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Non Aqueous Electrolytic Solution And Lithium Secondary Battery

Abstract: The present invention provides a lithium secondary battery which is improved in cycle characteristics and storage stability at an elevated temperature as well as protection from overcharge. In the battery, generation of a gas is also inhibited to prevent the battery from ex- pansion. A non-aqueous electrolytic so~ution for the lithium secondary battery has an electrolyte in a non- aqueous solvent. The non-aqueous solvent is composed of a cyclic carbonate compound, a linear carbonate compound and a cyclohexylbenzene compound having a benzene ring to which one or two halogen atoms are attached. A volume ratio of the cyclic carbonate compound and the linear carbonate compound in the non-aqueous solvent is in the range of 20:80 to 40:60, or the non-aqueous solvent fur- ther contains a small amount of a branched alkylbenzene compound.

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Patent Information

Application #
Filing Date
13 June 2006
Publication Number
27/2007
Publication Type
INA
Invention Field
MECHANICAL ENGINEERING
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2011-06-09
Renewal Date

Applicants

UBE INDUSTRIES, LTD.
1978-96, O-Aza Kogushi, Ube-shi, Yamaguchi, 7558633

Inventors

1. ABE, Koji
ABE, Koji., c/o Ube Chemical Factory, Ube Industries, Ltd., 1978-10, O-Aza Kogushi, Ube-shi, Yamaguchi, 7558633
2. HATTORI, Takashi
HATTORI, Takashi., c/o Ube Chemical Factory, Ube Industries, Ltd., 1978-10, O-Aza Kogushi, Ube-shi, Yamaguchi, 7558633
3. MATSUMORI, Yasuo
MATSUMORI, Yasuo., c/o Ube Chemical Factory, Ube Industries, Ltd., 1978-10, O-Aza Kogushi, Ube-shi, Yamaguchi, 7558633

Specification

Field of the invention The present invention relates to a non-aqueous elec¬trolytic solution used in preparation of a lithium secon¬dary battery excellent in battery performance. In more detail, the battery is improved in protection from over¬charge, the battery performance {cycle characteristic) is kept while repeating charge and discharge, and gas gen¬eration from decomposition is inhibited while storing the battery at an elevated temperature. The invention also relates to a lithium secondary battery. Background of the invention The lithium secondary battery has recently been widely used, for example, as an electric source for driv¬ing small-sized electronic devices. The lithium secondary battery comprises a positive electrode, a negative elec¬trode and a non-aqueous electrolytic solution. The posi¬tive electrode generally comprises complex oxide of lith¬ium such as LiCo02, and the negative electrode generally comprises a carbon material or metallic lithium. A cyclic carbonate such as ethylene carbonate (EC) and/or a linear carbonate such as dimethyl carbonate (DMC) have generally been used as a non-aqueous solvent in the non-aqueous electrolytic solution for the lithium secondary battery. The recent secondary battery should give a high voltage and a high energy density. It is difficult, how¬ever to improve both the battery performances and the safety. A battery of a high energy density should par¬ticularly show high protection from overcharge, compared with the conventional battery. It is also difficult to maintain the cycle characteristics and the storage sta¬bility at high temperatures. Further, the battery tends to generate a gas, which may expand the battery. In con¬sideration of the recent requirements on the lithium sec¬ondary battery, the performances of the battery so far developed do not satisfy the requirements. Therefore, the secondary battery should be further improved in safety while keeping the battery performances to satisfy future requirements for the high energy density. Japanese Patent Provisional Publication No. 2003- 317803 discloses an invention of adding sec-alkylbenzene or cycloalkylbenzene in which a fluorine atom is attached to the benzene ring to a non-aqueous solvent of a non¬aqueous electrolytic solution for a lithium secondary battery. The publication reports that a lithium secondary battery of a high energy density shows an excellent safety performance in a function of terminating progress i of overcharge by using the solution without lowering bat¬tery performance. The publication further describes that the non-aqueous solvent can further contain various known non-aqueous solvents. In working examples of the publica¬tion, ethylene carbonate (cyclic carbonate) and diethyl i carbonate (linear carbonate) are used in a weight ratio of 1:1 with a small amount of vinylene carbonate. Disclosure of the invention ) Problems to be solved by the invention The present inventors have noted that a lithium sec¬ondary battery prepared according to the description of Japanese Patent Provisional Publication No. 2003-317803 3 is improved in a function of terminating progress of overcharge. On the other hand, the inventors have found that the prepared battery does not reach a satisfactory level of discharging characteristics after repeated charge-discharge procedure (cycle characteristics). Means to solve the problem The present inventors have examined adjustment of the volume ratio of a cyclic carbonate compound and a linear carbonate compound in a non-aqueous solvent in the range of 20:80 to 40:60 (former: latter) in a non-aqueous electrolytic solution for a lithium secondary battery comprising an electrolyte in the non-aqueous solvent com¬prising the cyclic carbonate compound, the linear carbon¬ate compound and a cyclohexylbenzene compound having a benzene ring to which one or two halogen atoms are at¬tached. Namely, the inventors have so adjusted a mixing ratio that the amount of the linear carbonate would be larger than the amount of the cyclic carbonate based on both of volume and weight bases. The inventors have found that the obtained lithium secondary battery is improved in the safety from overcharge, and keeps a high level of discharging characteristics after the repeated charge- discharge procedure. Further, the present inventors have examined addi¬tion of a small amount such as 0.01 wt.% to 3 wt.% of a branched alkylbenzene compound to a non-aqueous electro¬lytic solution for a lithium secondary battery comprising an electrolyte in a non-aqueous solvent comprising a cy- i clic carbonate compound, a linear carbonate compound and a cyclohexylbenzene compound having a benzene ring to which one or two halogen atoms are attached. The inven¬tors have then found that the obtained lithium secondary battery is improved in the safety from overcharge, and >r keeps a high level of discharging characteristics after the repeated charge-discharge procedure. Therefore, the present invention resides in a non¬aqueous electrolytic solution for a lithium secondary battery comprising an electrolyte in a non-aqueous sol¬vent comprising a cyclic carbonate compound, a linear carbonate compound and a cyclohexylbenzene compound hav¬ing a benzene ring to which one or two halogen atoms are attached, wherein a volume ratio of the cyclic carbonate compound and the linear carbonate compound in the non¬aqueous solvent is in the range of 20:80 to 40:60. The invention further resides in a non-aqueous elec¬trolytic solution for a lithium secondary battery com¬prising an electrolyte in a non-aqueous solvent compris¬ing a cyclic carbonate compound, a linear carbonate com¬pound and a cyclohexylbenzene compound having a benzene ring to which one or two halogen atoms are attached, wherein the non-aqueous electrolytic solution further contains a branched alkyl benzene compound in an amount of 0.01 wt.% to 3 wt.%. In this non-aqueous electrolytic solution of the present invention, a volume ratio of the cyclic carbonate compound and the linear carbonate com¬pound in the non-aqueous solvent is also preferably in the range of 20:80 to 40:60 i The invention furthermore resides in a lithium sec¬ ondary battery comprising a positive electrode, a nega¬tive electrode and the non-aqueous electrolytic solution of the present invention defined above. The invention still furthermore resides in a method I of using a lithium secondary battery comprising a posi¬tive electrode, a negative electrode and a non-aqueous electrolytic solution of the present invention defined above, which comprises repeating charge and discharge of the battery under a charging condition that a charging j termination voltage is 4.2 V or higher. s~ In the present invention, the cyclohexylbenzene com¬pound having a benzene ring to which one or two halogen atoms are attached is represented by the following for¬mula (I) : in which X is a halogen atom, n is 1 or 2, and there is no specific limitation on the substitution position on the benzene ring. Effect of the invention Using the non-aqueous electrolytic solution of the present invention, a lithium secondary battery of a high energy density can be improved in safety from overcharge. The battery is excellent in cycle characteristics and storage characteristics at a high temperature. Further, generation of a gas is reduced to prevent the battery from expansion. The non-aqueous electrolytic solution according to the present invention particularly shows a relatively low viscosity. Accordingly, the electrolytic solution can well permeate into the battery. The present inventors consider that the obtained lithium secondary battery is improved in safety from overcharge and the cycle charac¬teristics for the reason mentioned above. The non-aqueous electrolytic solution according to the invention is ex¬cellent in permeability, and is advantageously injected into the battery. Therefore, the period for injection step in preparation of the battery can be shortened using the solution. In the present invention, the battery can be further improved in safety from overcharge using a small amount of a branched alkylbenzene compound in addi¬tion to the cyclohexylbenzene compound having a benzene ring to which one or two halogen atoms are attached. Best mode for carrying out the invention The preferred embodiments of the non-aqueous elec¬trolytic solution of the present invention are described below. The cyclic carbonate compound comprises at least two compounds selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, vi- nylene carbonate, dimethylvinylene carbonate and vinyl- ethylene carbonate. The cyclic carbonate compound comprises at least one compound selected from the group consisting of vinylene carbonate, dimethylvinylene carbonate and vinylethylene carbonate, and at least one compound selected from the group'consisting of ethylene carbonate, propylene carbon¬ate and butylene carbonate. The linear carbonate compound comprises at least one compound selected from the group consisting of methyl ethyl carbonate, dimethyl carbonate and diethyl carbon¬ate. The cyclohexylbenzene compound has a benzene ring to which one or two fluorine atoms are attached. The cyclohexylbenzene compound comprises at least one compound selected from the group consisting of 1- fluoro-2-cyclohexylbenzene, l-fluoro-3-cyclohexylbenzene and 1-fluoro-4-cyclohexylbenzene. The non-aqueous electrolytic solution has a dynamic viscosity at 25°C in the range of 2.3xl0"6 to 3.6xl0-6 m2/s. The branched alkylbenzene compound comprises at least one compound selected from the group consisting of isopropylbenzene, cyclohexylbenzene, tert-butylbenzene, 1,3-di-tert-butylbenzene, tert-pentylbenzene, 4-tert- butylbiphenyl, tert-pentylbiphenyl, bis(4-tert-butyl- phenyl) ether and bis(4-tert-pentylphenyl) ether. A weight ratio of the branched alkylbenzene compound to the cyclohexylbenzene compound can be in the range of 0.1 to 1. The linear carbonate compounds include linear alkyl carbonate compounds such as dimethyl carbonate (DMC), methyl ethyl carbonate {MEC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC), methyl butyl carbonate (MBC) and dibutyl carbonate (DBC). The alkyl moieties of the linear alkyl carbonate com¬pounds have 1 to 6 carbon atoms. The alkyl moieties can have a straight or branched chain structure. The proportion of the cyclic carbonate compound and the linear carbonate compound in the non-aqueous solvent preferably is in the range of 20:80 to 40:60 in terms of a volume ratio. If the electrolytic solution comprises the cyclic carbonate compound in excess of 40:60 in the volume ratio of the cyclic carbonate compound and the linear carbonate compound, the obtained solution tends to be too viscous to permeate into the battery. It is diffi¬cult to keep satisfactory cycle retention under the in¬fluence of the high viscosity. The influence is remark¬able in a battery of a high capacity or a high energy density such as a cylindrical battery or a square-shaped battery, particularly in a cylindrical or square-shaped battery having an electrode material layer of a high den¬sity in an electrode. If the electrolytic solution com¬prises the cyclic carbonate compound less than 20:80 in the volume ratio of the cyclic carbonate compound and the linear carbonate compound, the conductivity of the solu¬tion tends to be low and it is difficult to keep satis¬factory cycle retention. Therefore, the volume ratio of the cyclic carbonate compound and the linear carbonate compound in the non-aqueous solvent preferably is in the range of 20:80 to 40:60, and more preferably in the range of 20:80 to 35:65. The linear carbonate preferably has a methyl group to lower the viscosity. Accordingly, the linear carbonate preferably is dimethyl carbonate or methyl ethyl carbon¬ate. Methyl ethyl carbonate, which has low viscosity, a melting point of -20°C or lower and a boiling point of 100°C or higher, is a particularly preferred asymmetrical linear carbonate. The asymmetrical linear carbonate, namely methyl ethyl carbonate can be used in combination with a symmetrical linear carbonate, namely dimethyl car¬bonate and/or diethyl carbonate in a volume ratio of 100:0 to 51:49 {particularly, 100:0 to 70:30). In the present invention, the non-aqueous electro¬lytic solution, which contains a cyclohexylbenzene com¬pound having a benzene ring to which one or two halogen atoms are attached, preferably further contains at least two cyclic carbonate compounds and a branched alkylben- zene compound. The branched alkylbenzene compound can be contained in the solution in an amount of 0.01 wt.% to 3 wt.%. The interactions of the compounds can improve safety from overcharge, cyclic characteristics and high temperature storage characteristics. Further, gas genera¬tion is inhibited to prevent the battery from expansion. Therefore, an excellent lithium secondary battery can be obtained according to the invention. The non-aqueous electrolytic solution comprises an electrolyte in a non-aqueous solvent, which contains the compound represented by the formula (I) . In the formula (I), X is a halogen atom, such as fluorine, chlorine, bromine and iodine, preferably is fluorine or chlorine, and most preferably is fluorine. Examples of the compounds of the formula (I) having one X group include l-fluoro-2-cyclohexylbenzene, 1- fluoro-3-cyclohexylbenzene, 1-fluoro-4-cyclohexylbenzene, l-chloro-4-cyclohexylbenzene, l-bromo-4-cyclohexylbenzene and l-iodo-4-cyclohexylbenzene. Examples of the compounds having two X groups include 1,2-dichloro-3-cyclohexylben- zene, 1,3-dibromo-4-cyclohexyLbenzene, 1,4-dichloro-2- cyclohexylbenzene, 1,2-difluoro-4-cyclohexylbenzene and 1,3-difluoro-5-cyclohexylbenzene. Particularly preferred are 1-fluoro-4-cyclohexylbenzene and 1,2-difluoro-4- cyclohexylbenzene. The compounds can be used singly or in combination. An excess amount of the compound of the formula (I) might lower battery performances. On the other hand, the amount of the compound is too small, satisfactory battery performances might not be provided. Therefore, the amount preferably is 1 wt.% or more, more preferably is 1.5 wt.% or more, and most preferably is 2 wt.% or more, based on the weight of the non-aqueous electrolytic solution. Fur¬ther, the amount preferably is 10 wt.% or less, more preferably is 7 wt.% or less, and most preferably is 5 wt.% or less. The branched alkylbenzene compound, which is pref¬erably used in combination with the compound of the for¬mula (I), has a benzene ring such as benzene, biphenyl and diphenyl ether to which a branched alkyl group is attached. The compound most preferably has a benzene ring to which a branched alkyl group is attached. Examples of the branched alkylbenzene compounds in¬clude isopropylbenzene, cyclohexylbenzene, tert-butylben- zene, 1,3-di-tert-butylbenzene, tert-pentyl(amyl)benzene, 4-tert-butylbiphenyl, tert-pentyl(amyl)biphenyl, bis (4- ► tert-butylphenyl) ether and bis(4-tert- pentyl(amyl)phenyl) ether. Particularly preferred are cyclohexylbenzene, tert-butylbenzene and tert- pentyl(amyl)benzene. One compound can singly be used, or two or more compounds can be used in combination. An excess amount of the branched alkylbenzene com¬pound might lower battery performances. On the other hand, the amount of the compound is too small, satisfac¬tory battery performances might not be provided. There¬fore, the amount of the branched alkylbenzene compound preferably is 0.01 wt.% or more, more preferably is 0.1 wt.% or more, and most preferably is 0.5 wt.% or more, based on the weight of the non-aqueous electrolytic solu¬tion. Further, the amount preferably is 3 wt.% or less, more preferably is 2.5 wt.% or less, and most preferably is 2 wt.% or less. Addition of the branched alkylbenzene compound improves safety from overcharge. The weight ratio of the branched alkylbenzene com¬pound to the compound of the formula (I) preferably is 0.1 or more, more preferably is 0.2 or more, and most preferably is 0.25 or more. Further, the weight ratio preferably is 1 or less, more preferably is 0.8 or less, and most preferably is 0.75 or less. The cyclic carbonate compound contained in the non¬aqueous electrolytic solution according to the present invention preferably comprises at least two compounds selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbon¬ate, dimethylvinylene carbonate and vinylethylene carbon¬ate. The two compounds are more preferably selected from the group consisting of ethylene carbonate, propylene carbonate, vinylene carbonate and vinylethylene carbon¬ate. Ethylene carbonate and vinylene carbonate are par¬ticularly preferred. An excessive amount of the cyclic carbonate con¬tained in the non-aqueous electrolytic solution might lower battery performances. On the other hand, the amount of the compound is too small, satisfactory battery per¬formances might not be provided. Therefore, the amount of the cyclic carbonate compound contained in the non¬aqueous electrolytic solution preferably is 20 vol.% or more, and more preferably is 25 vol.% or more. Further, the amount preferably is 40 vol.% or less, and more preferably is 35 vol.% or less. The cyclic carbonate compound having an unsaturated carbon-carbon bond such as vinylene carbonate, dimethyl¬vinylene carbonate and vinylethylene carbonate is con¬tained in the non-aqueous solvent in an amount of pref¬erably 0.1 vol.% or more, more preferably 0.4 vol.% or more, and most preferably 0.8 vol.% or more. Further, the compound is contained in an amount of preferably 8 vol.% or less, more preferably 4 vol.% or less and most pref¬erably 3 vol.% or less. Other non-aqueous solvents can also be used in the present invention. Examples of the other solvents include lactones such as ybutyrolactone (GBL), y-valerolactone, and a-angelica lactone; ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxy- ethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane; ni- triles such as acetonitrile, and adiponitrile; linear esters such as methyl propionate, methyl pivalate, butyl pivalate, octyl pivalate, dimethyl oxalate, ethyl methyl oxalate, and diethyl oxalate; amides such as dimethylfor- mamide; and compounds having the S=0 bonding such as gly¬col sulfite, propylene sulfite, glycol sulfate, propylene sulfate, divinyl sulfone, 1,3-propane sultone, 1,4-butane sultone, and 1,4-butanediol dimethane sulfonate. The non-aqueous solvents can be mixed. Examples of combinations of the non-aqueous solvents include a combi¬nation of a cyclic carbonate and a linear carbonate, a combination of a cyclic carbonate and a lactone, a combi¬nation of a cyclic carbonate, a lactone and a linear es¬ter, a combination of a cyclic carbonate, a linear car¬bonate and a lactone, a combination of a cyclic carbon- ite, a linear carbonate and an ether, and a combination )f a cyclic carbonate, a linear carbonate and a linear sster. Preferred are the combination of the cyclic car¬bonate and the linear carbonate, and the combination of :he cyclic carbonate, the linear carbonate and the linear sster. An electrolyte is used in the non-aqueous electro- Lytic solution of the present invention. Examples of the electrolytes include LiPF6, LiBF4 and LiC104. The exam¬ples further include lithium salts comprising a chain ilkyl group such as LiN (S02CF3) 2, LiN(S02C2F5) 2, [iiC(S02CF3)3, LiPF4(CF3)2, LiPF3 (C2F5) 3, LiPF3(CF3)3, LiPF3 (iso-C3F7) 3, and LiPF5 (iso-C3F7) , and lithium salts comprising a cyclic alkylene group such as (CF2) 2 (S02) 2NLi, and (CF2) 3 (S02) 2NLi. The electrolyte can be used singly or in combination. The concentration of the electrolyte salts in the non-aqueous solvent prefera¬bly is not less than 0.3 M, more preferably is not less than 0.5 M, and most preferably is not less than 0.7 M. Further, the concentration preferably is not more than 2.5 M, more preferably is not more than 1.5 M, and most preferably is not more than 1.2 M. The electrolytic solution can be obtained according to the invention, for example by preparing a non-aqueous solvent containing the cyclic carbonate compound and the linear carbonate compound, dissolving the electrolyte in the solvent, and further dissolving the compound of the formula (I), and if necessary the branched alkyl benzene compound in the solution. The non-aqueous electrolytic solution of the inven¬tion has a dynamic viscosity at 25°C preferably in the range of 2.3xl0'6 to 3.6xl0~6 m2/s, more preferably in the ti range of 2.3xl0~6 to 3.2xl0~6 m2/s, and most preferably in the range of 2.0xl0"6 to 3.0xl0~6 m2/s. The dynamic vis¬cosity can be measured by a capillary measurement using a Cannon-Fenske viscometer. The non-aqueous electrolytic solution of the inven¬tion can contain air or carbon dioxide to reduce gas gen¬eration caused by decomposition of the electrolytic solu¬tion and to improve battery performances such as cycle and storage characteristics. Carbon dioxide or air can be incorporated (dis¬solved) in the non-aqueous electrolytic solution in the present invention according to a method (1) of contacting the non-aqueous electrolytic solution to air or a carbon dioxide-containing gas to introduce the air or the gas into the solution, and then injecting the solution into a battery, or a method of (2) injecting the non-aqueous electrolytic solution into the battery, and then intro¬ducing air or a carbon dioxide-containing gas into a bat¬tery before or after sealing the battery. The two methods can be used in combination. The amount of the moisture contained in the air or carbon dioxide-containing gas preferably is as small as possible. The amount of the moisture is so reduced that the due point of the air or gas preferably is lower than -40°C, and more preferably lower than -50°C. The non-aqueous electrolytic solution of the present invention is used for manufacturing a lithium secondary battery. There is no specific limitation with respect to materials of the lithium secondary battery other than the non-aqueous electrolytic solution of the present inven¬tion. The materials employed for the conventional lithium secondary battery can be used in the lithium secondary battery of the present invention. The positive electrode active material preferably is complex oxide of lithium with cobalt, manganese or nickel. The positive electrode active can be used singly or in combination. Examples of the complex lithium oxide include LiCo02, LiMn204, LiNi02 and LiCo^l^C^ (0.01 % cylindrical battery was prepared in the same manner as in Example 1 using the electrolytic solution. The retention of the discharging capacity after 200 cycles is set forth in Table 1. [Example 6] (Preparation of non-aqueous electrolytic solution) A non-aqueous solvent of EC:VC(vinylene carbon¬ate) :MEC having a volume ratio of 28:2:70 was prepared. LiPF6 was dissolved in the solvent to prepare 1 M non¬aqueous electrolytic solution. 2 wt.% (based on the non¬aqueous electrolytic solution) of l-fluoro-4-cyclohexyl- benzene (F4CHB) and 1 wt.% of cyclohexylbenzene (CHB) were added to the non-aqueous electrolytic solution. The 2-f dynamic viscosity of the electrolytic solution was 2.7xl0"6 m2/s at 25°C. {Preparation of lithium secondary battery and measurement of battery performance) 90 wt.% of LiCo02 (positive electrode active mate¬rial), 5 wt.% of acetylene black (conductive material), and 5 wt.% of polyvinylidene fluoride (binder) were mixed, l-methyl-2-pyrrolidone was added to the mixture to form slurry. A surface of aluminum foil was coated with the slurry. The mixture was dried, and molded under pres¬sure to form a positive electrode. 95 wt.% of artificial graphite (negative electrode active material) having a graphitic crystalline structure with a distance (d002) 0.335 nm between lattice faces (002), and 5 wt.% of polyvinylidene fluoride (binder) were mixed, l-methyl-2-pyrrolidone was added to the mix¬ture to give a slurry. A surface of copper foil was coated with the slurry. The mixture was dried, and molded under pressure to produce a negative electrode. A battery was prepared using a separator comprising a microporous polypropylene film (thickness: 20 ym) . The non-aqueous electrolytic solution was poured into the battery. Before sealing the battery, carbon dioxide hav¬ing the dew point of -60°C was introduced into the bat¬tery to prepare a cylindrical battery having the 18650 size (diameter: 18 mm, height: 65 mm) . A pressure release vent and an inner current breaker (PTC element) were at¬tached to the battery. The positive electrode had a den¬sity of 3.5 g/cm3, and the negative electrode had a den¬sity of 1.6 g/cm3. The positive electrode layer had a thickness of 70 u111 (per one side of the collector), and the negative electrode layer had a thickness of 60 pm (per one side of the collector). In a cycle test, the 18650 battery was charged with the constant current of 2.2 A (1C) at an elevated tem¬perature {45°C) to reach 4.3V. The battery was further charged under the constant voltage for 3 hours in total to reach the terminal voltage of 4.3 V. The battery was discharged under the constant current of 2.2 A (1C) to reach the terminal voltage of 3.0 V. The cycle of charge and discharge was repeated. The initial discharging ca¬pacity (mAh) was the essentially same as that of Compari¬son Example 1 (using 1 M LiPF6+EC/VC/MEC (volume ratio) = 28:2:70 as the non-aqueous electrolytic solution to which 3 wt.% of cyclohexylbenzene was added in place of a spe¬cific cyclohexyl benzene compound such as.l-fluoro-4- cyclohexylbenzene). The battery performance was measured after 200 cycles, and the retention of the discharging capacity relative to the initial discharging capacity (100%) was 82.1%. Further, the amount of the generated gas after 200 cycles was remarkably smaller than that in the case of using no l-fluoro-4-cyclohexylbenzene (Com¬parative Example 1). After the cycle of charge and discharge was repeated five times, the 18650 battery was fully charged to reach 4.2 V at an ordinary temperature (20°C), and further charged with the constant current of 2.2A (1C) to conduct an overcharge test. The temperature on the surface of the battery was 120°C or lower, which is the standard highest temperature for safety. The conditions for preparation of the 18650 battery and the battery performance thereof are set forth in Table 2. i [Example 7] A cylindrical battery was prepared in the same man¬ner as in Example 6, except that 2 wt.% (based on the non-aqueous electrolytic solution) of 1,2-difluoro-4- » cyclohexylbenzene (D4CHB) was used in place of 1-fluoro- if. 4-cyclohexylbenzene. The obtained cylindrical battery showed the retention of the discharging capacity after 200 cycles, as is set forth in Table 2. In the excessive charge test, the temperature on the surface of the bat¬tery was 120°C or lower. [Example 8] A cylindrical battery was prepared in the same man¬ner as in Example 6, except that 1 wt.% (based on the non-aqueous electrolytic solution) of tert-pentylbenzene (TPB) was used in place of cyclohexylbenzene. The ob¬tained cylindrical battery showed the retention of the discharging capacity after 200 cycles, as is set forth in Table 2. In the excessive charge test, the temperature on the surface of the battery was 120°C or lower. [Example 9] A cylindrical battery was prepared in the same man¬ner as in Example 6, except that 1 wt.% (based on the non-aqueous electrolytic solution) of tert-butylbenzene (TBB) was used in place of cyclohexylbenzene. The ob¬tained cylindrical battery showed the retention of the discharging capacity after 200 cycles, as is set forth in Table 2. In the excessive charge test, the temperature on the surface of the battery was 120°C or lower. [Example 10] A cylindrical battery was prepared in the same man¬ner as in Example 6, except that 1.5 wt.% (based on the non-aqueous electrolytic solution) of 1-fluoro-4-cyclo- hexylbenzene, 1 wt.% of tert-pentylbenzene (TPB) and 0.5 wt.% of cyclohexylbenzene (CHB) were used. The obtained cylindrical battery showed the retention of the discharg¬ing capacity after 200 cycles, as is set forth in Table 2. In the excessive charge test, the temperature on the surface of the battery was 120°C or lower. [Example 11] A non-aqueous solvent of EC:VC:MEC:PS(1,3- propanesultone) having a volume ratio of 28:2:69:1 was prepared. LiPF6 was dissolved in the solvent to prepare 1 M non-aqueous electrolytic solution. 2 wt.% (based on the non-aqueous electrolytic solution) of l-fluoro-3-cyclo- hexylbenzen^ {F3CHB) and 1 wt.% of cyclohexylbenzene (CHB) were added to the non-aqueous electrolytic solu¬tion. A cylindrical battery was prepared in the same man¬ner as in Example 6, except for the preparation of the solution. The obtained cylindrical battery showed the retention of the discharging capacity after 200 cycles, as is set forth in Table 2. In the excessive charge test, the temperature on the surface of the battery was 120°C or lower. [Example 12] A non-aqueous solvent of EC:VC:MEC:EMO(ethyl methyl oxalate) having a volume ratio of 28:2:69:1 was prepared. LiPFg was dissolved in the solvent to prepare 1 M non¬aqueous electrolytic solution. 2 wt.% (based on the non¬aqueous electrolytic solution) of l-fluoro-2- cyclohexylbenzene (F2CHB) and 1 wt.% of cyclohexylbenzene (CHB) were added to the non-aqueous electrolytic solu¬tion. A cylindrical battery was prepared in the same man¬ner as in Example 6, except for the preparation of the solution. The obtained cylindrical battery showed the retention of the discharging capacity after 200 cycles, as is set forth in Table 2. In the excessive charge test, the temperature on the surface of the battery was 120°C or lower. [Comparison Example 3] A cylindrical battery was prepared in the same man¬ner as in Example 6, except that a specific cyclohexyl¬benzene compound such as 1-fluoro-4-cyclohexylbenzene was not used, and 3 wt.% {based on the non-aqueous electro¬lytic solution) of cyclohexylbenzene (CHB) was used. The obtained cylindrical battery showed the retention of the discharging capacity after 200 cycles, as is set forth in Table 2. In the excessive charge test, the temperature on the surface of the battery was 120°C or lower. [Comparison Example 4] A cylindrical battery was prepared in the same man¬ner as in Example 6, except that a specific cyclohexyl¬benzene compound such as l-fluoro-4-cyclohexylbenzene was not used, and 3 wt.% (based on the non-aqueous electro¬lytic solution) of tert-butylbenzene (TBB) was used in place of cyclohexylbenzene. The obtained cylindrical bat¬tery showed the retention of the discharging capacity after 200 cycles, as is set forth in Table 2. In the ex¬cessive charge test, the temperature on the surface of the battery was higher than 140°C. The effect of protec¬tion from overcharge was not observed in the same manner as in the case using no tert-butylbenzene. Remark{*): The effect of protection from overcharge was not observed in the Comparison Example 4. The present invention is not limited to the examples described above. The various combinations can be possible according to the invention. Particularly, the combina- tions of solvents cannot be limited to the examples. Fur¬ther, the present invention can be applied to a square- shaped, coin-shaped or lamination battery, though the Examples relate to a cylindrical battery.

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4 2096-CHENP-2006 FORM-1 28-07-2014.pdf 2014-07-28
4 2096-CHENP-2006 OTHER PATENT DOCUMENT 13-05-2011.pdf 2011-05-13
5 2096-CHENP-2006 CORRESPONDENCE OTHERS.pdf 2011-11-21
5 2096-CHENP-2006 FORM-3 13-05-2011.pdf 2011-05-13
6 2096-CHENP-2006 CORRESPONDENCE PO.pdf 2011-11-21
6 2096-CHENP-2006 AMENDED CLAIMS 13-05-2011.pdf 2011-05-13
7 2096-CHENP-2006 DESCRIPTION (COMPLETE) GRANTED.pdf 2011-11-21
7 2096-CHENP-2006 AMENDED PAGES OF SPECIFICATION 13-05-2011.pdf 2011-05-13
8 2096-CHENP-2006 PCT.pdf 2011-11-21
8 2096-CHENP-2006 FORM 1.pdf 2011-11-21
9 2096-CHENP-2006 FORM 18.pdf 2011-11-21
9 2096-CHENP-2006 FORM 5.pdf 2011-11-21
10 2096-CHENP-2006 FORM 3.pdf 2011-11-21
11 2096-CHENP-2006 FORM 18.pdf 2011-11-21
11 2096-CHENP-2006 FORM 5.pdf 2011-11-21
12 2096-CHENP-2006 FORM 1.pdf 2011-11-21
12 2096-CHENP-2006 PCT.pdf 2011-11-21
13 2096-CHENP-2006 AMENDED PAGES OF SPECIFICATION 13-05-2011.pdf 2011-05-13
13 2096-CHENP-2006 DESCRIPTION (COMPLETE) GRANTED.pdf 2011-11-21
14 2096-CHENP-2006 AMENDED CLAIMS 13-05-2011.pdf 2011-05-13
14 2096-CHENP-2006 CORRESPONDENCE PO.pdf 2011-11-21
15 2096-CHENP-2006 FORM-3 13-05-2011.pdf 2011-05-13
15 2096-CHENP-2006 CORRESPONDENCE OTHERS.pdf 2011-11-21
16 2096-CHENP-2006 OTHER PATENT DOCUMENT 13-05-2011.pdf 2011-05-13
16 2096-CHENP-2006 FORM-1 28-07-2014.pdf 2014-07-28
17 2096-CHENP-2006 POWER OF ATTORNEY 13-05-2011.pdf 2011-05-13
17 2096-CHENP-2006 CORRESPONDENCE OTHERS 28-07-2014.pdf 2014-07-28
18 2096-CHENP-2006 EXAMINATION REPORT REPLY RECEIVED 13-05-2011.pdf 2011-05-13
18 Petition for POR.pdf 2014-08-01
19 2096-CHENP-2006_EXAMREPORT.pdf 2016-07-02
19 2096-CHENP-2006 CORRESPONDENCE OTHERS 07-07-2010.pdf 2010-07-07

ERegister / Renewals

3rd: 18 Jul 2011

From 11/11/2006 - To 11/11/2007

4th: 18 Jul 2011

From 11/11/2007 - To 11/11/2008

5th: 18 Jul 2011

From 11/11/2008 - To 11/11/2009

6th: 18 Jul 2011

From 11/11/2009 - To 11/11/2010

7th: 18 Jul 2011

From 11/11/2010 - To 11/11/2011

8th: 18 Jul 2011

From 11/11/2011 - To 11/11/2012

9th: 11 Oct 2012

From 11/11/2012 - To 11/11/2013

10th: 04 Oct 2013

From 11/11/2013 - To 11/11/2014

11th: 09 Oct 2014

From 11/11/2014 - To 11/11/2015