JP2001068154A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
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- JP2001068154A JP2001068154A JP2000175265A JP2000175265A JP2001068154A JP 2001068154 A JP2001068154 A JP 2001068154A JP 2000175265 A JP2000175265 A JP 2000175265A JP 2000175265 A JP2000175265 A JP 2000175265A JP 2001068154 A JP2001068154 A JP 2001068154A
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- JP
- Japan
- Prior art keywords
- electrolyte
- battery
- additive
- mixed
- secondary battery
- 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.)
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Classifications
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- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はリチウムイオンの挿
入・脱離が可能な正極と、リチウムイオンの挿入・脱離
が可能な負極と、電解質とを備えたリチウム二次電池に
係り、特に、溶質としてリチウム塩を溶解した電解質の
改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery comprising a positive electrode capable of inserting and removing lithium ions, a negative electrode capable of inserting and removing lithium ions, and an electrolyte. The present invention relates to improvement of an electrolyte in which a lithium salt is dissolved as a solute.
【０００２】[0002]
【従来の技術】近年、小型軽量でかつ高容量で充放電可
能な電池としてリチウム二次電池が実用化されるように
なり、小型ビデオカメラ、携帯電話、ノートパソコン等
の携帯用電子・通信機器等に用いられるようになった。
この種のリチウム二次電池は、負極活物質としてリチウ
ムイオンを吸蔵・脱離し得るカーボン系材料あるいはリ
チウム金属もしくはリチウム合金を用い、正極活物質と
して、ＬｉＣｏＯ2，ＬｉＮｉＯ2，ＬｉＭｎ2Ｏ4，Ｌｉ
ＦｅＯ2等のリチウム含有遷移金属酸化物を用い、有機
溶媒に溶質としてリチウム塩を溶解した電解質を用いて
構成される電池である。2. Description of the Related Art In recent years, lithium secondary batteries have come into practical use as small, lightweight, high-capacity, chargeable / dischargeable batteries, and portable electronic and communication equipment such as small video cameras, mobile phones, and notebook computers. And so on.
This type of lithium secondary battery uses a carbon-based material or lithium metal or lithium alloy capable of inserting and extracting lithium ions as a negative electrode active material, and uses LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , and Li as positive electrode active materials.
The battery comprises a lithium-containing transition metal oxide such as FeO 2 and an electrolyte in which a lithium salt is dissolved as a solute in an organic solvent.
【０００３】このようなリチウム二次電池に用いられる
電解質の溶媒として、エチレンカーボネート（ＥＣ）、
プロピレンカーボネート（ＰＣ）、ビニレンカーボネー
ト（ＶＣ）、ブチレンカーボネート（ＢＣ）、ジエチル
カーボネート（ＤＥＣ）、ジメチルカーボネート（ＤＭ
Ｃ）、メチルエチルカーボネート（ＭＥＣ）、１，２−
ジエトキシエタン（ＤＥＥ）、１，２−ジメトキシエタ
ン（ＤＭＥ）、エトキシメトキシエタン（ＥＭＥ）等の
単体、あるいは二成分以上の混合溶媒が使用されてい
る。また、この溶媒に溶解される溶質としては、ＬｉＰ
Ｆ6、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、ＬｉＡｓＦ6、Ｌｉ
Ｎ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2） 3、ＬｉＣＦ
3（ＣＦ2）3ＳＯ3等が使用されている。[0003] Used in such lithium secondary batteries
Ethylene carbonate (EC) as a solvent for the electrolyte,
Propylene carbonate (PC), vinylene carbonate
(VC), butylene carbonate (BC), diethyl
Carbonate (DEC), dimethyl carbonate (DM
C), methyl ethyl carbonate (MEC), 1,2-
Diethoxyethane (DEE), 1,2-dimethoxyethane
(DME), ethoxymethoxyethane (EME), etc.
Single or mixed solvent of two or more components
You. The solute dissolved in this solvent is LiP
F6, LiBFFour, LiCFThreeSOThree, LiAsF6, Li
N (CFThreeSOTwo)Two, LiC (CFThreeSOTwo) Three, LiCF
Three(CFTwo)ThreeSOThreeEtc. are used.
【０００４】[0004]
【発明が解決しようとする課題】ところで、この種のリ
チウム二次電池にあっては、高電圧に起因して負極と電
解質とが反応して、電解質、特に溶媒が分解されて劣化
し、サイクル特性、充電保存特性が悪いという問題が生
じた。このため、例えば、特開平７−８５８８８号公報
において、エチレンカーボネートおよびプロピレンカー
ボネートから選ばれる少なくとも１種以上の溶媒を１０
〜８０体積％と、ジエトキシエタン、鎖状カーボネート
およびアセトニトリルから選ばれる少なくとも１種以上
の溶媒を２０〜９０体積％とを混合した混合溶媒に溶質
としてＬｉ（ＣnＸ2n+1Ｙ）2Ｎ（Ｘはハロゲン、ｎは１
〜４の整数、ＹはＣＯ基またはＳＯ2基を示す）で表さ
れるイミド系リチウム塩を０．１〜３モル／リットル溶
解した組成を有する電解質を用いることが提案された。
これによりサイクル特性は改善された。However, in this type of lithium secondary battery, the negative electrode and the electrolyte react with each other due to the high voltage, and the electrolyte, particularly the solvent, is decomposed and degraded. There was a problem that the characteristics and charge storage characteristics were poor. For this reason, for example, in JP-A-7-85888, at least one solvent selected from ethylene carbonate and propylene carbonate is used in 10
And 80 vol%, diethoxyethane, linear carbonate and a solute of at least one or more kinds of the solvent a mixed solvent obtained by mixing 20 to 90 vol% selected from acetonitrile Li (C n X 2n + 1 Y) 2 N (X is halogen, n is 1
It has been proposed to use an electrolyte having a composition obtained by dissolving 0.1 to 3 mol / l of an imide-based lithium salt represented by the following formula: Y represents a CO group or an SO 2 group.
This improved the cycle characteristics.
【０００５】しかしながら、イミド系リチウム塩を電解
質の溶質として添加しても、この電解質は直接正極およ
び負極に接しているため、正極活物質あるいは負極活物
質により電解質の溶媒が分解されて、充電保存特性が悪
いという問題が生じた。そこで、本発明は上記課題を解
消するためになされたものであって、充電状態で保存し
ても電解質が正極活物質あるいは負極活物質により分解
されないようにして、充電保存特性に優れたリチウム二
次電池を提供することにある。However, even if an imide-based lithium salt is added as a solute for the electrolyte, the electrolyte is in direct contact with the positive electrode and the negative electrode, so that the solvent of the electrolyte is decomposed by the positive electrode active material or the negative electrode active material, and the battery is charged. There was a problem that the characteristics were poor. Accordingly, the present invention has been made to solve the above-mentioned problems, and has been made in order to prevent the electrolyte from being decomposed by the positive electrode active material or the negative electrode active material even when stored in a charged state, and to provide a lithium secondary battery having excellent charge storage characteristics. Another object is to provide a battery.
【０００６】[0006]
【課題を解決するための手段およびその作用・効果】上
記課題を解決するために、本発明のリチウム二次電池に
おいては、ＬｉＮ（ＣmＦ2m+1ＳＯ2）（ＣnＦ2n+1Ｓ
Ｏ2）（ただし、ｍおよびｎは各々独立した１〜４の整
数）で表されるイミド系リチウム塩あるいはＬｉＣ（Ｃ
pＦ2p+1ＳＯ2）（ＣqＦ2q+1ＳＯ2）（ＣrＦ2r+1ＳＯ2）
（ただし、ｐ、ｑおよびｒは各々独立した１〜４の整
数）で表されるメチド系リチウム塩の少なくとも一方が
電解質の溶質として用いられ、この電解質にフッ化物あ
るいはリン化合物からなる添加剤の少なくとも一方が添
加されている。To solve SUMMARY, operation, and effects thereof for solving the above problems, in the lithium secondary battery of the present invention, LiN (C m F 2m + 1 SO 2) (C n F 2n + 1 S
O 2 ) (where m and n are each independently an integer of 1 to 4) or an imide-based lithium salt represented by LiC (C
p F 2p + 1 SO 2) (C q F 2q + 1 SO 2) (C r F 2r + 1 SO 2)
(Where p, q and r are each independently an integer of 1 to 4), at least one of the methide-based lithium salts is used as a solute of the electrolyte, and the electrolyte contains an additive comprising a fluoride or a phosphorus compound. At least one is added.
【０００７】このようなイミド系リチウム塩あるいはメ
チド系リチウム塩の少なくとも一方が溶質として用いら
れた電解質に、フッ化物あるいはリン化合物からなる添
加剤の少なくとも一方が添加されていると、添加剤が正
極あるいは負極の表面に保護膜を形成するため、この保
護膜により電解質が直接、正極あるいは負極と接触する
ことが防止できるようになる。この結果、リチウム二次
電池を充電状態で保存しても電解質が分解されるのを防
止でき、充電保存特性が向上する。[0007] When at least one of an additive comprising a fluoride or a phosphorus compound is added to an electrolyte in which at least one of the imide-based lithium salt or the methide-based lithium salt is used as a solute, the additive becomes a positive electrode. Alternatively, since a protective film is formed on the surface of the negative electrode, the protective film can prevent the electrolyte from directly contacting the positive electrode or the negative electrode. As a result, even if the lithium secondary battery is stored in a charged state, the decomposition of the electrolyte can be prevented, and the charge storage characteristics are improved.
【０００８】また、添加剤として用いられるフッ化物と
しては、ＡｇＦ、ＣｏＦ2、ＣｏＦ3、ＣｕＦ、Ｃｕ
Ｆ2、ＦｅＦ2、ＦｅＦ3、ＬｉＦ、ＭｎＦ2、ＭｎＦ3、
ＳｎＦ2、ＳｎＦ4、ＴｉＦ3、ＴｉＦ4およびＺｒＦ4か
ら選択された少なくとも１種を用いるのが好ましく、リ
ン化合物としては、ＬｉＰＯ3およびＬｉ3ＰＯ4から選
択された少なくとも１種を用いるのが好ましい。そし
て、より好ましくは、ＡｇＦ、ＣｏＦ2、ＣｏＦ3、Ｃｕ
Ｆ、ＣｕＦ2、ＦｅＦ2、ＦｅＦ3、ＬｉＦ、ＭｎＦ2、Ｍ
ｎＦ3、ＳｎＦ2、ＳｎＦ4、ＴｉＦ3、ＴｉＦ4およびＺ
ｒＦ4から選択された少なくとも１種と、ＬｉＰＯ3およ
びＬｉ3ＰＯ4から選択された少なくとも１種との混合添
加物とするのがよい。The fluoride used as an additive includes AgF, CoF 2 , CoF 3 , CuF and CuF.
F 2 , FeF 2 , FeF 3 , LiF, MnF 2 , MnF 3 ,
SnF 2, SnF 4, TiF 3 , TiF 4 and it is preferable to use at least one selected from ZrF 4, as the phosphorus compound, to use at least one selected from LiPO 3 and Li 3 PO 4 preferable. And, more preferably, AgF, CoF 2 , CoF 3 , Cu
F, CuF 2 , FeF 2 , FeF 3 , LiF, MnF 2 , M
nF 3 , SnF 2 , SnF 4 , TiF 3 , TiF 4 and Z
It is preferable to use a mixed additive of at least one selected from rF 4 and at least one selected from LiPO 3 and Li 3 PO 4 .
【０００９】そして、添加剤の添加量が多くなると正極
あるいは負極の表面に形成される保護膜が厚くなって充
電保存特性が低下し、添加剤の添加量が少なくなると正
極あるいは負極の表面に充分な保護膜が形成されなくな
るため、これらの添加剤の添加量は電解質に対して０．
００１〜１０質量％とすることが望ましく、好ましくは
０．０１〜５質量％とするのがよい。さらに、ポリマー
でゲル化された電解質に上記の如き添加剤を添加する
と、充電保存特性向上効果が発揮されるため、このよう
な添加剤はポリマーでゲル化された電解質に用いるのが
好ましい。When the amount of the additive increases, the thickness of the protective film formed on the surface of the positive electrode or the negative electrode increases, and the charge storage characteristics deteriorate. On the other hand, when the amount of the additive decreases, the surface of the positive electrode or the negative electrode decreases. Since an appropriate protective film is not formed, the amount of these additives to be added is 0.1 to the electrolyte.
The content is desirably 001 to 10% by mass, preferably 0.01 to 5% by mass. Further, when the above-mentioned additives are added to the polymer gelled electrolyte, the effect of improving the charge storage characteristics is exhibited. Therefore, such additives are preferably used for the polymer gelled electrolyte.
【００１０】[0010]
【発明の実施の形態】以下に、本発明のリチウム二次電
池の実施の形態を説明する。 １．電解質（電解液）の調製 （１）実施例１ まず、エチレンカーボネート（ＥＣ：以下、単にＥＣと
いう）とジエチルカーボネート（ＤＥＣ：以下、単にＤ
ＥＣという）とを体積比で４０：６０となるように混合
した混合溶媒に、イミド系リチウム塩としてＬｉＮ（Ｃ
Ｆ3ＳＯ2 ）2を１．０モル／リットル溶解して電解液
（電解質）を調製した。この電解液に添加剤としてフッ
化リチウム（ＬｉＦ）を電解液に対して１質量％だけ添
加し、混合して実施例１の電解液ａを調製した。なお、
溶質として用いられたイミド系リチウム塩であるＬｉＮ
（ＣＦ3ＳＯ2）2は、ＬｉＮ（ＣmＦ2m+1ＳＯ2）（ＣnＦ
2n+1ＳＯ2）と表された場合のｍ＝１，ｎ＝１に相当
し、以下では（ｍ，ｎ）＝（１，１）と表す。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the lithium secondary battery according to the present invention will be described below. 1. Preparation of Electrolyte (Electrolyte) (1) Example 1 First, ethylene carbonate (EC: hereinafter simply referred to as EC) and diethyl carbonate (DEC: hereinafter simply D)
EC) is mixed with LiN (C) as an imide-based lithium salt in a mixed solvent in which the volume ratio is 40:60.
F 3 SO 2 ) 2 was dissolved at 1.0 mol / liter to prepare an electrolytic solution (electrolyte). Lithium fluoride (LiF) was added as an additive to the electrolytic solution in an amount of 1% by mass based on the electrolytic solution, and mixed to prepare an electrolytic solution a of Example 1. In addition,
LiN, an imide-based lithium salt used as a solute
(CF 3 SO 2 ) 2 is LiN (C m F 2m + 1 SO 2 ) (C n F
2n + 1 SO 2 ), where m = 1 and n = 1, and hereinafter represented as (m, n) = (1, 1).
【００１１】（２）実施例２ ＥＣとＤＥＣとを体積比で４０：６０となるように混合
した混合溶媒に、イミド系リチウム塩としてＬｉＮ（Ｃ
2Ｆ5ＳＯ2）2を１．０モル／リットル溶解して電解液を
調製した。この電解液に添加剤としてフッ化リチウム
（ＬｉＦ）を電解液に対して１質量％だけ添加し、混合
して実施例２の電解液ｂを調製した。なお、溶質として
用いられたイミド系リチウム塩であるＬｉＮ（Ｃ2Ｆ5Ｓ
Ｏ2）2は、ＬｉＮ（ＣmＦ2m+1ＳＯ2）（ＣnＦ2n+1Ｓ
Ｏ2）と表された場合の（ｍ，ｎ）＝（２，２）に相当
する。(2) Example 2 In a mixed solvent of EC and DEC mixed at a volume ratio of 40:60, LiN (C
2 F 5 SO 2 ) 2 was dissolved in 1.0 mol / liter to prepare an electrolytic solution. Lithium fluoride (LiF) was added as an additive to the electrolyte at only 1% by mass with respect to the electrolyte, and mixed to prepare an electrolyte b of Example 2. Note that LiN (C 2 F 5 S), which is an imide-based lithium salt used as a solute, was used.
O 2 ) 2 is LiN (C m F 2m + 1 SO 2 ) (C n F 2n + 1 S
(M 2) = (2, 2) when expressed as O 2 ).
【００１２】（３）実施例３ ＥＣとＤＥＣとを体積比で４０：６０となるように混合
した混合溶媒に、イミド系リチウム塩としてＬｉＮ（Ｃ
Ｆ3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）を１．０モル／リットル溶
解して電解液を調製した。この電解液に添加剤としてフ
ッ化リチウム（ＬｉＦ）を電解液に対して１質量％だけ
添加し、混合して実施例３の電解液ｃを調製した。な
お、溶質として用いられたイミド系リチウム塩であるＬ
ｉＮ（ＣＦ 3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）は、ＬｉＮ（ＣmＦ
2m+1ＳＯ2）（ＣnＦ2n+1ＳＯ2）と表された場合の
（ｍ，ｎ）＝（１，４）に相当する。(3) Example 3 EC and DEC are mixed in a volume ratio of 40:60.
In the mixed solvent thus obtained, LiN (C
FThreeSOTwo) (CFourF9SOTwo) Is dissolved at 1.0 mol / liter.
Then, an electrolytic solution was prepared. Fluorine as an additive to this electrolyte
Lithium nitride (LiF) in only 1% by weight of electrolyte
The mixture was added and mixed to prepare an electrolyte solution c of Example 3. What
L, which is an imide-based lithium salt used as a solute,
iN (CF ThreeSOTwo) (CFourF9SOTwo) Is LiN (CmF
2m + 1SOTwo) (CnF2n + 1SOTwo)
(M, n) = (1, 4).
【００１３】（４）実施例４ ＥＣとＤＥＣとを体積比で４０：６０となるように混合
した混合溶媒に、イミド系リチウム塩としてＬｉＮ（Ｃ
Ｆ3ＳＯ2）2を１．０モル／リットル溶解して電解液を
調製した。この電解液に添加剤としてリン酸三リチウム
（Ｌｉ3ＰＯ4）を電解液に対して１質量％だけ添加し、
混合して実施例４の電解液ｄを調製した。(4) Example 4 In a mixed solvent of EC and DEC mixed at a volume ratio of 40:60, LiN (C
F 3 SO 2 ) 2 was dissolved in 1.0 mol / liter to prepare an electrolytic solution. Trilithium phosphate (Li 3 PO 4 ) was added as an additive to the electrolyte by 1% by mass with respect to the electrolyte,
The electrolyte solution d of Example 4 was prepared by mixing.
【００１４】（５）実施例５ ＥＣとＤＥＣとを体積比で４０：６０となるように混合
した混合溶媒に、イミド系リチウム塩としてＬｉＮ（Ｃ
2Ｆ5ＳＯ2）2を１．０モル／リットル溶解して電解液を
調製した。この電解液に添加剤としてリン酸三リチウム
（Ｌｉ3ＰＯ4）を電解液に対して１質量％だけ添加し、
混合して実施例５の電解液ｅを調製した。(5) Example 5 In a mixed solvent of EC and DEC mixed at a volume ratio of 40:60, LiN (C
2 F 5 SO 2 ) 2 was dissolved in 1.0 mol / liter to prepare an electrolytic solution. Trilithium phosphate (Li 3 PO 4 ) was added as an additive to the electrolyte by 1% by mass with respect to the electrolyte,
The electrolyte solution e of Example 5 was prepared by mixing.
【００１５】（６）実施例６ ＥＣとＤＥＣとを体積比で４０：６０となるように混合
した混合溶媒に、イミド系リチウム塩としてＬｉＮ（Ｃ
Ｆ3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）を１．０モル／リットル溶
解して電解液を調製した。この電解液に添加剤としてリ
ン酸三リチウム（Ｌｉ3ＰＯ4）を電解液に対して１質量
％だけ添加し、混合して実施例６の電解液ｆを調製し
た。(6) Example 6 In a mixed solvent of EC and DEC mixed at a volume ratio of 40:60, LiN (C
F 3 SO 2 ) (C 4 F 9 SO 2 ) was dissolved at 1.0 mol / liter to prepare an electrolyte solution. Trilithium phosphate (Li 3 PO 4 ) was added as an additive to the electrolyte at 1% by mass with respect to the electrolyte, and mixed to prepare an electrolyte f of Example 6.
【００１６】（７）実施例７ ＥＣとＤＥＣとを体積比で４０：６０となるように混合
した混合溶媒に、メチド系リチウム塩としてＬｉＣ（Ｃ
Ｆ3ＳＯ2）3を１．０モル／リットル溶解して電解液を
調製した。この電解液に添加剤としてフッ化リチウム
（ＬｉＦ）を電解液に対して１質量％だけ添加し、混合
して実施例７の電解液ｇを調製した。なお、溶質として
用いられたメチド系リチウム塩であるＬｉＣ（ＣＦ3Ｓ
Ｏ2）3は、ＬｉＣ（ＣpＦ2p+1ＳＯ2）（ＣqＦ2q+1Ｓ
Ｏ2）（ＣrＦ2r+1ＳＯ2）と表わした場合のｐ＝１，ｑ
＝１，ｒ＝１、即ち、（ｐ，ｑ，ｒ）＝（１，１，１）
に相当する。(7) Example 7 A mixture of EC and DEC in a volume ratio of 40:60 was mixed with LiC (C
F 3 SO 2 ) 3 was dissolved in 1.0 mol / l to prepare an electrolyte solution. Lithium fluoride (LiF) was added as an additive to the electrolyte at only 1% by mass with respect to the electrolyte, and mixed to prepare an electrolyte g of Example 7. Note that LiC (CF 3 S), which is a methide-based lithium salt used as a solute, was used.
O 2 ) 3 is LiC (C p F 2p + 1 SO 2 ) (C q F 2q + 1 S
O 2) (C r F 2r +1 when SO 2) and represents p = 1, q
= 1, r = 1, that is, (p, q, r) = (1, 1, 1)
Is equivalent to
【００１７】（８）実施例８ ＥＣとＤＥＣとを体積比で４０：６０となるように混合
した混合溶媒に、メチド系リチウム塩としてＬｉＣ（Ｃ
Ｆ3ＳＯ2）3を１．０モル／リットル溶解して電解液を
調製した。この電解液に添加剤としてリン酸三リチウム
（Ｌｉ3ＰＯ4）を電解液に対して１質量％だけ添加し、
混合して実施例８の電解液ｈを調製した。(8) Example 8 A mixed solvent of EC and DEC in a volume ratio of 40:60 was mixed with LiC (C
F 3 SO 2 ) 3 was dissolved in 1.0 mol / l to prepare an electrolyte solution. Trilithium phosphate (Li 3 PO 4 ) was added as an additive to the electrolyte by 1% by mass with respect to the electrolyte,
The electrolyte h of Example 8 was prepared by mixing.
【００１８】（９）比較例１ ＥＣとＤＥＣとを体積比で４０：６０となるように混合
した混合溶媒に、イミド系リチウム塩としてＬｉＮ（Ｃ
Ｆ3ＳＯ2）2を１．０モル／リットル溶解し、添加剤を
添加することなく混合して比較例１の電解液ｘを調製し
た。(9) Comparative Example 1 In a mixed solvent of EC and DEC mixed at a volume ratio of 40:60, LiN (C
F 3 SO 2 ) 2 was dissolved in 1.0 mol / liter and mixed without adding any additives to prepare an electrolyte x of Comparative Example 1.
【００１９】（１０）比較例２ ＥＣとＤＥＣとを体積比で４０：６０となるように混合
した混合溶媒に、イミド系リチウム塩としてＬｉＮ（Ｃ
2Ｆ5ＳＯ2）2を１．０モル／リットル溶解し、添加剤を
添加することなく混合して比較例２の電解液ｙを調製し
た。(10) Comparative Example 2 In a mixed solvent of EC and DEC mixed at a volume ratio of 40:60, LiN (C
2 F 5 SO 2 ) 2 was dissolved in 1.0 mol / liter and mixed without adding any additives to prepare an electrolyte y of Comparative Example 2.
【００２０】（１１）比較例３ ＥＣとＤＥＣとを体積比で４０：６０となるように混合
した混合溶媒に、イミド系リチウム塩としてＬｉＮ（Ｃ
Ｆ3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）を１．０モル／リットル溶
解し、添加剤を添加することなく混合して比較例３の電
解液ｚを調製した。(11) Comparative Example 3 In a mixed solvent in which EC and DEC were mixed at a volume ratio of 40:60, LiN (C
F 3 SO 2 ) (C 4 F 9 SO 2 ) was dissolved in 1.0 mol / liter and mixed without adding any additives to prepare an electrolyte solution z of Comparative Example 3.
【００２１】（１２）比較例４ ＥＣとＤＥＣとを体積比で４０：６０となるように混合
した混合溶媒に、メチド系リチウム塩としてＬｉＣ（Ｃ
Ｆ3ＳＯ2）3を１．０モル／リットル溶解し、添加剤を
添加することなく混合して比較例４の電解液ｗを調製し
た。(12) Comparative Example 4 A mixed solvent of EC and DEC in a volume ratio of 40:60 was mixed with LiC (C
F 3 SO 2 ) 3 was dissolved in 1.0 mol / l and mixed without adding any additives to prepare an electrolyte w of Comparative Example 4.
【００２２】なお、上述した各実施例および比較例にお
いては、ＥＣとＤＥＣとを体積比で４０：６０となるよ
うに混合した混合溶媒を用いる例について説明したが、
電解質の溶媒としては、ＥＣおよびＤＥＣ以外にも、プ
ロピレンカーボネート（ＰＣ）、ブチレンカーボネート
（ＢＣ）、ジメチルカーボネート（ＤＭＣ）、スルホラ
ン（ＳＬ）、ビニレンカーボネート（ＶＣ）、メチルエ
チルカーボネート（ＭＥＣ）、テトラヒドロフラン（Ｔ
ＨＦ）、１，２−ジエトキシエタン（ＤＥＥ）、１，２
−ジメトキシエタン（ＤＭＥ）、エトキシメトキシエタ
ン（ＥＭＥ）等の単体、あるいはこれらの二成分以上の
混合溶媒を選択して用いても良い。In each of the above Examples and Comparative Examples, an example was described in which a mixed solvent in which EC and DEC were mixed at a volume ratio of 40:60 was used.
As a solvent for the electrolyte, in addition to EC and DEC, propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), sulfolane (SL), vinylene carbonate (VC), methyl ethyl carbonate (MEC), tetrahydrofuran (T
HF), 1,2-diethoxyethane (DEE), 1,2
A simple substance such as dimethoxyethane (DME) and ethoxymethoxyethane (EME), or a mixed solvent of two or more of these may be used.
【００２３】２．正極の作製 正極活物質としてのリチウム含有コバルト酸化物（Ｌｉ
ＣｏＯ2）粉末９０質量部と、人造黒鉛、アセチレンブ
ラック、グラファイト等の炭素系導電剤５質量部と、結
着剤としてのポリフッ化ビニリデン５質量部とを混合し
て、Ｎ−メチル−２−ピロリドン（ＮＭＰ）溶液にして
スラリーを調製した。このスラリーをドクターブレード
等を用いて、正極集電体（例えば、アルミニウム箔）の
片面に均一に塗布して、活物質層を塗布した正極板を形
成した。この後、１３０℃で２時間熱処理して、スラリ
ー作製に必要であった有機溶剤を除去した後、ロールプ
レス機により圧延して、正極板１（図１参照）を作製し
た。なお、正極活物質として、ＬｉＣｏＯ2に代えて、
ＬｉＮｉＯ2、ＬｉＭｎＯ2、ＬｉＭｎ2Ｏ4、リチウム含
有ＭｎＯ2、ＬｉＣｏ0.5Ｎｉ0.5Ｏ2、ＬｉＮｉ0.7Ｃｏ
0.2Ｍｎ0.1Ｏ2などのリチウム含有遷移金属酸化物を用
いてもよい。2. Preparation of positive electrode Lithium-containing cobalt oxide (Li
90 parts by mass of CoO 2 ) powder, 5 parts by mass of a carbon-based conductive agent such as artificial graphite, acetylene black, and graphite, and 5 parts by mass of polyvinylidene fluoride as a binder were mixed, and N-methyl-2- A slurry was prepared using a pyrrolidone (NMP) solution. This slurry was uniformly applied to one surface of a positive electrode current collector (for example, aluminum foil) using a doctor blade or the like to form a positive electrode plate coated with an active material layer. Thereafter, heat treatment was performed at 130 ° C. for 2 hours to remove the organic solvent necessary for preparing the slurry, and then rolling was performed with a roll press to prepare a positive electrode plate 1 (see FIG. 1). Note that, instead of LiCoO 2 as the positive electrode active material,
LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , lithium-containing MnO 2 , LiCo 0.5 Ni 0.5 O 2 , LiNi 0.7 Co
A lithium-containing transition metal oxide such as 0.2 Mn 0.1 O 2 may be used.
【００２４】３．負極の作製 負極活物質としての天然黒鉛（ｄ＝３．３５Å）粉末が
９５質量部で、結着剤としてのポリフッ化ビニリデンが
５質量部となるよう混合した後、Ｎ−メチル−２−ピロ
リドン（ＮＭＰ）溶液にしてスラリーを調製した。この
スラリーをドクターブレード等を用いて負極集電体（例
えば、銅箔）の片面に均一に塗布して、活物質層を塗布
した負極板を形成した。この後、１３０℃で２時間熱処
理して炭素材料からなる負極２（図１参照）を作製し
た。なお、炭素材料としては、天然黒鉛に代えて、人造
黒鉛、コークス、有機物焼成体などを用いてもよい。3. Preparation of Negative Electrode After mixing 95 parts by mass of natural graphite (d = 3.35 °) powder as a negative electrode active material and 5 parts by mass of polyvinylidene fluoride as a binder, N-methyl-2-pyrrolidone was used. (NMP) solution was used to prepare a slurry. This slurry was uniformly applied to one surface of a negative electrode current collector (for example, copper foil) using a doctor blade or the like to form a negative electrode plate coated with an active material layer. Thereafter, heat treatment was performed at 130 ° C. for 2 hours to produce a negative electrode 2 made of a carbon material (see FIG. 1). Note that, as the carbon material, artificial graphite, coke, a fired organic material, or the like may be used instead of natural graphite.
【００２５】４．リチウム二次電池の作製 ついで、リチウム二次電池の作製例を図１に基づいて説
明する。上述のようにして作製した負極２を、周端縁に
絶縁パッキング６を配設した断面形状がコの字状の負極
缶（例えば、フェライト系ステンレス鋼よりなる）４の
内底面に負極集電体が密着するように固定した。一方、
上述のようにして作製した正極１を、断面形状が逆コの
字状の正極缶（例えば、ステンレス鋼よりなる）５の内
底面に正極集電体が密着するように固定した。これらの
負極２と正極１との間に、上述のようにして調製した実
施例１〜８の電解液ａ〜ｈおよび比較例１〜４の電解液
ｘ，ｙ，ｚ，ｗを含浸したポリオレフィン系樹脂からな
る微多孔膜、好適にはポリプロピレン製微多孔膜（セパ
レータ）３を介在させて重ね合わせた。4. Production of Lithium Secondary Battery Next, an example of producing a lithium secondary battery will be described with reference to FIG. The negative electrode 2 produced as described above is placed on the inner bottom surface of a negative can (for example, made of ferritic stainless steel) 4 having a U-shaped cross section in which an insulating packing 6 is provided on the peripheral edge. The body was fixed so that it adhered. on the other hand,
The positive electrode 1 manufactured as described above was fixed to the inner bottom surface of a positive electrode can (made of, for example, stainless steel) 5 having an inverted U-shaped cross section so that the positive electrode current collector was in close contact therewith. Polyolefin impregnated between the negative electrode 2 and the positive electrode 1 with the electrolytes a to h of Examples 1 to 8 and the electrolytes x, y, z, and w of Comparative Examples 1 to 4 prepared as described above. They were laminated with a microporous membrane made of a base resin, preferably a polypropylene microporous membrane (separator) 3 interposed.
【００２６】この後、正極缶５の周端縁を絶縁パッキン
グ６の方にカシメて液密に封口し、定格容量が８ｍＡｈ
のリチウム二次電池Ａ〜ＨおよびＸ，Ｙ，Ｚ，Ｗを作製
した。なお、電池Ａは実施例１の電解液ａを注入したも
のであり、電池Ｂは実施例２の電解液ｂを注入したもの
であり、電池Ｃは実施例３の電解液ｃを注入したもので
あり、電池Ｄは実施例４の電解液ｄを注入したものであ
り、電池Ｅは実施例５の電解液ｅを注入したものであ
り、電池Ｆは実施例６の電解液ｆを注入したものであ
り、電池Ｇは実施例７の電解液ｇを注入したものであ
り、電池Ｈは実施例８の電解液ｈを注入したものであ
る。また、電池Ｘは比較例１の電解液ｘを注入したもの
であり、電池Ｙは比較例２の電解液ｙを注入したもので
あり、電池Ｚは比較例３の電解液ｚを注入したものであ
り、電池Ｗは比較例４の電解液ｗを注入したものであ
る。Thereafter, the peripheral edge of the positive electrode can 5 is caulked toward the insulating packing 6 and sealed in a liquid-tight manner so that the rated capacity is 8 mAh.
, And X, Y, Z and W were manufactured. The battery A was obtained by injecting the electrolytic solution a of Example 1, the battery B was obtained by injecting the electrolytic solution b of Example 2, and the battery C was obtained by injecting the electrolytic solution c of Example 3. The battery D was obtained by injecting the electrolyte d of Example 4, the battery E was obtained by injecting the electrolyte e of Example 5, and the battery F was obtained by injecting the electrolyte f of Example 6. The battery G was prepared by injecting the electrolyte g of Example 7, and the battery H was obtained by injecting the electrolyte h of Example 8. The battery X was injected with the electrolyte x of Comparative Example 1, the battery Y was injected with the electrolyte y of Comparative Example 2, and the battery Z was injected with the electrolyte z of Comparative Example 3. In the battery W, the electrolyte w of Comparative Example 4 was injected.
【００２７】５．充放電サイクル試験 上述のように作製した各電池Ａ〜ＨおよびＸ，Ｙ，Ｚ，
Ｗを室温（２５℃）にて、１ｍＡの充電々流で４．１Ｖ
になるまで定電流充電した後、１ｍＡの放電々流で２．
５Ｖになるまで定電流放電して、初期放電容量を求め
た。ついで、これらの各電池Ａ〜ＨおよびＸ，Ｙ，Ｚ，
Ｗを１ｍＡの充電々流で４．１Ｖになるまで定電流充電
した後、６０℃の温度で１０日間保存した後、１ｍＡの
放電々流で２．５Ｖになるまで定電流放電して、高温保
存後の放電容量を求めた。ついで、初期放電容量に対す
る高温保存後の放電容量の割合を容量残存率して算出す
ると下記の表１に示すような結果となった。5. Charge / discharge cycle test Each of the batteries A to H and X, Y, Z,
W at room temperature (25 ° C.), 4.1 V with 1 mA charging current
After charging at a constant current until the current becomes 1.
Constant current discharge was performed until the voltage reached 5 V, and the initial discharge capacity was determined. Next, these batteries A to H and X, Y, Z,
W was charged at a constant current of 1 V with a charge current of 4.1 mA until it reached 4.1 V, stored at a temperature of 60 ° C. for 10 days, and then discharged at a constant current of 1 mA with a discharge current of 2.5 mA until it reached 2.5 V. The discharge capacity after storage was determined. Next, when the ratio of the discharge capacity after high-temperature storage to the initial discharge capacity was calculated as the remaining capacity ratio, the results shown in Table 1 below were obtained.
【００２８】[0028]
【表１】 [Table 1]
【００２９】上記表１より明らかなように、イミド系リ
チウム塩あるいはメチド系リチウム塩を溶質とした電解
液にＬｉＦなどのフッ化物あるいはＬｉ3ＰＯ4などのリ
ン化合物が無添加の電池Ｘ，Ｙ，Ｘ，Ｗの容量残存率は
３４％〜４２％と低いのに対し、イミド系リチウム塩あ
るいはメチド系リチウム塩を溶質とした電解液にＬｉＦ
などのフッ化物あるいはＬｉ3ＰＯ4などのリン化合物を
添加した電池Ａ〜Ｈの容量残存率は６９％〜７６％と高
くなっており、充電保存特性が優れていることが分か
る。これは、ＬｉＦなどのフッ化物あるいはＬｉ3ＰＯ4
などのリン化合物を添加剤として電解液中に添加する
と、正極１あるいは負極２の表面に保護膜が形成され、
この保護膜により電解液が直接正極１あるいは負極２と
接触することがなくなり、結果として、リチウム二次電
池を充電状態で保存しても電解液が分解されるのが防止
されて、充電保存特性が向上したと考えられる。As is clear from Table 1, batteries X and Y in which a fluoride such as LiF or a phosphorus compound such as Li 3 PO 4 is not added to an electrolyte containing an imide-based lithium salt or a methide-based lithium salt as a solute. , X and W have a low residual capacity of 34% to 42%, while an electrolyte containing imide-based lithium salt or methide-based lithium salt as a solute has LiF
The remaining capacity of the batteries A to H to which a fluoride such as Li or a phosphorus compound such as Li 3 PO 4 is added is as high as 69% to 76%, which indicates that the charge storage characteristics are excellent. This is a fluoride such as LiF or Li 3 PO 4
When a phosphorus compound such as is added to the electrolyte as an additive, a protective film is formed on the surface of the positive electrode 1 or the negative electrode 2,
This protective film prevents the electrolyte solution from directly contacting the positive electrode 1 or the negative electrode 2, and as a result, prevents the electrolyte solution from being decomposed even when the lithium secondary battery is stored in a charged state, and has a charge storage characteristic. It is considered that has improved.
【００３０】６．添加剤の検討（実施例９〜２３） ついで、添加剤について検討した。ここでは、イミド系
リチウム塩としてＬｉＮ（Ｃ2Ｆ5ＳＯ2）2を用いた電解
液を使用し、この電解液に下記の表２に示す種々の添加
剤（フッ化物としては、ＡｇＦ、ＣｏＦ2、ＣｏＦ3、Ｃ
ｕＦ、ＣｕＦ2、ＦｅＦ2、ＦｅＦ3、ＬｉＦ（上記電池
Ｂ）、ＭｎＦ2、ＭｎＦ3、ＳｎＦ2、ＳｎＦ4、Ｔｉ
Ｆ3、ＴｉＦ4、ＺｒＦ4を用い、リン化合物しては、Ｌ
ｉ3ＰＯ4（上記電池Ｅ）、ＬｉＰＯ3を用いた）を添加
した場合の容量残存率を上述と同様に求めると、下記の
表２に示すような結果となった。なお、これらの添加剤
の添加量は電解液に対して１質量％である。6. Examination of Additives (Examples 9 to 23) Next, additives were examined. Here, an electrolytic solution using LiN (C 2 F 5 SO 2 ) 2 as an imide-based lithium salt was used, and various additives (AgF and CoF as fluorides) shown in Table 2 below were added to the electrolytic solution. 2, CoF 3, C
uF, CuF 2 , FeF 2 , FeF 3 , LiF (Battery B), MnF 2 , MnF 3 , SnF 2 , SnF 4 , Ti
Using F 3 , TiF 4 , and ZrF 4 , the phosphorus compound is L
When the remaining capacity ratio when i 3 PO 4 (using the above-mentioned battery E and LiPO 3 ) was added was determined in the same manner as described above, the results shown in Table 2 below were obtained. In addition, the addition amount of these additives is 1 mass% with respect to an electrolyte solution.
【００３１】なお、ＡｇＦを添加した電解液を実施例９
の電解液としこの電解液を用いた電池をＢ１とし、Ｃｏ
Ｆ2を添加した電解液を実施例１０の電解液としこの電
解液を用いた電池をＢ２とし、ＣｏＦ3を添加した電解
液を実施例１１の電解液としこの電解液を用いた電池を
Ｂ３とし、ＣｕＦを添加した電解液を実施例１２の電解
液としこの電解液を用いた電池をＢ４とし、ＣｕＦ2を
添加した電解液を実施例１３の電解液としこの電解液を
用いた電池をＢ５とし、ＦｅＦ2を添加した電解液を実
施例１４の電解液としこの電解液を用いた電池をＢ６と
し、ＦｅＦ3を添加した電解液を実施例１５の電解液と
しこの電解液を用いた電池をＢ７とした。The electrolyte solution containing AgF was used in Example 9
B1 is a battery using this electrolyte as the electrolyte of
The electrolytic liquid containing F 2 as the electrolytic solution of Example 10 the cell using the electrolytic solution is B2, the electrolytic liquid containing CoF 3 an electrolyte solution of Example 11 the battery using the electrolytic solution B3 The electrolyte using CuF was used as the electrolyte of Example 12, the battery using this electrolyte was used as B4, the electrolyte using CuF 2 was used as the electrolyte of Example 13, and the battery using this electrolyte was used. B5, the electrolyte containing FeF 2 was used as the electrolyte of Example 14, and the battery using this electrolyte was called B6. The electrolyte containing FeF 3 was used as the electrolyte of Example 15, and this electrolyte was used. The battery was designated as B7.
【００３２】同様に、ＭｎＦ2を添加した電解液を実施
例１６の電解液としこの電解液を用いた電池をＢ８と
し、ＭｎＦ3を添加した電解液を実施例１７の電解液と
しこの電解液を用いた電池をＢ９とし、ＳｎＦ2を添加
した電解液を実施例１８の電解液としこの電解液を用い
た電池をＢ１０とし、ＳｎＦ4を添加した電解液を実施
例１９の電解液としこの電解液を用いた電池をＢ１１と
し、ＴｉＦ3を添加した電解液を実施例２０の電解液と
しこの電解液を用いた電池をＢ１２とし、ＴｉＦ 4を添
加した電解液を実施例２１の電解液としこの電解液を用
いた電池をＢ１３とし、ＺｒＦ4を添加した電解液を実
施例２２の電解液としこの電解液を用いた電池をＢ１４
とし、ＬｉＰＯ3を添加した電解液を実施例２３の電解
液としこの電解液を用いた電池をＥ１とした。Similarly, MnFTwoImplement electrolyte solution
A battery using this electrolyte as the electrolyte of Example 16 was designated as B8.
And MnFThreeWas added to the electrolyte solution of Example 17.
The battery using this electrolyte was designated as B9, and SnFTwoAdd
The obtained electrolyte was used as the electrolyte of Example 18 and this electrolyte was used.
The battery that was used was designated as B10, and SnFFourImplement electrolyte solution
A battery using this electrolyte as the electrolyte of Example 19 was designated as B11.
And TiFThreeIs added to the electrolyte solution of Example 20.
A battery using this electrolyte was designated as B12, and TiF FourWith
The added electrolyte was used as the electrolyte of Example 21 and this electrolyte was used.
The battery was B13, ZrFFourThe electrolyte solution containing
A battery using this electrolyte as the electrolyte of Example 22 was replaced with B14
And LiPOThreeWas added to the electrolytic solution of Example 23.
A battery using this electrolyte as a liquid was designated as E1.
【００３３】[0033]
【表２】 [Table 2]
【００３４】上記表２より明らかなように、イミド系リ
チウム塩を溶質とした電解液にフッ化物としてＡｇＦ、
ＣｏＦ2、ＣｏＦ3、ＣｕＦ、ＣｕＦ2、ＦｅＦ2、ＦｅＦ
3、ＬｉＦ、ＭｎＦ2、ＭｎＦ3、ＳｎＦ2、ＳｎＦ4、Ｔ
ｉＦ3、ＴｉＦ4、ＺｒＦ4を添加し、リン化合物してＬ
ｉ3ＰＯ4、ＬｉＰＯ3を添加した電解液を用いた電池
Ｂ，Ｂ１〜Ｂ１４およびＥ，Ｅ１は、いずれも容量残存
率が７０％〜７８％と高くなっており、充電保存特性が
優れていることが分かる。このことから、イミド系リチ
ウム塩を溶質とした電解液に添加されるフッ化物は、Ａ
ｇＦ、ＣｏＦ2、ＣｏＦ3、ＣｕＦ、ＣｕＦ2、ＦｅＦ2、
ＦｅＦ3、ＬｉＦ、ＭｎＦ2、ＭｎＦ3、ＳｎＦ2、ＳｎＦ
4、ＴｉＦ3、ＴｉＦ4、ＺｒＦ4から選択することが好ま
しく、リン化合物は、Ｌｉ3ＰＯ4、ＬｉＰＯ3から選択
することが好ましということができる。As is clear from the above Table 2, AgF as fluoride was added to the electrolyte containing imide type lithium salt as a solute.
CoF 2 , CoF 3 , CuF, CuF 2 , FeF 2 , FeF
3, LiF, MnF 2, MnF 3, SnF 2, SnF 4, T
iF 3 , TiF 4 , and ZrF 4 were added, and phosphorus compound was added to L
Batteries B, B1 to B14 and E, E1 using the electrolyte solution to which i 3 PO 4 and LiPO 3 were added all had a high remaining capacity ratio of 70% to 78%, and had excellent charge storage characteristics. You can see that there is. From this, the fluoride added to the electrolytic solution using the imide-based lithium salt as a solute is A
gF, CoF 2 , CoF 3 , CuF, CuF 2 , FeF 2 ,
FeF 3 , LiF, MnF 2 , MnF 3 , SnF 2 , SnF
4 , TiF 3 , TiF 4 , and ZrF 4 , and the phosphorus compound is preferably selected from Li 3 PO 4 and LiPO 3 .
【００３５】７．添加剤の混合についての検討（実施例
２４〜２９） ついで、添加剤の混合について検討した。ここでは、イ
ミド系リチウム塩としてＬｉＮ（Ｃ2Ｆ5ＳＯ2）2を用い
た電解液を使用し、この電解液に下記の表３に示すフッ
化物とリン化合物、フッ化物同士およびリン化合物同士
を混合して用い、容量残存率を上述と同様に求めると、
下記の表３に示すような結果となった。7. Examination on Mixing of Additives (Examples 24 to 29) Next, mixing of additives was examined. Here, an electrolytic solution using LiN (C 2 F 5 SO 2 ) 2 as the imide-based lithium salt is used, and this electrolytic solution contains a fluoride and a phosphorus compound shown in Table 3 below, a fluoride compound and a phosphorus compound compound. Are used in combination, and the remaining capacity ratio is determined in the same manner as described above.
The results are as shown in Table 3 below.
【００３６】なお、ＬｉＦとＬｉ3ＰＯ4を１：１（質量
比、以下同様である）に混合して混合添加剤とし、この
混合添加剤を電解液に対して１質量％添加した電解液を
実施例２４の電解液としこの電解液を用いた電池をＩと
した。また、ＬｉＦとＬｉＰＯ3を１：１に混合して混
合添加剤とし、この混合添加剤を電解液に対して１質量
％添加した電解液を実施例２５の電解液としこの電解液
を用いた電池をＪとした。また、ＴｉＦ4とＬｉ3ＰＯ4
を１：１に混合して混合添加剤とし、この混合添加剤を
電解液に対して１質量％添加した電解液を実施例２６の
電解液としこの電解液を用いた電池をＫとした。An electrolyte prepared by mixing LiF and Li 3 PO 4 at a ratio of 1: 1 (mass ratio, the same applies hereinafter) to form a mixed additive, and adding the mixed additive to the electrolytic solution at 1% by mass. Was used as the electrolyte of Example 24, and a battery using this electrolyte was designated as I. Further, LiF and LiPO 3 were mixed at a ratio of 1: 1 to obtain a mixed additive, and an electrolytic solution obtained by adding this mixed additive to the electrolytic solution at 1% by mass was used as the electrolytic solution of Example 25, and this electrolytic solution was used. The battery was designated as J. Also, TiF 4 and Li 3 PO 4
Was mixed at a ratio of 1: 1 to obtain a mixed additive. An electrolytic solution obtained by adding the mixed additive to the electrolytic solution at 1% by mass was used as the electrolytic solution of Example 26, and a battery using this electrolytic solution was designated as K.
【００３７】また、ＴｉＦ4とＬｉＰＯ3を１：１に混合
して混合添加剤とし、この混合添加剤を電解液に対して
１質量％添加した電解液を実施例２７の電解液としこの
電解液を用いた電池をＬとした。また、ＬｉＦとＴｉＦ
4を１：１に混合して混合添加剤とし、この混合添加剤
を電解液に対して１質量％添加した電解液を実施例２８
の電解液としこの電解液を用いた電池をＭとした。さら
に、Ｌｉ3ＰＯ4とＬｉＰＯ3を１：１に混合して混合添
加剤とし、この混合添加剤を電解液に対して１質量％添
加した電解液を実施例２９の電解液としこの電解液を用
いた電池をＮとした。Further, TiF 4 and LiPO 3 were mixed at a ratio of 1: 1 to obtain a mixed additive, and an electrolyte obtained by adding 1% by mass of the mixed additive to the electrolyte was used as an electrolyte of Example 27. The battery using the liquid was designated as L. LiF and TiF
4 was mixed at a ratio of 1: 1 to obtain a mixed additive.
The battery using this electrolyte was designated as M. Further, Li 3 PO 4 and LiPO 3 were mixed at a ratio of 1: 1 to obtain a mixed additive, and an electrolyte obtained by adding 1% by mass of the mixed additive to the electrolyte was used as an electrolyte of Example 29. The battery using was designated as N.
【００３８】[0038]
【表３】 [Table 3]
【００３９】上記表３より明らかなように、フッ化物同
士（実施例２８）あるいはリン化合物同士（実施例２
９）からなる混合添加剤を添加した電池Ｍあるいは電池
Ｎは、これらの添加剤を単独で用いた電池（表２参照）
とほぼ同等の容量残存率であることが分かる。一方、フ
ッ化物とリン化合物からなる混合添加剤（実施例２４〜
２７）を添加した電池Ｉ，Ｊ，Ｋ，Ｌは、これらの添加
剤を単独で用いた電池（表２参照）よりも容量残存率が
向上していることが分かる。このことから、イミド系リ
チウム塩を溶質とした電解液に添加されるフッ化物ある
いはリン化合物からなる添加剤としては、混合添加剤と
することが好ましく、特に、フッ化物とリン化合物から
なる混合添加剤とすることが好ましということができ
る。As is clear from Table 3 above, fluorides (Example 28) or phosphorus compounds (Example 2)
The battery M or the battery N to which the mixed additive of 9) was added was a battery using these additives alone (see Table 2).
It can be seen that the capacity remaining rate is almost equal to On the other hand, a mixed additive composed of a fluoride and a phosphorus compound (Examples 24 to 24)
It can be seen that the batteries I, J, K, and L to which 27) was added had a higher remaining capacity ratio than the batteries using these additives alone (see Table 2). For this reason, it is preferable that the additive comprising a fluoride or a phosphorus compound to be added to the electrolytic solution containing the imide-based lithium salt as a solute is a mixed additive, and in particular, a mixed additive comprising a fluoride and a phosphorus compound. It can be said that the agent is preferable.
【００４０】８．添加剤の添加量の検討（実施例３０〜
３５） ついで、添加剤の添加量について検討した。ここでは、
イミド系リチウム塩としてＬｉＮ（Ｃ2Ｆ5ＳＯ2）2を用
いた電解液を使用し、フッ化物としてのＬｉＦとリン化
合物としてのＬｉ3ＰＯ4を１：１の割合で混合して混合
添加剤とし、この混合添加剤を下記の表４に示すような
添加量だけ添加した電解液を用いた電池の容量残存率を
上述と同様に求めると、下記の表４に示すような結果と
なった。8. Examination of additive amount (Examples 30 to 30)
35) Next, the amount of the additive was examined. here,
An electrolytic solution using LiN (C 2 F 5 SO 2 ) 2 as an imide-based lithium salt is used, and LiF as a fluoride and Li 3 PO 4 as a phosphorus compound are mixed at a ratio of 1: 1 and mixed and added. When the remaining capacity ratio of a battery using an electrolyte solution in which this mixed additive was added in an amount as shown in Table 4 below was obtained in the same manner as described above, the results shown in Table 4 below were obtained. Was.
【００４１】なお、この混合添加剤を電解液に対して
０．００１質量％添加した電解液を実施例３０の電解液
としこの電解液を用いた電池をＯとした。また、０．０
１質量％添加した電解液を実施例３１の電解液としこの
電解液を用いた電池をＰとし、０．１質量％添加した電
解液を実施例３２の電解液としこの電解液を用いた電池
をＱとした。さらに、この混合添加剤を電解液に対して
２質量％添加した電解液を実施例３３の電解液としこの
電解液を用いた電池をＲとし、５質量％添加した電解液
を実施例３４の電解液としこの電解液を用いた電池をＳ
とし、１０質量％添加した電解液を実施例３５の電解液
としこの電解液を用いた電池をＴとした。なお、下記の
表４には実施例２４の電解液（混合添加剤の添加量が１
質量％のもの）を用いた電池Ｉの容量残存率も示してい
る。The electrolyte prepared by adding 0.001% by mass of this mixed additive to the electrolyte was used as the electrolyte of Example 30, and the battery using this electrolyte was designated O. Also, 0.0
An electrolyte containing 1% by mass of the electrolyte was used as the electrolyte of Example 31, and a battery using this electrolyte was designated as P. An electrolyte containing 0.1% by mass was used as the electrolyte of Example 32, and a battery using this electrolyte was used. Is Q. Further, an electrolytic solution obtained by adding 2% by mass of this mixed additive to the electrolytic solution was used as the electrolytic solution of Example 33, a battery using this electrolytic solution was denoted by R, and an electrolytic solution containing 5% by mass of the electrolytic solution of Example 34 was used. A battery using this electrolyte as an electrolyte was S
The electrolyte containing 10% by mass was used as the electrolyte of Example 35, and a battery using this electrolyte was designated as T. In Table 4 below, the electrolyte solution of Example 24 (the amount of the mixed additive added was 1
In addition, the remaining capacity ratio of the battery I using the mass%) is also shown.
【００４２】[0042]
【表４】 [Table 4]
【００４３】上記表４より明らかなように、ＬｉＦとＬ
ｉ3ＰＯ4からなる混合添加剤の添加量が少なすぎても多
すぎても効果的な添加効果が得られないため、混合添加
剤の添加量は、電解液に対して０．００１〜１０質量％
となるように添加することが望ましく、特に、０．０１
〜５質量％となるように添加することが好ましい。これ
は、添加量が少なすぎると添加剤の被膜が正極あるいは
負極表面に均一に形成されにくく、また、添加量が多す
ぎると被膜が厚くなりすぎて抵抗が大きくなるためと考
えられる。As is clear from Table 4 above, LiF and L
If the amount of the i 3 PO 4 mixed additive is too small or too large, an effective addition effect cannot be obtained. mass%
It is desirable to add so that
It is preferable to add so that it may be ~ 5 mass%. This is presumably because, if the amount is too small, it is difficult to form a film of the additive uniformly on the surface of the positive electrode or the negative electrode, and if the amount is too large, the film becomes too thick and the resistance becomes large.
【００４４】このことは、ＬｉＦとＬｉ3ＰＯ4からなる
混合添加剤のみに限らず、他の混合添加剤を用いても、
フッ化物あるいはリン化合物同士の混合添加剤、または
それらを単独で用いてもほぼ同様な傾向が認められた。
したがって、フッ化物、リン化合物、これら同士の混合
添加剤、あるいはフッ化物とリン化合物との混合添加剤
の添加量は、電解液に対して０．００１〜１０質量％と
なるように添加することが望ましく、特に、０．０１〜
５質量％となるように添加することが好ましい。This is not limited to only the mixed additive composed of LiF and Li 3 PO 4 , and even if other mixed additives are used,
Almost the same tendency was observed when a mixed additive of fluorides or phosphorus compounds was used, or when these were used alone.
Therefore, the amount of addition of the fluoride, the phosphorus compound, the mixed additive thereof, or the mixed additive of the fluoride and the phosphorus compound should be 0.001 to 10% by mass with respect to the electrolytic solution. Is desirable, in particular, 0.01 to
It is preferable to add so that it may become 5 mass%.
【００４５】９．ポリマー電解質についての検討（実施
例３６〜３７） ついで、電解液をポリマー材料でゲル化してポリマー電
解質とした場合の添加剤の影響について検討した。ここ
では、イミド系リチウム塩としてＬｉＮ（Ｃ2Ｆ5Ｓ
Ｏ2）2を使用し、フッ化物としてのＬｉＦとリン化合物
としてのＬｉ3ＰＯ 4を１：１の割合で混合した混合添加
剤を用いた。そして、まず、極板上にキャストでポリマ
ー膜（ポリエチレンオキシド（ＰＥＯ）あるいはポリフ
ッ化ビニリデン（ＰＶｄＦ）等）を形成し、その後、電
解液を添加してゲル化させた。これらの電池の容量残存
率を上述と同様に求めると、下記の表５に示すような結
果となった。9. Examination of polymer electrolyte (implementation
Examples 36 to 37) Next, the electrolyte was gelled with a polymer material to form a polymer electrolyte.
The effect of additives on degrading was investigated. here
In this case, LiN (CTwoFFiveS
OTwo)TwoLiF as a fluoride and phosphorus compound
Li asThreePO FourMixed in a 1: 1 ratio
Agent was used. First, cast the polymer on the electrode plate
-Film (polyethylene oxide (PEO) or polyf
Vinylidene difluoride (PVdF), etc.
The solution was added to cause gelation. The remaining capacity of these batteries
When the ratio is obtained in the same manner as described above, the results shown in Table 5 below are obtained.
Result.
【００４６】なお、ポリマー材料（分子量が２０万のも
の）としてのポリエチレンオキシド（ＰＥＯ）を添加し
てポリマー電解質としたものを実施例３６の電解質と
し、これを用いた電池をＵとした。また、ポリフッ化ビ
ニリデン（ＰＶｄＦ）を添加してポリマー電解質とした
ものを実施例３７の電解質とし、これを用いた電池をＶ
とした。なお、下記の表５には実施例２４の電解液を用
いた電池Ｉの容量残存率も示している。A polymer electrolyte obtained by adding polyethylene oxide (PEO) as a polymer material (having a molecular weight of 200,000) was used as the electrolyte of Example 36, and a battery using this was designated U. The polymer electrolyte obtained by adding polyvinylidene fluoride (PVdF) was used as the electrolyte of Example 37.
And Table 5 below also shows the remaining capacity of the battery I using the electrolyte of Example 24.
【００４７】[0047]
【表５】 [Table 5]
【００４８】上記表５より明らかなように、ポリエチレ
ンオキシド（ＰＥＯ）あるいはポリフッ化ビニリデン
（ＰＶｄＦ）などの分子量が２０万のポリマー材料を添
加したポリマー電解質にＬｉＦとＬｉ3ＰＯ4からなる混
合添加剤が添加されていると、容量残存率、即ち、充電
保存特性が向上することがわかる。このことは、ＬｉＦ
とＬｉ3ＰＯ4からなる混合添加剤のみに限らず、他の混
合添加剤を用いても、フッ化物あるいはリン化合物同士
の混合添加剤、またはそれらを単独で用いてもほぼ同様
な傾向が認められた。これらの結果からすると、ＬｉＮ
（Ｃ2Ｆ5ＳＯ2）2からなるイミド系リチウム塩が添加さ
れた電解質に、フッ化物、リン化合物あるいはこれらを
混合したものを添加した場合には、ポリマー電解質とし
て用いると特に充電保存特性が向上するということがで
きる。As is clear from Table 5, a mixed additive composed of LiF and Li 3 PO 4 is added to a polymer electrolyte containing a polymer material having a molecular weight of 200,000 such as polyethylene oxide (PEO) or polyvinylidene fluoride (PVdF). It can be seen that the addition of C improves the residual capacity ratio, that is, the charge storage characteristics. This means that LiF
It is not limited to the mixed additive consisting of and Li 3 PO 4, and the similar tendency is recognized even when using another mixed additive, a mixed additive of fluorides or phosphorus compounds, or using them alone. Was done. Based on these results, LiN
When a fluoride, a phosphorus compound or a mixture thereof is added to an electrolyte to which an imide-based lithium salt composed of (C 2 F 5 SO 2 ) 2 is added, particularly when used as a polymer electrolyte, the charge storage characteristics are particularly poor. Can be improved.
【００４９】以上に詳述したように、イミド系リチウム
塩あるいはメチド系リチウム塩の少なくとも一方が溶質
として用いられた電解質に、フッ化物あるいはリン化合
物からなる添加剤の少なくとも一方が添加されている
と、これらの添加剤が正極あるいは負極の表面に保護膜
を形成する。この保護膜は電解質が直接、正極あるいは
負極と接触することが防止するように作用するため、充
電状態で保存しても電解質が分解されるのを防止でき、
充電保存性が向上する。この結果、充電保存特性の優
れ、信頼性の高いリチウム二次電池を提供できるように
なる。As described in detail above, when at least one of an additive comprising a fluoride or a phosphorus compound is added to an electrolyte in which at least one of an imide-based lithium salt and a methide-based lithium salt is used as a solute. These additives form a protective film on the surface of the positive electrode or the negative electrode. Since this protective film acts to prevent the electrolyte from directly contacting the positive electrode or the negative electrode, the electrolyte can be prevented from being decomposed even when stored in a charged state,
The charge storage property is improved. As a result, a highly reliable lithium secondary battery having excellent charge storage characteristics can be provided.
【図１】 本発明の一実施形態のリチウム二次電池の断
面を示す図である。FIG. 1 is a diagram showing a cross section of a lithium secondary battery according to one embodiment of the present invention.
１…正極、２…負極、３…セパレータ、４…負極缶、５
…正極缶、６…絶縁パッキングDESCRIPTION OF SYMBOLS 1 ... Positive electrode, 2 ... Negative electrode, 3 ... Separator, 4 ... Negative electrode can, 5
... positive electrode can, 6 ... insulating packing
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤谷 伸 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 Ｆターム(参考） 5H029 AJ04 AK03 AL07 AM03 AM04 AM05 AM07 BJ03 BJ16 EJ11 EJ12 HJ01 HJ02 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shin Fujitani 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. F-term (reference) 5H029 AJ04 AK03 AL07 AM03 AM04 AM05 AM07 BJ03 BJ16 EJ11 EJ12 HJ01 HJ02
Claims (5)
極と、リチウムイオンの挿入・脱離が可能な負極と、電
解質とを備えたリチウム二次電池であって、 前記電解質はＬｉＮ（ＣmＦ2m+1ＳＯ2）（ＣnＦ2n+1Ｓ
Ｏ2）（ただし、ｍおよびｎは各々独立した１〜４の整
数）で表されるイミド系リチウム塩あるいはＬｉＣ（Ｃ
pＦ2p+1ＳＯ2）（ＣqＦ2q+1ＳＯ2）（ＣrＦ2r+1ＳＯ2）
（ただし、ｐ、ｑおよびｒは各々独立した１〜４の整
数）で表されるメチド系リチウム塩の少なくとも一方が
前記電解質の溶質として用いられ、 前記電解質にフッ化物あるいはリン化合物からなる添加
剤の少なくとも一方が添加されていることを特徴とする
リチウム二次電池。1. A lithium secondary battery comprising a positive electrode capable of inserting and removing lithium ions, a negative electrode capable of inserting and removing lithium ions, and an electrolyte, wherein the electrolyte is LiN (C m F 2m + 1 SO 2 ) (C n F 2n + 1 S
O 2 ) (where m and n are each independently an integer of 1 to 4) or an imide-based lithium salt represented by LiC (C
p F 2p + 1 SO 2) (C q F 2q + 1 SO 2) (C r F 2r + 1 SO 2)
(Where p, q and r are each independently an integer of 1 to 4) wherein at least one of the methide-based lithium salts is used as a solute of the electrolyte, and an additive comprising a fluoride or a phosphorus compound in the electrolyte. A lithium secondary battery characterized by adding at least one of the following.
ｇＦ、ＣｏＦ2、ＣｏＦ3、ＣｕＦ、ＣｕＦ2、ＦｅＦ2、
ＦｅＦ3、ＬｉＦ、ＭｎＦ2、ＭｎＦ3、ＳｎＦ2、ＳｎＦ
4、ＴｉＦ3、ＴｉＦ4およびＺｒＦ4から選択された少な
くとも１種が用いられ、前記リン化合物からなる添加剤
として、ＬｉＰＯ3およびＬｉ3ＰＯ4から選択された少
なくとも１種が用いられたことを特徴とする請求項１に
記載のリチウム二次電池。2. An additive comprising the fluoride, A
gF, CoF 2 , CoF 3 , CuF, CuF 2 , FeF 2 ,
FeF 3 , LiF, MnF 2 , MnF 3 , SnF 2 , SnF
4 , at least one selected from TiF 3 , TiF 4 and ZrF 4 is used, and at least one selected from LiPO 3 and Li 3 PO 4 is used as an additive comprising the phosphorus compound. The lithium secondary battery according to claim 1, wherein:
および前記リン化合物の両方が用いられたことを特徴と
する請求項１または請求項２に記載のリチウム二次電
池。3. The lithium secondary battery according to claim 1, wherein both the fluoride and the phosphorus compound are used as additives for the electrolyte.
て０．０１〜５質量％であることを特徴とする請求項１
から請求項３のいずれかに記載のリチウム二次電池。4. The method according to claim 1, wherein the amount of the additive is 0.01 to 5% by mass with respect to the electrolyte.
The lithium secondary battery according to any one of claims 1 to 3.
ることを特徴とする請求項１から請求項４のいずかに記
載のリチウム二次電池。5. The lithium secondary battery according to claim 1, wherein the electrolyte is gelled with a polymer.
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| JP2000175265A JP4020571B2 (en) | 1999-06-25 | 2000-06-12 | Lithium secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17978999 | 1999-06-25 | ||
| JP11-179789 | 1999-06-25 | ||
| JP2000175265A JP4020571B2 (en) | 1999-06-25 | 2000-06-12 | Lithium secondary battery |
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| Publication Number | Publication Date |
|---|---|
| JP2001068154A true JP2001068154A (en) | 2001-03-16 |
| JP4020571B2 JP4020571B2 (en) | 2007-12-12 |
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| Application Number | Title | Priority Date | Filing Date |
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