WO2006046785A1 - Nonaqueous electrolyte for battery - Google Patents
Nonaqueous electrolyte for battery Download PDFInfo
- Publication number
- WO2006046785A1 WO2006046785A1 PCT/KR2004/002728 KR2004002728W WO2006046785A1 WO 2006046785 A1 WO2006046785 A1 WO 2006046785A1 KR 2004002728 W KR2004002728 W KR 2004002728W WO 2006046785 A1 WO2006046785 A1 WO 2006046785A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- battery
- nonaqueous electrolyte
- electrolyte
- lithium
- high temperature
- Prior art date
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Natural products CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 claims description 6
- PEQJBOMPGWYIRO-UHFFFAOYSA-N n-ethyl-3,4-dimethoxyaniline Chemical compound CCNC1=CC=C(OC)C(OC)=C1 PEQJBOMPGWYIRO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000003660 carbonate based solvent Substances 0.000 claims 2
- 239000003792 electrolyte Substances 0.000 abstract description 20
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 6
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003247 decreasing effect Effects 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 206010042674 Swelling Diseases 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 229910003307 Ni-Cd Inorganic materials 0.000 description 2
- 229910018095 Ni-MH Inorganic materials 0.000 description 2
- 229910018477 Ni—MH Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- -1 Ii CO Chemical class 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a nonaqueous electrolyte for a battery, and more particularly to a novel nonaqueous electrolyte for a battery in which a furanone based derivative is added to a conventional nonaqueous electrolyte for a lithium battery to inhibit decomposition of the electrolyte and thereby the rate of increase of the battery thickness when it is allowed to stand at a high temperature is significantly decreased and capacity storage characteristics at high temperature are improved.
- a secondary lithium battery having a small and slim size which is used in a notebook computer, a camcorder, a mobile phone, and the like is composed of an cathode made of mixed oxides of lithium from which lithium ions can be released and inserted, a anode made of carbon material or lithium, and an electrolyte in which a suitable amount of a lithium salt is dissolved in a mixed organic solvent.
- This lithium battery is generally used in the form of a coin-, 18650 cylinder-, or a 063048 square- type battery.
- the lithium battery has an average discharge voltage of about 3.6 to 3.7 V and thus provides an advantage of obtaining relatively high power as compared to other alkaline batteries or a Ni-MH or Ni-Cd batteries.
- IiBF , IiClO and IiN are typically used and they serve as a source of
- the nonaqueous electrolyte thus prepared has markedly lower ionic conductivity as compared to an aqueous electrolyte used in a Ni-MH or Ni-Cd battery, and therefore may present a disadvantage with regard to a high efficiency charging/discharging, and the like.
- lithium ions from a lithium metal complex oxide used as an cathode in initial charging of the lithium battery migrate to a graphite (crystalline or amorphous) electrode used as a anode and are intercalated between layers of the graphite electrode.
- the electrolyte reacts with carbon atoms constituting the anode to form compounds such as Ii CO , Ii O and IiOH at the
- a thin square-type battery has a problem suffering from swelling of the battery thickness upon charging thereof, due to production of gas such as CO, CO , CH
- the present invention to provide a novel nonaqueous electrolyte for a lithium battery in which a furanone based derivative is added to a conventional nonaqueous electrolyte for a lithium battery to inhibit decomposition of the electrolyte and thereby the rate of increase of the battery thickness when allowed to stand at a high temperature is significantly decreased and capacity storage characteristics at high temperature are improved.
- Rg. 1 is a graph showing charging/discharging characteristics of a lithium battery prepared in an example in accordance with the present invention.
- Rg. 2 is a graph showing electrochemical characteristics of an nonaqueous electrolyte prepared in an example in accordance with the present invention. Best Mode for Carrying Out the Invention
- organic solvents used in preparing a nonaqueous electrolyte for a lithium battery in accordance with the present invention mention may be made of cyclic carbonate based organic solvents such as ethylene carbonate (EC) and propylene carbonate (PC), and linear carbonate based organic solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC) and ethylpropyl carbonate (EPC).
- DMC dimethyl carbonate
- DEC diethyl carbonate
- EMC ethylmethyl carbonate
- MPC methylpropyl carbonate
- EPC ethylpropyl carbonate
- a mixture of at least one cyclic carbonate based organic solvent and at least one linear carbonate based organic solvent may be used, and more preferably a mixture of ethylene carbonate, ethylmethyl carbonate and diethyl carbonate may be used in a ratio of 1:1:1.
- solvents such as propyl acetate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate and fluorobenzene may be ad ⁇ ditionally mixed and used, if desired.
- the mixing ratio of the respective organic solvents is not particularly limited as long as it does not interfere with the purpose of the present invention, and follows the mixing ratio used in preparing a conventional nonaqueous electrolyte for a lithium battery.
- lithium salts contained in the nonaqueous electrolyte in accordance with the present invention mention may be made of IiPF , IiClO , IiAsF , IiBF ,
- IiN C F SO ) , and the like, and they may be used alone or as a mixture of two or
- IiPF lithium salt
- ionic conductivity ranges from 0.8 to 2.0 M. Where the concentration of the lithium salt added is below 0.8 M, ionic conductivity may be lowered. Where it exceeds 2.0 M, the viscosity of the electrolyte increases and thus ionic conductivity may be lowered.
- the nonaqueous electrolyte in accordance with the present invention is char ⁇ acterized in that 0.01 to 20.0% by weight, and preferably 0.1 to 10% by weight of tetronic acid, which is a furanone based derivative having the following formula (I), is added thereto.
- tetronic acid which is a furanone based derivative having the following formula (I)
- the above-mentioned content is less than 0.01% by weight, it is difficult to decrease the rate of increase of the battery thickness when it is allowed to stand at a high temperature, by inhibiting decomposition of the eletrolyte.
- performances of the battery such as service life may be lowered.
- the nonaqueous electrolyte for a lithium battery in accordance with the present invention can be used to prepare the lithium battery by a conventional method. Even when the lithium battery thus prepared is allowed to stand at a high temperature (80°C , 10 days), production of gas inside the battery due to disintegration of the eletrolyte is inhibited and thus swelling of the battery thickness is prevented and capacity storage characteristics at a high temperature become excellent.
- EXAMPLES AND COMPARATIVE EXAMPLE [28] [29] Ethylene carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) were mixed in a ratio of 1 : 1 : 1 (v/v) and IM of IiPF as solute was dissolved
- a lithium battery was prepared in the form of a square type 423048 battery.
- Graphite was used as the active material of the anode and PVDF was used as a binding agent.
- IiCoO was used as the active material of the cathode and PVDF was used as the active material of the cathode.
- the binding agent As the conductive agent, acetylene black was used.
- the prepared lithium battery was tested for swelling thereof at a high temperature (80°C , 10 days) under a fully charged state of 4.2 V after formation charging/ discharging and standard charging/discharging procedures and the results are shown in Table 1. Meanwhile, a service life (standard charging/discharging) characteristic (50 cycles) was determined and shown in Rg. 1. Electrochemical characteristics were determined for the electrolytes (Example 2) to which 1.0% by weight of tetronic acid was added, respectively and the electrolyte to which no tetronic acid was added (Comparative Example) and are shown in Fig. 2.
- a novel nonaqueous electrolyte for a lithium battery in which the rate of increase of the battery thickness even when it is allowed to stand at a high temperature is significantly decreased and capacity storage characteristics at high temperature are improved.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a nonaqueous electrolyte for a battery, and more particularly to a novel nonaqueous electrolyte for a battery in which a furanone based derivative is added to a conventional nonaqueous electrolyte for the lithium battery to inhibit decomposition of the electrolyte, and thereby the rate of increase of the battery thickness when it is allowed to stand at a high temperature is significantly decreased and capacity storage characteristics at high temperature are improved.
Description
Description
NONAQUEOUS ELECTROLYTE FOR BATTERY
Technical Field
[1] The present invention relates to a nonaqueous electrolyte for a battery, and more particularly to a novel nonaqueous electrolyte for a battery in which a furanone based derivative is added to a conventional nonaqueous electrolyte for a lithium battery to inhibit decomposition of the electrolyte and thereby the rate of increase of the battery thickness when it is allowed to stand at a high temperature is significantly decreased and capacity storage characteristics at high temperature are improved. Background Art
[2] A secondary lithium battery having a small and slim size which is used in a notebook computer, a camcorder, a mobile phone, and the like is composed of an cathode made of mixed oxides of lithium from which lithium ions can be released and inserted, a anode made of carbon material or lithium, and an electrolyte in which a suitable amount of a lithium salt is dissolved in a mixed organic solvent. This lithium battery is generally used in the form of a coin-, 18650 cylinder-, or a 063048 square- type battery. The lithium battery has an average discharge voltage of about 3.6 to 3.7 V and thus provides an advantage of obtaining relatively high power as compared to other alkaline batteries or a Ni-MH or Ni-Cd batteries.
[3] In order to provide such a high drive voltage, there is a need for an electrolyte composition which is electrochemically stable in a charging/discharging area of 0 to 4.2 V, and thus in order to increase imbibition between a carbonate based organic solvent such as ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and a separator, fluorobenzene (FB) is appropriately added thereto and used as an electrolyte solvent. As the solute for the electrolyte, lithium salts such as IiPF ,
6
IiBF , IiClO and IiN (C F SO ) are typically used and they serve as a source of
4 4 2 5 3 2 lithium ions in the battery thus enabling its basic operation. However, the nonaqueous electrolyte thus prepared has markedly lower ionic conductivity as compared to an aqueous electrolyte used in a Ni-MH or Ni-Cd battery, and therefore may present a disadvantage with regard to a high efficiency charging/discharging, and the like. [4] lithium ions from a lithium metal complex oxide used as an cathode in initial charging of the lithium battery migrate to a graphite (crystalline or amorphous) electrode used as a anode and are intercalated between layers of the graphite electrode. At this time, since lithium ions are highly reactive, the electrolyte reacts with carbon
atoms constituting the anode to form compounds such as Ii CO , Ii O and IiOH at the
2 3 2 surface of the graphite anode. These compounds form a passivation layer at the surface of the graphite cathode, called an SEE (Solid Electrolyte Interface) film. Once the SEI film is formed, it plays a role as an ion tunnel to pass only lithium ions. The SEI film solvates lithium ions through such an ion tunnel effect and thereby organic solvent molecules having a large molecular weight moving along with lithium ions in the electrolyte, such as EC, DMC and DEC, are prevented from inserting into the graphite cathode thus disrupting the structure thereof. Once the SEI film is formed, lithium ions cannot undergo side reaction with the graphite cathode or other materials and the quantity of electric charge consumed to form the SEI film is discharged as non¬ reversible capacity which has a characteristic that it is not reversibly reactive. Therefore, further decomposition of the electrolyte does not occur and the amount of lithium ions in the electrolyte is reversibly maintained with maintenance of stable charging/discharging (See J. Power Sources (1994) 51: 79-104).
[5]
Disclosure of Invention Technical Problem
[6] Meanwhile, a thin square-type battery has a problem suffering from swelling of the battery thickness upon charging thereof, due to production of gas such as CO, CO , CH
2 and C H resulting from decomposition of the carbonate based organic solvent during
4 2 6 formation of the SEI (See J. Power Sources (1998) 72: 66-70). Further, when it is stored at a high temperature in a fully charged state (for example, left at a temperature of 85°C for 4 hours after full charging up to 4.2 V), the SFJ film is gradually dis¬ integrated by increased electrochemical and thermal energy as time lapses, and thereby the side reaction between the exposed surface of the cathode and the surrounding electrolyte occurs continuously. Then, continuous production of gas causes elevated internal pressure inside the battery and as a result, in case of the square-type battery and PLI (polymer lithium ion) battery, the thickness thereof increases thus resulting in difficulty of a set mounting.
[7]
Technical Solution
[8] The present invention to provide a novel nonaqueous electrolyte for a lithium battery in which a furanone based derivative is added to a conventional nonaqueous electrolyte for a lithium battery to inhibit decomposition of the electrolyte and thereby
the rate of increase of the battery thickness when allowed to stand at a high temperature is significantly decreased and capacity storage characteristics at high temperature are improved.
[9] In accordance with one aspect of the present invention, the above and other objects can be accomplished by the provision of a nonaqueous electrolyte for a battery containing 0.8 to 2 M of lithium salt dissolved therein, wherein 0.01 to 20% by weight of tetronic acid having the following formula (I) is added:
[10]
[11] (Formula I)
Advantageous Effects
[12] Present invention to provide a novel nonaqueous electrolyte for a lithium battery in which a furanone based derivative is added to a conventional nonaqueous electrolyte for a lithium battery to inhibit decomposition of the electrolyte and thereby the rate of increase of the battery thickness when allowed to stand at a high temperature is sig¬ nificantly decreased and capacity storage characteristics at high temperature are improved. Brief Description of the Drawings
[13] The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
[14] Rg. 1 is a graph showing charging/discharging characteristics of a lithium battery prepared in an example in accordance with the present invention; and
[15] Rg. 2 is a graph showing electrochemical characteristics of an nonaqueous electrolyte prepared in an example in accordance with the present invention. Best Mode for Carrying Out the Invention
[16] Now, the present invention will be described in more detail.
[17] As organic solvents used in preparing a nonaqueous electrolyte for a lithium battery in accordance with the present invention, mention may be made of cyclic carbonate based organic solvents such as ethylene carbonate (EC) and propylene carbonate (PC), and linear carbonate based organic solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC),
methylpropyl carbonate (MPC) and ethylpropyl carbonate (EPC). Preferably, a mixture of at least one cyclic carbonate based organic solvent and at least one linear carbonate based organic solvent may be used, and more preferably a mixture of ethylene carbonate, ethylmethyl carbonate and diethyl carbonate may be used in a ratio of 1:1:1. In addition, solvents such as propyl acetate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate and fluorobenzene may be ad¬ ditionally mixed and used, if desired. The mixing ratio of the respective organic solvents is not particularly limited as long as it does not interfere with the purpose of the present invention, and follows the mixing ratio used in preparing a conventional nonaqueous electrolyte for a lithium battery.
[18] As examples of lithium salts contained in the nonaqueous electrolyte in accordance with the present invention, mention may be made of IiPF , IiClO , IiAsF , IiBF ,
6 4 6 4
IiN (C F SO ) , and the like, and they may be used alone or as a mixture of two or
2 5 3 2 more. More preferably, IiPF may be used. The concentration of the lithium salt
6 ranges from 0.8 to 2.0 M. Where the concentration of the lithium salt added is below 0.8 M, ionic conductivity may be lowered. Where it exceeds 2.0 M, the viscosity of the electrolyte increases and thus ionic conductivity may be lowered.
[19] The nonaqueous electrolyte in accordance with the present invention is char¬ acterized in that 0.01 to 20.0% by weight, and preferably 0.1 to 10% by weight of tetronic acid, which is a furanone based derivative having the following formula (I), is added thereto. Where the above-mentioned content is less than 0.01% by weight, it is difficult to decrease the rate of increase of the battery thickness when it is allowed to stand at a high temperature, by inhibiting decomposition of the eletrolyte. In addition, if the above-mentioned content exceeds 20% by weight, performances of the battery such as service life may be lowered.
[20]
[21]
[22] (Formula I)
[23] The nonaqueous electrolyte for a lithium battery in accordance with the present invention can be used to prepare the lithium battery by a conventional method. Even when the lithium battery thus prepared is allowed to stand at a high temperature (80°C
, 10 days), production of gas inside the battery due to disintegration of the eletrolyte is inhibited and thus swelling of the battery thickness is prevented and capacity storage characteristics at a high temperature become excellent.
[24]
Mode for the Invention
[25] Now, the present invention will be described in more detail with reference to the following Examples. These examples are provided only for illustrating the present invention and should not be construed as limiting the scope and sprit of the present invention.
[26] [27] EXAMPLES AND COMPARATIVE EXAMPLE [28] [29] Ethylene carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) were mixed in a ratio of 1 : 1 : 1 (v/v) and IM of IiPF as solute was dissolved
6 therein to obtain a basic electrolyte. To the basic electrolyte thus obtained was added tetronic acid in the amount prescribed in Table 1 below to prepare an electrolyte of the present invention(Examples 1 to 5).
[30] A lithium battery was prepared in the form of a square type 423048 battery. Graphite was used as the active material of the anode and PVDF was used as a binding agent. IiCoO was used as the active material of the cathode and PVDF was used as
2 the binding agent. As the conductive agent, acetylene black was used.
[31] The prepared lithium battery was tested for swelling thereof at a high temperature (80°C , 10 days) under a fully charged state of 4.2 V after formation charging/ discharging and standard charging/discharging procedures and the results are shown in Table 1. Meanwhile, a service life (standard charging/discharging) characteristic (50 cycles) was determined and shown in Rg. 1. Electrochemical characteristics were determined for the electrolytes (Example 2) to which 1.0% by weight of tetronic acid was added, respectively and the electrolyte to which no tetronic acid was added (Comparative Example) and are shown in Fig. 2.
[32] Table 1
[33] ΔIR(mΩ): Changes in internal resistance of the battery before and after being left at a high temperature
[34] ΔV(volt): Changes in voltage of the battery before and after being left at a high temperature
[35] ΔT(mm): Changes in thickness of the battery before and after being left at a high temperature
[36] (High temperature conditions: 80°C +2°C, 10 days)
Industrial Applicability
[37] In accordance with the present invention, provided is a novel nonaqueous electrolyte for a lithium battery in which the rate of increase of the battery thickness even when it is allowed to stand at a high temperature is significantly decreased and capacity storage characteristics at high temperature are improved.
[38] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modi¬ fications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims
[1] A Nonaqueous electrolyte for a battery containing 0.8 to 2 M of lithium salt dissolved therein, wherein 0.01 to 20% by weight of tetronic acid having the following formula (I) is added:
(Formula I)
[2] The nonaqueous electrolyte as set forth in claim 1, wherein the lithium salt is at least one material selected from the group consisting of IiPF , IiClO , IiAsF , IiBF and IiN(C F SO ) .
4 2 5 3 2
[3] The nonaqueous electrolyte as set forth in claim 1, wherein a mixture of at least one cyclic carbonate based solvent and at least one linear carbonate based solvent is used as a solvent.
[4] A secondary lithium battery comprising a nonaqueous electrolyte for a battery as set forth in claim 1.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004800442961A CN100454654C (en) | 2004-10-27 | 2004-10-27 | Nonaqueous electrolyte for battery |
| PCT/KR2004/002728 WO2006046785A1 (en) | 2004-10-27 | 2004-10-27 | Nonaqueous electrolyte for battery |
| US11/718,031 US20090226820A1 (en) | 2004-10-27 | 2004-10-27 | Nonaqueous Electrolyte for Battery |
| JP2007537788A JP2008518392A (en) | 2004-10-27 | 2004-10-27 | Non-aqueous electrolyte for batteries |
| EP04793586A EP1807899A4 (en) | 2004-10-27 | 2004-10-27 | Nonaqueous electrolyte for battery |
| TW093133152A TWI259597B (en) | 2004-10-27 | 2004-10-29 | Nonaqueous electrolyte for battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2004/002728 WO2006046785A1 (en) | 2004-10-27 | 2004-10-27 | Nonaqueous electrolyte for battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2006046785A1 true WO2006046785A1 (en) | 2006-05-04 |
Family
ID=36228004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2004/002728 WO2006046785A1 (en) | 2004-10-27 | 2004-10-27 | Nonaqueous electrolyte for battery |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20090226820A1 (en) |
| EP (1) | EP1807899A4 (en) |
| JP (1) | JP2008518392A (en) |
| CN (1) | CN100454654C (en) |
| TW (1) | TWI259597B (en) |
| WO (1) | WO2006046785A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102431845B1 (en) * | 2017-04-28 | 2022-08-10 | 삼성에스디아이 주식회사 | Electrolyte of rechargeable lithium battery and rechargeable lithium battery including same |
| US11824160B2 (en) * | 2018-03-12 | 2023-11-21 | Tesla, Inc. | Battery systems based on two-additive electrolyte systems including 2-furanone, and method of formation process of same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5350646A (en) * | 1991-03-07 | 1994-09-27 | Centre National De La Recherche Scientifique | Ionically conductive polymeric materials |
| JPH11273725A (en) * | 1998-03-20 | 1999-10-08 | Ube Ind Ltd | Electrolytic solution for lithium secondary battery and lithium secondary battery using it |
| KR20040020640A (en) * | 2002-08-31 | 2004-03-09 | 삼성에스디아이 주식회사 | Organic electrolytic solution and lithium battery employing the same |
| KR20050034118A (en) * | 2003-10-08 | 2005-04-14 | 제일모직주식회사 | Nonaqueous electrolyte for battery |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0763023B2 (en) * | 1986-06-09 | 1995-07-05 | 松下電器産業株式会社 | Organic electrolyte battery |
| JPH0770326B2 (en) * | 1986-06-09 | 1995-07-31 | 松下電器産業株式会社 | Organic electrolyte battery |
| JPH0763015B2 (en) * | 1987-11-18 | 1995-07-05 | 松下電器産業株式会社 | Organic electrolyte battery |
| JPH0582168A (en) * | 1991-09-25 | 1993-04-02 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| US5432029A (en) * | 1993-05-14 | 1995-07-11 | Sharp Kabushiki Kaisha | Lithium secondary battery |
| JP3730491B2 (en) * | 1999-07-28 | 2006-01-05 | 三菱化学株式会社 | Battery having control electrode surface |
| JP4474715B2 (en) * | 1999-10-13 | 2010-06-09 | パナソニック株式会社 | Non-aqueous electrochemical device and its electrolyte |
| JP2003163031A (en) * | 2001-09-12 | 2003-06-06 | Daicel Chem Ind Ltd | ELECTROLYTE, NONAQUEOUS ELECTROCHEMICAL EQUIPMENT AND alpha-SUBSTITUTIONAL OXY-gamma-BUTYROLACTONE DERIVATIVE |
| JP2003243031A (en) * | 2002-02-19 | 2003-08-29 | Japan Storage Battery Co Ltd | Non-aqueous electrolyte secondary battery |
-
2004
- 2004-10-27 US US11/718,031 patent/US20090226820A1/en not_active Abandoned
- 2004-10-27 EP EP04793586A patent/EP1807899A4/en not_active Withdrawn
- 2004-10-27 WO PCT/KR2004/002728 patent/WO2006046785A1/en active Application Filing
- 2004-10-27 JP JP2007537788A patent/JP2008518392A/en active Pending
- 2004-10-27 CN CNB2004800442961A patent/CN100454654C/en not_active Expired - Fee Related
- 2004-10-29 TW TW093133152A patent/TWI259597B/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5350646A (en) * | 1991-03-07 | 1994-09-27 | Centre National De La Recherche Scientifique | Ionically conductive polymeric materials |
| JPH11273725A (en) * | 1998-03-20 | 1999-10-08 | Ube Ind Ltd | Electrolytic solution for lithium secondary battery and lithium secondary battery using it |
| KR20040020640A (en) * | 2002-08-31 | 2004-03-09 | 삼성에스디아이 주식회사 | Organic electrolytic solution and lithium battery employing the same |
| KR20050034118A (en) * | 2003-10-08 | 2005-04-14 | 제일모직주식회사 | Nonaqueous electrolyte for battery |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP1807899A4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1807899A1 (en) | 2007-07-18 |
| EP1807899A4 (en) | 2009-11-11 |
| CN101048912A (en) | 2007-10-03 |
| TWI259597B (en) | 2006-08-01 |
| CN100454654C (en) | 2009-01-21 |
| US20090226820A1 (en) | 2009-09-10 |
| TW200614561A (en) | 2006-05-01 |
| JP2008518392A (en) | 2008-05-29 |
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