JPH10116627A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH10116627A JPH10116627A JP8289266A JP28926696A JPH10116627A JP H10116627 A JPH10116627 A JP H10116627A JP 8289266 A JP8289266 A JP 8289266A JP 28926696 A JP28926696 A JP 28926696A JP H10116627 A JPH10116627 A JP H10116627A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- fluoro
- lithium
- secondary battery
- charge
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 15
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229940021013 electrolyte solution Drugs 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- UCCWJJZPOSPPIC-UHFFFAOYSA-N COOCF Chemical compound COOCF UCCWJJZPOSPPIC-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 SnO Chemical class 0.000 description 2
- 150000004651 carbonic acid esters Chemical class 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910021115 PF 6 Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、リチウム二次電池
に係わり、詳しくは充放電効率が極めて高いリチウム二
次電池を得ることを目的とした、電解液の溶媒の改良に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery, and more particularly to an improvement in a solvent for an electrolytic solution for obtaining a lithium secondary battery having extremely high charge / discharge efficiency.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
電解液の溶媒として有機溶媒を使用するリチウム二次電
池が、従前のアルカリ二次電池に比べて、高電圧化乃至
高容量化が可能であることから注目されている。アルカ
リ電解液を使用しないリチウム二次電池の場合は、電池
設計をする際に水の分解電圧を考慮する必要が無いから
である。2. Description of the Related Art In recent years,
BACKGROUND ART A lithium secondary battery using an organic solvent as a solvent for an electrolytic solution has attracted attention because it can achieve higher voltage and higher capacity than conventional alkaline secondary batteries. This is because in the case of a lithium secondary battery that does not use an alkaline electrolyte, it is not necessary to consider the decomposition voltage of water when designing the battery.
【０００３】リチウム二次電池の負極材料には、金属リ
チウム、リチウム合金、黒鉛、コークスなどが使用され
るが、リチウムと有機溶媒とが反応して、リチウムイオ
ン導電性の良くない被膜が負極の表面に形成されるた
め、充放電効率（充電電気量に対する放電電気量の比
率）が良くないという問題がある。As a negative electrode material of a lithium secondary battery, metallic lithium, lithium alloy, graphite, coke, and the like are used, and a film having poor lithium ion conductivity is formed by a reaction between lithium and an organic solvent. Since it is formed on the surface, there is a problem that the charge / discharge efficiency (the ratio of the amount of discharged electricity to the amount of charged electricity) is not good.
【０００４】リチウム二次電池の充放電効率を改善する
ために、電解液の溶媒として、γ−ブチロラクトン（γ
−ＢＬ）の３位又は４位の水素を塩素又はフッ素で置換
した塩素化又はフッ素化γ−ブチロラクトンを使用する
ことが提案されている（特開昭６２−２９００７３号公
報参照）。同公報によれば、塩素化又はフッ素化により
ラクトン環のＣ−Ｏ結合が切れにくくなるため溶媒が安
定化し、その結果充放電効率が改善されるとのことであ
る。In order to improve the charging and discharging efficiency of a lithium secondary battery, γ-butyrolactone (γ
It has been proposed to use chlorinated or fluorinated γ-butyrolactone in which the hydrogen at the 3- or 4-position of —BL) has been replaced with chlorine or fluorine (see Japanese Patent Application Laid-Open No. 62-290073). According to the gazette, chlorination or fluorination makes it difficult to break the C—O bond of the lactone ring, so that the solvent is stabilized, and as a result, the charge / discharge efficiency is improved.
【０００５】しかしながら、リチウム二次電池の充放電
効率は、リチウムと有機溶媒との反応により負極の表面
に形成される被膜のリチウムイオン導電性の良否による
ところが大きいため、上記従来の技術では、充放電効率
が極めて高いリチウム二次電池を得ることは困難であ
る。However, the charge / discharge efficiency of a lithium secondary battery largely depends on the quality of lithium ion conductivity of a film formed on the surface of a negative electrode due to the reaction between lithium and an organic solvent. It is difficult to obtain a lithium secondary battery having extremely high discharge efficiency.
【０００６】本発明は、以上の事情に鑑みてなされたも
のであって、リチウムイオン導電性の良い被膜を形成す
る有機溶媒を使用した、充放電効率が極めて高いリチウ
ム二次電池を提供することを目的とする。The present invention has been made in view of the above circumstances, and provides a lithium secondary battery having an extremely high charge / discharge efficiency using an organic solvent which forms a film having good lithium ion conductivity. With the goal.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
の本発明に係るリチウム二次電池（本発明電池）は、一
般式：Ｒ1 ＣＯＯＲ2 （Ｒ1 及びＲ2 は、互いに同一又
は異なって、炭素数１〜３のアルキル基又は水素原子の
一部若しくは全部がフッ素で置換された炭素数１〜３の
フッ化アルキル基であり、Ｒ1 及びＲ2 の少なくとも一
方は水素原子の一部若しくは全部がフッ素で置換された
炭素数１〜３のフッ化アルキル基である）で表されるフ
ッ化カルボン酸エステルを電解液の溶媒として使用した
ものである。In order to achieve the above object, a lithium secondary battery (battery of the present invention) according to the present invention has a general formula: R 1 COOR 2 (R 1 and R 2 are the same or different from each other) An alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms in which part or all of hydrogen atoms are substituted with fluorine, and at least one of R 1 and R 2 is a hydrogen atom Or a part thereof is a fluoroalkyl group having 1 to 3 carbon atoms substituted with fluorine) as a solvent for the electrolytic solution.
【０００８】一般式：Ｒ1 ＣＯＯＲ2 で表されるフッ化
カルボン酸エステルの具体例としては、ＣＨ2 ＦＣ００
ＣＨ3 、ＣＨＦ2 Ｃ００ＣＨ3 、ＣＦ3 Ｃ００ＣＨ3 、
ＣＨ 3 Ｃ００ＣＨ2 Ｆ、ＣＨ3 Ｃ００ＣＨＦ2 、ＣＨ3
Ｃ００ＣＦ3 、ＣＦ3 Ｃ００ＣＨ2 ＣＦ3 、ＣＦ3 Ｃ０
０ＣＦ2 ＣＦ3 、ＣＦ3 ＣＨ2 Ｃ００ＣＦ3 、ＣＦ3Ｃ
Ｆ2 Ｃ００ＣＦ3 、ＣＦ3 ＣＨ2 Ｃ００ＣＨ2 ＣＦ3 、
ＣＦ3 ＣＦ2 Ｃ００ＣＦ2 ＣＦ3 、ＣＨ3 ＣＨ2 ＣＨ2
ＣＯＯＣＦ3 、ＣＨ3 ＣＨ2 ＣＨ2 ＣＯＯＣＨ2 Ｃ
Ｆ3 、ＣＨ3 ＣＨ2 ＣＨ2 ＣＯＯＣＨ2 ＣＨ2 ＣＦ3 、
ＣＦ3 ＣＦ2 ＣＦ2ＣＯＯＣＦ3 及びＣＨ3 ＣＨ2 ＣＦ
2 ＣＯＯＣＨ3 が例示される。General formula: R1COORTwoFluoride represented by
Specific examples of the carboxylic acid ester include CHTwoFC00
CHThree, CHFTwoC00CHThree, CFThreeC00CHThree,
CH ThreeC00CHTwoF, CHThreeC00CHFTwo, CHThree
C00CFThree, CFThreeC00CHTwoCFThree, CFThreeC0
0CFTwoCFThree, CFThreeCHTwoC00CFThree, CFThreeC
FTwoC00CFThree, CFThreeCHTwoC00CHTwoCFThree,
CFThreeCFTwoC00CFTwoCFThree, CHThreeCHTwoCHTwo
COOCFThree, CHThreeCHTwoCHTwoCOOCHTwoC
FThree, CHThreeCHTwoCHTwoCOOCHTwoCHTwoCFThree,
CFThreeCFTwoCFTwoCOOCFThreeAnd CHThreeCHTwoCF
TwoCOOCHThreeIs exemplified.
【０００９】上記フッ化カルボン酸エステルは、二種以
上を併用してもよい。また、フッ化カルボン酸エステル
のみを使用してもよく、必要に応じて従来公知の他の溶
媒との混合溶媒の形態で使用してもよい。混合溶媒の形
態で使用する場合は、上記フッ化カルボン酸エステルの
一種又は二種以上を１０体積％以上含む混合溶媒が好ま
しい。上記フッ化カルボン酸エステルの含有比率が１０
体積％未満の場合は、負極の表面に形成される被膜のリ
チウムイオン導電性が充分でないため、充放電効率が極
めて高いリチウム二次電池を得ることが困難になる。The above fluorocarboxylic acid esters may be used in combination of two or more. Further, only the fluorinated carboxylic acid ester may be used, and if necessary, it may be used in the form of a mixed solvent with another conventionally known solvent. When used in the form of a mixed solvent, a mixed solvent containing one or more of the above fluorocarboxylic acid esters in an amount of 10% by volume or more is preferable. When the content ratio of the fluorocarboxylic acid ester is 10
When the content is less than% by volume, the lithium ion conductivity of the film formed on the surface of the negative electrode is not sufficient, so that it is difficult to obtain a lithium secondary battery having extremely high charge / discharge efficiency.
【００１０】上記フッ化カルボン酸エステルを他の溶媒
との混合溶媒の形態で使用する場合の他の溶媒として
は、エチレンカーボネート（ＥＣ）、プロピレンカーボ
ネート（ＰＣ）、ブチレンカーボネート（ＢＣ）等の環
状炭酸エステル；ジメチルカーボネート（ＤＭＣ）、エ
チルメチルカーボネート（ＥＭＣ）、ジエチルカーボネ
ート（ＤＥＣ）等の鎖状炭酸エステル；１，２−ジメト
キシエタン（ＤＭＥ）、エトキシメトキシエタン（ＥＭ
Ｅ）、１，２−ジエトキシエタン（ＤＥＥ）、テトラヒ
ドロフラン（ＴＨＦ）、２−メチルテトラヒドロフラン
（２ＭｅＴＨＦ）、１，３−ジオキソラン（ＤＯＸ
Ｌ）、２−メチル−１，３−ジオキソラン（２ＭｅＤＯ
ＸＬ）、４−メチル−１，３−ジオキソラン（４ＭｅＤ
ＯＸＬ）等のエーテル類が例示される。これらの溶媒
は、必要に応じて二種以上使用してもよい。When the above fluorinated carboxylic acid ester is used in the form of a mixed solvent with another solvent, other solvents include cyclic solvents such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate (BC). Carbonic acid esters; chain-like carbonic acid esters such as dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC); 1,2-dimethoxyethane (DME), ethoxymethoxyethane (EM
E), 1,2-diethoxyethane (DEE), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1,3-dioxolane (DOX)
L), 2-methyl-1,3-dioxolane (2MeDO
XL), 4-methyl-1,3-dioxolane (4MeD
Ethers such as OXL). Two or more of these solvents may be used as necessary.
【００１１】本発明は、リチウム二次電池の電解液の溶
媒の改良に関する。それゆえ、電解液の溶媒を除く部材
には、次に示す如き従来公知のものを特に制限無く用い
ることができる。The present invention relates to an improvement in a solvent for an electrolytic solution of a lithium secondary battery. Therefore, as the member for removing the solvent of the electrolytic solution, a conventionally known member as shown below can be used without particular limitation.
【００１２】正極活物質の具体例としては、ＬｉＣｏＯ
2 、ＬｉＮｉＯ2 、ＬｉＭｎ2 Ｏ4、ＬｉＶＯ2 及びＬ
ｉＮｂＯ2 が挙げられる。As a specific example of the positive electrode active material, LiCoO
2 , LiNiO 2 , LiMn 2 O 4 , LiVO 2 and L
iNbO 2 .
【００１３】負極材料としては、リチウムイオンを電気
化学的に吸蔵及び放出することが可能な物質及び金属リ
チウムが例示される。リチウムイオンを電気化学的に吸
蔵及び放出することが可能な物質の具体例としては、黒
鉛、コークス等の炭素材料；リチウム−アルミニウム合
金、リチウム−鉛合金、リチウム−錫合金等のリチウム
合金；ＳｎＯ2 、ＳｎＯ、ＴｉＯ2 、Ｎｂ2 Ｏ3 等の電
位が正極活物質に比べて卑な金属酸化物が挙げられる。Examples of the negative electrode material include a substance capable of electrochemically storing and releasing lithium ions and lithium metal. Specific examples of substances capable of electrochemically storing and releasing lithium ions include carbon materials such as graphite and coke; lithium alloys such as lithium-aluminum alloy, lithium-lead alloy, and lithium-tin alloy; SnO. 2 , metal oxides such as SnO, TiO 2 , and Nb 2 O 3 which have a lower potential than the positive electrode active material.
【００１４】非水電解液の溶質の具体例としては、Ｌｉ
ＰＦ6 、ＬｉＡｓＦ6 、ＬｉＳｂＦ6 、ＬｉＣｌＯ4 、
ＬｉＢＦ4 、ＬｉＣＦ3 ＳＯ3 、ＬｉＮ（ＣＦ3 Ｓ
Ｏ2 ）2が挙げられる。A specific example of the solute in the non-aqueous electrolyte is Li
PF 6, LiAsF 6, LiSbF 6 , LiClO 4,
LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 S
O 2 ) 2 .
【００１５】本発明電池においては、フッ化カルボン酸
エステルと負極のリチウムとの反応によりリチウムイオ
ン導電性の良い被膜が負極の表面に形成される。このた
め、本発明電池は充放電効率が極めて高い。In the battery of the present invention, a film having good lithium ion conductivity is formed on the surface of the negative electrode by the reaction between the fluorocarboxylic acid ester and lithium of the negative electrode. For this reason, the battery of the present invention has extremely high charge / discharge efficiency.
【００１６】[0016]
【実施例】本発明を実施例に基づいてさらに詳細に説明
するが、本発明は下記実施例に何ら限定されるものでは
なく、その要旨を変更しない範囲で適宜変更して実施す
ることが可能なものである。EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples and can be carried out by appropriately changing the scope of the invention without changing its gist. It is something.
【００１７】表１及び表２に示す電解液（溶質濃度は全
て１モル／リットル）を調製し、それぞれの電解液を使
用して、３極式の試験セルＡ１〜Ａ３６，Ｂ１〜Ｂ７を
組み立てた。試験セルＢ２は、特開昭６２−２９００７
３号公報で提案されている溶媒を使用した試験セルであ
る。図１は組み立てた試験セルの断面模式図であり、図
示の試験セルＣは、作用極（ニッケル電極；電極面積１
ｃｍ2 ）１、作用極１に比べて充分に大きな電気化学的
容量を有する対極（リチウム電極；電極面積１０ｃ
ｍ2 ）２、参照極（リチウム電極；電極面積０．３ｃｍ
2 ）３、ルギン管４、絶縁性の密閉容器５及び電解液６
からなる。Electrolyte solutions shown in Tables 1 and 2 (all solute concentrations were 1 mol / liter) were prepared, and triode test cells A1 to A36 and B1 to B7 were assembled using the respective electrolyte solutions. Was. Test cell B2 is disclosed in
3 is a test cell using a solvent proposed in Japanese Patent Publication No. FIG. 1 is a schematic cross-sectional view of an assembled test cell. The illustrated test cell C has a working electrode (nickel electrode; electrode area 1).
cm 2 ) 1, a counter electrode (lithium electrode; electrode area 10 c) having a sufficiently large electrochemical capacity as compared with the working electrode 1
m 2 ) 2, reference electrode (lithium electrode; electrode area 0.3 cm)
2 ) 3, Luggin tube 4, insulating closed container 5, and electrolyte 6
Consists of
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】次いで、上記の各試験セルを、２５°Ｃに
て、電流密度１ｍＡ／ｃｍ2 で５分間充電した後、１ｍ
Ａ／ｃｍ2 で参照極を基準とする作用極の電位が０．５
Ｖに達するまで放電して、各試験セルの充放電効率を下
式より求めた。これらの充放電効率を先の表１及び表２
に示す。Next, each of the test cells was charged at 25 ° C. at a current density of 1 mA / cm 2 for 5 minutes.
A / cm 2 , the potential of the working electrode with respect to the reference electrode is 0.5
The battery was discharged until the voltage reached V, and the charge / discharge efficiency of each test cell was determined by the following equation. These charge and discharge efficiencies are shown in Tables 1 and 2 above.
Shown in
【００２１】充放電効率（％）＝放電時間（分）÷充電
時間（５分）×１００Charge / discharge efficiency (%) = discharge time (min) / charge time (5 minutes) × 100
【００２２】表１及び表２に示すように、試験セルＡ１
〜Ａ３６は、試験セルＢ１〜Ｂ７に比べて、充放電効率
が格段に高い。この事実から、本発明で規定するフッ化
カルボン酸エステルを単一溶媒又は混合溶媒の形態で電
解液に使用することにより、充放電効率が大きく向上す
ることが分かる。As shown in Tables 1 and 2, the test cell A1
-A36 have much higher charge / discharge efficiency than the test cells B1 to B7. From this fact, it is understood that the use of the fluorinated carboxylic acid ester defined in the present invention in the form of a single solvent or a mixed solvent in the electrolytic solution greatly improves the charge and discharge efficiency.
【００２３】〈フッ化カルボン酸エステルを混合溶媒の
形態で使用する場合のフッ化カルボン酸エステルの好適
な比率〉表３に示す電解液（溶質濃度は全て１モル／リ
ットル）を調製し、それぞれの電解液を使用して試験セ
ルＡ３７〜Ａ３９，Ｂ８を組み立て、各試験セルの充放
電効率を先と同様にして求めた。これらの充放電効率を
表３に示す。表３には、試験セルＡ６の充放電効率も表
１より転記して示してある。<Preferred Ratio of Fluorocarboxylic Acid Esters When Fluorocarboxylic Acid Esters are Used in Mixed Solvent Form> Electrolyte solutions shown in Table 3 (all solute concentrations are 1 mol / l) are prepared. The test cells A37 to A39 and B8 were assembled using the above electrolyte solution, and the charge / discharge efficiency of each test cell was determined in the same manner as above. Table 3 shows the charge / discharge efficiency. In Table 3, the charge / discharge efficiency of the test cell A6 is also transcribed from Table 1.
【００２４】[0024]
【表３】 [Table 3]
【００２５】表３より、ＣＨ3 ＣＯＯＣＦ3 をエチレン
カーボネートとの混合溶媒の形態で使用する場合は、混
合溶媒中のＣＨ3 ＣＯＯＣＦ3 の比率を１０体積％以上
とすることが好ましいことが分かる。なお、本発明で規
定する他のフッ化カルボン酸エステルについても、従来
公知の他の溶媒との混合溶媒の形態で使用する場合は、
その混合溶媒中の比率を１０体積％以上とすることが好
ましいことを確認した。Table 3 shows that when CH 3 COOCF 3 is used in the form of a mixed solvent with ethylene carbonate, the ratio of CH 3 COOCF 3 in the mixed solvent is preferably at least 10% by volume. Incidentally, also for other fluorocarboxylic acid esters defined in the present invention, when used in the form of a mixed solvent with other conventionally known solvents,
It was confirmed that the ratio in the mixed solvent was preferably 10% by volume or more.
【００２６】上記の実施例では、本発明で規定するフッ
化カルボン酸エステルを１種類使用する場合について説
明したが、２種類以上のフッ化カルボン酸エステルを使
用した場合にも、同様に、充放電効率の極めて高いリチ
ウム二次電池が得られることを確認した。In the above embodiment, the case where one kind of fluorinated carboxylic acid ester defined in the present invention is used has been described. It was confirmed that a lithium secondary battery having extremely high discharge efficiency was obtained.
【００２７】[0027]
【発明の効果】負極のリチウムと反応してリチウムイオ
ン導電性の良い被膜を負極の表面に形成する特定のフッ
化カルボン酸エステルが電解液の溶媒として使用されて
いるので、本発明電池は充放電効率が極めて高い。As the specific fluorinated carboxylate which reacts with the lithium of the negative electrode to form a film having good lithium ion conductivity on the surface of the negative electrode is used as a solvent for the electrolytic solution, the battery of the present invention is not charged. Extremely high discharge efficiency.
【図１】実施例で組み立てた試験セルの断面模式図であ
る。FIG. 1 is a schematic cross-sectional view of a test cell assembled in an example.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 能間 俊之 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiyuki Noma 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Koji Nishio 2-chome Keihanhondori, Moriguchi-shi, Osaka No. 5-5 in Sanyo Electric Co., Ltd.
Claims (2)
Ｒ2 は、互いに同一又は異なって、炭素数１〜３のアル
キル基又は水素原子の一部若しくは全部がフッ素で置換
された炭素数１〜３のフッ化アルキル基であり、Ｒ1 及
びＲ2 の少なくとも一方は水素原子の一部若しくは全部
がフッ素で置換された炭素数１〜３のフッ化アルキル基
である）で表されるフッ化カルボン酸エステルが電解液
の溶媒として使用されているリチウム二次電池。1. A compound represented by the general formula: R 1 COOR 2 wherein R 1 and R 2 are the same or different from each other, and a part or all of an alkyl group having 1 to 3 carbon atoms or a hydrogen atom is substituted with fluorine. And at least one of R 1 and R 2 is a fluoroalkyl group having 1 to 3 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine. A lithium secondary battery in which the represented fluorocarboxylic acid ester is used as a solvent for an electrolytic solution.
ステルのみからなる溶媒又は前記フッ化カルボン酸エス
テルを１０体積％以上含有する混合溶媒である請求項１
記載のリチウム二次電池。2. The solvent of the electrolytic solution is a solvent consisting of the fluorocarboxylic acid ester alone or a mixed solvent containing the fluorocarboxylic acid ester in an amount of 10% by volume or more.
The lithium secondary battery according to the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28926696A JP3311611B2 (en) | 1996-10-11 | 1996-10-11 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28926696A JP3311611B2 (en) | 1996-10-11 | 1996-10-11 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10116627A true JPH10116627A (en) | 1998-05-06 |
| JP3311611B2 JP3311611B2 (en) | 2002-08-05 |
Family
ID=17740942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28926696A Expired - Fee Related JP3311611B2 (en) | 1996-10-11 | 1996-10-11 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3311611B2 (en) |
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| JP2002343424A (en) * | 2001-05-15 | 2002-11-29 | Japan Storage Battery Co Ltd | Non-aqueous electrolyte secondary battery |
| JP2003297422A (en) * | 2002-04-02 | 2003-10-17 | Sony Corp | Battery |
| JP2004095354A (en) * | 2002-08-30 | 2004-03-25 | Sharp Corp | Gel electrolyte secondary battery and method for producing the same |
| US6790982B2 (en) | 2000-11-28 | 2004-09-14 | Asahi Glass Company, Limited | Process for producing a fluorine atom-containing sulfonyl fluoride compound |
| US6894187B2 (en) | 2000-07-11 | 2005-05-17 | Asahi Glass Company, Limited | Method for producing a fluorine-containing compound |
| JP2005268094A (en) * | 2004-03-19 | 2005-09-29 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution and lithium ion secondary battery, as well as fluorine containing ester compound |
| US7053237B2 (en) | 2001-01-16 | 2006-05-30 | Asahi Glass Company, Limited | Process for producing a fluorinated ester, a fluorinated acyl fluoride and a fluorinated vinyl ether |
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| CN104364958A (en) * | 2012-06-05 | 2015-02-18 | 日本电气株式会社 | lithium secondary battery |
| US9673450B2 (en) | 2011-09-02 | 2017-06-06 | Solvay Sa | Lithium ion battery |
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1996
- 1996-10-11 JP JP28926696A patent/JP3311611B2/en not_active Expired - Fee Related
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| US6956138B2 (en) | 2000-07-11 | 2005-10-18 | Asahi Glass Company, Limited | Method for producing a fluorine-containing compound |
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| JP2003297422A (en) * | 2002-04-02 | 2003-10-17 | Sony Corp | Battery |
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| US9673450B2 (en) | 2011-09-02 | 2017-06-06 | Solvay Sa | Lithium ion battery |
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