Specification
SPECIFICATION
Title of Invention: NON-AQUEOUS ELECTROLYTE SOLUTION AND ELECTRICITY-STORAGE DEVICE USING SAME Technical Field
[0001]
The present invention relates to a nonaqueous electrolytic solution capable of improving electrochemical characteristics at high temperatures, an energy storage device using it, and a specific organic phosphorus compound. Background Art
[0002]
In recent years, energy storage devices, especially lithium secondary batteries have been widely used as power supplies for electronic devices, such as mobile telephones, notebook-size personal computers and the like, power supplies for electric vehicles, as well as for electric power storage, etc. The batteries mounted on these electronic devices and vehicles may be used at midsummer high temperatures or in the environments warmed through heat generation by those electronic devices.
A lithium secondary battery, a type of energy storage device is mainly constituted of a positive electrode and a negative electrode containing a material capable of absorbing and releasing lithium, and a nonaqueous electrolytic solution containing a lithium salt and a non-aqueous solvent. For the non-aqueous solvent, used are carbonates, such as ethylene carbonate (EC), propylene carbonate (PC), etc.
As the negative electrode of the lithium secondary battery, known are metal lithium, and metal compounds (metal elemental
substances, oxides, alloys with lithium, etc.) and carbon materials capable of absorbing and releasing lithium. In particular, a lithium secondary battery using a nonaqueous electrolytic solution and using a carbon material capable of absorbing and releasing lithium, such as coke, graphite (artificial graphite, natural graphite) or the like, has been widely put into practical use. The above-mentioned negative electrode material stores and releases lithium and electron at an extremely electronegative potential equivalent to that for lithium metal, and therefore especially at high temperatures, there is a possibility that many solvents would be reductively decomposed by the negative electrode material of the type; and consequently, the solvent in the electrolytic solution would be partly reductively decomposed on the negative electrode irrespective of the type of the negative electrode material, and as a result, there occurs a problem in that lithium ion movement is thereby retarded owing to deposition of decomposed products and gas generation and the battery characteristics, such as cycle properties and the like especially at high temperatures are thereby worsened. Further, it is known that a lithium secondary battery using a lithium metal or its alloy, or a metal elemental substance, such as tin, silicon or the like or its metal oxide as the negative electrode material therein may have a high initial battery capacity but the battery capacity and the battery performance thereof, such as cycle properties greatly worsens, since the micronized powdering of the material is promoted during cycles thereby bringing about accelerated reductive decomposition of the non-aqueous solvent, as compared with the negative electrode of a carbon material. [0004]
On the other hand, a material capable of absorbing and releasing lithium, such as LiCoO2, LiMn2O4, LiNiO2 and LiFePO4 that are used as a positive electrode material stores and releases lithium and electron at a lithium-based electropositive voltage of not lower than 3.5 V, and therefore especially at high temperatures, there is a possibility that many solvents would be oxidatively decomposed by the positive electrode material of the type; and consequently, the solvent in the electrolytic solution would be partly oxidatively decomposed on the positive electrode irrespective of the type of the positive electrode material, and as a result, there occurs a problem in that lithium ion movement is thereby retarded owing to deposition of decomposed products and gas generation and the battery characteristics, such as cycle properties and the like are thereby worsened. [0005]
Despite the situation, electronic appliances equipped with lithium secondary batteries therein are offering more and more an increasing range of functions and are being in a stream of further increase in power consumption. With that, the capacity of lithium secondary batteries is being much increased, and the space volume for the nonaqueous electrolytic solution in the battery is decreased by increasing the density of the electrode and by reducing the useless space volume in the battery. Accordingly, the situation is that even decomposition of only a small amount of nonaqueous electrolytic solution may worsen battery performance at high temperatures.
PTL 1 proposes a nonaqueous electrolytic solution containing a phosphoric acid ester compound, such as triethylphosphonoacetate or the like, and indicates the possibility of enhancing continuous
charging characteristics and high-temperature storage
characteristics.
Citation List
Patent Literature
[0006]
PTL 1: WO2008/123038 Summary of THE Invention Technical Problem [0007]
An object of the present invention is to provide a nonaqueous electrolytic solution capable of improving electrochemical characteristics at high temperatures, an energy storage device using it, and a specific organic phosphorus compound. Solution to Problem [0008]
The present inventors have investigated in detail the performance of the nonaqueous electrolytic solutions in the above-mentioned prior art. As a result, the current situation is that the nonaqueous electrolytic solution of the above-mentioned patent literature could hot be said to be sufficiently satisfactory for the problem of improving the cycle properties of batteries at high temperatures especially under high charging voltage.
Given the situation, the present inventors have assiduously studied for the purpose of solving the above-mentioned problems, and have found that, when at least one specific organic phosphorus compound is added to a nonaqueous electrolytic solution of an electrolyte salt dissolved in a non-aqueous solvent, then the electrochemical characteristics of energy storage devices, especially the cycle properties of lithium batteries at high
temperatures can be improved, and have completed the present
invention.
[0009]
Specifically, the present invention provides the following (1) to (3) :
(1) A nonaqueous electrolytic solution of an electrolyte salt dissolved in a non-aqueous solvent, which comprises at least one organic phosphorus compound represented by the following general formula (I): [0010] [Chem. 1]
[0011]
(In the formula, R1 and R2 each independently represent an alkyl group having from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 6 carbon atoms, an alkenyl group having from 2 to 6 carbon atoms, an alkynyl group having from 3 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a cycloalkoxy group having from 3 to 6 carbon atoms, an alkenyloxy group having from 2 to 6 carbon atoms, an alkynyloxy group having from 3 to 6 carbon atoms, a halogenoalkyl group having from 1 to 6 carbon atoms, a halogenoalkoxy group having from 1 to 6 carbon atoms, an aryl group having from 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, or an aryloxy group having from 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and in a case where
R1 and R2 each are an alkyl group or an alkoxy group, R1 and R2 may-bond to form a cyclic structure.
R3 and R4 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having from 1 to 4 carbon atoms; m indicates an integer of from 1 to 4; n indicates 0 or 1; and q indicates 1 or 2.
In case where q is 1 and n is 0, X represents an alkoxy group having from 1 to 6 carbon atoms, an alkynyloxy group having from 3 to 6 carbon atoms, an alkyloxyalkoxy group having from 2 to 6 carbon atoms, an aryloxy group having from 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, -O-lZ-OC (=O) -C (=O) -OR5, -O-L2-C (=O) -OR5, or -0-L5-CN; in case where q is 1 and n is 1, X represents an alkyl group having from 1 to 6 carbon atoms, an alkynyl group having from 2 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an alkynyloxy group having from 3 to 6 carbon atoms, an alkyloxyalkoxy group having from 2 to 6 carbon atoms, or -C(=O)-0R5; in case where q is 2, X represents -O-L3-O-, -OC (=O) -C (=O) O- or a single bond. Further, R5 represents an alkyl group having from 1 to 6 carbon atoms; L1 and L3 each represent an alkylene group having from 2 to 6 carbon atoms, or an alkynylene group having from 4 to 8 carbon atoms; L2 and L5 each represent an alkyl ene group having from 1 to 6 carbon atoms. However, when q is 1, n is 0 and X is an alkoxy group having from 1 to 6 carbon atoms, then R1 and R2 bond to form a cyclic structure; when q is 1, n is 0 and X is an aryloxy group having from 6 to 12 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom, then R3 and R4 are both hydrogen atoms.) [0012]
(2) An energy storage device comprising a positive electrode, a negative electrode, and a nonaqueous electrolytic solution of an electrolyte salt dissolved in a non-aqueous solvent, wherein the nonaqueous electrolytic solution is the nonaqueous electrolytic solution of the above (1).
(3) An organic phosphorus compound represented by the following general formula (II): [0013] [Chem. 2]
[0014]
(In the formula, R1 and R2 each independently represent an alkyl group having from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 6 carbon atoms, an alkenyl group having from 2 to 6 carbon atoms, an alkynyl group having from 3 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a cycloalkoxy group having from 3 to 6 carbon atoms, an alkenyloxy group having from 2 to 6 carbon atoms, an alkynyloxy group having from 3 to 6 carbon atoms, a halogenoalkyl group having from 1 to 6 carbon atoms, a halogenoalkoxy group having from 1 to 6 carbon atoms, an aryl group having from 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, or an aryloxy group having from 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and in a case where R1 and R2 each are an alkyl group or an alkoxy group, R1 and R2 may bond to form a cyclic structure.
R3 and R4 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having from 1 to 4 carbon atoms; m indicates an integer of from 1 to 4; and q indicates 1 or 2. In case where q is 1, X1 represents an alkynyloxy group having from 3 to 6 carbon atoms, an aryloxy group having from 7 to 12 carbon atoms in which at least one hydrogen atom on the benzene ring is substituted with a trif luoromethyl group, -O-L1-OC (=O) -C (=O) -OR5, O-L2-C (=O)-OR5, or -O-L5-CN; in case where q is 2, X1 represents -O-L4-O-, or -OC(=O)-C(=O)O-. Further, R5 represents an alkyl group having from 1 to 6 carbon atoms; L1 represents an alkylene group having from 2 to 6 carbon atoms, or an alkynylene group having from 4 to 8 carbon atoms; L2 and L5 each represent an alkylene group having from 1 to 6 carbon atoms; and L4 represents an alkynylene group having from 4 to 8 carbon atoms.) Advantageous Effects of Invention [0015]
According to the present invention, there are provided a nonaqueous electrolytic solution capable of improving electrochemical characteristics at high temperatures, especially high-temperature cycle properties of energy storage devices, and an energy storage device, such as lithium batteries and others using the nonaqueous electrolytic solution. Description of Embodiments [0016]
The present invention relates to a nonaqueous electrolytic solution and an energy storage device using it. [0017] [Nonaqueous electrolytic solution]
The nonaqueous electrolytic solution of the present
invention comprises an electrolyte salt dissolved in a non-aqueous solvent, and comprises at least one organic phosphorus compound represented by the above-mentioned general formula (I). [0018]
Though not always clear, the reason why the nonaqueous electrolytic solution of the present invention can remarkably improve the cycle property of energy storage devices at high temperatures may be considered as follows:
The organic phosphorus compound in the present invention, as represented by the above-mentioned general formula (I), has three different substituents of a group P(=0)C-, a group C=0 and a specific substituent X. The site of the substituent X forms a dense and highly heat-resistant surface film through decomposition on a positive electrode and a negative electrode, and on the other hand, the compound contains two different, relatively weakly electron-attractive substituents of P(=0)C- and C=0 as the site that gently traps lithium ions inside the surface film, and therefore the lithium ion conductivity of the surface film greatly increases. Consequently, as compared with any other compound having only two of those three substituents, for example, triethylphosphonoacetate or the like compound having two, P (=0) C-and C=0 of those substituents, the compound could attain the effect of remarkably improving high-temperature cycle properties, which, however, the other compounds that have two such substituents could not attain. In a case where R1 and R2 bond to form a ring and even when the substituent X is an alkoxy group in the case, the cyclic structure moiety to be formed by R1 and R2 bonding to each other can form a dense and highly heat-resistant surface film on a positive electrode and a negative electrode, and therefore it is
considered that the compound of the case could also attain the same
effect.
[0019]
The organic phosphorus compound to be contained in the nonaqueous electrolytic solution of the present invention is represented by the following general formula (I): [0020] [Chem. 3]
[0021]
(In the formula, R1 and R2 each independently represent an alkyl group having from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 6 carbon atoms, an alkenyl group having from 2 to 6 carbon atoms, an alkynyl group having from 3 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a cycloalkoxy group having from 3 to 6 carbon atoms, an alkenyloxy group having from 2 to 6 carbon atoms, an alkynyloxy group having from 3 to 6 carbon atoms, a halogenoalkyl group having from 1 to 6 carbon atoms, a halogenoalkoxy group having from 1 to 6 carbon atoms, an aryl group having from 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, or an aryloxy group having from 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and in a case where R1 and R2 each are an alkyl group or an alkoxy group, R1 and R2 may bond to form a cyclic structure.
R3 and R4 each independently represent a hydrogen atom, a
halogen atom, or an alkyl group having from 1 to 4 carbon atoms; m indicates an integer of from 1 to 4; n indicates 0 or 1; and q indicates 1 or 2.
In case where q is 1 and n is 0, X represents an alkoxy group having from 1 to 6 carbon atoms, an alkynyloxy group having from 3 to 6 carbon atoms, an alkyloxyalkoxy group having from 2 to 6 carbon atoms, an aryloxy group having from 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, -O-lZ-OC (=0) -C (=0) -OR5, -0-L2-C (=0) -OR5, or -0-L5-CN; in case where q is 1 and n is 1, X represents an alkyl group having from 1 to 6 carbon atoms, an alkynyl group having from 2 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an alkynyloxy group having from 3 to 6 carbon atoms, an alkyloxyalkoxy group having from 2 to 6 carbon atoms, or -C(=0)-0R5; in case where q is 2, X represents -0-L3-0-, -0C (=0)-C (=0)0- or a single bond. Further, R5 represents an alkyl group having from 1 to 6 carbon atoms; L1 and L3 each represent an alkylene group having from 2 to 6 carbon atoms, or an alkynylene group having from 4 to 8 carbon atoms; L2 and L5 each represent an alkylene group having from 1 to 6 carbon atoms. However, when q is 1, n is 0 and X is an alkoxy group having from 1 to 6 carbon atoms, then R1 and R2 bond to form a cyclic structure; when q is 1, n is 0 and X is an aryloxy group having from 6 to 12 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom, then R3 and R4 are both hydrogen atoms.) [0022]
In the above-mentioned general formula (I), R1 and R2 each independently represent an alkyl group having from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 6 carbon atoms, an alkenyl
group having from 2 to 6 carbon atoms, an alkynyl group having from 3 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a cycloalkoxy group having from 3 to 6 carbon atoms, an alkenyloxy group having from 2 to 6 carbon atoms, an alkynyloxy group having from 3 to 6 carbon atoms, a halogenoalkyl group having from 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom, a halogenoalkoxy group having from 1 to 6 carbon atoms, an aryl group having from 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, or an aryloxy group having from 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and above all, preferably an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an alkynyloxy group having from 3 to 6 carbon atoms, more preferably an alkoxy group having 1 or 2 carbon atoms. [0023]
As specific examples of R1 and R2, preferably mentioned are a linear alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, etc.; a branched alkyl group, such as an iso-propyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, etc.; a cycloalkyl group, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.; an alkenyl group, such as a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 4-pentenyl group, a 5-hexenyl group, a 2-methyl-2-propenyl group, a 3-methyl-2-butenyl group, etc.; an alkynyl group, such as a 2-propynyl group, a 3-butynyl group, a 4-pentynyl group, a 5-hexynyl group, a 2-methyl-2-propynyl group, a 2,2-dimethyl-2-propynyl group, etc.; a linear alkoxy group, such
as a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, etc.; a branched alkoxy group, such as an iso-propoxy group, a sec-butoxy group, a tert-butoxy group, a tert-amyloxy group, etc.; a cycloalkoxy group, such as a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, etc.; an alkenyloxy group, such as a 2-propenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, a 4-pentenyloxy group, a 5-hexenyloxy group, etc.; an alkynyloxy group, such as a 2-propynyloxy group, a 3-butynyloxy group, a 4-pentynyloxy group, a 5-hexynyloxy group, a 2-methyl-2-propenyloxy group, a 3-methyl-2-butenyloxy group, etc.; an alkynyloxy group, such as a 2-propynyloxy group, a 3-butynyloxy group, a 4-pentynyloxy group, a 5-hexynyloxy group, a 2-methyl-2-propynyloxy group, a 2,2-dimethyl-2-propynyloxy group, etc.; an alkyl group in which the hydrogen atom is partly substituted with a fluorine atom, such as a fluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, etc.; an alkoxy group in which the hydrogen atom is partly substituted with a fluorine atom, such as a fluoromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, etc.; an aryl group, such as a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-tert-butylphenyl group, a 2,4,6-trimethylphenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 2,4,6-trifluorophenyl group, a pentafluorophenyl group, a 4-trifluoromethylphenyl group, etc.; an aryloxy group, such as a phenyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, a 4-methylphenyloxy group, a
4-tert-butylphenyloxy group, a 2, 4, 6-trimethylphenyloxy group, a 2-fluorophenyloxy group, a 3-fluorophenyloxy group, a 4-fluorophenyloxy group, a 2,4-difluorophenyloxy group, a 2,6-difluorophenyloxy group, a 3,4-difluorophenyloxy group, a 2, 4, 6-trifluorophenyloxy group, a pentafluorophenyloxy group, a 4-trifluoromethylphenyloxy group, etc.; a substituent to form a ring with R1 and R2, such a butane-1, 4-diyl group, a pentane-1,5-diyl group, -(CH2)30-, -(GH2)40-, an ethane-1,2-dioxy group, a propane-1,2-dioxy group, a propane-1,3-dioxy group, a butane-2,3-dioxy group, etc. Of those, preferred are a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a phenyl group, a phenyloxy group, and an ethane-1,2-dioxy group; and more preferred are a methoxy group, and an ethoxy group.
In a case where q is 1, n is 0 and X is an alkoxy group having from 1 to 6 carbon atoms, R1 and R2 may bond to form a cyclic structure. [0024]
R3 and R4 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having from 1 to 4 carbon atoms; and above all, each is preferably a hydrogen atom, or an alkyl group having from 1 to 4 carbon atoms.
As specific examples of R3 and R4, preferably mentioned are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an iso-propyl group, a sec-butyl group, and a tert-butyl group; and above all, preferred are a hydrogen atom, a fluorine atom, a methyl group and an ethyl group, and more preferred is a hydrogen atom.
When q is 1, n is 0 and X is an aryloxy group having from 6 to 12 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom, then R3 and R4 are both hydrogen atoms. [0025]
m indicates an integer of from 1 to 4, n indicates 0 or 1, and q indicates 1 or 2. m is preferably 1 or 2, n is preferably 0, and q is preferably 2. [0026]
In case where q is 1 and n is 0, X represents an alkoxy group having from 1 to 6 carbon atoms, an alkynyloxy group having from 3 to 6 carbon atoms, an alkyloxyalkoxy group having from 2 to 6 carbon atoms, an aryloxy group having from 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, -O-lZ-OC (=O) -C (=O) -OR5, -O-L2-C (=O) -OR5, or -O-L5-CN, and above all, X is preferably an alkynyloxy group having from 3 to 6 carbon atoms, an aryloxy group having from 6 to 12 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom, or -O-L2-C(=O)-0R5.
In case where q is 1 and n is 1, X represents an alkyl group having from 1 to 6 carbon atoms, an alkynyl group having from 2 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, an alkynyloxy group having from 3 to 6 carbon atoms, an alkyloxyalkoxy group having from 2 to 6 carbon atoms, or -C (=O) -OR5, and above all, X is preferably -C(=O)-0R5.
In case where q is 2, X represents -O-L3-O-, -0C (=O) -C(=O)O-or a single bond. Above all, X is preferably -0-L3-O-.
Further, L1 and L3 each represent an alkylene group having from 2 to 6 carbon atoms, or an alkynylene group having from 4 to
8 carbon atoms; L2 and L5 each represent an alkylene group having
from 1 to 6 carbon atoms.
[0027]
As specific examples of L1 and L3, preferably mentioned are an ethane-l,2-diyl group, a propane-1,3-diyl group, a propane-l,2-diyl group, a butane-1,4-diyl group, a butane-2,3-diyl group, a 2-butyne-l, 4-diyl group, a 3-hexyne-2,5-diyl group, and a 2,5-dimethyl-3-hexyne-2,5-diyl group; and above all, preferred are an ethane-l,2-diyl group, a propane-1,3-diyl group, a butane-2,3-diyl group, and a 2-butyne-l,4-diyl group.
As specific examples of L2 and L5, preferably mentioned are a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a butane-1,1-diyl group, and a butane-1,2-diyl group; and above all, preferred are a methylene group, an ethane-1,2-diyl group, and an ethane-1,1-diyl group. [0028]
As specific examples of R5, preferably mentioned are a linear alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, ann-pentyl group, an n-hexyl group, etc.; and a branched alkyl group, such as an iso-propyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, etc.; and above all, preferred are a methyl group and an ethyl group. [0029]
Specific examples of X are mentioned below.
(i) In the case where q is 1 and n is 0:
X is preferably a linear alkyloxy group, such as a methoxy
group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentoxy group, an n-hexyloxy group, etc.; a branched alkyloxy group, such as an iso-propoxy group, a sec-butoxy group, a tert-butoxy group, a tert-amyloxy group, etc.; analkynyloxy group, such as a 2-propynyloxy group, a 2-butynyloxy group, a 3-butynyloxy group, a 4-pentynyloxy group, a 5-hexynyloxy group, a l-methyl-2-propynyloxy group, a l-methyl-2-butynyloxy group, a
1, l-dimethyl-2-propynyloxy group, etc.; an alkyloxyalkoxy group, such as a 2-methoxyethoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-methoxypropoxy group, a 3-methoxypropoxy group, etc.; a phenoxy group in which at least one hydrogen atom is substituted with a halogen atom, such as a 2-fluorophenoxy group, a 3-fluorophenoxy group, a 4-fluorophenoxy group, a 2,4-dif luorophenoxy group, a 3, 5-dif luorophenoxy group, a 2,3, 5-trifluorophenoxy group, a 2, 4, 6-trifluorophenoxy group, a 2,3, 5, 6-tetrafluorophenoxy group, a pentafluorophenoxy group, a 2-trifluoromethylphenoxy group, a 3-trifluoromethylphenoxy group, a 4-trifluoromethylphenoxy group, a 2,4-bis(trifluromethyl)phenoxy group, a 3, 5-bis(trifluoromethyl)phenoxy group, a 2-chlorophenoxy group, a 3-chlorophenoxy group, a 4-chlorophenoxy group, a 2,4-dichlorophenoxy group, a 3,5-dichlorophenoxy group, a
2, 3,5-trichlorophenoxy group, a 2,4, 6-trichlorophenoxy group, a 2, 3,5, 6-tetrachlorophenoxy group, a pentachlorophenoxy group, a 2-trichloromethylphenoxy group, a 3-trichloromethylphenoxy group, a 4-trichloromethylphenoxy group, a 2,4-bis(trichloromethyl)phenoxy group, a 3,5-bis(trichloromethyl)phenoxy group, etc.; an alkoxy group having an oxalate structure, such as -OCH2CH2OC (=O)-C (=O) OCH3,
-OCH2CH2OC (=O) -C (=O) OCH2CH3, -OCH2CH2CH2OC (=O) -C (=O) OCH3/
-OCH2CH2CH2OC (=O) -C (=O) OCH2CH3, etc.; an alkynyloxy group having an oxalate structure, such as -OCH2C=CCH2OC (=O)-C (=O) 0CH3, -OCH2C=CCH2OC (=O) -C (=O) OCH2CH3/ etc.; an alkoxy group having an alkoxycarbonyl group, such as -0CH2C (=O) 0CH3, -0CH2 (C=O)OCH2CH3/ -OCH (CH3) C (=O)OCH3, -OCH (CH3) C (=O) OCH2CH3, -OCH (CH2CH3) C (=O) OCH3, -OCH(CH2CH3)C(=O)OCH2CH3, etc.; or an alkoxy group having a cyano group, such as -OCH2CN, -OCH2CH2CN, -OCH(CH3)CN, -OCH2CH2CH2CN, -OCH(CH2CH3)CN, -OCH2CH2CH2CH2CN, etc. Above all, preferred is a 2-propynyloxy group, a l-methyl-2-propynyloxy group, a 1,l-dimethyl-2-propynyloxy group, a 2-trifluoromethylphenoxy group, a 4-trifluoromethylphenoxy group, -0CH2C (=O) OCH3, -C€H2C (=O) OCH2CH3, -OCH(CH3) C (=O)OCH3, or 0CH(CH3) C (=O) O CH2CH3; and more preferred is a 2-propynyloxy group, -0CH2C (=O) OCH3, -OCH2C (=O) OCH2CH3, -OCH {CH3) C (=O) OCH3, -OCH (CH3) C (=O) OCH2CH3, -OCH2CN, -OCH2CH2CN, or -OCH(CH3)CN.
(ii) In the case where q is 1 and n is 1: X is preferably a linear alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, etc.; a branched alkyl group, such as an iso-propyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, etc.; an alkynyl group, such as an ethynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, etc.; a linear alkyloxy group, such as a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, etc.; a branched alkyloxy group, such as an iso-propoxy group, a sec-butoxy group, a tert-butoxy group, a tert-amyloxy group, etc.; an alkyloxyalkoxy group, such as a 2-methoxyethoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy
group, a 2-methoxypropoxy group, a 3-methoxypropoxy group, etc.; or an alkoxycarbonyl group, such as -C(=O)-OCH3, -C (=O) -OCH2CH3, etc. Above all, preferred is a methyl group, an ethyl group, an n-propyl group, an ethynyl group, a 2-propynyl group, a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-ethoxyethoxy .group, -C (=O)-OCH3, or -C (=O) -OCH2CH3; and more preferred is a methyl group, an ethyl group, an ethynyl group, a 2-propynyl group, -C(=O)-OCH3, or -C(=O)-0CH2CH3.
(iii) In the case where q is 2:
X is preferably an alkanedioxy group, such as an ethane-l,2-dioxy group, a propane-l,2-dioxy group, a propane-1,3-dioxy group, a butane-1,4-dioxy group, a butane-2,3-dioxy group, etc.; an alkynedioxy group, such as a 2-butyne-l,4-dioxy group, a 3-hexyne-2,5-dioxy group, a 2,5-dimethyl-3-hexyne-2,5-dioxy group, etc.; -C(=0)-C(=0)-, a single bond, etc. Above all, preferred is an ethane-l,2-dioxy group, a 2-butyne-l,4-dioxy group, or a single bond. [0030]
Specific examples of the organic phosphorus compound represented by the above-mentioned general formula (I) are mentioned below.
(i) As the case where q is 1 and n is 0:
Preferably mentioned are 2-propynyl
2-(dimethylphosphoryl)acetate, l-methyl-2-propynyl
2-(dimethylphosphoryl)acetate, 1, l-dimethyl-2-propynyl
2-(dimethylphosphoryl)acetate, 2-propynyl
2-(diethylphosphoryl)acetate, l-methyl-2-propynyl
2-(diethylphosphoryl)acetate, 1, l-dimethyl-2-propynyl
2-(diethylphosphoryl)acetate, 2-propynyl
2-(dipropylphosphoryl)acetate, l-methyl-2-propynyl
2-(dipropylphosphoryl) acetate, 1,l-dimethyl-2-propynyl
2-(dipropylphosphoryl)acetate, 2-propynyl
2-(dibutylphosphoryl)acetate, l-methyl-2-propynyl
2-(dibutylphosphoryl)acetate, 1, l-dimethyl-2-propynyl
2-(dibutylphosphoryl)acetate, 2-propynyl
2- (di-isopropylphosphoryl) acetate, l-methyl-2-propynyl
2- (di-isopropylphosphoryl) acetate, 1, l-dimethyl-2-propynyl
2-(di-isopropylphosphoryl)acetate, 2-propynyl
2-(dicyclopropylphosphoryl)acetate, 2-propynyl
2-(dicyclobutylphosphoryl)acetate, 2-propynyl
2-(dicyclopentylphosphoryl)acetate, 2-propynyl
2-(dicyclohexylphosphoryl)acetate, l-methyl-2-propynyl
2-(dicyclohexylphosphoryl)acetate, 1,1-dimethy1-2-propynyl
2-(dicyclohexylphosphoryl)acetate, 2-propynyl
2- (di (2-propenyl) phosphoryl) acetate, l-methyl-2-propynyl
2-(di(2-propenyl)phosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(di(2-propenyl)phosphoryl)acetate, 2-propynyl
2- (di (2-butenyl)phosphoryl) acetate, l-methyl-2-propynyl
2-(di(2-butenyl)phosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(di(2-butenyl)phosphoryl)acetate, 2-propynyl
2-(di(3-butenyl)phosphoryl)acetate, 2-propynyl
2-(di(4-pentenyl)phosphoryl)acetate, 2-propynyl
2-(di(5-hexenyl)phosphoryl)acetate, 2-propynyl
2-(bis (2-methyl-2-propenyl)phosphoryl)acetate, 2-propynyl
2- (bis (3-methyl-2-butenyl)phosphoryl)acetate, 2-propynyl
2-(di(2-propynyl)phosphoryl)acetate, 1-methy1-2-propynyl
2- (di (2-propynyl)phosphoryl) acetate, 1, l-dimethyl-2-propynyl
2-(di(2-propynyl)phosphoryl)acetate, 2-propynyl
2-(di(3-butynyl)phosphoryl)acetate, 2-propynyl
2-(di(4-pentynyl)phosphoryl)acetate, 2-propynyl
2-(di(5-hexynyl)phosphoryl)acetate, 2-propynyl
2-(bis(l-methyl-2-propynyl)phosphoryl)acetate, 2-propynyl
2-(bis(1,l-dimethyl-2-propynyl)phosphoryl) acetate, 2-propynyl
2-(bis(3,3,3-trifluoroethyl)phosphoryl)acetate,
1-methyl-2-propynyl
2-(bis(3,3,3-trifluoroethyl)phosphoryl)acetate,
1,l-dimethyl-2-propynyl
2- (bis (3,3,3-trifluoroethyl)phosphoryl)acetate, 2-propynyl
2- (diphenylphosphoryl)acetate, l-methyl-2-propynyl
2-(diphenylphosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(diphenylphosphoryl) acetate, 2-propynyl
2-(bis(4-methylphenyl)phosphoryl)acetate, l-methyl-2-propynyl
2-(bis(4-methylphenyl)phosphoryl)acetate,
1,1-dimethyl-2-propynyl
2-(bis(4-methylphenyl)phosphoryl)acetate, 2-propynyl
2- (bis(4-fluorophenyl)phosphoryl)acetate, l-methyl-2-propynyl
2-(bis(4-fluorophenyl)phosphoryl)acetate,
1,1-dimethyl-2-propynyl
2-(bis(4-fluorophenyl)phosphoryl)acetate, 2-propynyl
2-(dimethylphosphoryl)propanoate, 2-propynyl
2-(diethylphosphoryl)propanoate, 2-propynyl
2-(diphenylphosphoryl)propanoate, 2-propynyl
2-(dimethylphosphoryl)butanoate, 2-propynyl
2-(diethylphosphoryl)butanoate, 2-propynyl
2-(diphenylphosphoryl)butanoate, 2-propynyl
3-(dimethylphosphoryl)propanoate, 2-propynyl
3-(diethylphosphoryl)propanoate, 2-propynyl
3-(diphenylphosphoryl)propanoate, 2-propynyl
4-(dimethylphosphoryl)butanoate, 2-propynyl
4-(diethylphosphoryl)butanoate, 2-propynyl
4-(diphenylphosphoryl)butanoate, 2-propynyl
2-(dimethylphosphoryl)-2-fluoroacetate, 2-propynyl
2-(diethylphosphoryl)-2-fluoroacetate, 2-propynyl
2-(diphenylphosphoryl)-2-fluoroacetate, 2-propynyl
2- (methoxy(methyl)phosphoryl)acetate, l-methyl-2-propynyl
2- (methoxy(methyl)phosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(methoxy(methyl)phosphoryl)acetate, 2-propynyl
2-(ethoxy(ethyl)phosphoryl)acetate, l-methyl-2-propynyl
2-(ethoxy(ethyl)phosphoryl)acetate, 1,l-dimethyl-2-propynyl
2- (ethoxy(ethyl)phosphoryl)acetate, 2-propynyl
2-(cyclohexyloxy(methyl)phosphoryl)acetate, 2-propynyl
2-(methyl(2-propenyloxy)phosphoryl)acetate, 2-propynyl
2-(methyl(2-propynyloxy)phosphoryl)acetate, 2-propynyl
2-(methoxy(methyl)phosphoryl)propanoate, 2-propynyl
2-(ethoxy(ethyl)phosphoryl)propanoate, 2-propynyl
2-(methoxy(methyl)phosphoryl)butanoate, 2-propynyl
2-(ethoxy(ethyl)phosphoryl)butanoate, 2-propynyl
3-(methoxy(methyl)phosphoryl)propanoate, 2-propynyl
3-(ethoxy(ethyl)phosphoryl)propanoate, 2-propynyl
4-(methoxy(methyl)phosphoryl)butanoate, 2-propynyl
4-(ethoxy(ethyl)phosphoryl)butanoate, 2-propynyl
2-(methoxy(methyl)phosphoryl)-2-fluoroacetate, 2-propynyl
2-(ethoxy(ethyl)phosphoryl)-2-fluoroacetate, 2-propynyl
2-(dimethoxyphosphoryl)acetate, 2-butynyl
2-(dimethoxyphosphoryl)acetate, 3-butynyl
2-(dimethoxyphosphoryl)acetate, 4-pentynyl
2-(dimethoxyphosphoryl)acetate, 5-hexynyl
2-(dimethoxyphosphoryl)acetate, l-methyl-2-propynyl
2-(dimethoxyphosphoryl)acetate, l-methyl-2-butynyl
2-(dimethoxyphosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(dimethoxyphosphoryl)acetate, 2-propynyl
2-(diethoxyphosphoryl)acetate, 2-butynyl
2-(diethoxyphosphoryl)acetate, 3-butynyl
2-(diethoxyphosphoryl)acetate, 4-pentynyl
2-(diethoxyphosphoryl)acetate, 5-hexynyl
2-(diethoxyphosphoryl)acetate, l-methyl-2-propynyl
2-(diethoxyphosphoryl)acetate, l-methyl-2-butynyl
2-(diethoxyphosphoryl)acetate, 1, l-dimethyl-2-propynyl
2-(diethoxyphosphoryl)acetate, 2-propynyl
2-(dipropoxyphosphoryl)acetate, l-methyl-2-propynyl
2-(dipropoxyphosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(dipropoxyphosphoryl)acetate, 2-propynyl
2-(dibutoxyphosphoryl)acetate, 1-methyl-2-propynyl
2-(dibutoxyphosphoryl)acetate, 1, l-dimethyl-2-propynyl
2-(dibutoxyphosphoryl)acetate, 2-propynyl
2-(di-isopropoxyphosphoryl) acetate, l-methyl-2-propynyl
2-(di-isopropoxyphosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(di-isopropoxyphosphoryl)acetate, 2-propynyl
2-(di(cyclopropyloxy)phosphoryl)acetate, 2-propynyl
2-(di(cyclobutyloxy)phosphoryl)acetate, 2-propynyl
2-(di(cyclopentyloxy)phosphoryl)acetate, 2-propynyl
2-(di(cyclohexyloxy)phosphoryl)acetate, l-methyl-2-propynyl
2-(di(cyclohexyloxy)phosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(di(cyclohexyloxy)phosphoryl)acetate, 2-propynyl
2-(di(2-propenyloxy)phosphoryl)acetate, l-methyl-2-propynyl
2-(di(2-propenyloxy)phosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(di(2-propenyloxy)phosphoryl) acetate, 2-propynyl
2-(di(2-butenyloxy)phosphoryl)acetate, l-methyl-2-propynyl
2-(di(2-butenyloxy)phosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(di(2-butenyloxy)phosphoryl)acetate, 2-propynyl
2-(di(3-butenyloxy)phosphoryl)acetate, 2-propynyl
2-(di(4-pentenyloxy)phosphoryl)acetate, 2-propynyl
2-(di(5-hexenyloxy)phosphoryl)acetate, 2-propynyl
2-(bis(2-methyl-2-propenyloxy)phosphoryl)acetate, 2-propynyl
2-(bis(3-methyl-2-butenyloxy)phosphoryl)acetate, 2-propynyl
2-(di(2-propynyloxy)phosphoryl)acetate, l-methyl-2-propynyl
2-(di(2-propynyloxy)phosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(di(2-propynyloxy)phosphoryl)acetate, 2-propynyl
2-(di(3-butynyloxy)phosphoryl)acetate, 2-propynyl
2-(di(4-pentynyloxy)phosphoryl)acetate, 2-propynyl
2-(di(5-hexynyloxy)phosphoryl)acetate, 2-propynyl
2-(bis(l-methyl-2-propynyloxy)phosphoryl)acetate, 2-propynyl 2-(bis(1, l-dimethyl-2-propynyloxy)phosphoryl)acetate, 2-propynyl 2- (bis(3,3,3-trifluoroethoxy)phosphoryl)acetate, l-methyl-2-propynyl
2-(bis(3, 3,3-trifluoroethoxy)phosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(bis(3, 3,3-trifluoroethoxy)phosphoryl)acetate, 2-propynyl
2-(diphenoxyphosphoryl)acetate, 1-methyl-2-propynyl
2-(diphenoxyphosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(diphenoxyphosphoryl)acetate, 2-propynyl
2- (bis(4-methylphenoxy)phosphoryl)acetate, 1-methyl-2-propynyl 2-(bis(4-methylphenoxy)phosphoryl)acetate, 1,l-dimethyl-2-propynyl
2-(bis(4-methylphenoxy)phosphoryl)acetate, 2-propynyl
2-(bis(4-fluorophenoxy)phosphoryl)acetate, l-methyl-2-propynyl
2-(bis(4-fluorophenoxy)phosphoryl)acetate,
1,l-dimethyl-2-propynyl
2-(bis(4-fluorophenoxy)phosphoryl)acetate, 2-propynyl
2-(dimethoxyphosphoryl)propanoate, 2-propynyl
2-(diethoxyphosphoryl)propanoate, 2-propynyl
2-(diphenoxyphosphoryl)propanoate, 2-propynyl
2-(dimethoxyphosphoryl)butanoate, 2-propynyl
2-(diethoxyphosphoryl)butanoate, 2-propynyl
2-(diphenoxyphosphoryl)butanoate, 2-propynyl
3-(dimethoxyphosphoryl)propanoate, 2-propynyl
3-(diethoxyphosphoryl)propanoate, 2-propynyl
3-(diphenoxyphosphoryl)propanoate, 2-propynyl
4-(dimethoxyphosphoryl)butanoate, 2-propynyl
4-(diethoxyphosphoryl)butanoate, 2-propynyl
4-(diphenoxyphosphoryl)butanoate, 2-propynyl
2-(dimethoxyphosphoryl)-2-fluoroacetate, 2-propynyl
2- (diethoxyphosphoryl)-2-fluoroacetate, 2-propynyl
2-(diphenoxyphosphoryl)-2-fluoroacetate, 2-methoxyethyl
2- (dimethoxyphosphoryl)acetate, 2-ethoxyethyl
2- (dimethoxyphosphoryl)acetate, 2-butoxyethyl
2-(dimethoxyphosphoryl)acetate, 2-methoxypropyl
2- (dimethoxyphosphoryl)acetate, 3-methoxypropyl
2- (dimethoxyphosphoryl)acetate, 2-methoxyethyl
2- (diethoxyphosphoryl)acetate, 2-ethoxyethyl
2- (diethoxyphosphoryl)acetate, 2-butoxyethyl
2- (diethoxyphosphoryl)acetate, 2-methoxypropyl
2-(diethoxyphosphoryl)acetate, 3-methoxypropyl
2- (diethoxyphosphoryl)acetate, 2-fiuorophenyl
2- (dimethoxyphosphoryl)acetate, 2-fIuorophenyl
2- (diethoxyphosphoryl)acetate, 4-fIuorophenyl
2-(dimethoxyphosphoryl)acetate, 4-fIuorophenyl
2- (diethoxyphosphoryl)acetate, 2,4-difIuorophenyl
2- (dimethoxyphosphoryl)acetate, 2,4-difIuorophenyl
2-(diethoxyphosphoryl)acetate, 2,4,6-trifIuorophenyl
2-(dimethoxyphosphoryl)acetate, 2,4,6-trifIuorophenyl
2- (diethoxyphosphoryl)acetate, pentafIuorophenyl
2-(dimethoxyphosphoryl)acetate, pentafIuorophenyl
2-(diethoxyphosphoryl)acetate, 2-trifluoromethylphenyl
2-(dimethoxyphosphoryl)acetate, 2-trifluoromethylphenyl
2-(diethoxyphosphoryl)acetate, 3-trif luoromethylphenyl
2-(dimethoxyphosphoryl)acetate, 3-trifluoromethylphenyl
2-(diethoxyphosphoryl)acetate, 4-trifluoromethylphenyl
2-(dimethoxyphosphoryl)acetate, 4-trifluoromethylphenyl
2-(diethoxyphosphoryl)acetate, 2,4-bis(trifluoromethyl)phenyl
2-(dimethoxyphosphoryl)acetate, 2,4-bis(trifluoromethyl)phenyl
2-(diethoxyphosphoryl)acetate, 3,5-bis{trifluoromethyl)phenyl
2-(dimethoxyphosphoryl)acetate, 3,5-bis(trifluoromethyl)phenyl
2-(diethoxyphosphoryl)acetate, 2-chlorophenyl
2-(dimethoxyphosphoryl)acetate, 2-chlorophenyl
2-(diethoxyphosphoryl)acetate, 4-chlorophenyl
2- (dimethoxyphosphoryl)acetate, 4-chlorophenyl
2-(diethoxyphosphoryl)acetate, 2,4-dichlorophenyl
2-(dimethoxyphosphoryl)acetate, 2,4-dichlorophenyl
2- (diethoxyphosphoryl)acetate, 2,4,6-trichlorophenyl
2-(dimethoxyphosphoryl)acetate, 2,4,6-trichlorophenyl
2-(diethoxyphosphoryl)acetate, pentachlorophenyl
2-(dimethoxyphosphoryl)acetate, pentachlorophenyl
2-(diethoxyphosphoryl)acetate, 2-trichloromethylphenyl 2-(dimethoxyphosphoryl)acetate, 2-trichloromethylphenyl 2-(diethoxyphosphoryl)acetate, 3-trichloromethylphenyl 2-(dimethoxyphosphoryl)acetate, 3-trichloromethylphenyl 2-(diethoxyphosphoryl)acetate, 4-trichloromethylphenyl 2-(dimethoxyphosphoryl)acetate, 4-trichloromethylphenyl 2-(diethoxyphosphoryl)acetate, 2, 4-bis(trichloromethyl)phenyl 2-(dimethoxyphosphoryl)acetate, 2,4-bis(trichloromethyl)phenyl 2-(diethoxyphosphoryl)acetate, 3,5-bis(trichloromethyl)phenyl 2-(dimethoxyphosphoryl)acetate, 3,5-bis(trichloromethyl)phenyl 2-(diethoxyphosphoryl)acetate,
2-(2-(dime thoxyphosphoryl)acetoxy)ethyl methyl oxalate,
2-(2-(dimethoxyphosphoryl)acetoxy)ethyl ethyl oxalate,
2-(2-(diethoxyphosphoryl)acetoxy)ethyl methyl oxalate,
2-(2-(diethoxyphosphoryl)acetoxy)ethyl ethyl oxalate,
2-(3-(diethoethoxyphosphoryl)acetoxy) propyl methyl oxalate,
2-(3-(diethoxyphosphoryl)acetoxy)propyl ethyl oxalate,
4-(2-(diethoxyphosphoryl)acetoxy)-2-butyn-l-yl methyl oxalate,
4-(2-(diethoxyphosphoryl)acetoxy)-2-butyn-l-yl ethyl oxalate,
methyl 2-((diethoxyphosphoryl)acetoxy)acetate, ethyl
2-( (diethoxyphosphoryl)acetoxy)acetate, methyl
2-(2-(dimethoxyphosphoryl)acetoxy)propanoate, ethyl
2-(2-(dimethoxyphosphoryl)acetoxy)propanoate, methyl
2-(2-(diethoxyphosphoryl)acetoxy)propanoate, ethyl
2-(2-(diethoxyphosphoryl)acetoxy)propanoate, methyl
2-(2-(diethoxyphosphoryl)acetoxy)butanoate, ethyl
2-(2-(diethoxyphosphoryl)acetoxy)butanoate, cyanomethyl 2-(dimethoxyphosphoryl)acetate, cyanomethyl
2-(diethoxyphosphoryl)acetate, 2-cyanoethyl
2-(dimethoxyphosphoryl)acetate, 2-cyanoethyl
2-(diethoxyphosphoryl) acetate, 1-cyanoethyl
2-(diethoxyphosphoryl) acetate, 3-cyanopropyl
2-(diethoxyphosphoryl)acetate, 1-cyanopropyl
2-(diethoxyphosphoryl)acetate, 4-cyanobutyl
2-(diethoxyphosphoryl) acetate, etc.
Further, as preferred examples of the compound where (i) q is 1 and n is 0 and where R1 and R2 form a ring, there are mentioned
methyl 2-(1-oxidophospholan-l-yl) acetate, ethyl
2-(1-oxidophospholan-l-yl)acetate, 2-propynyl
2-(1-oxidophospholan-l-yl)acetate, methyl
2-(1-oxidophosphorinan-l-yl)acetate, ethyl
2-(1-oxidophosphorinan-l-yl)acetate, 2-propynyl
2-(1-oxidophosphorinan-l-yl)acetate, methyl
2-(2-oxido-l,2-oxaphospholan-2-yl)acetate, ethyl
2-(2-oxido-l,2-oxaphospholan-2-yl)acetate, 2-propynyl
2-(2-oxido-l,2-oxaphospholan-2-yl)acetate, methyl
2-(2-oxido-l,2-oxaphosphorinan-2-yl)acetate, ethyl
2-(2-oxido-l,2-oxaphosphorinan-2-yl)acetate, 2-propynyl
2-(2-oxido-l,2-oxaphosphorinan-2-yl)acetate, methyl
2-(2-oxido-l,3,2-dioxaphospholan-2-yl)acetate, ethyl
2-(2-oxido-l,3,2-dioxaphospholan-2-yl)acetate, 2-propynyl
2-(2-oxido-l,3,2-dioxaphospholan-2-yl)acetate, methyl
2-(2-oxido-l,3,2-dioxaphosphorinan-2-yl)acetate, ethyl
2-(2-oxido-l,3,2-dioxaphosphorinan-2-yl)acetate, 2-propynyl
2-(2-oxido-l,3,2-dioxaphosphorinan-2-yl)acetate, methyl
2-(4, 5-dimethyl-2-oxido-l,3,2-dioxaphospholan-2-yl)acetate;
ethyl
2-(4,5-dimethyl-2-oxido-l,3,2-dioxaphospholan-2-yl)acetate,
2-propynyl
2-(4,5-dimethyl-2-oxido-l,3,2-dioxaphospholan-2-yl)acetate,
etc.
[0031]
(ii) As the case where q is 1 and n is 1:
Preferably mentioned are (dimethoxyphosphoryl)methyl
acetate, (diethoxyphosphoryl) methyl acetate,
(dimethoxyphosphoryl)methyl propanoate,
(diethoxyphosphoryl)methyl propanoate,
(dimethoxyphosphoryl)methyl butanoate,
(diethoxyphosphoryl)methyl butanoate,
(dimethoxyphosphoryl)methyl isobutyrate,
(diethoxyphosphoryl)methyl isobutyrate,
(dimethoxyphosphoryl)methyl propiolate,
(diethoxyphosphoryl)methyl propiolate,
(dimethoxyphosphoryl)methyl 3-butynoate,
(diethoxyphosphoryl)methyl 3-butynoate,
(dimethoxyphosphoryl)methyl methyl carbonate,
(diethoxyphosphoryl)methyl methyl carbonate,
(dimethoxyphosphoryl)methyl ethyl carbonate,
(diethoxyphosphoryl)methyl ethyl carbonate,
(dimethoxyphosphoryl)methyl 2-propynyl carbonate,
(diethoxyphosphoryl)methyl 2-propynyl carbonate,
(dimethoxyphosphoryl)methyl l-methyl-2-propynyl carbonate,
(diethoxyphosphoryl)methyl l-methyl-2-propynyl carbonate,
(dimethoxyphosphoryl)methyl methoxyethyl carbonate,
(diethoxyphosphoryl)methyl methoxyethyl carbonate,
(dimethoxyphosphoryl)methyl ethoxyethyl carbonate,
(diethoxyphosphoryl)methyl ethoxyethyl carbonate,
(dimethoxyphosphoryl)methyl methyl oxalate,
(diethoxyphosphoryl)methyl methyl oxalate,
(dimethoxyphosphoryl)methyl ethyl oxalate,
(diethoxyphosphoryl)methyl ethyl oxalate, etc. [0032]
(iii) As the case where q is 2:
Preferably mentioned are ethane-l,2-diyl
bis(2-(dimethoxyphosphoryl)acetate), ethane-1,2-diyl
bis(2-(diethoxyphosphoryl)acetate), propane-1,2-diyl
bis(2-(dimethoxyphosphoryl)acetate), propane-1,2-diyl
bis(2-(diethoxyphosphoryl)acetate), propane-1,3-diyl
bis(2-(dimethoxyphosphoryl)acetate), propane-1,3-diyl
bis(2-(diethoxyphosphoryl)acetate), butane-1,4-diyl
bis(2-(dimethoxyphosphoryl)acetate), butane-1,4-diyl
bis(2-(diethoxyphosphoryl)acetate), butane-2,3-diyl
bis(2-(dimethoxyphosphoryl)acetate), butane-2,3-diyl
bis(2-(diethoxyphosphoryl)acetate), 2-butyne-l,4-diyl
bis(2-(dimethoxyphosphoryl)acetate), 2-butyne-l,4-diyl
bis(2-(diethoxyphosphoryl)acetate), 3-hexyne-2,5-diyl
bis(2-(diethoxyphosphoryl)acetate), 2, 5-dimethyl-3-hexyne-2,5-diyl bis(2-(diethoxyphosphoryl)acetate),
bis((dimethoxyphosphoryl)methyl) oxalate,
bis((diethoxyphosphoryl)methyl) oxalate, etc. [0033]
Of the above-mentioned (i) to (iii), more preferred is one or more selected from 2-propynyl 2-(dimethylphosphoryl)acetate, 2-propynyl 2-(diethylphosphoryl)acetate, 2-propynyl
2-(methoxy(methyl)phosphoryl) acetate, 2-propynyl
2-(ethoxy(ethyl)phosphoryl)acetate, 2-propynyl
2-(dimethoxyphosphoryl)acetate, 2-propynyl
2-(diethoxyphosphoryl)acetate, 2-propynyl
2-(diphenylphosphoryl)acetate, 2-propynyl
2- (diphenoxyphosphoryl)acetate, 2-propynyl
2-(diethoxyphosphoryl)-2-fluloracetate, 2-propynyl
2-(dimethoxyphosphoryl)propanoate, 2-propynyl
2-(diethoxyphosphoryl)propanoate, 2-propynyl
3-(dimethoxyphosphoryl)propanoate, 2-propynyl
3-(diethoxyphosphoryl)propanoate, l-methyl-2-propynyl
2-(diethoxyphosphoryl)acetate, 1,1-dimethyl-2-propynyl
2-(diethoxyphosphoryl)acetate, 2-methoxyethyl
2-(dimethoxyphosphoryl)acetate, 2-methoxyethyl
2-(diethoxyphosphoryl)acetate, 2-trifluoromethylphenyl
2-(dimethoxyphosphoryl)acetate, 3-trifluoromethylphenyl
2-(diethoxyphosphoryl)acetate, 4-trifluoromethylphenyl
2-(dimethoxyphosphoryl)acetate, 4-trifluoromethylphenyl
2-(diethoxyphosphoryl)acetate, methyl
2-(2-oxido-l,3,2-dioxaphospholan-2-yl)acetate, ethyl
2-(2-oxido-l,3,2-dioxaphospholan-2-yl)acetate, 2-propynyl
2-(2-oxido-l, 3,2-dioxaphospholan-2-yl)acetate,
2-(2-(diethoxyphosphoryl)acetoxy)ethyl methyl oxalate,
-2-(2-(diethoxyphosphoryl)acetoxy)ethyl ethyl oxalate, methyl
2-(2-(diethoxyphosphoryl)acetoxy)propanoate, ethyl
2-(2-(diethoxyphosphoryl)acetoxy)propanoate,
(dimethoxyphosphoryl)methyl acetate, (diethoxyphosphoryl)methyl acetate, (dimethoxyphosphoryl)methyl methyl oxalate,
(diethoxyphosphoryl)methyl methyl oxalate, ethane-l,2-diyl
bis (2- (dimethoxyphosphoryl) acetate), ethane-1, 2-diyl
bis(2-(diethoxyphosphoryl)acetate), butane-2,3-diyl
bis(2-(dimethoxyphosphoryl)acetate), butane-2,3-diyl
bis(2-(diethoxyphosphoryl)acetate), 2-butyne-l,4-diyl bis(2-(dimethoxyphosphoryl)acetate), 2-butyne-l,4-diyl bis(2-(diethoxyphosphoryl)acetate),
bis((dimethoxyphosphoryl)methyl) oxalate,
bis((diethoxyphosphoryl)methyl) oxalate, cyanomethyl
2-(dimethoxyphosphoryl)acetate, cyanomethyl
2-(diethoxyphosphoryl)acetate, 2-cyanoethyl
2-(dimethoxyphosphoryl) acetate, 2-cyanoethyl
2-(diethoxyphosphoryl) acetate, and 1-cyanoethyl
2-(diethoxyphosphoryl) acetate; and even more preferred are
2-propynyl 2-(diethylphosphoryl)acetate, 2-propynyl
2-(ethoxy(ethyl)phosphoryl)acetate, 2-propynyl
2-(dimethoxyphosphoryl)acetate, 2-propynyl
2-(diethoxyphosphoryl)acetate, 2-propynyl
2-(diphenoxyphosphoryl)acetate, 2-propynyl
2-(diethoxyphosphoryl)-2-fluoroacetate, 2-propynyl
3-(diethoxyphosphoryl)propanoate, l-methyl-2-propynyl
2-(diethoxyphosphoryl) acetate, 1, l-dimethyl-2-propynyl
2-(diethoxyphosphoryl) acetate, 2-methoxyethyl
2-(diethoxyphosphoryl) acetate, 2-trifluoromethylphenyl
2-(diethoxyphosphoryl)acetate, 4-trifluoromethylphenyl
2-(diethoxyphosphoryl)acetate, methyl
2-(2-oxido-l,3,2-dioxaphospholan-2-yl)acetate, 2-propynyl 2-(2-oxido-l,3,2-dioxaphospholan-2-yl)acetate, 2-(2-(diethoxyphosphoryl)acetoxyl)ethyl methyl oxalate, methyl 2-(2-(diethoxyphosphoryl)acetoxyl)propanoate,
(diethoxyphosphoryl)methyl acetate, (diethoxyphosphoryl)methyl
methyl oxalate, ethane-l,2-diyl
bis(2-(diethoxyphosphoryl)acetate), 2-butyne-l,4-diyl bis(2-(diethoxyphosphoryl)acetate),
bis((dimethoxyphosphoryl)methyl) oxalate,
bis ((diethoxyphosphoryl)methyl) oxalate, and 2-cyanoethyl 2- (diethoxyphosphoryl)acetate.
The compounds of which the substituents fall within any of the above-mentioned ranges are preferred, as capable of considerably improving the electrochemical characteristics of energy storage devices at high temperatures. [0034]
In the nonaqueous electrolytic solution of the present invention, the content of the organic phosphorus compound represented by the above-mentioned general formula (I) is preferably from 0.001 to 10% by mass of the nonaqueous electrolytic solution. When the content is at most 10% by mass, then the risk of excessive formation of a surface film on the electrode to worsen the high-temperature cycle property of batteries could be low; and when at least 0.001% by mass, then the surface film formation would be sufficient and the effect of improving high-temperature cycle properties could be improved. The content is more preferably at least 0.05% by mass of the nonaqueous electrolytic solution, even more preferably at least 0.2% by mass, and its upper limit is preferably at most 8% by mass, more preferably at most 5% by mass, even more preferably at most 2% by mass. [0035]
In the nonaqueous electrolytic solution of the present invention, combining the organic phosphorus compound represented
by the above-mentioned general formula (I) with the nonaqueous
solvent, electrolyte salt and other additives to be mentioned below
exhibits a specific effect of synergistically improving
electrochemical characteristics at high temperatures.
[0036]
[Nonaqueous Solvent]
The nonaqueous solvent for use in the nonaqueous electrolytic solution of the present invention includes cyclic carbonates, linear esters, lactones, ethers, and amides. Preferably, the solvent contains, both a cyclic carbonate and a linear ester.
The term "linear ester" is used here as a concept including linear carbonates and linear carboxylates.
As the cyclic carbonates, there may be mentioned at least one selected from ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 4-fluoro-l,3-dioxolan-2-one (FEC), trans or cis-4,5-difluoro-l,3-dioxolan-2-one (hereinafter the two are collectively called "DFEC"), vinylene carbonate (VC), and vinylethylene carbonate (VEC).
Of those, preferred is use of at least one cyclic carbonate having a carbon-carbon double bond or a fluorine atom, as markedly improving high-temperature cycle properties; and more preferred is use of both a cyclic carbonate having a carbon-carbon double bond and a cyclic carbonate having a fluorine atom. As the cyclic carbonate having a carbon-carbon double bond, more preferred are VC and VEC; and as the cyclic carbonate having a fluorine atom, more preferred are FEC and DFEC. [0037]
The content of the carbon-carbon double bond-containing cyclic carbonate is preferably at least 0.07% by volume relative to the total volume of the nonaqueous solvent, more preferably at least 0.2% by volume, even more preferably at least 0.7% by volume, and the upper limit thereof is preferably at most 7% by volume, more preferably at most 4% by volume, even more preferably at most 2.5% by volume. The range is preferred as capable of markedly improving the stability of surface film during high-temperature cycles.
The content of the fluorine atom-containing cyclic carbonate is preferably at least 0.07% by volume relative to the total volume of the nonaqueous solvent, more preferably at least 4% by volume, even more preferably at least 7% by volume, and the upper limit thereof is preferably at most 35% by volume, more preferably at most 25% by volume, even more preferably at most 15% by volume. The range is preferred as capable of markedly improving the stability of surface film during high-temperature cycles.
In case where the nonaqueous solvent contains both a carbon-carbon double bond-containing cyclic carbonate and a fluorine atom-containing cyclic carbonate, the content of the carbon-carbon double bond-containing cyclic carbonate relative to the content of the fluorine atom-containing cyclic carbonate is preferably at least 0.2% by volume, more preferably at least 3% by volume, even more preferably at least 7% by volume, and its upper limit is preferably at most 40% by volume, more preferably at most 30% by volume, even more preferably at most 15% by volume. The range is preferred as capable of markedly improving the stability of surface film during high-temperature cycles.
Preferably, the nonaqueous solvent contains ethylene
carbonate and/or propylene carbonate, as the resistance of the surface film formed on electrodes can be reduced. Preferably, the content of ethylene carbonate and/or propylene carbonate is at least 3% by volume relative to the total volume of the nonaqueous solvent, more preferably at least 5% by volume, even more preferably at least 7% by volume, and its upper limit is preferably at most 45% by volume, more preferably at most 35% by volume, even more preferably at most 25% by volume. [0038]
One kind of those solvents may be used, but using two or more different kinds thereof as combined is preferred as further improving electrochemical characteristics at high temperatures. Even more preferably, three or more different kinds are combined. Preferred combinations of the cyclic carbonates include EC and PC; EC and VC; PC and VC; VC and FEC; EC and FEC; PC and FEC; FEC and DFEC; EC and DFEC; PC and DFEC; VC and DFEC; VEC and DFEC; EC and PC and VC; EC and PC and FEC; EC and VC and FEC; EC and VC and VEC; PC and VC and FEC; EC and VC and DFEC; PC and VC and DFEC; EC and PC and VC and FEC; EC and PC and VC and DFEC; etc. Of those combinations, more preferred combinations are EC and VC; EC and FEC; PC and FEC; EC and PC and VC; EC and PC and FEC; EC and VC and FEC; PC and VC and FEC; EC and PC and VC and FEC; etc. [0039]
As the linear esters, preferably mentioned are asymmetric linear carbonates, such as methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, and ethyl propyl carbonate, etc.; symmetric linear carbonates, such as dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, dibutyl carbonate, etc.; pivalates,
such as methyl pivalate, ethyl pivalate, propyl pivalate, etc.; linear carboxylates, such as methyl propionate, ethyl propionate, methyl acetate, ethyl acetate, etc.
Of the above-mentioned linear esters, preferred are methyl group-having linear esters selected from dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, methyl propionate, methyl acetate and ethyl acetate; and more preferred are methyl group-having linear carbonates.
Preferably, two or more different types of linear carbonates are used here. More preferably, a combination of a symmetric linear carbonate and an asymmetric linear carbonate is used; and even more preferably, the content of the symmetric linear carbonate is larger than that of the asymmetric linear carbonate. [0040]
Not specifically defined, the content of the linear ester is preferably within a range of from 60 to 90% by volume relative to the total volume of the nonaqueous solvent. When the content is at least 60% by volume, then the viscosity of the nonaqueous electrolytic solution would not be too high; and when at most 90% by volume, then the risk of lowering the electric conductivity of the nonaqueous electrolytic solution to worsen electrochemical characteristics at high temperatures maybe low. For these reasons, the above-mentioned range is preferred here.
Preferably, two or more different types of linear carbonates are used here. More preferably, a combination of a symmetric linear carbonate and an asymmetric linear carbonate is used; and even more preferably, the content of the symmetric linear carbonate is larger than that of the asymmetric linear carbonate.
The ratio by volume of the symmetric linear carbonate to the linear carbonate is preferably at least 51% by volume, more preferably at least 55% by volume, and its upper limit is preferably at most 95% by volume, more preferably at most 85% by volume. Especially preferably, the symmetric linear carbonate for use herein contains dimethyl carbonate. Also preferably, the asymmetric linear carbonate for use herein has a methyl group, and especially preferred is use of methyl ethyl carbonate here.
The above-mentioned embodiments are preferred as improving electrochemical characteristics at high temperatures.
The ratio of the cyclic carbonate to the linear ester, cyclic carbonate/linear ester (by volume) is preferably from 10/90 to 45/55, more preferably from 15/85 to 40/60, even more preferably from 20/80 to 35/65, from the viewpoint of improving electrochemical characteristics at high temperatures. [0041]
As other nonaqueous solvents preferred for use herein, there are mentioned cyclic ethers, such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, etc.; linear ethers, such as 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, etc.; amides, such as dimethylformamide, etc.; sulfones, such as sulfolane, etc.; lactones, such as y-butyrolactone, y-valerolactone, a-angelicalactone, etc. [0042]
For the purpose of markedly improving electrochemical characteristics at high temperatures, it is desirable that any other additive is further added to the nonaqueous electrolytic solution.
As preferred examples of the other additives, further mentioned are phosphorus-containing compounds, such as trimethyl phosphate, tributyl phosphate, trioctyl phosphate, methyl methylenebisphosphonate, ethyl methylenebisphosphonate, methyl ethylenebisphosphonate, ethyl ethylenebisphosphonate, methyl butylenebisphosphonate, ethyl butylenebisphosphonate, methyl dime thy lphosphonoacet ate, ethyl dime thy lphosphonoacetate, methyl diethylphosphonoacetate, ethyl diethylphosphonoacetate, methyl pyrophosphate, ethyl pyrophosphate, etc.; benzene compounds with an aliphatic hydrocarbon group having from 1 to 6 carbon atoms and bonding to the benzene ring via a tertiary carbon atom or a quaternary carbon atom, such as cyclohexylbenzene, fluorocyclohexylbenzene (l-fluoro-2-cyclohexylbenzene, l-fluoro-3-cyclohexylbenzene, l-fluoro-4-cyclohexylbenzene), tert-butylbenzene, 1,3-di-tert-butylbenzene, tert-amylbenzene, l-fluoro-4-tert-butylbenzene, etc.; oxalates, such as dimethyl oxalate, ethylmethyl oxalate, diethyl oxalate, etc.; nitriles, such as acetonitrile, propionitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, etc.; isocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, etc.; triple bond-having compounds such as 2-propynylmethyl carbonate, 2-propynyl acetate, 2-propynyl formate, 2-propynyl methacrylate, 2-propynyl methanesulfonate, di(2-propynyl) oxalate, di(2-propynyl) glutarate, 2-butyne-l,4-diyl dimethanesulfonate, 2-butyne-l,4-diyl diformate, 2,4-hexadiyne-l,6-diyl dimethanesulfonate, etc.; S=0 group-containing compounds selected from sultones, such as 1,3-propanesultone, 1,3-butanesultone, 1, 4-butanesultone, etc., cyclic sulfites, such as ethylene sulfite,
hexahydrobenzo[l,3,2]dioxathiol-2-oxide (also referred to as
1,2-cyclohexanediol cyclic sulfite),
5-vinyl-hexahydrobenzo[1,3,2]dioxathiol-2-oxide, 4-(methylsulfonylmethyl)-l,3,2-dioxathiolane-2-oxide, etc., sulfonates such as butane-1,4-diyl dimethanesulfonate, pentane-1,5-diyl dimethanesulfonate, propane-l,2-diyl dimethanesulfonate, butane-2,3-diyl dimethanesulfonate, dimethyMethylene disulfonate, methylenemethane disulfonate, 2-trifluoromethylphenyl methanesulfonate, pentafluorophenyl methanesulfonate, etc., and vinyl sulf ones, such as di vinyl sulf one, 1,2-bis(vinylsulfonyl)ethane, bis(2-vinylsulfonylethyl) ether, etc.; phosphoric acid anhydrides, such as tetramethyldiphosphonic acid anhydride, tetraethyldiphosphonic acid anhydride, etc.; linear carboxylic acid anhydrides, such as acetic anhydride, propionic anhydride, etc.; cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, 3-sulfo-propionic acid anhydride, etc.; cyclic phosphazenes, such as methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene,
ethoxypentafluorocyclotetraphosphazene, etc.; aromatic compounds,
such as partial hydrides of biphenyl, terphenyl (o-, m-, p-form),
diphenyl ether, fluorobenzene, difluorobenzene (o-, m-, p-form),
anisole, 2,4-difluoroanisole or terphenyl
(1,2-dicyclohexylbenzene, 2-phenylbicyclohexyl,
1,2-diphenylcyclohexane, o-cyclohexylbiphenyl), etc. [0043]
Of the above, more preferred are nitriles and/or aromatic compounds, since the nonaqueous electrolytic solution containing
any of them can markedly improve battery characteristics at high temperatures. Of nitriles, more preferred is at least one selected from succinonitrile, glutaronitrile, adiponitrile and pimelonitrile. Of aromatic compounds, more preferred are biphenyl, cyclohexylbenzene, tert-butylbenzene, and tert-amylbenzene. The content of nitrile and/or aromatic compound in the nonaqueous electrolytic solution is preferably from 0.001 to 5% by mass. When the content is more than 0.001% by mass, then the surface film formation would be sufficient and the effect of improving high-temperature cycle properties could be thereby improved. The content is more preferably at least 0.005% by mass in the nonaqueous electrolytic solution, even more preferably at least 0.01% by mass, still more preferably at least 0.03% by mass, and its upper limit is preferably at most 3% by mass, more preferably at most 1% by mass, even more preferably at most 0.4% by mass. [0044]
Also preferably, the nonaqueous electrolytic solution contains any of (a) a triple bond-having compound, (b) a cyclic or linear S=0 group-having compound selected from sultones, cyclic sulfites, sulfonates, and vinyl sulfones, or (c) a phosphorus-containing compound, as capable of markedly improving electrochemical characteristics at high temperatures.
As the triple bond-having compound (a), preferred is 2-propynyl methyl carbonate, 2-propynyl methacrylate, 2-propynyl methanesulfonate, di (2-propynyl) oxalate, or 2-butyne-l,4-diyl dimethanesulfonate; and more preferred is at least one selected from 2-propynyl methanesulfonate, di(2-propynyl) oxalate, and 2-butyne-l,4-diyl dimethanesulfonate.
The content of the triple bond-having compound in the
nonaqueous electrolytic solution is preferably from 0.001 to 5% by mass. When the content is more than 0.001% by mass, then the surface film formation would be sufficient and the effect of improving high-temperature cycle properties could be thereby improved. The content is more preferably at least 0.005% by mass in the nonaqueous electrolytic solution, even more preferably at least 0.01% by mass, still more preferably at least 0.03% by mass, and its upper limit is preferably at most 3% by mass, more preferably at most 1% by mass, even more preferably at most 0.7% by mass. [0045]
As the cyclic S=O group-having compound (but not containing
a triple bond) (b), preferred is at least one selected from
1,3-propanesultone, 1,3-butanesultone, 1,4-butanesultone,
2,4-butanesultone, methylene methanedisulfonate, ethylene
sulfite, and
4-(methylsulfonylmethyl)-l,3,2-dioxathiolane-2-oxide; and more preferred is at least one selected from 1,3-propanesultone, 1,4-butanesultone, and 2, 4-butanesultone.
As the linear S=0 group-having compound, preferred is butane-2,3-diyl dimethanesulfonate, butane-l,4-diyl dimethanesulfonate, dimethyl methanedisulfonate, 2-trifluoromethylphenyl methanesulfonate, pentafluorophenyl methanesulfonate, divinyl sulfone, or bis(2-vinylsulfonylethyl) ether; more preferred is at least one sulfonate selected from butane-2,3-diyl dimethanesulfonate, butane-1, 4-diyl dimethanesulfonate, dimethyl methanedisulfonate, 2-trifluoromethylphenyl methanesulfonate, and pentafluorophenyl methanesulfonate; and even more preferred is at least one selected from butane-2,3-diyl dimethanesulfonate, and pentafluorophenyl
methanesulfonate.
The content of the S=0 group-having compound in the nonaqueous electrolytic solution is preferably from 0.001 to 5% by mass. When the content is more than 0.001% by mass, then the surface film formation would be sufficient and the effect of improving high-temperature cycle properties could be thereby improved. The content is more preferably at least 0.005% by mass in the nonaqueous electrolytic solution, even more preferably at least 0.01% by mass, still more preferably at least 0.03% by mass, and its upper limit is preferably at most 3% by mass, more preferably at most 1% by mass, even more preferably at most 0.7% by mass. [0046]
As the phosphorus-containing compound (c), more preferred is at least one selected from trimethyl phosphate, methyl methylenebisphosphonate, ethyl methylenebisphosphonate, methyl diethylphosphonoacetate, ethyl diethylphosphonoacetate, and ethyl pyrophosphate; and even more preferred is at least one selected from ethyl methlenebisphosphonate, ethyl diethylphosphonoacetate and ethyl pyrophosphate.
The content of the phosphorus-containing compound in the nonaqueous electrolytic solution is preferably from 0.001 to 5% by mass. When the content is more than 0.001% by mass, then the surface film formation would be sufficient and the effect of improving high-temperature cycle properties could be thereby improved. The content is more preferably at least 0.005% by mass in the nonaqueous electrolytic solution, even more preferably at least 0.01% by mass, still more preferably at least 0.03% by mass, and its upper limit is preferably at most 3% by mass, more preferably at most 1% by mass, even more preferably at most 0.7% by mass, and
r
especially preferably at most 0.4% by mass.
[0047]
[Electrolyte Salt]
As the electrolyte salt for use in the present invention, preferably mentioned are the following lithium salts and onium salts. (Lithium Salt)
The lithium salt includes inorganic lithium salts, such as
LiPF6, LiPO2F2, Li2PO3F, LiBF4, LiClO4, LiSO3F, etc; linear
fluoroalkyl group-having lithium salts, such as LiN(SO2CF3)2,
LiN(SO2C2F5)2, LiCF3S03/ LiC (SO2CF3) 3, LiPF4(CF3)2, LiPF3 (C2F5) 3,
LiPF3(CF3)3, LiPF3(iso-C3F7)3, LiPF5 (iso-C3F7) , etc.; cyclic
fluoroalkylene chain-having lithium salts, such as (CF2)2 (SO2)2NLi,
(CF2)3(SO2)2NLi, etc.; and lithium salts with an oxalate complex
as the anion therein, such as lithium bis[oxalate-0,0']borate,
lithium difluoro[oxalate-O,O']borate, lithium
difluorobis[oxalate-O,O*]phosphate, lithium
tetrafluoro[oxalate-O,O' ]phosphate, etc. One or more of these.as
combined may be used here. Of those, preferred is at least one
selected from LiPF6/ LiPO2F2/ Li2PO3F, LiBF4, LiSO3F, LiN(SO2CF3)2 and
LiN(SO2C2F5)2, LiN(SO2F)2, lithium
difluorobis[oxalate-O,O']phosphate and lithium tetrafluoro[oxalate-O,O1]phosphate; and more preferred is at least one selected from LiPF6, LiP02F2, LiBF4, LiN(SO2CF3)2, LiN(SO2F)2, and lithium difluorobis [oxalate-O,O']phosphate. The concentration of the lithium salt is, in general, preferably at least 0.3 M relative to the above-mentioned nonaqueous solvent, more preferably at least 0.7 M, even more preferably at least 1.1 M. The upper limit of the content is preferably at most 2.5 M,
more preferably at most 2.0 M, even more preferably at most 1.6 M.
A preferred combination of these lithium salts to be
contained in the nonaqueous electrolytic solution comprises LiPF6
and contains at least one lithium salt selected from LiPO2F2, LiBF4,
LiN(SO2CF3)2, LiN(SO2F)2 and lithium
difluorobis[oxalate-0,O']phosphate. The proportion of the lithium salt except LiPF6 in the nonaqueous solvent is preferably at least 0.001 M, as readily exhibiting the effect of improving electrochemical characteristics at high temperatures, and is also preferably at most 0.005 M as free from the risk of lowering the effect of improving electrochemical characteristics at high temperatures. More preferably, the proportion is at least 0.01 M, even more preferably at least 0.03 M, and most preferably at least 0.04 M. The upper limit of the proportion is preferably at most 0.4 M, more preferably at most 0.2 M. [0048] (Onium Salt)
Preferred examples of the onium salt are various salts of a combination of an onium cation and an anion mentioned below.
As specific examples of the onium cation, preferably
mentioned are a tetramethylammonium cation, an
ethyltrimethylammonium cation, a diethyldimethylammonium cation,
a triethylmethylammonium cation, a tetraethylammonium cation, an
N,N-dimethylpyrrolidinium cation, an
N-ethyl-N-methylpyrrolidinium cation, an
N,N-diethylpyrrolidinium cation, a spiro-(N,N')-bipyrrolidinium
cation, an N,N'-dimethylimidazolinium cation, an
N-ethyl-N'-methylimidazolinium cation, an
N/N'-diethylimidazolinium cation, an ^N'-dimethylimidazolinium cation, an N-ethyl-N' -methylimidazolinium cation, an N,N'-diethylimidazolinium cation, etc.
Preferred examples of the anion include a PF6 anion, a BF4 anion, a C1O4 anion, an AsF6 anion, a CF3SO3 anion, an N(CF3SO 2)2 anion, an N(C2F5SO2)2 anion, etc.
One alone or two or more different types of these onium salts may be used here either singly or as combined. [0049] [Production of Nonaqueous Electrolytic Solution]
The nonaqueous electrolytic solution of the present invention may be produced, for example, by mixing the above-mentioned nonaqueous solvents, adding the above-mentioned electrolyte salt, and further adding thereto the organic phosphorus compound represented by the above-mentioned general formula (I) to the resulting nonaqueous electrolytic solution.
Preferably, the nonaqueous solvent to be used and the compound to be added to the nonaqueous electrolytic solution are previously purified to reduce as much as possible the content of impurities therein within a range not extremely detracting from the productivity. [0050]
The nonaqueous electrolytic solution of the present invention can be used in the first to fourth energy storage devices mentioned below, in which as the nonaqueous electrolyte, not only a liquid one but also a gelled one may be used. Further, the nonaqueous electrolytic solution of the present invention can also be used for solid polymer electrolytes. Especially preferably, the solution is used in the first energy storage device where a
I
i
lithium salt is used as the electrolyte salt (that is, for lithium batteries), or in the fourth energy storage device (that is, for lithium ion capacitors); and more suitably, the solution is used for lithium batteries, even more preferably for lithium secondary batteries. [0051] [First Energy Storage Device (lithium battery)]
The lithium battery in this specification means a generic name for a lithium primary battery and a lithium secondary battery. In this specification, the term, lithium secondary battery is used as a concept that includes so-called lithium ion secondary batteries. The lithium battery of the present invention comprises a positive electrode, a negative electrode, and the above-mentioned nonaqueous electrolytic solution of an electrolyte salt dissolved in a nonaqueous solvent. The other constitutive members, such as the positive electrode, the negative electrode and others than the nonaqueous electrolytic solution are not specifically defined for use herein.
For example, as the positive electrode active material for lithium secondary batteries, usable is a complex metal oxide of lithium and one or more selected from cobalt, manganese and nickel. One alone or two or more of these positive electrode active materials may be used here either singly or as combined.
The lithium complex metal oxide includes, for example, LiCoO2, LiMn2O4, LiNiO2, LiCo1-xNixO2 (0.01
Documents
Application Documents
| # |
Name |
Date |
| 1 |
8020-CHENP-2013 ABSTRACT 03-10-2013.pdf |
2013-10-03 |
| 1 |
8020-CHENP-2013 FORM-1 01-01-2015.pdf |
2015-01-01 |
| 2 |
8020-CHENP-2013 CORRESPONDENCE OTHERS 03-10-2013.pdf |
2013-10-03 |
| 2 |
8020-CHENP-2013 CORRESPONDENCE OTHES 01-01-2015.pdf |
2015-01-01 |
| 3 |
abstract8020-CHENP-2013.jpg |
2014-07-11 |
| 3 |
8020-CHENP-2013 POWER OF ATTORNEY 03-10-2013.pdf |
2013-10-03 |
| 4 |
8020-CHENP-2013 CORRESPONDENCE OTHERS 03-04-2014.pdf |
2014-04-03 |
| 4 |
8020-CHENP-2013 PCT 03-10-2013.pdf |
2013-10-03 |
| 5 |
8020-CHENP-2013 FORM-3 03-04-2014.pdf |
2014-04-03 |
| 5 |
8020-CHENP-2013 FORM-5 03-10-2013.pdf |
2013-10-03 |
| 6 |
8020-CHENP-2013.pdf |
2013-10-09 |
| 6 |
8020-CHENP-2013 FORM-3 03-10-2013.pdf |
2013-10-03 |
| 7 |
8020-CHENP-2013 FORM-1 03-10-2013.pdf |
2013-10-03 |
| 7 |
8020-CHENP-2013 DESCRIPTION (COMPLETE) 03-10-2013.pdf |
2013-10-03 |
| 8 |
8020-CHENP-2013 ENGLISH TRANSLATION 03-10-2013.pdf |
2013-10-03 |
| 8 |
8020-CHENP-2013 CLAIMS 03-10-2013.pdf |
2013-10-03 |
| 9 |
8020-CHENP-2013 FORM-2 03-10-2013.pdf |
2013-10-03 |
| 10 |
8020-CHENP-2013 CLAIMS 03-10-2013.pdf |
2013-10-03 |
| 10 |
8020-CHENP-2013 ENGLISH TRANSLATION 03-10-2013.pdf |
2013-10-03 |
| 11 |
8020-CHENP-2013 FORM-1 03-10-2013.pdf |
2013-10-03 |
| 11 |
8020-CHENP-2013 DESCRIPTION (COMPLETE) 03-10-2013.pdf |
2013-10-03 |
| 12 |
8020-CHENP-2013.pdf |
2013-10-09 |
| 12 |
8020-CHENP-2013 FORM-3 03-10-2013.pdf |
2013-10-03 |
| 13 |
8020-CHENP-2013 FORM-3 03-04-2014.pdf |
2014-04-03 |
| 13 |
8020-CHENP-2013 FORM-5 03-10-2013.pdf |
2013-10-03 |
| 14 |
8020-CHENP-2013 CORRESPONDENCE OTHERS 03-04-2014.pdf |
2014-04-03 |
| 14 |
8020-CHENP-2013 PCT 03-10-2013.pdf |
2013-10-03 |
| 15 |
abstract8020-CHENP-2013.jpg |
2014-07-11 |
| 15 |
8020-CHENP-2013 POWER OF ATTORNEY 03-10-2013.pdf |
2013-10-03 |
| 16 |
8020-CHENP-2013 CORRESPONDENCE OTHES 01-01-2015.pdf |
2015-01-01 |
| 16 |
8020-CHENP-2013 CORRESPONDENCE OTHERS 03-10-2013.pdf |
2013-10-03 |
| 17 |
8020-CHENP-2013 FORM-1 01-01-2015.pdf |
2015-01-01 |
| 17 |
8020-CHENP-2013 ABSTRACT 03-10-2013.pdf |
2013-10-03 |