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)

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• 2004
  • 2004-10-27 EP EP04793586A patent/EP1807899A4/en not_active Withdrawn
  • 2004-10-27 CN CNB2004800442961A patent/CN100454654C/zh not_active Expired - Fee Related
  • 2004-10-27 WO PCT/KR2004/002728 patent/WO2006046785A1/en not_active Ceased
  • 2004-10-27 US US11/718,031 patent/US20090226820A1/en not_active Abandoned
  • 2004-10-27 JP JP2007537788A patent/JP2008518392A/ja active Pending
  • 2004-10-29 TW TW093133152A patent/TWI259597B/zh not_active IP Right Cessation

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