Specification
SPECIFICATION NONAQUEOUS ELECTROLYTE SOLUTION AND LITHIUM SECONDARY
BATTERY USING SAME
[0001]
The present invention relates to a nonaqueous electrolytic solution that can produce a lithium secondary battery exhibiting excellent battery characteristics, such as electrical capacity, cycle property and storage property, and to a lithium secondary battery using the nonaqueous electrolytic solution.
Background Art [0002]
In recent years, lithium secondary batteries have been widely used as driving power supplies for small electronic devices and the like. Such lithium secondary batteries are mainly constituted of a positive electrode comprised of a lithium compound oxide, a negative electrode comprised of a carbon material or a lithium metal, and a nonaqueous electrolytic solution. As the nonaqueous electrolytic solution, carbonates such as ethylene carbonate (EC) and propylene carbonate (PC) are used.
A lithium secondary battery using, for example, LiCo02, LiMn204 or LiNi02 as a positive electrode material brings about a reduction of the battery performance, when part of the solvent of the nonaqueous electrolytic solution locally undergoes an oxidative decomposition during the charging,
because the decomposition products inhibit the desired electrochemical reaction of the battery. Such a reduction is considered to be attributed to an electrochemical oxidation of the solvent at the interface between the positive electrode
Also, a lithium secondary battery using, for example, a highly crystallized carbon material, such as natural graphite or artificial graphite, as a negative electrode material brings about a reduction of the battery performance, when the solvent of the nonaqueous electrolytic solution undergoes a reductive decomposition on the surface of the negative electrode during the charging. Even in the case of EC, which is widely used as a solvent for the nonaqueous electrolytic solution, it partly undergoes reductive decomposition during repeated charging and discharging cycles, resulting in reduction of the battery performance.
Particularly, decomposition of the nonaqueous electrolytic solution on the positive electrode and the negative electrode causes gas generation, which leads to expansion of the battery and impairs mobility of lithium ions as a result of trapping of the gas between the electrodes, thereby reducing the battery performance. [0003]
Techniques for improving the battery characteristics of such lithium secondary batteries are known, for example, in Patent Documents 1 to 5. Patent Document 1 discloses a nonaqueous electrolytic solution containing 0.05% to 10% by volume of glycol sulfite (also referred to as ethylene sulfite) as a cyclic sulfite. However, this document
does not describe the retention of capacity at high temperatures.
Patent Document 2 discloses a nonaqueous electrolytic solution containing erythritan sulfite as a
merely 3 cycles are tested, and cycle property, for example, after 100 cycles is not evaluated. This document also does not describe cycle property in a high-temperature environment.
Patent Document 3 discloses a nonaqueous electrolytic solution containing ethylene sulfite, erythritan sulfite and the like to improve cycle property. However, this nonaqueous electrolytic solution exhibits a low charging and discharging efficiency and insufficient characteristics in a high-temperature environment.
Patent Document 4 discloses a nonaqueous electrolytic solution containing ethylene sulfite and vinylene carbonate. In an optimum Example, this document describes that the retention of capacity after 100 cycles at 45°C is 90.0%. However, a nonaqueous electrolytic solution having a higher retention of capacity is still desired.
Patent Document 5 discloses a nonaqueous electrolytic solution containing l,3,2-dioxathiolane-2,2-dioxide and the like as a sulfate compound for lithium secondary batteries and describes excellent storage property of the battery which is left to stand at high temperatures in a charged state. In this nonaqueous electrolytic solution, the battery characteristics are
improved to some extent but are still far from satisfaction. Nonaqueous electrolytic solutions and lithium secondary batteries having further improved characteristics are needed.
[Patent Document 1] Japanese Unexamined Patent Application Publication No. 9-120837
[Patent Document 2] Japanese Unexamined Patent Application Publication No. 2000-188127
[Patent Document 3] Japanese Unexamined Patent Application Publication No. 2002-270230
[Patent Document 4] Japanese Unexamined Patent Application Publication No. 2002-25611
[Patent Document 5] Japanese Unexamined Patent Application Publication No. 2004-185931
Disclosure of the Invention [0005]
It is an object of the present invention to provide a nonaqueous electrolytic solution having excellent battery characteristics such as electrical capacity, cycle property and storage property and capable of maintaining excellent long-term battery performance, and to provide a lithium secondary battery using the nonaqueous electrolytic solution.
The inventors have found that incorporation of a specific amount of a specific 1,2-cyclohexanediol derivative into a nonaqueous electrolytic solution can reduce gas generation even when the battery is stored at high temperatures in a highly charged state, and can maintain the
battery performance such as long-term cycle property, and have accomplished the present invention.
Thus, the present invention provides the following aspects (1) and (2):
salt is dissolved in a nonaqueous solvent, comprising 0.01% to 30% by weight of at least one compound selected from the group consisting of 1,2-cyclohexanediol cyclic sulfite, 1,2-cyclohexanediol cyclic carbonate, hexahydro-1,3,2-benzodioxathiol-2,2-dioxide, and 1,2-cyclohexanediol derivatives represented by the following general formula (X) , on the basis of the weight of the nonaqueous electrolytic solution: [0006]
wherein R1 to R10 each independently represent a hydrogen atom, a CI to C12 alkyl group, a C2 to C12 alkenyl group, a C2 to C12 alkynyl group, a C6 to C18 aryl group, or a CI to C12 alkoxy group, and may bond to each other to form a ring structure, and any hydrogen atom of R1 to R10 may be substituted by a halogen atom, with the proviso that the case where all of R1 to R10 are hydrogen atoms is excluded; and X
represents a >S=0 group or a >C=0 group.
[0008]
(2) A lithium secondary battery comprising a positive
electrode, a negative electrode, and a nonaqueous electrolytic
nonaqueous solvent, wherein the nonaqueous electrolytic solution comprises 0.01% to 30% by weight of at least one compound selected from the group consisting of 1,2-cyclohexanediol cyclic sulfite, 1,2-cyclohexanediol cyclic carbonate, hexahydro-1,3,2-benzodioxathiol-2,2-dioxide, and 1,2-cyclohexanediol derivatives represented by the general formula (X) , on the basis of the weight of the nonaqueous electrolytic solution.
The lithium secondary battery using the nonaqueous electrolytic solution of the present invention can exhibit excellent battery characteristics such as electrical capacity, cycle property and storage property, and more particularly, can exhibit excellent long-term battery performance in a high-temperature environment.
Detailed Description of the Invention
[0009]
[1,2-Cyclohexanediol cyclic sulfite]
1,2-Cyclohexanediol cyclic sulfites used in the present invention are sulfite compounds represented by the following general formula (I): [0010] [Formula 2]
[0011]
18-4) represented by the formula (I) include a cis isomer (CAS No. 19456-18-9) represented by the following formula (II) and a trans isomer (GAS No. 19456-19-0) represented by the following formula (III): [0012]
The trans isomer is preferred to the cis isomer, but a mixture (hereinafter, may be referred to as "isomer mixture") of the trans and cis isomers mixed at a specific ratio may also be used. In particular, the ratio of the trans isomer to the cis isomer (weight ratio) preferably ranges from 50/50 to 100/0. In the case of the isomer mixture, the ratio more preferably ranges from 55/45 to 90/10.
The trans isomer has a higher dipole moment (3.6 debye) than that (2.9 debye) of the cis isomer and is more strained than the cis form. Thus, it is believed that the strained sulfite compound acts on the interface
of a negative electrode and facilitates intercalation and deintercalation of Li ions.
[0014]
[1,2-Cyclohexanediol cyclic carbonate]
1,3-benzodioxol-2-ones) used in the present invention are alicyclic cyclic carbonates represented by the following formula (IV): [0015] [Formula 4]
[0016]
1,2-Cyclohexanediol cyclic carbonates represented by the formula (IV) include a cis isomer (CAS No. 19456-20-3) represented by the following formula (V) and a trans isomer (CAS No. 20192-66-9) represented by the following formula (VI). The trans isomer is a mixture of optical isomers. These isomers may be used alone or in combination.
[0017]
[Hexahydro-1,3,2-benzodioxathiol-2, 2-dioxide]
Hexahydro-l,3,2-benzodioxathiol-2,2-dioxides used in the present invention are sulfate compounds represented by the following formula (VII):
[Formula 6]
)
[0020]
Hexahydro-1,3,2-benzodioxathiol-2,2-dioxide represented by the formula (VII) include a cis isomer
(CAS No. 6970-90-7) represented by the following formula
(VIII) and a trans isomer (CAS No. 6970-91-8) represented by the following formula (IX). The trans isomer is a mixture of optical isomers. These isomers may be used alone or in combination.
[0021]
[0022]
In the 1, 2-cyclohexanediol cyclic carbonates and hexahydro-1,3,2-benzodioxathiol-2, 2-dioxides, the trans isomers are preferred to the cis isomers. In the case of using mixtures of the trans and cis isomers, the weight
ratio of the trans isomer to the cis isomer preferably ranges from 50/50 to 95/5 and more preferably from 55/45 to 90/10. [0023]
1,2-Cyclohexanediol derivatives used in the present invention is represented by the following general formula (X) : [0024]
In the general formula (X), R1 to R10 each independently represent a hydrogen atom, a Cl to C12 alkyl group, a C2 to C12 alkenyl group, a C2 to C12 alkynyl group, a C6 to C18 aryl group, or a Cl to C12 alkoxy group, and may bond to each other to form a ring structure and any hydrogen atom of R1 to R10 may be substituted by a halogen atom, with the proviso that the case where all of R1 to R10 are hydrogen atoms is excluded.
X represents a >S=0 group or a >C=0 group. When X is the >S=0 group, the formula (X) represents alicyclic cyclic sulfite compounds (1,2-cyclohexanediol cyclic sulfite derivatives). When X is the >C=0 group, the
formula (X) represents alicyclic cyclic carbonate compounds (1,2-cyclohexanediol cyclic carbonate derivatives).
The 1,2-cyclohexanediol derivatives used in the
cyclic sulfite compounds and the alicyclic cyclic
carbonate compounds.
[0026]
In the general formula (X) , preferably, R1 to R10 each independently represent a hydrogen atom, a CI to C8 alkyl group, a C2 to C8 alkenyl group, a C2 to C8 alkynyl group, a C6 to C12 aryl group, or a CI to C8 alkoxy group. More preferably, R1 to R10 each independently represent a hydrogen atom, a CI to C6 alkyl group, a C2 to C6 alkenyl group, a C2 to C6 alkynyl group, a C6 to C12 aryl group, or a Cl to C4 alkoxy group- Most preferably, R1 to R10 each represent a C2 to C4 alkenyl group or a C2 to C4 alkynyl group.
In the case where all of R1 to R10 are hydrogen atoms, the formula (X) represents the 1,2-cyclohexanediol cyclic sulfite or the 1,2-cyclohexanediol cyclic carbonate. [0027]
The 1, 2-cyclohexanediol derivatives represented by the general formula (X) include isomers represented by the following general formulae (XI) and (XII) . These isomers may be used alone or in combination. [0028] [Formula 9]
[0029]
Specific examples of 1,2-cyclohexanediol derivatives represented by the general formula (X) are shown below:
(1) Alicyclic cyclic sulfite compounds (in the case of X representing a >S=0 group)
Specific examples of the alicyclic cyclic sulfite compounds represented by the general formula (X) include 1,2-cyclohexanediol cyclic sulfite derivatives
(hexahydro-1,3,2-benzodioxathiol-2-oxide derivatives). Specific examples of the derivatives include 4-propyl-1,2-cyclohexanediol cyclic sulfite, 3-vinyl-l,2-cyclohexanediol cyclic sulfite, 4-vinyl-l,2-cyclohexanediol cyclic sulfite, l-methyl-4-(1-methylethenyl)-1,2-cyclohexanediol cyclic sulfite, 3-time thylethyl) -1,2-cyclohexanediol cyclic sulfite, 4- (1-methylethyl)-1,2-cyclohexanediol cyclic sulfite, 3-methyl-6-(1-methylethy1)-1,2-cyclohexanediol cyclic sulfite, 3-methoxy-l,2-cyclohexanediol eyelie sulfite, 3-methoxy-3-methyl-6-(1-methylethenyl)-1,2-cyclohexanediol cyclic sulfite, 4-bicyclo[2.2.1]hepti-2-yl-l,2-cyclohexanediol cyclic sulfite, (IS,2S,3R,5R)-(+)-
pinanediol cyclic sulfite, and (lR,2R,3S,5S)-(-)-pinanediol cyclic sulfite. Among these, at least one compound selected from the group consisting of 4-vinyl-1,2-cyclohexanediol cyclic sulfite (5-vinyl-hexahydro-
cyclohexanediol cyclic sulfite is particularly preferred-
[0030]
(2)Alicyclic cyclic carbonate compounds (in the case of X
representing a >C=0 group)
Specific examples of the alicyclic cyclic carbonate compounds represented by the general formula (I) include 1,2-cyclohexanediol cyclic carbonate derivatives (hexahydro-1,3-benzodioxol-2-one derivatives). Specific examples of the derivatives include 4-propyl-l,2-cyclohexanediol cyclic carbonate, 3-vinyl-l,2-cyclohexanediol cyclic carbonate, 4-vinyl-l,2-cyclohexanediol cyclic carbonate, l-methyl-4-(1-methylethenyl)-1,2-cyclohexanediol cyclic carbonate, 3-(1-methylethyl)-1,2-cyclohexanediol cyclic carbonate, 4-(1-methylethyl)-1,2-cyclohexanediol cyclic carbonate, 3-methyl-6-(1-methylethyl)-1,2-cyclohexanediol cyclic carbonate, 3-methoxy-l,2-cyclohexanediol cyclic carbonate, 3-methoxy-3-methyl-6-(1-methylethenyl)-1,2-cyclohexanediol cyclic carbonate, 4-bicyclo[2.2.1]hepti-2-yl-l,2-cyclohexanediol cyclic carbonate, (1S,2S,3R,5R)-(+)-pinanediol cyclic carbonate, and (lR,2R,3S,5S)-(-)-pinanediol cyclic carbonate. Among these, at least one compound selected from the group consisting of 4-vinyl-1,2-cyclohexanediol cyclic carbonate (5-vinyl-hexahydro-
1,3-benzodioxol-2-one) and 4-propyl-l,2-cyclohexanediol
cyclic carbonate is particularly preferred.
[0031]
[Nonaqueous Electrolytic Solution]
invention contains 0.01% to 30% by weight of at least one compound selected from the group consisting of 1,2-cyclohexanediol cyclic sulfite, 1,2-cyclohexanediol cyclic carbonate, hexahydro-l,3,2-benzodioxathiol-2,2-dioxide, and 1,2-cyclohexanediol derivatives represented by the general formula (X) , on the basis of the weight of the nonaqueous electrolytic solution, and a nonaqueous solvent in which an electrolyte salt is dissolved. [0032]
In the nonaqueous electrolytic solution of the present invention, when a content of 1,2-cyclohexanediol cyclic sulfite exceeds 10% by weight in the nonaqueous electrolytic solution, cycle property may get worse. When a content of the compound is less than 0.01% by weight, target cycle property may not be obtained. Therefore, the content of the compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and most preferably 0.3% by weight or more, on the basis of the weight of the nonaqueous electrolytic solution. Furthermore, the upper limit of the content of the compound is desirably 10% by weight or less, preferably 8% by weight or less, more preferably 5% by weight or less, and most preferably 3% by weight or less. [0033]
In the nonaqueous electrolytic solution of the present invention, when a content of 1,2-cyclohexanediol cyclic carbonate exceeds 30% by weight in the nonaqueous electrolytic solution, cycle property may get worse. When
cycle property may not be obtained. Therefore, the content of the compound is preferably 0.1% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight or more, on the basis of the weight of the nonaqueous electrolytic solution. Furthermore, the upper limit of the content of the compound is preferably 30% by weight or less, more preferably 25% by weight or less, and most preferably 20% by weight or less. [0034]
In the nonaqueous electrolytic solution of the present invention, when a content of hexahydro-1,3,2-benzodioxathiol-2,2-dioxide exceeds 10% by weight in the nonaqueous electrolytic solution, cycle property may get worse. When a content of the compound is less than 0.01% by weight, target cycle property may not be obtained. Therefore, the content of the compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and most preferably 0.3% by weight or more, on the basis of the weight of the nonaqueous electrolytic solution. Furthermore, the upper limit of the content of the compound is preferably 10% by weight or less, more preferably 7% by weight or less, and most preferably 5% by weight or less.
In the nonaqueous electrolytic solution of the present invention, when a content of 1,2-cyclohexanediol cyclic sulfite derivatives (hexahydro-1,3,2-
weight in the nonaqueous electrolytic solution, cycle property may get worse. When a content of the compound is less than 0.01% by weight, target cycle property may not be obtained. Therefore, the content of the compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and most preferably 0.3% by weight or more, on the basis of the weight of the nonaqueous electrolytic solution. Furthermore, the upper limit of the content of the compound is preferably 20% by weight or less, more preferably 10% by weight or less, and most preferably 5% by weight or less. [0036]
A content of 1,2-cyclohexanediol cyclic carbonate derivatives (hexahydro-1,3-benzodioxol-2-one derivatives) exceeding 20% by weight in the nonaqueous electrolytic solution may impair cycle property. A content of the compound of less than 0.01% by weight cannot lead to target cycle property. Therefore, the content of the compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and most preferably 0.3% by weight or more, on the basis of the weight of the nonaqueous electrolytic solution. Furthermore, the upper limit of the content of the compound is preferably 20% by weight or less, more preferably 10% by weight or less,
and most preferably 5% by weight or less. [0037]
In the case of combined use of an alicyclic cyclic sulfite compound (1,2-cyclohexanediol cyclic sulfite
(1,2-cyclohexanediol cyclic carbonate derivative), the content of each compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and most preferably 1% by weight or more, on the basis of the weight of the nonaqueous electrolytic solution. Furthermore, the upper limit of the content of each compound is preferably 20% by weight or less, more preferably 14% by weight or less, and most preferably 10% by weight or less. [0038] [Other Additives]
In the nonaqueous electrolytic solution of the present invention, from the viewpoint of the improvement of charging and discharging characteristics, preferred is a combined use of at least one compound selected from the group consisting of 1,2-cyclohexanediol cyclic sulfite, 1,2-cyclohexanediol cyclic carbonate, hexahydro-1,3,2-benzodioxathiol-2,2-dioxide, and 1,2-cyclohexanediol derivatives represented by the general formula (X) and at least one compound selected from the group consisting of vinylene carbonate (VC), 1,3-propane sultone (PS), and triple bond-containing compounds.
When a content of vinylene carbonate and 1,3-propane sultone is significantly large, battery
characteristics may get worse, whereas, when a content of these compounds is significantly low, target battery characteristics may not be obtained.
More specifically/ a content of vinylene carbonate
the nonaqueous electrolytic solution reduces the effect of addition. A content of the compound exceeding 10% by volume may impair cycle property. Therefore, the content of the compounds is preferably 0.1% by volume or more, more preferably 0.5% by volume or more, and most preferably 1% by volume or more, on the basis of the volume of the nonaqueous electrolytic solution. Furthermore, the upper limit of the content of the compound is preferably 10% by volume or less, more preferably 5% by volume or less, and most preferably 3% by volume or less.
A content of 1,3-propane suitone of less than 0.1% by volume on the basis of the volume of the nonaqueous electrolytic solution reduces the effect of addition. A content of the compound exceeding 10% by volume may impair cycle property. Therefore, the content of the compound is preferably 0.1% by volume or more, more preferably 0.5% by volume or more, and most preferably 1% by volume or more, on the basis of the volume of the nonaqueous electrolytic solution. Furthermore, the upper limit of the content of the compound is preferably 10% by volume or less, more preferably 5% by volume or less, and most preferably 3% by volume or less. [0039]
A large density of an electrode mixture for high-
capacity batteries typically leads to deterioration of cycle property. Thus, a combined use of a triple bond-containing compound is preferred to improve cycle property.
Examples of the triple bond-containing compounds
carbonate (EPC), dipropargyl carbonate (DPC), dipropargyl oxalate (DPO), propargyl methanesulfonate, dipropargyl sulfite, methyl propargyl sulfite, and ethyl propargyl sulfite.
A content of the triple bond-containing compound of less than 0.01% by volume on the basis of the volume of the nonaqueous electrolytic solution reduces the effect of addition. A content of the compound exceeding 10% by volume may impair cycle property. Therefore, the content of the compound is preferably 0.01% by volume or more, more preferably 0.1% by volume or more, and most preferably 0.5% by volume or more, on the basis of the volume of the nonaqueous electrolytic solution. Furthermore, the upper limit of the content of the compound is preferably 10% by volume or less, more preferably 5% by volume or less, and most preferably 3% by volume or less. [0040] [Nonaqueous Solvent]
Examples of nonaqueous solvents used in the nonaqueous electrolytic solution of the present invention include cyclic carbonates, linear carbonates, linear esters, ethers, amides, phosphoric esters, sulfones, lactones, nitriles, and compounds containing a >S=0 group.
Examples of the cyclic carbonates include ethylene
carbonate (EC), propylene carbonate (PC), butylene carbonate, fluoroethylene carbonate, dimethylvinylene carbonate, and vinylethylene carbonate. In particular, incorporation of EC and/or PC having a high dielectric constant is most preferred
Examples of the linear carbonates include asymmetric carbonates such as methyl ethyl carbonate (MEC), methyl propyl carbonate, methyl butyl carbonate, and ethyl propyl carbonate; and symmetric carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, and dibutyl carbonate, [0041]
Examples of the linear esters include methyl propionate, methyl pivalate, butyl pivalate, hexyl pivalate, octyl pivalate, dimethyl oxalate, ethyl methyl oxalate, and diethyl oxalate. Examples of the ethers include tetrahydrofuran, 2-methyl tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane. Examples of the amides include dimethylformamide. Examples of the phosphoric esters include trimethyl phosphate and trioctyl phosphate. Examples of the sulfones include divinylsulfone. Examples of the lactones include y-butyrolactone, y-
valerolactone, and a-angelicalactone. Examples of the nitriles include acetonitrile and adiponitrile.
Examples of the preferred compounds containing a >S=0 group include 1,4-propane suitone, divinylsulfone, 1,4-butanediol dimethanesulfonate, glycol sulfite, propylene sulfite, glycol sulfate, propylene sulfate, dipropargyl sulfite, methyl propargyl sulfite, ethyl propargyl
sulfite, and divinylsulfone. [0042]
These nonaqueous solvents may generally be used in combination to achieve appropriate properties. Examples
carbonates and linear carbonates; combinations of cyclic carbonates and lactones; combinations of lactones and linear esters; combinations of cyclic carbonates, lactones, and linear esters; combinations of cyclic carbonates, linear carbonates, and lactones; combinations of cyclic carbonates and ethers; combinations of cyclic carbonates, linear carbonates, and ethers; and combinations of cyclic carbonates, linear carbonates, and linear esters. The mixing ratio in such combinations is not particularly limited.
Among these, combinations of cyclic carbonates and linear carbonates are preferred. In particular, combinations of cyclic carbonates such as EC and PC, and linear carbonates such as MEC and DEC are preferred for improvements in cycle property. The proportion of cyclic carbonates and linear carbonates is preferably determined such that the volume ratio of cyclic carbonates to linear carbonates ranges from 10:90 to 40:60, more preferably from 20:80 to 40:60, and most preferably from 25:75 to 35:65. [0043] [Electrolyte Salts]
Examples of electrolyte salts used in the present invention include lithium salts such as LiPF6/ LiBF4, and LiClCu; alkyl-containing lithium salts such as LiN(S02CF3) 2,
LiN(S02C2F5)2, LiCF3S03, LiC (S02CF3) 3, LiPF4(CF3)2, LiPF3 (C2F5.) 3, LiPF3(CF3)3, LiPF3(iso-C3F7)3/ and LiPF5 (iso-C3F7) ; and cycloalkylene-containing lithium salts such as (CF2) 2 (S02) 2NLi and (CF2) 3 (S02) 2NLi.
preferred are LiPF6, LiBF4, and LiN (S02CF3) 2. The most preferred electrolyte salt is LiPF6. These electrolyte salts may be used alone or in combination. [0044]
Examples of preferred combinations of these electrolyte salts include a combination of LiPF6 and LiBF4, a combination of LiPF6 and LiN (S02CF3) 2, and a combination of LiBF4 and LiN (S02CF3) 2. Particularly preferred is a combination of LiPF6 and LiBF4. A proportion of LiPF6 below the level of the molar ratio of LiPF6 to LiBF4 of 80:20 or at a proportion of LiPF6 above the level of the molar ratio of LiPF6 to LiBF4 of 99:1 may impair cycle property. Therefore, the molar ratio of LiPF6 to LiBF4 preferably ranges from 80:20 to 99:1 and more preferably from 90:10 to 98:2.
The electrolyte salts can be mixed at any ratio. In the case of a combined use of any other electrolyte salt with LiPF6, a proportion (molar ratio) of the other electrolyte salt of less than 0.01 % on the basis of the total amount of the electrolyte salts may not significantly improve storage property at high temperatures. A proportion of the salt of more than 45 % may impair storage property at high temperatures. Therefore, the proportion (molar ratio) of the compounds desirably ranges from 0.01% to 45%, preferably from 0.03% to 20%, more preferably from 0.05% to 10%, and most
preferably from 0.05% to 5%.
The concentration of the total amount of these electrolyte salts is generally 0.3 M or more, more preferably 0.5 M or more, and most preferably 0.7 M or more, on the
the upper limit of the concentration thereof is preferably 2.5
M or less, more preferably 1.5 M or less, and most preferably
1.2 M or less .
[0045]
[Preparation of Nonaqueous Electrolytic Solution]
The nonaqueous electrolytic solution of the present invention may be prepared, for example, by mixing nonaqueous solvents, dissolving an electrolyte salt and at least one compound selected from the group consisting of 1,2-cyclohexanediol cyclic sulfite, 1,2-cyclohexanediol cyclic carbonate, hexahydro-1,3,2-benzodioxathiol-2,2-dioxide, and 1,2-cyclohexanediol derivatives represented by the general formula (X) therein, and optionally dissolving at least one compound selected from the group consisting of vinylene carbonate (VC), 1,3-propane sultone (PS), and triple bond-containing compounds, therein.
It is preferred that the nonaqueous solvents, 1,2-cyclohexanediol cyclic sulfite, 1,2-cyclohexanediol cyclic carbonate, hexahydro-1,3,2-benzodioxathiol-2,2-dioxide, 1,2-cyclohexanediol derivatives represented by the general formula (X), VC, PS, triple bond-containing compounds, and other additives used are previously purified to reduce impurities as much as possible within the scope not
causing decreased productivity. [0046]
Incorporation of, for example, air or carbon dioxide in the nonaqueous electrolytic solution of the present invention
electrolytic solution and can improve battery characteristics such as long-term cycle property and charging and storage property.
Methods for incorporating (dissolving) air or carbon dioxide in the nonaqueous electrolytic solution include (1) bringing the nonaqueous electrolytic solution into contact with air or carbon dioxide-containing gas before the solution is fed into a battery; or (2) feeding the solution into a battery and then incorporating air or carbon dioxide-containing gas in the solution before or after the battery is sealed. It is preferred that the air or carbon dioxide-containing gas contain moisture as little as possible and have a dew point of -40CC or below, and more preferably -50°C or below.
In the present invention, use of a nonaqueous electrolytic solution containing dissolved carbon dioxide is
particularly preferred in order to improve charging and discharging characteristics at high temperatures. The amount of dissolved carbon dioxide is desirably 0.001% by weight or more, preferably 0.05% by weight or more, and more preferably 0.2% by weight or more. A nonaqueous electrolytic solution containing saturated carbon dioxide is most preferred. [0047]
The nonaqueous electrolytic solution of the present
invention may further contain an aromatic compound to enhance the safety of overcharged batteries.
Examples of such aromatic compounds include the following groups (a) to (c) :
fluoro-2-cyclohexylbenzene, 1-fluoro-3-cyclohexylbenzene, and l-fluoro-4-cyclohexylbenzene), and biphenyl;
(b) tert-Butylbenzene, l-fluoro-4-tert-butylbenzene, tert-amylbenzene, 4-tert-butylbiphenyl, 4-tert-amylbiphenyl, and 1,3-di-tert-butylbenzene;
(c) Terphenyls (o-, m- and p-), diphenyl ether, 2-fluorodiphenyl ether, 4-diphenyl ether, fluorobenzene, difluorobenzenes (o-, m- and p-), 2-fluorobiphenyl, 4-fluorobiphenyl, 2, 4-difluoroanisole, and partially hydrogenated terphenyls (1,2-dicyclohexylbenzene, 2-phenylbicyclohexyl, 1,2-diphenylcyclohexane, and o-cyclohexylbiphenyl).
Among these, groups (a) and (b) are preferred. Most preferred is at least one compound selected from the group consisting of cyclohexylbenzene, fluorocyclohexylbenzene compounds (1-fluoro-4-cyclohexylbenzene and the like), tert-butylbenzene, tert-amylbenzene, and 1,3-di-tert-butylbenzene.
A total content of the aromatic compound of less than 0.1% by weight on the basis of the weight of the nonaqueous electrolytic solution may not effectively prevent overcharging. A total content of the compound of more than 5% by weight may impair cycle property. Therefore, the total content of the compound preferably ranges from 0.1% to 5% by weight. [0048]
[Lithium Secondary Battery]
The lithium secondary battery of the present invention comprises a positive electrode, a negative electrode, and a nonaqueous electrolytic solution in which an electrolyte salt
as a positive electrode and a negative electrode, other than the nonaqueous electrolytic solution can be used without limitation.
For example, usable positive electrode active materials include complex metal oxides of lithium with cobalt, manganese, or nickel. Such positive electrode active materials may be used alone or in combination.
Examples of such lithium-containing complex metal oxides include LiCo02, LiMn204, LiNi02, LiCoi-xNix02 (0.01S=0 group or a >C=0 group.
2 . The nonaqueous electrolytic solution according to claim
1, wherein the 1,2-cyclohexanediol derivatives represented
by the general formula (X) are 1,2-cyclohexanediol cyclic sulfite derivatives and/or 1,2-cyclohexanediol cyclic carbonate derivatives.
1 or 2, wherein the content of 1,2-cyclohexanediol cyclic sulfite ranges from 0.01% to 10% by weight, the content of 1,2-cyclohexanediol cyclic carbonate ranges from 0.1% to 25% by weight, the content of hexahydro-1,3,2-benzodioxathiol-2,2-dioxide ranges from 0.01% to 10% by weight, and the content of 1,2-cyclohexanediol derivatives represented by the general formula (X) ranges from 0.01% to 20% by weight, on the basis of the weight of the nonaqueous electrolytic solution.
4. The nonaqueous electrolytic solution according to any
one of claims 1 to 3, wherein the nonaqueous solvent contains
a cyclic carbonate and a linear carbonate.
5. The nonaqueous electrolytic solution according to any one of claims 1 to 4, wherein the nonaqueous electrolytic solution further contains at least one compound selected from the group consisting of vinylene carbonate, 1,3-propane sultone, and triple bond-containing compounds.
6. A lithium secondary battery comprising a positive electrode, a negative electrode, and a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent, wherein the nonaqueous electrolytic
solution comprises 0.01% to 30% by weight of at least one compound selected from the group consisting of 1,2-cyclohexanediol cyclic sulfite, 1,2-cyclohexanediol cyclic carbonate, hexahydro-1,3,2-benzodioxathiol-2,2-
by the general formula (X) , on the basis of the weight of the nonaqueous electrolytic solution.
7. The lithium secondary battery according to claim 6, wherein the content of 1,2-cyclohexanediol cyclic sulfite ranges from 0.01% to 10% by weight, the content of 1,2-cyclohexanediol cyclic carbonate ranges from 0.1% to 25% by weight, the content of hexahydro-1,3,2-ben2odioxathiol-2,2-dioxide ranges from 0,01% to 10% by weight, and the content of 1,2-cyclohexanediol derivatives represented by the general formula (X) ranges from 0.01% to 20% by weight, on the basis of the weight of the nonaqueous electrolytic solution.