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WO2009088174A2 - Solution électrolyte non aqueuse pour batterie secondaire au lithium et batterie secondaire au lithium la contenant - Google Patents

Solution électrolyte non aqueuse pour batterie secondaire au lithium et batterie secondaire au lithium la contenant Download PDF

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Publication number
WO2009088174A2
WO2009088174A2 PCT/KR2008/007850 KR2008007850W WO2009088174A2 WO 2009088174 A2 WO2009088174 A2 WO 2009088174A2 KR 2008007850 W KR2008007850 W KR 2008007850W WO 2009088174 A2 WO2009088174 A2 WO 2009088174A2
Authority
WO
WIPO (PCT)
Prior art keywords
carbonate
electrolyte solution
aqueous electrolyte
secondary battery
lithium secondary
Prior art date
Application number
PCT/KR2008/007850
Other languages
English (en)
Other versions
WO2009088174A3 (fr
Inventor
Soo-Jin Kim
Jeong-Ju Cho
Mi-Young Son
Su-Jin Yoon
Original Assignee
Lg Chem, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lg Chem, Ltd. filed Critical Lg Chem, Ltd.
Publication of WO2009088174A2 publication Critical patent/WO2009088174A2/fr
Publication of WO2009088174A3 publication Critical patent/WO2009088174A3/fr

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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
    • H01M10/05—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
    • 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
    • H01M10/42—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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 an electrolyte solution for lithium secondary batteries, which may solve the swelling phenomenon caused by the addition of vinylethylene carbonate, and a lithium secondary battery containing the same.
  • a lithium secondary battery developed in the early 1990' includes an anode made of carbon material capable of intercalating or disintercalating lithium ions, a cathode made of lithium-containing oxide, and a nonaqueous electrolyte solution obtained by dissolving a suitable amount of lithium salt in a mixed organic solvent.
  • the lithium secondary battery has an average discharge voltage of about 3.6 to 3.7V, which is advantageously higher than those of other batteries such as alkali batteries or nickel-cadmium batteries.
  • an electrolyte composition electrochemically stable in a charging/discharging voltage range from 0 to 4.5 V is required.
  • a mixed solvent in which a cyclic carbonate compound such as ethylene carbonate or propylene carbonate and a linear carbonate compound such as dimethyl carbonate, ethylmethyl carbonate or diethyl carbonate are suitably mixed is used as a solvent of electrolyte.
  • a solute of electrolyte commonly uses a lithium salt such as LiPF 6 , LiBF 4 and LiClO 4 , which acts as a source for supplying lithium ions in a battery and thus enables the lithium battery to operate.
  • Lithium ions coming out from a cathode active material such as lithium metal oxide during an initial charging process of a lithium secondary battery are moved to an anode active material such as graphite and then intercalated between layers of the anode active material.
  • electrolyte reacts with carbon of the anode active material on the surface of the anode active material such as graphite, thereby generating compounds such as Li 2 CO 3 , Li 2 O and LiOH.
  • SEI Solid Electrolyte Interface
  • the SEI film plays a role of ion tunnel, which allows only lithium ions to pass. Due to the effects of ion tunnel, the SEI film prevents an organic solvent molecule moving together with lithium ions in the electrolyte solution and having a great molecular weight from being intercalated into layers of the anode active material and thus breaking down the anode structure. Thus, since the electrolyte solution is not contacted with the anode active material, the electrolyte solution is not decomposed, and also an amount of lithium ions in the electrolyte solution is reversibly kept, thereby ensuring stable charging/discharging.
  • the SEI film is insufficient to play a role of a continuous protective film of an anode, so the life cycle and performance of a battery are deteriorated as the battery repeats charging/discharging.
  • the SEI film of a lithium secondary battery is thermally unstable.
  • the battery may be easily collapsed due to electrochemical energy and thermal energy, which are increased as time goes. In this reason, the battery performance is further deteriorated under a high temperature circumstance.
  • VEC vinylethylene carbonate
  • a cathode to generate gas when a battery is kept at a high temperature or repeatedly fully charged and discharged over a normal temperature, thereby giving side effects of causing swelling of the battery.
  • the thickness of the battery is increased to cause problems in a set such as cellular phones and notebooks, which is one of most serious claims from customers.
  • Korean Laid-open Patent Publication No. 2003-59729, Japanese Laid- open Patent Publication No. 2003-323915, No. 2002-134169 and No. 2003-173816 disclose non-aqueous electrolyte solutions containing 1,3-divinyltetramethyldisiloxane.
  • 1,3-divinyltetramethyldisiloxane is just disclosed as an additive to improve life cycle or low-temperature characteristics of a battery, and the above documents do not give any teaching in relation to addition of vinylethylene carbonate or improvement of side effects caused by vinylethylene carbonate. Disclosure of Invention Technical Problem
  • the present invention is designed to solve the problems of the prior art, and therefore it is an object of the present invention to provide a non- aqueous electrolyte solution for a lithium secondary battery, which may significantly improve side effects of causing swelling of a battery without deteriorating the improvement of deterioration of life cycle and performance of the battery, caused by the addition of vinylethylene carbonate, and a lithium secondary battery containing the same.
  • the present invention provides a nonaqueous electrolyte solution for a lithium secondary battery, which includes a lithium salt and an organic solvent, wherein the non-aqueous electrolyte solution includes 0.5 to 5 weight% of vinylethylene carbonate and 0.1 to 5 weight% of 1,3-divinyltetramethyldisiloxane simultaneously, based on the total weight of the nonaqueous electrolyte solution.
  • the organic solvent is preferably any one selected from the group consisting of a cyclic carbonate selected from the group consisting of propylene carbonate, ethylene carbonate and vinylene carbonate, or their mixtures, a linear carbonate selected from the group consisting of diethyl carbonate, dimethyl carbonate, methylethyl carbonate and dipropyl carbonate, or their mixtures, dimethyl sulfoxide, acetonitrile, dimethoxyethane, sulforan, gamma-butyrolactone, ethylene sulfite, tetrahydrofuran, ethyl propionate and propyl propionate, or their mixtures.
  • the organic solvent more preferably includes ethylene carbonate or a mixture of ethylene carbonate and propylene carbonate.
  • FIG. 1 is a graph showing the changes of capacity and thickness of batteries according to repeated charging/discharging at a normal temperature according to an embodiment and a comparative example;
  • FIG. 2 is a graph showing the changes of capacity and thickness of batteries according to repeated charging/discharging at 45 0 C according to the embodiment and the comparative example.
  • FIG. 3 is a graph showing the change of thickness of batteries according to time when the batteries according to the embodiment and the comparative example are kept under a high temperature circumstance.
  • a non-aqueous electrolyte solution for a lithium secondary battery according to the present invention includes a lithium salt and an organic solvent.
  • the non-aqueous electrolyte solution includes 0.5 to 5 weight% of vinylethylene carbonate and 0.1 to 5 weight% of 1,3-divinyltetramethyldisiloxane simultaneously, based on the total weight of the non-aqueous electrolyte solution.
  • VEC vinylethylene carbonate
  • a battery is kept at a high temperature or repeatedly fully charged and discharged over a normal temperature, vinylethylene carbonate is easily decomposed in a cathode to generate gas, thereby giving side effects of causing swelling of a battery.
  • the inventors had been screening various materials, and then found that swelling of a battery may be significantly improved without deteriorating the effects obtained by the addition of vinylethylene carbonate, when 1,3-divinyltetramethyldisiloxane and vinylethylene carbonate are added simultaneously.
  • the present invention has been completed under such a background.
  • the non-aqueous electrolyte for a lithium secondary battery if the content of vinylethylene carbonate is less than 0.5 weight%, the improvement of life cycle and performance of a battery, obtained by the addition of vinylethylene carbonate, is insufficient. If the content exceeds 5 weight%, resistance of the battery is greatly increased, so much gas is generated when the battery is kept at a high temperature. Also, if the content of 1,3-divinyltetramethyldisiloxane is less than 0.1 weight%, the improvement of swelling of a battery, obtained by the addition of vinylethylene carbonate, is not expected. If the content exceeds 5 weight%, ion conductivity of the electrolyte solution itself is decreased.
  • the lithium salt included as an electrolyte may use any one commonly used for electrolyte solutions for lithium secondary batteries.
  • the lithium salt may be LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiN(C 2 F 5 SOz) 2 , LiN(CF 3 SO 2 ),, CF 3 SO 3 Li, LiC(CF 3 SO 2 ),, LiC 4 BO 8 and so on.
  • non-aqueous electrolyte of the lithium secondary battery without deteriorating the purpose of the present invention.
  • organic solvent included in the non-aqueous electrolyte solution of the present invention may use any one commonly used for lithium secondary batteries.
  • the organic solvent may use a cyclic carbonate such as propylene carbonate, ethylene carbonate and vinylene carbonate, a linear carbonate such as diethyl carbonate, dimethyl carbonate, methylethyl carbonate and dipropyl carbonate, dimethyl sulfoxide, acetonitrile, dimethoxyethane, sulforan, gamma-butyrolactone, ethylene sulfite, tetrahydrofuran, ethyl propionate and propyl propionate, in single or in mixture.
  • a cyclic carbonate such as propylene carbonate, ethylene carbonate and vinylene carbonate
  • a linear carbonate such as diethyl carbonate, dimethyl carbonate, methylethyl carbonate and dipropyl carbonate
  • dimethyl sulfoxide acetonitrile, dimethoxyethane, sulforan, gamma-butyrolactone, ethylene sul
  • ethylene carbonate or a mixture of ethylene carbonate and propylene carbonate may more easily dissociate a lithium salt in an electrolyte due to high dielectric constants, so it contributes to improvement of charging/discharging capacity of a battery.
  • propylene carbonate is mixed, a volume ratio of propylene carbonate is preferably 1/4 to 1 with respect to ethylene carbonate.
  • linear carbonate with low viscosity and low dielectric constant such as dimethyl carbonate and diethyl carbonate may be more preferably used in mixture, which allows making an electrolyte solution with high electric conductivity.
  • the non-aqueous electrolyte solution for a lithium secondary battery according to the present invention is applied to a lithium secondary battery having an anode made of carbon material, metal alloy, lithium-containing oxide, silicon-containing material bondable to lithium or the like, which may intercalate or disintercalate lithium ions, and a cathode made of lithium-containing oxide or the like.
  • the carbon material capable of intercalating or disintercalating lithium ions may employ any material capable of being used as a carbon material anode of a lithium secondary battery such as low-crystalline carbon and high-crystalline carbon.
  • the low- crystalline carbon is representatively soft carbon or hard carbon
  • the high- crystalline carbon is representatively natural graphite, Kish graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches, and high-temperature sintered carbon such as petroleum or coal tar pitch derived cokes.
  • alloys containing silicon or oxides such as Li 4 Ti 5 Oi 2 may be used for an anode.
  • the anode may have a binding agent, which may use various kinds of binder polymer such as PVDF-co-HFP, polyvinylidenefluoride, poly aery lonitrile, polymethylmethacrylate, and styrene-butadiene rubber (SBR).
  • binder polymer such as PVDF-co-HFP, polyvinylidenefluoride, poly aery lonitrile, polymethylmethacrylate, and styrene-butadiene rubber (SBR).
  • a separator is commonly interposed between the cathode and the anode, and the separator may use common porous polymer films used as conventional separators, such as porous polymer films made using ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer and ethylene/methacrylate copolymer, in single or in laminate.
  • the separator may use common porous non-woven fabrics such as a non- woven fabric made of glass fiber with a high melt point or polyethylene terephthalate fiber, but not limitedly.
  • the secondary battery of the present invention has an appearance, not specially limited, but the appearance may be a cylindrical shape using a can, an angled shape, a pouch shape or a coin shape.
  • the appearance may be a cylindrical shape using a can, an angled shape, a pouch shape or a coin shape.
  • LiPF 6 was added to a solvent in which ethylene carbonate (EC), propylene carbonate
  • PC polystyrene
  • DEC diethyl carbonate
  • a non-aqueous electrolyte solution was prepared in the same way as the embodiment
  • a non-aqueous electrolyte solution was prepared in the same way as the embodiment
  • Pouch-type lithium secondary batteries with a thickness of 3.8 mm were made in a common way using the non-aqueous electrolyte solutions prepared in the embodiments and the comparative example, LiCoO 2 as a cathode and artificial graphite as an anode.
  • the made pouch-type batteries to which the electrolyte solutions were injected were impregnated in the electrolyte solutions at a normal temperature for a certain time, and then an activation process was executed. Subsequently, the batteries were degassed and resealed, and then charged/discharged one time at a room temperature. At this time, the batteries were charged to 4.2V under a constant current/constant voltage condition, and then discharged to 3.0V under a constant current condition.
  • life cycle, performance characteristics and status of components were measured in the following way.
  • FIG. 1 and the embodiment 1, respectively, and one battery for the embodiment 2 were initially charged/discharged, and then charged/discharged at 1.0 C-rate 400 times at a normal temperature in the same voltage region.
  • the changes of capacity and thickness of the batteries according to the repetition number of charging/discharging are shown in FIG. 1.
  • upper lines represent the change of capacity of the batteries
  • lower lines represent the change of thickness of the batteries.
  • Both embodiments 1 and 2 exhibited improved sustainable yields of capacity in comparison to the comparative example, and it was found that battery swelling was lowered as the life cycle test was executed.
  • the batteries made according to the embodiments and the comparative example were initially charged/discharged, and then charged to 4.2V, respectively.
  • the batteries were put into a temperature control oven and heated from 25 0 C to 9O 0 C during 1 hour, then preserved at 9O 0 C for 4 hours, then cooled to 25 0 C during 1 hour, and then preserved at 25 0 C for a hour.
  • the thickness of the batteries was measured using suitable equipment at 30 minute intervals. The measurement results are shown in FIG. 3. Seeing the graph of FIG. 3, it would be found that both of the embodiments 1 and 2 exhibit a meaningfully decreased swelling in comparison to the comparative example.
  • the non-aqueous electrolyte solution for a lithium secondary battery according to the present invention may exhibit sufficient effects in capacity, life cycle and improvement in performance deterioration of a battery by the addition of vinylethylene carbonate, and also greatly solve the problem of battery swelling caused by the addition of vinylethylene carbonate when a battery is stored at a high temperature or repeatedly fully charged/discharged over a normal temperature.

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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

Solution électrolyte non aqueuse pour une batterie secondaire au lithium comprenant un sel de lithium et un solvant organique. La solution électrolyte non aqueuse comprend de 0,5 à 5 % en poids de carbonate de vinyléthylène et de 0,1 à 5 % en poids de 1,3-divinyltétraméthyldisiloxane simultanément, par rapport au poids total de la solution électrolyte non aqueuse. Le 1,3-divinyltétraméthyldisiloxane peut résoudre en grande partie l'effet secondaire du gonflement des batteries sans effets de détérioration tels que l'amélioration de la détérioration de la performance et du cycle de vie à la suite de l'ajout de carbonate de vinyléthylène.
PCT/KR2008/007850 2008-01-09 2008-12-31 Solution électrolyte non aqueuse pour batterie secondaire au lithium et batterie secondaire au lithium la contenant WO2009088174A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2008-0002747 2008-01-09
KR1020080002747A KR20090076677A (ko) 2008-01-09 2008-01-09 리튬 이차전지용 비수 전해액 및 이를 구비한 리튬이차전지

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WO2009088174A2 true WO2009088174A2 (fr) 2009-07-16
WO2009088174A3 WO2009088174A3 (fr) 2009-09-03

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2357692A4 (fr) * 2008-11-20 2013-08-21 Lg Chemical Ltd Batterie secondaire lithium aux caractéristiques améliorées
CN114784374A (zh) * 2022-04-01 2022-07-22 惠州锂威新能源科技有限公司 一种锂离子电池电解液用添加剂、电解液及锂离子电池

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115974106B (zh) * 2022-12-15 2024-03-22 福建省龙德新能源有限公司 六氟磷酸钠及其重结晶方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100440485B1 (ko) * 2002-01-04 2004-07-14 주식회사 엘지화학 새로운 비수전해액 및 이를 이용한 리튬 이차 전지
JP4438956B2 (ja) * 2005-04-04 2010-03-24 信越化学工業株式会社 非水電解液及びこれを用いた二次電池
JP4948025B2 (ja) * 2006-04-18 2012-06-06 三洋電機株式会社 非水系二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2357692A4 (fr) * 2008-11-20 2013-08-21 Lg Chemical Ltd Batterie secondaire lithium aux caractéristiques améliorées
CN114784374A (zh) * 2022-04-01 2022-07-22 惠州锂威新能源科技有限公司 一种锂离子电池电解液用添加剂、电解液及锂离子电池

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Publication number Publication date
KR20090076677A (ko) 2009-07-13
WO2009088174A3 (fr) 2009-09-03

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