LiPO 2 F 2 , and a value obtained by dividing a bulk resistance at a temperature of â30° C. by an internal resistance value in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.05 to 0.7.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and the non-aqueous electrolyte solution described above, wherein the non-aqueous secondary battery contains a compound having at least one functional group selected from a group consisting of âNâ, âNH 4 , âNâO, âNHâNHâ, and (NO 3 )â, and a value obtained by dividing a bulk resistance at a temperature of â30° C. by an internal resistance value in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.05 to 0.7.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and a non-aqueous electrolyte solution, wherein the negative-electrode active material layer contains at least one compound selected from a group consisting of imide salt and (SO 4 ) 2â , the imide salt is at least one selected from a group consisting of lithium salt and onium salt, and a bulk resistance at a temperature of 25° C. in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.025 ohm or smaller.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and the non-aqueous electrolyte solution described above, wherein the non-aqueous secondary battery contains at least one compound selected from a group consisting of organic acid, salt thereof, acid anhydride, and Li 2 O, the organic acid includes at least one of acetic acid, oxalic acid, and formic acid, and a value obtained by dividing a bulk resistance at a temperature of â30° C. by an internal resistance value in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.05 to 0.7.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and a non-aqueous electrolyte solution, wherein the negative-electrode active material layer contains at least one compound selected from a group consisting of imide salt and (SO 4 ) 2â , the imide salt is at least one selected from a group consisting of lithium salt and onium salt, and a bulk resistance at a temperature of â30° C. in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.07 ohm or smaller.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and the non-aqueous electrolyte solution described above, wherein the non-aqueous secondary battery contains a compound having at least one functional group selected from a group consisting of âNâ, âNH 4 , âNâO, âNHâNHâ, and (NO 3 )â, and the non-aqueous secondary battery has a capacity retention rate of 70% or higher, the capacity retention rate being calculated by dividing a 5 C discharge capacity by a 1 C discharge capacity after a storage test for 4 hours at 85° C.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and the non-aqueous electrolyte solution described above, wherein the non-aqueous secondary battery contains at least one compound selected from a group consisting of organic acid, salt thereof, acid anhydride, and Li 2 O, the organic acid includes at least one acetic acid, oxalic acid, and formic acid, and the non-aqueous secondary battery has a capacity retention rate of 70% or higher, the capacity retention rate being calculated by dividing a 5 C discharge capacity by a 1 C discharge capacity after a storage test for 4 hours at 85° C.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and the non-aqueous electrolyte solution described above, wherein the non-aqueous secondary battery contains a compound having at least one functional group selected from a group consisting of âNâ, âNH 4 , âNâO, âNHâNHâ, and (NO 3 )â, and the non-aqueous secondary battery has a 0° C. ionic conductivity of 10 mS/cm or higher after a storage test for 4 hours at 85° C.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a po
FIELD OF THE INVENTION
The present invention relates to a non-aqueous electrolyte solution, a non-aqueous secondary battery, a cell pack, and a hybrid power system.
BACKGROUND OF THE INVENTION
A non-aqueous secondary battery such as a lithium ion battery (LIB) is characterized in a light weight, high energy, and a long service life, and is widely used as a power source of various portable electronic devices. In recent years, applications of the non-aqueous secondary batteries are widened to an industrial field represented by a power tool such as an electric tool, an in-vehicle device in an electric bicycle, or the like. Furthermore, attention is also focused in the field of a power storage field such as a home energy storage system.
Patent Document 1 discusses a non-aqueous electrolyte solution of a lithium ion battery. In the technique of Patent Document 1, durability is evaluation by measuring a capacity after a predetermined cycle through a high-temperature cycle test or the like.
Patent Document 2 discusses a non-aqueous electrolyte solution for a lithium secondary battery, capable of improving an initial capacity and an output power characteristic at a room temperature and a low temperature. In the technique of Patent Document 2, the non-aqueous electrolyte solution contains an organic solvent, lithium salt, and a phosphorus compound.
Patent Document 3 discusses a battery technique capable of improving a service life and a rate characteristic by modifying a positive electrode material of the secondary battery.
CITATION LIST
Patent Documents
Patent Document 1: Japanese Unexamined Patent Application Publication No. 2014-194930
Patent Document 2: Japanese Translation of PCT International Application Publication No. 2016-531388
Patent Document 3: Japanese Unexamined Patent Application Publication No. 10-208742
SUMMARY OF THE INVENTION
However, it is known that an acetonitrile-based electrolyte solution is required to form a film on a surface of a negative electrode in order to suppress reductive electrolysis, and a film formation agent used in the prior art is insufficient.
From the discussion described above, it is known that, if a film that can withstand the acetonitrile electrolyte solution is not sufficiently formed, reductive decomposition proceeds at the time of initial charging or each test under a high-temperature environment to cause gas generation, capacity reduction, or the like.
Meanwhile, if a highly durable film is formed, insertion or dissociation of lithium ions to or from the negative electrode is inhibited, so that it is difficult to exhibit high ion conductivity which is the characteristic of the acetonitrile.
In this regard, in order to address the problems of the prior art, the present invention provides a non-aqueous electrolyte solution, a non-aqueous secondary battery, a cell pack, and a hybrid power system, particularly, capable of improving desired battery performance in an acetonitrile electrolyte solution.
According to the present invention, there is provided a non-aqueous electrolyte solution containing a non-aqueous solvent, PO 2 F 2 anions, and cyclic acid anhydride.
In the present invention, it is preferable that a content of the PO 2 F 2 anions is 0.001 mass % or more and 1 mass % or less with respect to the non-aqueous electrolyte solution.
In the present invention, it is preferable that the PO 2 F 2 anions are obtained by dissociating LiPO 2 F 2 .
In the present invention, it is preferable that the cyclic acid anhydride includes at least one of succinic anhydride, maleic anhydride, and phthalic anhydride.
In the present invention, it is preferable that the cyclic acid anhydride includes at least succinic anhydride.
In the present invention, it is preferable that a content of the cyclic acid anhydride is 0.01 mass % or more and 1 mass % or less with respect to the non-aqueous electrolyte solution.
In the present invention, it is preferable that the non-aqueous solvent contains at least acetonitrile.
In the present invention, it is preferable that the non-aqueous electrolyte solution further contains PF 6 anions.
In the present invention, it is preferable that the PF 6 anions are obtained by dissociating LiPF 6 .
In the present invention, it is preferable that the non-aqueous electrolyte solution further contains linear carbonate.
In the present invention, it is preferable that the linear carbonate is at least one selected from a group consisting of diethyl carbonate, ethyl methyl carbonate, and dimethyl carbonate.
In the present invention, it is preferable that the non-aqueous solvent contains acetonitrile, and a molar mixing ratio of the linear carbonate relative to the acetonitrile is 0.15 or higher and 2 or lower.
In the present invention, it is preferable that the non-aqueous solvent contains acetonitrile, and a molar mixing ratio of the linear carbonate relative to the acetonitrile is 0.25 or higher and 2 or lower.
In the present invention, it is preferable that the non-aqueous solvent contains acetonitrile, and a molar mixing ratio of the linear carbonate relative to the acetonitrile is 0.4 or higher and 2 or lower.
In the present invention, it is preferable that the non-aqueous electrolyte solution further contains imide salt.
In the present invention, it is preferable that the imide salt includes at least one selected from a group consisting of LiN(SO 2 F) 2 and LiN(SO 2 CF 3 ) 2 .
In the present invention, it is preferable that a main component of the lithium salt is the imide salt, or the imide salt and the lithium salt other than the imide salt are contained as the main component in the same amount.
In the present invention, it is preferable that the imide salt is contained in a molarity relationship of âLiPF 6 â¤imide saltâ.
In the present invention, it is preferable that a content of the imide salt is 0.5 mol or more and 3.0 mol or less with respect to a non-aqueous solvent of 1 L.
In the present invention, it is preferable that the non-aqueous solvent contains acetonitrile, and a molar mixing ratio of PF 6 anions relative to the acetonitrile is 0.01 or higher and lower than 0.08.
In the present invention, it is preferable that the non-aqueous electrolyte solution further contains cyclic carbonate without saturated secondary carbon.
In the present invention, it is preferable that the cyclic carbonate without saturated secondary carbon includes at least one selected from a group consisting of ethylene carbonate and vinylene carbonate.
In the present invention, it is preferable that the cyclic carbonate without saturated secondary carbon is vinylene carbonate, and a content of vinylene carbonate of 4 volume % or less is contained in the non-aqueous electrolyte solution.
In the present invention, it is preferable that a â30° C. ionic conductivity of the non-aqueous electrolyte solution is 3 mS/cm or higher.
In the present invention, it is preferable that a 0° C. ionic conductivity of the non-aqueous electrolyte solution is 10 mS/cm or higher.
In the present invention, it is preferable that a 20° C. ionic conductivity of the non-aqueous electrolyte solution is 15 mS/cm or higher.
According to the present invention, there is provided a non-aqueous electrolyte solution containing a non-aqueous solvent and lithium salt, wherein activation energy in ion conduction is 15 kJ/mol or lower at a temperature of â20 to 0° C.
In the present invention, it is preferable that activation energy in the ion conduction is 15 kJ/mol or lower at a temperature of 0 to 20° C.
In the present invention, it is preferable that the non-aqueous electrolyte solution further contains a compound expressed as the following Formula (1).
[Chemical Formula 1]
âNâFormula (1)
In the present invention, it is preferable that the compound is a nitrogen-containing cyclic compound.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution contains acetonitrile and LiPO 2 F 2 , and a value obtained by dividing a bulk resistance at a temperature of â30° C. by an internal resistance value in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.05 to 0.7.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and the non-aqueous electrolyte solution described above, wherein the non-aqueous secondary battery contains a compound having at least one functional group selected from a group consisting of âNâ, âNH 4 , âNâO, âNHâNHâ, and (NO 3 )â, and a value obtained by dividing a bulk resistance at a temperature of â30° C. by an internal resistance value in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.05 to 0.7.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and a non-aqueous electrolyte solution, wherein the negative-electrode active material layer contains at least one compound selected from a group consisting of imide salt and (SO 4 ) 2â , the imide salt is at least one selected from a group consisting of lithium salt and onium salt, and a bulk resistance at a temperature of 25° C. in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.025 ohm or smaller.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and the non-aqueous electrolyte solution described above, wherein the non-aqueous secondary battery contains at least one compound selected from a group consisting of organic acid, salt thereof, acid anhydride, and Li 2 O, the organic acid includes at least one of acetic acid, oxalic acid, and formic acid, and a value obtained by dividing a bulk resistance at a temperature of â30° C. by an internal resistance value in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.05 to 0.7.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and a non-aqueous electrolyte solution, wherein the negative-electrode active material layer contains at least one compound selected from a group consisting of imide salt and (SO 4 ) 2â , the imide salt is at least one selected from a group consisting of lithium salt and onium salt, and a bulk resistance at a temperature of â30° C. in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.07 ohm or smaller.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and the non-aqueous electrolyte solution described above, wherein the non-aqueous secondary battery contains a compound having at least one functional group selected from a group consisting of âNâ, âNH 4 , âNâO, âNHâNHâ, and (NO 3 )â, and the non-aqueous secondary battery has a capacity retention rate of 70% or higher, the capacity retention rate being calculated by dividing a 5 C discharge capacity by a 1 C discharge capacity after a storage test for 4 hours at 85° C.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and the non-aqueous electrolyte solution described above, wherein the non-aqueous secondary battery contains at least one compound selected from a group consisting of organic acid, salt thereof, acid anhydride, and Li 2 O, the organic acid includes at least one acetic acid, oxalic acid, and formic acid, and the non-aqueous secondary battery has a capacity retention rate of 70% or higher, the capacity retention rate being calculated by dividing a 5 C discharge capacity by a 1 C discharge capacity after a storage test for 4 hours at 85° C.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and the non-aqueous electrolyte solution described above, wherein the non-aqueous secondary battery contains a compound having at least one functional group selected from a group consisting of âNâ, âNH 4 , âNâO, âNHâNHâ, and (NO 3 )â, and the non-aqueous secondary battery has a 0° C. ionic conductivity of 10 mS/cm or higher after a storage test for 4 hours at 85° C.
According to the present invention, there is provided a non-aqueous secondary battery including: a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector; a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector; and the non-aqueous electrolyte solution described above, wherein the non-aqueous secondary battery contains at least one compound selected from a group consisting of organic acid, salt thereof, acid anhydride, and Li 2 O, the organic acid includes at least one of acetic acid, oxalic acid, and formic acid, and the non-aqueous secondary battery has a 0° C. ionic conductivity of 10 mS/cm or higher after a storage test for 4 hours at 85° C.
In the present invention, it is preferable that the positive-electrode active material is a lithium-containing composite metal oxide expressed as âLi 2 MO 2 â (where âMâ contains Ni and one or more metal elements selected from a group consisting of Mn, Co, Al, and Mg, a content ratio of the Ni element is more than 50%, and âzâ denotes a number greater than 0.9 and smaller than 1.2).
In the present invention, it is preferable that a difference of the negative electrode electric potential around injection of the non-aqueous electrolyte solution is 0.3 V or higher.
In the present invention, it is preferable that a gas generation amount in a storage test at 60° C. for 200 hours is 0.008 ml or less per 1 mAh.
In the present invention, it is preferable that a resistance increase rate in a full-charge storage test at 60° C. for 720 hours is 400% or lower.
According to the present invention, there is provided a cell pack comprising the non-aqueous secondary battery described above, wherein the positive-electrode active material layer contains a lithium-containing compound including Fe, the negative-electrode active material layer contains graphite or at least one or more elements selected from a group consisting of Ti, V, Sn, Cr, Mn, Fe, Co, Ni, Zn, Al, Si, and B, the non-aqueous electrolyte solution contains cyclic carbonate without saturated secondary carbon, the cyclic carbonate without saturated secondary carbon is at least one selected from a group consisting of ethylene carbonate and vinylene carbonate, the non-aqueous secondary battery is configured by connecting one module or two or more modules, in which the module is obtained by connecting four cells in series, in parallel or the non-aqueous secondary battery is configured by connecting four modules, in which the module is obtained by connecting two or more cells in parallel, in series, an operation voltage range per cell is within a range of 1.8 to 3.7 V, an average operation voltage is 2.5 to 3.5 V, and the module is mounted with a battery management system (BMS).
According to the present invention, there is provided a hybrid power system obtained by combining the cell pack described above, and a module or cell pack having a secondary battery other than a lithium ion battery.
According to the present invention, there is provided a cell pack comprising the non-aqueous secondary battery described above, wherein the positive-electrode active material layer contains a lithium-containing compound including Fe, the negative-electrode active material layer contains graphite or at least one or more elements selected from a group consisting of Ti, V, Sn, Cr, Mn, Fe, Co, Ni, Zn, Al, Si, and B, the non-aqueous electrolyte solution contains cyclic carbonate without saturated secondary carbon, the cyclic carbonate without saturated secondary carbon is at least one selected from a group consisting of ethylene carbonate and vinylene carbonate, the cell pack is configured by connecting one cell pack or two or more cell packs in parallel on the basis of Formula (2) and Formula (3), in which the number of cells and the number of modules of the non-aqueous secondary battery are defined, or the non-aqueous secondary battery is configured by connecting modules on the basis of Formula (2) and Formula (3), the module being obtained by connecting two or more cells in parallel, an operation voltage range per cell is within a range of 1.8 to 3.7 V, an average operation voltage is 2.5 to 3.5 V, and the module is mounted with a battery management system (BMS).
Formula (2): Number of cells connected in series per module (X): X=2, 4, 8, or 16
Formula (3): Number of modules connected in series per cell pack (Y): Y=16/X.
According to the present invention, there is provided a hybrid power system including the cell pack described above, and a module or cell pack having a secondary battery other than a lithium ion battery in combination.
Using the non-aqueous electrolyte solution according to the present invention, it is possible to delay generation of gas in the event of high-temperature operation and overcharging, reinforce the negative electrode SEI, and obtain excellent low-temperature characteristics or output power characteristics and excellent high-temperature characteristics.
As described above, using the non-aqueous electrolyte solution and the non-aqueous secondary battery using the same according to the present invention, it is possible to provide an acetonitrile electrolyte solution capable of improving desired battery performance.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a plan view schematically illustrating an exemplary non-aqueous secondary battery according to an embodiment of the invention;
FIG. 2 is a cross-sectional view taken along the line A-A of the non-aqueous secondary battery of FIG. 1 ;
FIGS. 3 ( a ) and ( b ) are a schematic explanatory diagram illustrating a cell pack according to a forty fourth embodiment;
FIG. 4 is a schematic explanatory diagram illustrating a hybrid power system according to a forty fifth embodiment;
FIG. 5 is a schematic explanatory diagram illustrating a cell pack according to a forty sixth embodiment; and
FIG. 6 is a schematic explanatory diagram illustrating a hybrid power system according to forty seventh embodiment.
DESCRIPTION OF EMBODIMENTS
Embodiments of the invention (hereinafter, simply referred to as âembodimentâ) will now be described in details.
First Embodiment: Non-Aqueous Electrolyte Solution
First, a technical change at the time of development of the present invention will be described. Acetonitrile has a high potential as a solvent of the electrolyte solution due to excellent balance between viscosity and relative dielectric constant. For this reason, an electrolyte solution for a lithium ion battery provided with acetonitrile as a non-aqueous solvent has an excellent low-temperature characteristic. However, since acetonitrile has low resistance to reduction, there has been a problem that, when a reduction reaction site of the negative electrode is activated at a high temperature in the case of a lithium ion battery, the reductive decomposition of acetonitrile rapidly proceeds. For this reason, when the lithium ion battery is stored at a high temperature, reduction of acetonitrile is promoted, and gas is generated to cause battery swelling disadvantageously. In this regard, the inventors have developed the invention for suppressing battery swelling when the lithium ion battery using the electrolyte solution is at a high temperature by appropriately adjusting the type and the content of the additives to be added in the non-aqueous electrolyte solution, particularly an electrolyte solution containing acetonitrile. That is, this embodiment includes the following characteristic parts.
A non-aqueous electrolyte solution according to a first embodiment contains a non-aqueous solvent, PO 2 F 2 anions, and cyclic acid anhydride.
In this manner, the non-aqueous electrolyte solution according to the first embodiment contains PO 2 F 2 anions and cyclic acid anhydride in addition to the non-aqueous solvent.
The PO 2 F 2 anions and the cyclic acid anhydride form a robust passive film called a solid electrolyte interface (SEI) on the negative electrode when an electrolyte solution containing them is used in the non-aqueous secondary battery. Although the SEI has ion conductivity, it does not have electron conductivity, so that reductive decomposition of the electrolyte solution is suppressed. Due to the PO 2 F 2 anions and the cyclic acid anhydride, the SEI formed on the negative electrode is reinforced, so that the reductive decomposition of the electrolyte solution is effectively suppressed. As a result, when the non-aqueous secondary battery is heated to a high temperature, a reduction reaction of the electrolyte solution is promoted, and generation of gas is suppressed, so that battery swelling is suppressed.
The non-aqueous secondary battery using the non-aqueous electrolyte solution according to this embodiment can suppress reductive decomposition of the non-aqueous electrolyte solution in the event of high-temperature heating and suppress battery swelling at a high temperature.
For this reason, the non-aqueous secondary battery according to this embodiment can be applied to a high-temperature region, for example, at a temperature of 60° C. and is applicable to, for example, outdoor applications in summer or the like.
The non-aqueous secondary battery according to this embodiment has a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a current collector, a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a current collector, and a non-aqueous electrolyte solution.
The non-aqueous electrolyte solution contains, for example, a non-aqueous solvent, lithium salt, PO 2 F 2 anions, and at least one selected from a group consisting of succinic anhydride (SAH), maleic anhydride (MAH), and phthalic anhydride (PAH) as the cyclic acid anhydride. Specifically, the non-aqueous electrolyte solution contains, for example, acetonitrile, imide salt such as LiPF 6 , LiN(SO 2 F) 2 or LiN(SO 2 CF 3 ) 2 , SAH, and LiPO 2 F 2 . In this case, in the non-aqueous secondary battery, there is no particular limitation in the negative electrode, the positive electrode, the separator, and the battery casing.
The configuration described above has a remarkable effect of suppressing an increase of resistance during high-temperature heating and obtaining low-temperature characteristics.
Second Embodiment: Non-Aqueous Electrolyte Solution
According to the second embodiment, in the non-aqueous electrolyte solution of the first embodiment, the content of PO 2 F 2 anions preferably has a range of 0.001 mass % or more and 1 mass % or less with respect to the non-aqueous electrolyte solution.
The non-aqueous electrolyte solution according to the second embodiment preferably contains acetonitrile, PF 6 anions, PO 2 F 2 anions, cyclic acid anhydride, and imide salt. Among them, the PO 2 F 2 anions and the cyclic acid anhydride contribute to suppression of an increase of internal resistance during high-temperature heating. In addition, the imide salt contributes to improvement of the low-temperature characteristics. Here, the imide salt refers to lithium salt expressed as expressed as âLiN(SO 2 C m F 2m+1 ) 2 â (where âmâ denotes an integer of 0 to 8).
Due to the composition of the non-aqueous electrolyte solution according to this embodiment, it is possible to suppress an increase of internal resistance during high-temperature heating and obtain excellent low-temperature characteristics.
Note that the low-temperature characteristics can be determined on the basis of the ionic conductivity at a low temperature (specifically, â10° C. or â30° C.).
According to the second embodiment, the content of PO 2 F 2 anions has a range of 0.001 mass % or more and 1 mass % or less with respect to the non-aqueous electrolyte solution. In addition, the content of cyclic acid anhydride preferably has a range of 0.01 mass % or more and 1 mass % or less with respect to the non-aqueous electrolyte solution. Furthermore, the non-aqueous electrolyte solution contains imide salt with a molarity relationship of âLiPF 6 â¤imide saltâ. Here, the contents of PO 2 F 2 anions and the cyclic acid anhydride are expressed as mass ratios by assuming that a sum of all components of the non-aqueous electrolyte solution is set to 100 mass %. In addition, the molarities of LiPF 6 and imide salt are measured for the non-aqueous solvent of â1 Lâ.
By defining the contents and the molarities as described above, PO 2 F 2 anions and cyclic acid anhydride form a robust SEI on the negative electrode. In this manner, since a passive film called âSEIâ is formed on the negative electrode, it is possible to effectively suppress an increase of resistance during high-temperature heating.
Since the imide salt is contained with a molarity relationship of âLiPF 6 â¤imide saltâ, it is possible to suppress a decrease of the ionic conductivity at a low temperature and obtain excellent low-temperature characteristics.
The content of PO 2 F 2 anions is more preferably 0.05 mass % or more and 1 mass % or less with respect to the non-aqueous electrolyte solution. In addition, the content of cyclic acid anhydride is more preferably 0.1 mass % or more and 0.5 mass % or less with respect to the non-aqueous electrolyte solution.
The content of imide salt is preferably 0.5 mol or more and 3 mol or less with respect to the non-aqueous solvent of â1 Lâ.
As a result, it is possible to more effectively suppress an increase of resistance during high-temperature heating and obtain more excellent low-temperature characteristics.
According to this embodiment, it is possible to suppress a resistance increase rate to 400% or lower in a full-charge storage test for 720 hours at 60° C., but not limited thereto. In addition, preferably, it is possible to suppress the resistance increase rate to 300% or lower. More preferably, it is possible to suppress the resistance increase rate to 250% or lower.
According to this embodiment, the ionic conductivity at a temperature of â10° C. is preferably 10 mS/cm or higher, but not limited thereto. More preferably, the ionic conductivity at a temperature of â10° C. is 12 mS/cm or higher, and furthermore preferably, 12.5 mS/cm or higher.
According to this embodiment, the ionic conductivity at a temperature of â30° C. is 3 mS/cm or higher, and more preferably, 5 mS/cm or higher, but not limited thereto. Furthermore preferably, the ionic conductivity at a temperature of â30° C. is 6 mS/cm or higher, and furthermore preferably, the ionic conductivity at a temperature of â30° C. is 6.5 mS/cm or higher.
The non-aqueous secondary battery using the non-aqueous electrolyte solution according to this embodiment may function as a battery through initial charging. However, a part of the electrolyte solution is decomposed at the time of the initial charging for stabilization. In this case, since the content of PO 2 F 2 anions or cyclic acid anhydride in the electrolyte solution is originally small, and they are incorporated into the SEI, or due to other reasons, it was difficult to detect a component after the initial charging in some cases.
For this reason, in the non-aqueous secondary battery using the LiPF 6 -based acetonitrile electrolyte solution, if the aforementioned properties are provided after the initial charging, it can be inferred that the components of the non-aqueous electrolyte solution according to this embodiment are contained.
The non-aqueous secondary battery using the non-aqueous electrolyte solution according to the first and second embodiments may include a positive electrode, a negative electrode, and a non-aqueous electrolyte solution. In addition, the resistance increase rate may be 400% or lower in a full-charge storage test for 720 hours at 60° C., and the ionic conductivity at â10° C. may be 10 mS/cm or higher.
The non-aqueous secondary battery using the non-aqueous electrolyte solution according to the first and second embodiments can suppress a resistance increase rate during high-temperature heating and obtain excellent low-temperature characteristics.
For this reason, the non-aqueous secondary battery according to this embodiment is applicable to a wide temperature range from approximately 60° C. to â30° C. such as outdoor applications in summer and cold region use.
Third Embodiment: Non-Aqueous Electrolyte Solution
According to the third embodiment, in the non-aqueous electrolyte solution according to the first or second embodiment, the PO 2 F 2 anions are preferably obtained by dissociating LiPO 2 F 2 .
In this manner, the electrolyte solution contains PO 2 F 2 anions and lithium ions. By analyzing both ions, it is possible to check whether or not LiPO 2 F 2 as the lithium salt is contained.
Fourth Embodiment: Non-Aqueous Electrolyte Solution
According to a fourth embodiment, in any one of the first to third embodiments, the cyclic acid anhydride preferably contains at least one selected from a group consisting of succinic anhydride, maleic anhydride, and phthalic anhydride. Only one of these cyclic acid anhydrides or a plurality of cyclic acid anhydrides may be contained. Alternatively, any cyclic acid anhydride other than the aforementioned cyclic acid anhydrides may also be contained. As a result, it is possible to form a robust SEI on the negative electrode and suppress an increase of the resistance during high-temperature heating.
Fifth Embodiment: Non-Aqueous Electrolyte Solution
According to the fifth embodiment, the cyclic acid anhydride of the non-aqueous electrolyte solution of the fourth embodiment preferably includes at least succinic anhydride. As a result, it is possible to more effectively form a robust SEI on the negative electrode.
Sixth Embodiment: Non-Aqueous Electrolyte Solution
According to the sixth embodiment, in the non-aqueous electrolyte solution of any one of the first to fifth embodiments, the content of cyclic acid anhydride is preferably 0.01 mass % or more and 1 mass % or less with respect to the non-aqueous electrolyte solution.
The content of the cyclic acid anhydride is calculated on a mass percentage basis relative to a total mass of all components contained in the non-aqueous electrolyte solution. More preferably, the content of the cyclic acid anhydride is 0.1 mass % or more and 0.7 mass % or less, and furthermore preferably, 0.5 mass % or less with respect to the non-aqueous electrolyte solution.
As a result, it is possible to more effectively delay generation of gas in the event of overcharge.
Seventh Embodiment: Non-Aqueous Electrolyte Solution
According to the seventh embodiment, in the non-aqueous electrolyte solution of any one of the first to sixth embodiments, the non-aqueous solvent preferably contains at least acetonitrile.
The non-aqueous solvent may contain acetonitrile alone or any other type of non-aqueous solvents other than the acetonitrile. Specific examples of the non-aqueous solvents applicable to this embodiment will be described below. Since the electrolyte solution containing acetonitrile contains LiPO 2 F 2 and cyclic acid anhydride, the SEI is reinforced. For this reason, even under a high-temperature environment, dissolution of the SEI of the negative electrode is suppressed. Therefore, reductive decomposition of acetonitrile is suppressed.
Eighth Embodiment: Non-Aqueous Electrolyte Solution
According to an eighth embodiment, the non-aqueous electrolyte solution of any one of the first to seventh embodiments preferably contains PF 6 anions.
In this manner, since PF 6 anions are contained, hydrogen is removed from an α-position of acetonitrile, and generation of HF is promoted, so that LiF as an element of the negative electrode SEI is effectively formed. In addition, a suitable amount of water more effectively promotes a reaction of forming the negative electrode SEI of the cyclic acid anhydride. Therefore, since PF 6 anions are contained, organic/inorganic complexation of the negative electrode SEI efficiently proceeds, so that it is possible to more effectively delay generation of gas during overcharge.
Specifically, the composition of the non-aqueous electrolyte solution according to the eighth embodiment includes, for example, acetonitrile, LiPF 6 , SAH, and LiPO 2 F 2 . In this case, in the non-aqueous secondary battery, there is no particular limitation in the negative electrode, the positive electrode, the separator, and the battery casing.
Ninth Embodiment: Non-Aqueous Electrolyte Solution
According to a ninth embodiment, in the non-aqueous electrolyte solution of the eighth embodiment, PF 6 anions are preferably obtained by dissociating LiPF 6 .
In this manner, the PF 6 anions and the lithium ions exist in the electrolyte solution. By analyzing both the ions, it is possible to check whether or not the lithium salt and the LiPF 6 are contained.
According to this embodiment, the electrolyte solution is preferably obtained by mixing LiPO 2 F 2 and then adding LiPF 6 . In this manner, by defining the mixing sequence of the electrolyte solution, it is possible to control the dissolution speed of LiPF 6 and suppress generation of a decomposition product.
The electrolyte solution is preferably obtained by mixing acetonitrile and cyclic acid anhydride and then adding LiPF 6 . As a result, it is possible to suppress an abrupt temperature increase when adding LiPF 6 and suppress generation of HF that causes an increase of internal resistance due to sacrificial reaction of the cyclic acid anhydride.
A temperature increase at the time of adding LiPF 6 is preferably suppressed to 50° C. or lower. As a result, it is possible to appropriately suppress thermal decomposition of LiPF 6 that may be generated at a temperature of 60° C. or higher.
Tenth Embodiment: Non-Aqueous Electrolyte Solution
According to a tenth embodiment, the non-aqueous electrolyte solution of any one of the first to ninth embodiments preferably further contains linear carbonate.
The combined use of acetonitrile and linear carbonate advantageously acts to suppress association between acetonitrile and LiPF 6 .
Specifically, the composition of the non-aqueous electrolyte solution according to the tenth embodiment includes, for example, acetonitrile, LiPF 6 , LiN(SO 2 F) 2 , LiN(SO 2 CF 3 ) 2 , SAH (1% or less), LiPO 2 F 2 , and VC (4% or less). In this case, in the non-aqueous secondary battery, there is no particular limitation in the negative electrode, the positive electrode, the separator, and the battery casing.
Using the configuration described above, a remarkable effect appears on the high-temperature durability of the non-aqueous secondary battery, so that it is possible to obtain a long service life even under a high-temperature environment.
Eleventh Embodiment: Non-Aqueous Electrolyte Solution
According to the eleventh embodiment, the linear carbonate of the non-aqueous electrolyte solution of the tenth embodiment includes, for example, at least one selected from a group consisting of diethyl carbonate, ethyl methyl carbonate, and dimethyl carbonate.
A specific composition according to the eleventh embodiment is a non-aqueous electrolyte solution containing LiPF 6 , acetonitrile (AcN), and diethyl carbonate (DEC). In addition, the lithium salt may include LiPF 6 , LiN(SO 2 F) 2 , or LiB(C 2 O 4 ) 2 (LiBOB). In addition, the non-aqueous electrolyte solution preferably contains succinic anhydride (SAH).
According to the eleventh embodiment, the non-aqueous electrolyte solution preferably contains LiPF 6 and LiN(SO 2 F) 2 as the lithium salt, acetonitrile as the solvent, and cyclic acid anhydride and LiPO 2 F 2 as the additive. As a result, it is possible to suppress cycle degradation at a low temperature by suppressing an interface (film) resistance to be low.
In the non-aqueous electrolyte solution described above, a total mass of the additive is preferably less than 5%. Note that the additive refers to a general element used as a protection film formation agent such as VC, MAH, SAH, PAH, and ES. As a result, it is possible to suppress an interface (film) resistance to be low and suppress cycle degradation at a low temperature.
In the non-aqueous electrolyte solution described above, it is preferable that the amount of LiPO 2 F 2 is 0.005 to 1 mass %, and the amount of vinylene carbonate is 4 mass % or less. As a result, by setting the amount of LiPO 2 F 2 and the amount of vinylene carbonate to a predetermined range, it is possible to provide a secondary battery having excellent high-temperature durability and excellent low-temperature performance.
The non-aqueous secondary battery using the non-aqueous electrolyte solution according to the eleventh embodiment may be used for a cold region.
Twelfth Embodiment: Non-Aqueous Electrolyte Solution
According to the twelfth embodiment, in the non-aqueous electrolyte solution of the tenth or eleventh embodiment, the molar mixing ratio of the linear carbonate relative to acetonitrile is preferably set to 0.15 or higher and 2 or lower.
The combined use of the acetonitrile and the linear carbonate advantageously acts to suppress association between acetonitrile and LiPF 6 . However, the linear carbonate has low polarity. In this regard, the molar mixing ratio of the linear carbonate relative to acetonitrile is adjusted in order to appropriately suppress a decrease of ionic conductivity in a low temperature range even when the linear carbonate is contained.
That is, according to the twelfth embodiment, the molar mixing ratio of the linear carbonate relative to the acetonitrile that affects solubility is adjusted to a particular range. The molar mixing ratio of the linear carbonate relative to acetonitrile is expressed as âC/Aâ, where âAâ denotes the number of moles of the acetonitrile and âCâ denote the number of moles of the linear carbonate.
That is, according to the twelfth embodiment, the molar mixing ratio (C/A) of the linear carbonate relative to acetonitrile is adjusted to 0.15 or higher and 2 or lower.
According to this embodiment, it is preferable that the following conditions are satisfied: (1) the non-aqueous electrolyte solution contains LiPF 6 and a non-aqueous solvent, and the non-aqueous solvent contains acetonitrile and linear carbonate; (2) the content of LiPF 6 is 1.5 mol or less with respect to a non-aqueous solvent of 1 L; (3) the molar mixing ratio of LiPF 6 relative to acetonitrile is 0.08 or higher and 0.16 or lower; and (4) the molar mixing ratio of the linear carbonate relative to acetonitrile is set to 0.15 or higher and 2 or lower.
As a result, it is possible to more effectively address a tradeoff problem between prevention of association of LiPF 6 and suppression of a decrease of the ionic conductivity. Specifically, it is possible to obtain an ionic conductivity of 3 mS/cm or higher at a temperature of â30° C. without observing precipitation of white sediments as aggregate. According to this embodiment, preferably, it is possible to obtain an ionic conductivity of 3.5 mS/cm or higher at a temperature of â30° C. without inhibiting ion conduction caused by the aggregate. More preferably, it is possible to obtain an ionic conductivity of 4 mS/cm or higher without inhibiting ion conduction caused by the aggregate. Furthermore preferably, it is possible to obtain an ionic conductivity of 4.5 mS/cm or higher without forming the aggregate.
The specific composition and application of the twelfth embodiment are similar to those of the eleventh embodiment.
Thirteenth Embodiment: Non-Aqueous Electrolyte Solution
According to the thirteenth embodiment, in the non-aqueous electrolyte solution of the tenth or eleventh embodiment, the molar mixing ratio of the linear carbonate relative to acetonitrile is preferably set to 0.25 or higher and 2 or lower.
According to the thirteenth embodiment, a limitation is further added to the twelfth embodiment. As a result, even when the linear carbonate is contained, it is possible to more effectively and appropriately suppress a decrease of the ionic conductivity in a low temperature range.
Fourteenth Embodiment: Non-Aqueous Electrolyte Solution
According to the fourteenth embodiment, in the non-aqueous electrolyte solution of the tenth or eleventh embodiment, the molar mixing ratio of linear carbonate relative to acetonitrile is preferably 0.4 or higher and 2 or lower.
According to the fourteenth embodiment, a limitation is further added to the thirteenth embodiment. As a result, even when the linear carbonate is contained, it is possible to more effectively and appropriately suppress a decrease of the ionic conductivity in a low-temperature range.
Fifteenth Embodiment: Non-Aqueous Electrolyte Solution
According to the fifteenth embodiment, the non-aqueous electrolyte solution of any one of the first to fourteenth embodiments preferably contains imide salt.
A technical change at the time of development of the fifteenth embodiment will be described. In the existing electrolyte solution, imide salt such as lithium bis (fluorosulfonyl) imide (LiN(SO 2 F) 2 ) is employed in order to improve the ionic conductivity and the cycle characteristics of the battery, or the like. Here, the imide salt is lithium salt expressed as âLiN(SO 2 C m F 2m+1 ) 2 â, where âmâ denotes an integer of 0 to 8. However, in the non-aqueous electrolyte solution containing imide salt, corrosion proceeds so as to form a soluble complex with aluminum used as a positive electrode current collector of the lithium secondary battery through charging/discharging, so that elution is generated in the electrolyte solution disadvantageously. In this regard, the inventors achieved the present invention to provide an electrolyte solution capable of suppressing aluminum elution through charging/discharging even when the imide salt is contained.
According to the fifteenth embodiment, the non-aqueous electrolyte solution contains a non-aqueous solvent, PO 2 F 2 anions, lithium salt, and cyclic acid anhydride, and the lithium salt includes imide salt.
Here, according to the fifteenth embodiment, the non-aqueous electrolyte solution preferably contains the PF 6 anions of the eighth embodiment. The PF 6 anions react with water to produce hydrogen fluoride (hereinafter, referred to as âHFâ) and PF 5 . The fluorine ion derived from HF reacts with aluminum as the positive electrode current collector to generate a passive film on a surface. As a result, it is possible to suppress corrosion of the positive electrode containing aluminum and elution of aluminum in the electrolyte solution.
If the acetonitrile is heated in presence of PF 5 , hydrogen is released from the α-position so as to promote generation of HF from the PF 6 anion. As a result, even under a high-temperature environment where corrosion of aluminum proceeds, restoration of the passive film is promoted, so that it is possible to further suppress elution of aluminum. That is, it is possible to suppress elution of aluminum even in charging/discharging.
According to the fifteenth embodiment, the non-aqueous electrolyte solution preferably contains water of 1 ppm or more and 200 ppm or less, and more preferably, 1 ppm or more and 30 ppm or less. This is because an appropriate amount of water contributes to passivation of aluminum in the non-aqueous electrolyte solution.
A specific composition of the non-aqueous electrolyte solution according to the fifteenth embodiment includes, for example, acetonitrile, imide salt such as LiN(SO 2 F) 2 or LiN(SO 2 CF 3 ) 2 , SAH, and LiPO 2 F 2 . In this case, in the non-aqueous secondary battery, there is no particular limitation in the negative electrode, the positive electrode, the separator, and the battery casing.
Sixteenth Embodiment: Non-Aqueous Electrolyte Solution
According to the sixteenth embodiment, the imide salt of the non-aqueous electrolyte solution of the fifteenth embodiment preferably includes at least one selected from a group consisting of LiN(SO 2 F) 2 and LiN(SO 2 CF 3 ) 2 . Only one or both of these imide salts may be included. Alternatively, any other imide salt may also be contained.
<div id="p
CLAIMS
Claims ( 16 )
The invention claimed is:
1. A non-aqueous secondary battery comprising:
a positive electrode having a positive-electrode active material layer formed on one surface or both surfaces of a positive electrode current collector;
a negative electrode having a negative-electrode active material layer formed on one surface or both surfaces of a negative electrode current collector; and
a non-aqueous electrolyte solution,
wherein the non-aqueous electrolyte solution contains acetonitrile and LiPO 2 F 2 , and
a value obtained by dividing a bulk resistance at a temperature of â30° C. by an internal resistance value in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.05 to 0.7, and
wherein an impedance is measured from a voltage/current response signal by applying an AC signal while changing a frequency of the AC signal within a range of 1000 kHz to 0.01 Hz, and the bulk resistance is obtained from a value intersecting with an abscissa of a complex impedance plot (cole-cole plot) and the internal resistance is obtained by adding the bulk resistance to a width of an arc of a high frequency side.
2. The non-aqueous secondary battery according to claim 1 , wherein the non-aqueous secondary battery contains a compound having at least one functional group selected from a group consisting of âNâ, âNH 4 , âNâO, âNHâNHâ, and (NO 3 ).
3. The non-aqueous secondary battery according to claim 1 , wherein the negative-electrode active material layer contains at least one compound selected from a group consisting of imide salt and (SO 4 ) 2â ,
wherein the imide salt is at least one selected from a group consisting of lithium salt and onium salt, and
wherein a bulk resistance at a temperature of 25° C. in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.025 ohm or smaller.
4. The non-aqueous secondary battery according to claim 1 , wherein the non-aqueous secondary battery contains at least one compound selected from a group consisting of organic acid, salt thereof, acid anhydride, and Li 2 O, and
the organic acid includes at least one of acetic acid, oxalic acid, and formic acid.
5. The non-aqueous secondary battery according to claim 1 , wherein the negative-electrode active material layer contains at least one compound selected from a group consisting of imide salt and (SO 4 ) 2â ,
wherein the imide salt is at least one selected from a group consisting of lithium salt and onium salt, and
wherein the bulk resistance at a temperature of â30° C. in measurement of electrochemical impedance spectroscopy for the non-aqueous secondary battery is 0.07 ohm or smaller.
6. The non-aqueous secondary battery according to claim 1 , wherein the non-aqueous secondary battery contains a compound having at least one functional group selected from a group consisting of âNâ, âNH 4 , âNâO, âNHâNHâ, and (NO 3 ),
wherein the non-aqueous secondary battery has a capacity retention rate of 70% or higher, the capacity retention rate being calculated by dividing a first capacity for a 5C discharge by a second capacity for a 1C discharge after a storage test for 4 hours at 85° C. and multiplying by 100%, and
wherein the 1C discharge is a current value at which a fully charged battery is discharged in one hour at a constant current to terminate the discharge and the 5C discharge is a current value at which a fully charged battery is discharged in twelve minutes at a constant current to terminate the discharge.
7. The non-aqueous secondary battery according to claim 1 , wherein the non-aqueous secondary battery contains at least one compound selected from a group consisting of organic acid, salt thereof, acid anhydride, and Li 2 O,
wherein the organic acid includes at least one of acetic acid, oxalic acid, and formic acid,
wherein the non-aqueous secondary battery has a capacity retention rate of 70% or higher, the capacity retention rate being calculated by dividing a first capacity for a 5C discharge by a second capacity for a 1C discharge after a storage test for 4 hours at 85° C. and multiplying by 100%, and
wherein the 1C discharge is a current value at which a fully charged battery is discharged in one hour at a constant current to terminate the discharge and the 5C discharge is a current value at which a fully charged battery is discharged in twelve minutes at a constant current to terminate the discharge.
8. The non-aqueous secondary battery according to claim 1 , wherein the non-aqueous secondary battery contains a compound having at least one functional group selected from a group consisting of âNâ, âNH 4 , âNâO, âNHâNHâ, and (NO 3 ), and
the non-aqueous secondary battery has a 0° C. ionic conductivity of 10 mS/cm or higher after a storage test for 4 hours at 85° C.
9. The non-aqueous secondary battery according to claim 1 , wherein the non-aqueous secondary battery contains at least a compound selected from a group consisting of organic acid, salt thereof, acid anhydride, and Li 2 O,
the organic acid includes at least one of acetic acid, oxalic acid, and formic acid, and
the non-aqueous secondary battery has a 0° C. ionic conductivity of 10 mS/cm or higher after a storage test for 4 hours at 85° C.
10. The non-aqueous secondary battery according to claim 1 , wherein the positive-electrode active material is a lithium-containing composite metal oxide expressed as Li Z MO 2 ,
wherein M contains Ni and one or more metal elements selected from a group consisting of Mn, Co, Al, and Mg, a content ratio of the Ni element is more than 50%, and
z is a number greater than 0.9 and smaller than 1.2.
11. The non-aqueous secondary battery according to claim 1 , wherein a gas generation amount in a storage test at 60° C. for 200 hours is 0.008 ml or less per 1 mAh.
12. The non-aqueous secondary battery according to claim 1 , wherein a resistance increase rate in a full-charge storage test at 60° C. for 720 hours is 400% or lower.
13. A cell pack comprising the non-aqueous secondary battery according to claim 1 ,
wherein the positive-electrode active material layer contains a lithium-containing compound including Fe,
wherein the negative-electrode active material layer contains graphite or at least one or more elements selected from a group consisting of Ti, V, Sn, Cr, Mn, Fe, Co, Ni, Zn, Al, Si, and B,
wherein the non-aqueous electrolyte solution contains cyclic carbonate without saturated secondary carbon,
wherein the cyclic carbonate without saturated secondary carbon is at least one selected from a group consisting of ethylene carbonate and vinylene carbonate,
wherein the cell pack includes:
one module having four cells of the non-aqueous second battery connected in series, or
at least two modules, connected in parallel, each of the at least two modules having four cells of the non-aqueous second battery connected in series, or
four modules, connected in series, each of the four modules having at least two cells of the non-aqueous second battery connected in parallel,
wherein an operation voltage range per cell is within a range of 1.8 to 3.7 V,
wherein an average operation voltage range per cell is 2.5 to 3.5 V, and
wherein the module is mounted with a battery management system (BMS).
14. A hybrid power system obtained by combining the cell pack according to claim 13 , and a module or cell pack having a secondary battery other than a lithium ion battery.
15. A cell pack comprising the non-aqueous secondary battery according to claim 1 , wherein the positive-electrode active material layer contains a lithium-containing compound including Fe,
wherein the negative-electrode active material layer contains graphite or at least one or more elements selected from a group consisting of Ti, V, Sn, Cr, Mn, Fe, Co, Ni, Zn, Al, Si, and B,
wherein the non-aqueous electrolyte solution contains cyclic carbonate without saturated secondary carbon,
wherein the cyclic carbonate without saturated secondary carbon is at least one selected from a group consisting of ethylene carbonate and vinylene carbonate,
wherein the cell pack is configured by connecting modules on the basis of Formula (2) and Formula (3), the module being obtained by connecting two or more cells in parallel,
Formula (2)=Number of cells connected in series per module (X): X=2, 4, 8, or 16,
Formula (3)=Number of modules connected in series per cell pack (Y): Y=16/X,
wherein an operation voltage range per cell is within a range of 1.8 to 3.7 V,
wherein an average operation voltage range per cell is 2.5 to 3.5 V, and
wherein the module is mounted with a battery management system (BMS).
16. A hybrid power system comprising the cell pack according to claim 15 , and a module or cell pack having a secondary battery other than a lithium ion battery in combination.
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