JP3349368B2 - Lithium battery - Google Patents
Lithium batteryInfo
- Publication number
- JP3349368B2 JP3349368B2 JP28926496A JP28926496A JP3349368B2 JP 3349368 B2 JP3349368 B2 JP 3349368B2 JP 28926496 A JP28926496 A JP 28926496A JP 28926496 A JP28926496 A JP 28926496A JP 3349368 B2 JP3349368 B2 JP 3349368B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- carbonate
- electrolytic solution
- lithium battery
- ethylene carbonate
- 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.)
- Expired - Fee Related
Links
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
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、リチウム電池に係
わり、詳しくは正極缶などに腐食が起こりにくい、信頼
性の高いリチウム電池を提供することを目的とした、正
極缶などの正極部材及び電解液の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium battery, and more particularly, to a positive electrode member such as a positive electrode can and the like, which aims to provide a highly reliable lithium battery in which a positive electrode can is hardly corroded. Liquid improvement.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】リチウ
ム電池では、電解液の溶媒として有機溶媒が使用される
ので、正極活物質を適宜選択することにより、高電圧且
つ高容量な電池を得ることが可能である。電池設計の際
に水の分解電圧を考慮する必要がないからである。2. Description of the Related Art In a lithium battery, an organic solvent is used as a solvent for an electrolytic solution, so that a high voltage and high capacity battery can be obtained by appropriately selecting a positive electrode active material. Is possible. This is because it is not necessary to consider the decomposition voltage of water when designing the battery.
【０００３】ところで、リチウム電池の正極缶、正極集
電体及び正極タブ（本明細書においては、これらを正極
部材と称することがある）には、安価なため、ステンレ
ス鋼が汎用されている。実用されているステンレス鋼と
しては、ＳＵＳ３０４及びＳＵＳ４３０が挙げられる。By the way, stainless steel is widely used for a positive electrode can, a positive electrode current collector, and a positive electrode tab (these may be referred to as a positive electrode member in this specification) of a lithium battery because they are inexpensive. Stainless steels in practical use include SUS304 and SUS430.
【０００４】しかしながら、正極の開回路電圧が通常３
Ｖ（ｖｓ．Ｌｉ／Ｌｉ+ ）以上になるリチウム電池の正
極部材にＳＵＳ３０４などをそのまま使用すると、それ
が電解液と反応して腐食し、洩液や電池特性の低下を招
く。However, the open circuit voltage of the positive electrode is usually 3
If SUS304 or the like is used as it is for a positive electrode member of a lithium battery having a voltage of V (vs. Li / Li + ) or more, it reacts with an electrolytic solution to corrode, resulting in a leakage solution and a decrease in battery characteristics.
【０００５】このため、ステンレス鋼をリチウム電池の
正極部材として使用する場合は、電解液に対する耐食性
を高める目的で、アニール処理が施される。[0005] Therefore, when stainless steel is used as a positive electrode member of a lithium battery, an annealing treatment is performed for the purpose of improving corrosion resistance to an electrolytic solution.
【０００６】しかしながら、この処理によっても、腐食
を充分に抑制できないのが実情である。したがって、正
極部材の電解液に対する耐食性の改善は、この種の電池
の実用電池としての信頼性を高める上で急務と考えられ
ている。However, the fact is that corrosion cannot be sufficiently suppressed even by this treatment. Therefore, improvement of the corrosion resistance of the positive electrode member to the electrolytic solution is considered to be an urgent need for improving the reliability of this type of battery as a practical battery.
【０００７】本発明は、このような事情を考慮してなさ
れたものであって、正極部材が腐食しにくい、信頼性の
高いリチウム電池を提供することを目的とする。The present invention has been made in view of such circumstances, and has as its object to provide a highly reliable lithium battery in which a positive electrode member is hardly corroded.
【０００８】[0008]
【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電池（本発明電池）において
は、電解液の溶媒として、エチレンカーボネート又はエ
チレンカーボネートを１０体積％以上含む混合溶媒が、
電解液の溶質としてＬｉＣＦ3 ＳＯ3 が、また正極缶、
正極集電体及び正極タブの少なくとも１つに、ＳＵＳ３
１６Ｌが、それぞれ使用される。In order to achieve the above object, in the lithium battery (battery of the present invention) according to the present invention, ethylene carbonate or a mixed solvent containing 10 vol% or more of ethylene carbonate is used as a solvent for the electrolytic solution. ,
LiCF 3 SO 3 as a solute of the electrolyte, a positive electrode can,
At least one of the positive electrode current collector and the positive electrode tab has SUS3
16L are used respectively.
【０００９】電解液の溶媒としてエチレンカーボネート
と他の溶媒との混合溶媒を使用する場合の好適な混合溶
媒としては、エチレンカーボネート（ＥＣ）と、プロピ
レンカーボネート（ＰＣ）、ブチレンカーボネート（Ｂ
Ｃ）、ジメチルカーボネート（ＤＭＣ）、ジエチルカー
ボネート（ＤＥＣ）、メチルエチルカーボネート（ＭＥ
Ｃ）、γ−ブチロラクトン（γ−ＢＬ）、１，２−ジメ
トキシエタン（ＤＭＥ）、１，２−ジエトキシエタン
（ＤＥＥ）、１，２−エトキシメトキシエタン（ＥＭ
Ｅ）、テトラヒドロフラン（ＴＨＦ）、スルホラン（Ｓ
Ｌ）及び１，３−ジオキソラン（ＤＯＸＬ）から選ばれ
た少なくとも１種の有機溶媒とからなる混合溶媒が挙げ
られる。When a mixed solvent of ethylene carbonate and another solvent is used as a solvent for the electrolytic solution, preferred mixed solvents are ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (B
C), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (ME
C), γ-butyrolactone (γ-BL), 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), 1,2-ethoxymethoxyethane (EM
E), tetrahydrofuran (THF), sulfolane (S
L) and a mixed solvent comprising at least one organic solvent selected from 1,3-dioxolane (DOXL).
【００１０】本発明は、一次電池、二次電池を問わず適
用可能である。本発明はリチウム電池の正極部材及び電
解液の改良に関するものゆえ、これら以外の部材には、
次に示す如き従来公知の材料を特に制限無く用いること
ができる。[0010] The present invention is applicable to both primary batteries and secondary batteries. The present invention relates to the improvement of the positive electrode member and the electrolyte of the lithium battery.
Conventionally known materials as shown below can be used without particular limitation.
【００１１】正極活物質の具体例としては、二酸化マン
ガン、ＬｉＣｏＯ2 、ＬｉＮｉＯ2、ＬｉＭｎ2 Ｏ4 、
ＬｉＶＯ2 及びＬｉＮｂＯ2 が挙げられる。Specific examples of the positive electrode active material include manganese dioxide, LiCoO 2 , LiNiO 2 , LiMn 2 O 4 ,
LiVO 2 and LiNbO 2 are mentioned.
【００１２】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
チウムが挙げられる。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 inserting and extracting 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.
【００１３】本発明によれば、正極部材が腐食しにくい
リチウム電池が提供される。正極部材の耐食性が改善さ
れる理由は、本発明者らにおいても現在のところ定かで
ないが、モリブデンを含有しないステンレス鋼（従来実
用されているＳＵＳ３０４及びＳＵＳ４３０はこれに該
当する）を正極部材に使用したり、エチレンカーボネー
トを含まない溶媒を使用したり、或いはＬｉＡｓＦ6 な
どを使用したりした場合に比べて正極部材の耐食性が大
きく改善されることから、ＳＵＳ３１６Ｌとエチレンカ
ーボネートとＬｉＣＦ3 ＳＯ3 との反応生成物が正極部
材の表面に被膜となって析出し、これが腐食の進行を抑
制するためではないかと考えている。According to the present invention, there is provided a lithium battery in which the positive electrode member is hardly corroded. The reason why the corrosion resistance of the positive electrode member is improved is not clear at present even by the present inventors. However, stainless steel not containing molybdenum (the conventionally used SUS304 and SUS430 correspond to this) is used for the positive electrode member. Since the corrosion resistance of the positive electrode member is greatly improved as compared with the case where a solvent containing no ethylene carbonate is used, or the use of LiAsF 6 or the like, SUS316L, ethylene carbonate and LiCF 3 SO 3 are used. It is thought that the reaction product is deposited as a film on the surface of the positive electrode member, and this may suppress the progress of corrosion.
【００１４】[0014]
【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.
【００１５】（実験１） この実験では、使用する溶質及びステンレス鋼とステン
レス鋼の腐食の関係を調べた。電解液として、エチレン
カーボネートに種々の溶質を１モル／リットル溶かした
有機溶液を使用して、３極式の試験セルＡ８〜Ａ１３，
Ｂ１６〜Ｂ４４を組み立て、腐食電流を室温（２５°
Ｃ）下にて測定して、各試験セルに使用したステンレス
鋼の耐食性を調べた。試験セルのうち、Ａ１２が本発明
電池に相当する試験セルであり、他は比較試験セルであ
る。腐食電流は、作用極の参照極に対する電位を４Ｖに
設定したときの作用極と対極との間に流れる電流（μＡ
／ｃｍ2 ）として求めた。表１及び表２に、各試験セル
に使用したステンレス鋼、モリブデン含有率、電解液
（溶媒及び溶質）及び腐食電流の測定値を示す。(Experiment 1) In this experiment, the relationship between solutes used and corrosion of stainless steel and stainless steel was examined. An organic solution in which various solutes are dissolved in ethylene carbonate at 1 mol / liter is used as an electrolytic solution, and three-electrode type test cells A8 to A13,
Assemble B16 to B44 and set the corrosion current to room temperature (25 °
C) Measurements were made below to examine the corrosion resistance of the stainless steel used for each test cell. Among the test cells, A12 is a test cell corresponding to the battery of the present invention, and the others are comparative test cells. The corrosion current was determined by measuring the current (μA) flowing between the working electrode and the counter electrode when the potential of the working electrode with respect to the reference electrode was set to 4 V.
/ Cm 2 ). Tables 1 and 2 show the measured values of stainless steel, molybdenum content, electrolyte solution (solvent and solute), and corrosion current used for each test cell.
【００１６】図１は、この実験のために組み立てた試験
セルの断面模式図であり、図示の試験セルＣは、作用極
（ステンレス電極；電極面積１ｃｍ2 ）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１０ｃｍ2 ）２、参照極（リチウム
電極；電極面積０．３ｃｍ2 ）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。FIG. 1 is a schematic cross-sectional view of a test cell assembled for this experiment. The test cell C shown in the drawing has a working electrode (stainless steel electrode; electrode area 1 cm 2 ) 1 which is sufficiently larger than the working electrode 1. Electrode (lithium electrode; electrode area 10 cm 2 ) 2, reference electrode (lithium electrode; electrode area 0.3 cm 2 ) 3, luggin tube 4, insulating closed container 5 and electrolyte 6 Become.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【表２】 [Table 2]
【００１９】表１及び表２に示すように、作用極にＳＵ
Ｓ３１６Ｌを使用し、電解液の溶媒としてエチレンカー
ボネートを使用し、且つ電解液の溶質としてＬｉＣＦ3
ＳＯ3 を使用した試験セルＡ１２は、ＳＵＳ３１６Ｌ以
外のステンレス鋼を使用した作用極を使用したり、Ｌｉ
ＣＦ3 ＳＯ3 以外の電解液の溶質を使用したりした他の
試験セルに比べて、腐食電流が小さい。この事実から、
正極部材が腐食しにくいリチウム電池を得るためには、
正極部材に使用するステンレス鋼としてＳＵＳ３１６Ｌ
を使用するのみならず、電解液の溶質としてＬｉＣＦ3
ＳＯ3 を使用する必要があることが分かる。As shown in Tables 1 and 2, SU was applied to the working electrode.
S316L, ethylene carbonate as a solvent for the electrolytic solution, and LiCF 3 as a solute for the electrolytic solution.
The test cell A12 using SO 3 uses a working electrode using stainless steel other than SUS316L,
Corrosion current is smaller than that of other test cells using a solute of an electrolytic solution other than CF 3 SO 3 . From this fact,
In order to obtain a lithium battery in which the positive electrode member is less likely to corrode,
SUS316L as stainless steel used for the positive electrode member
As well as LiCF 3 as a solute of the electrolyte.
It can be seen that SO 3 needs to be used.
【００２０】（実験２） この実験では、使用する溶媒とステンレス鋼の腐食の関
係を調べた。すなわち電解液として、種々の溶媒にＬｉ
ＣＦ3 ＳＯ3 を１モル／リットル溶かした有機溶液を使
用して、３極式の試験セルＡ１５、Ｂ５３〜Ｂ６０を組
み立て、実験１と同じ方法で腐食電流を測定した。表３
に、各試験セルに使用したステンレス鋼、ステンレス鋼
のモリブデン含有率、電解液（溶媒及び溶質）及び腐食
電流の測定値を示す。(Experiment 2) In this experiment, the relationship between the solvent used and the corrosion of stainless steel was examined. That is, as an electrolytic solution, Li is used in various solvents.
Triode test cells A15 and B53 to B60 were assembled using an organic solution in which CF 3 SO 3 was dissolved at 1 mol / liter, and the corrosion current was measured in the same manner as in Experiment 1. Table 3
Table 2 shows the measured values of the stainless steel used for each test cell, the molybdenum content of the stainless steel, the electrolytic solution (solvent and solute), and the corrosion current.
【００２１】[0021]
【表３】 [Table 3]
【００２２】表３に示すように、作用極にＳＵＳ３１６
Ｌを使用し、電解液の溶媒としてエチレンカーボネート
を使用し、且つ電解液の溶質としてＬｉＣＦ3 ＳＯ3 を
使用した試験セルＡ１５は、電解液の溶媒としてエチン
レンカーボネート以外の溶媒を使用した試験セルＢ５３
〜Ｂ６０に比べて、腐食電流が遙に小さい。この事実か
ら、正極部材が腐食しにくいリチウム電池を得るために
は、正極部材に使用するステンレス鋼としてＳＵＳ３１
６Ｌを使用し、電解液の溶質としてＬｉＣＦ3ＳＯ3 を
使用するのみならず、電解液の溶媒としてエチレンカー
ボネートを含有する混合溶媒を使用する必要があること
が分かる。As shown in Table 3, the working electrode was SUS316.
L15, a test cell A15 using ethylene carbonate as a solvent for the electrolytic solution, and LiCF 3 SO 3 as a solute for the electrolytic solution, a test cell using a solvent other than ethynylene carbonate as the solvent for the electrolytic solution B53
Corrosion current is much smaller than B60. From this fact, in order to obtain a lithium battery in which the positive electrode member is hardly corroded, SUS31 is used as stainless steel for the positive electrode member.
It can be seen that it is necessary to use 6 L, not only LiCF 3 SO 3 as a solute of the electrolytic solution, but also a mixed solvent containing ethylene carbonate as a solvent of the electrolytic solution.
【００２３】[0023]
【発明の効果】正極部材が腐食しにくいので、本発明電
池は信頼性が高い。The battery of the present invention has high reliability because the positive electrode member is hardly corroded.
【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 (51)Int.Cl.7 識別記号 ＦＩ Ｈ０１Ｍ 10/40 Ｈ０１Ｍ 10/40 Ａ (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 (56)参考文献 特開 平６−150967（ＪＰ，Ａ) 特開 平７−220758（ＪＰ，Ａ) 特開 平８−213001（ＪＰ，Ａ) 特開 平２−236972（ＪＰ，Ａ) 特開 平４−121962（ＪＰ，Ａ) 特開 平６−111849（ＪＰ，Ａ) 特開 平７−94212（ＪＰ，Ａ) 特開 平９−22702（ＪＰ，Ａ) 特開 平９−180707（ＪＰ，Ａ) 特開 平９−213307（ＪＰ，Ａ) 特開 昭62−93868（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 6/16 H01M 10/40 H01M 4/64 - 4/80 H01M 2/02 H01M 2/26 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI H01M 10/40 H01M 10/40 A (72) Inventor Toshiyuki No. 2-5-5 Keihanhondori, Moriguchi-shi, Osaka SANYO ELECTRIC (72) Inventor Koji Nishio 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (56) References JP-A-6-150967 (JP, A) JP-A-7-220758 (JP, A) JP-A-8-213001 (JP, A) JP-A-2-236972 (JP, A) JP-A-4-121962 (JP, A) JP-A 6-111849 (JP, A) JP-A-7-94212 (JP, A) JP-A-9-22702 (JP, A) JP-A-9-180707 (JP, A) JP-A-9-213307 (JP, A) JP-A-62-93868 JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) H01M 6/16 H01M 10/40 H01M 4/6 4-4/80 H01M 2/02 H01M 2/26
Claims (2)
はエチレンカーボネートを１０体積％以上含む混合溶媒
であり、電解液の溶質がＬｉＣＦ3 ＳＯ3 であり、且つ
正極缶、正極集電体及び正極タブの少なくとも１つが、
ＳＵＳ３１６Ｌからなるリチウム電池。The solvent of the electrolytic solution is ethylene carbonate or a mixed solvent containing 10% by volume or more of ethylene carbonate, the solute of the electrolytic solution is LiCF 3 SO 3 , and the positive electrode can, the positive electrode current collector and the positive electrode tab are provided. At least one of
Lithium battery made of SUS316L.
上含む混合溶媒が、エチレンカーボネートと、プロピレ
ンカーボネート、ブチレンカーボネート、ジメチルカー
ボネート、ジエチルカーボネート、メチルエチルカーボ
ネート、γ−ブチロラクトン、１，２−ジメトキシエタ
ン、１，２−ジエトキシエタン、１，２−エトキシメト
キシエタン、テトラヒドロフラン、スルホラン及び１，
３−ジオキソランから選ばれた少なくとも１種の有機溶
媒とからなる混合溶媒である請求項１記載のリチウム電
池。2. A mixed solvent containing 10% by volume or more of ethylene carbonate, comprising ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, , 2-diethoxyethane, 1,2-ethoxymethoxyethane, tetrahydrofuran, sulfolane and 1,
The lithium battery according to claim 1, which is a mixed solvent comprising at least one organic solvent selected from 3-dioxolane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28926496A JP3349368B2 (en) | 1996-10-11 | 1996-10-11 | Lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28926496A JP3349368B2 (en) | 1996-10-11 | 1996-10-11 | Lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10116623A JPH10116623A (en) | 1998-05-06 |
| JP3349368B2 true JP3349368B2 (en) | 2002-11-25 |
Family
ID=17740915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28926496A Expired - Fee Related JP3349368B2 (en) | 1996-10-11 | 1996-10-11 | Lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3349368B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4462022B2 (en) * | 2004-12-02 | 2010-05-12 | パナソニック株式会社 | Flat type non-aqueous electrolyte battery |
| JP4873889B2 (en) * | 2005-06-02 | 2012-02-08 | パナソニック株式会社 | Lithium primary battery |
| JP4967464B2 (en) * | 2006-06-07 | 2012-07-04 | パナソニック株式会社 | Non-aqueous electrolyte secondary battery |
| US7923153B2 (en) * | 2008-04-29 | 2011-04-12 | Eveready Battery Company, Inc. | Linear ether electrolyte with asymmetric end groups for use in lithium batteries |
| JP2011091019A (en) * | 2009-01-30 | 2011-05-06 | Equos Research Co Ltd | Collector for positive electrode of secondary battery, collector for negative electrode of secondary battery, positive electrode of secondary battery, negative electrode of secondary battery, and secondary battery |
| JP2011070861A (en) * | 2009-03-31 | 2011-04-07 | Equos Research Co Ltd | Battery case and lithium ion battery using it |
| CN101771142B (en) * | 2010-02-10 | 2012-09-19 | 力佳电源科技(深圳)有限公司 | Tab material of flexible-packaging lithium battery as well as electroplating method and application method thereof |
-
1996
- 1996-10-11 JP JP28926496A patent/JP3349368B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10116623A (en) | 1998-05-06 |
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