JP2000208169A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JP2000208169A JP2000208169A JP11008695A JP869599A JP2000208169A JP 2000208169 A JP2000208169 A JP 2000208169A JP 11008695 A JP11008695 A JP 11008695A JP 869599 A JP869599 A JP 869599A JP 2000208169 A JP2000208169 A JP 2000208169A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- carbonate
- battery according
- positive electrode
- lithium
- 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
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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は非水電解液二次電池
に関するものであり、特に低温特性、長期安定性、サイ
クル特性等に優れた非水電解液二次電池に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a non-aqueous electrolyte secondary battery having excellent low-temperature characteristics, long-term stability and cycle characteristics.
【０００２】[0002]
【従来の技術】近年、電気製品の軽量化、小型化に伴
い、高いエネルギー密度を有するリチウム二次電池の開
発が進められ、一部は既に実用に供されている。現在、
開発が進められているリチウム二次電池は、負極活物質
としてリチウム金属やリチウムを吸蔵・放出する黒鉛を
用い、正極活物質としてＬｉＣｏＯ2 、 ＬｉＮｉＯ2 、
ＬｉＭｎ2 Ｏ4 などのリチウム遷移金属複合酸化物を用
い、電解液として有機溶媒にリチウム塩を溶解した非水
電解液を用いたものである。なかでも安全性等の点から
して黒鉛を負極活物質とするリチウム二次電池が有望と
考えられている。2. Description of the Related Art In recent years, as electric appliances have become lighter and smaller, development of lithium secondary batteries having a high energy density has been promoted, and some of them have already been put to practical use. Current,
Lithium secondary batteries, which are being developed, use lithium metal or graphite that stores and releases lithium as the negative electrode active material, and LiCoO 2, LiNiO 2 ,
A lithium transition metal composite oxide such as LiMn 2 O 4 is used, and a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent is used as an electrolyte. Among them, lithium secondary batteries using graphite as a negative electrode active material are considered to be promising from the viewpoint of safety and the like.
【０００３】[0003]
【発明が解決しようとする課題】非水電解液を構成する
有機溶媒としては、エチレンカーボネート、プロピレン
カーボネート等の環状カーボネート；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
ト等の鎖状カーボネート；γ−ブチロラクトン等のラク
トンなど種々のものが提案されている。なかでもプロピ
レンカーボネートは誘電率が高く、リチウム塩をよく溶
解し、しかも融点が低く、低温下でも高い電気伝導度を
有する電解液を与えるので、非水電解液の溶媒として最
も好ましいものの一つと考えられている。しかしながら
プロピレンカーボネートにリチウム塩を溶解してなる非
水電解液は、負極活物質として結晶性の高い黒鉛又は黒
鉛化炭素と組合せて用いると、充電に際しプロピレンカ
ーボネートが分解するという問題がある。The organic solvent constituting the non-aqueous electrolyte includes cyclic carbonates such as ethylene carbonate and propylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; γ-butyrolactone and the like. Various lactones have been proposed. Among them, propylene carbonate is considered to be one of the most preferred solvents for non-aqueous electrolytes because it has a high dielectric constant, dissolves lithium salts well, and has a low melting point and gives an electrolyte with high electrical conductivity even at low temperatures. Have been. However, when a non-aqueous electrolyte obtained by dissolving a lithium salt in propylene carbonate is used in combination with highly crystalline graphite or graphitized carbon as a negative electrode active material, there is a problem that propylene carbonate is decomposed during charging.
【０００４】従って黒鉛と組合せて用いても安定で、か
つ高い電気伝導度を有する非水電解液を求めて検討が進
められている。その一つはプロピレンカーボネートに代
えてエチレンカーボネートを用いることである。しかし
エチレンカーボネートは凝固点が３６．４℃と高いの
で、単独では用いられず、低粘度溶媒と混合して用いる
方向で検討が進められている。低粘度溶媒は一般に沸点
が低いので、大量に用いると安全性の点で問題があり、
少量しか用いないと低温での電気伝導度及び粘度の点で
問題がある。このような問題点を解決する溶媒の一つと
してエチレンカーボネートとジエチルカーボネートとの
混合溶媒を用いた非水電解液が提案されているが、この
ものも電池のサイクル特性等の点で未だ満足すべきもの
ではない。[0004] Therefore, studies are being made on non-aqueous electrolyte solutions which are stable even when used in combination with graphite and have high electrical conductivity. One of them is to use ethylene carbonate instead of propylene carbonate. However, since ethylene carbonate has a high freezing point of 36.4 ° C., it is not used alone, and is being studied in the direction of mixing with a low-viscosity solvent. Since low-viscosity solvents generally have a low boiling point, there is a problem in terms of safety when used in large quantities,
If only a small amount is used, there is a problem in terms of electric conductivity and viscosity at low temperatures. A non-aqueous electrolyte using a mixed solvent of ethylene carbonate and diethyl carbonate has been proposed as one of the solvents for solving such problems. However, such a solvent is still not satisfactory in terms of battery cycle characteristics and the like. Not a kimono.
【０００５】上記のような問題点を解決するものとし
て、特開平５−７４４８６号及び特開平８−４５５４５
号公報には、ビニレンカーボネートを含む有機溶媒にリ
チウム塩を溶解した非水電解液を用いることが提案され
ている。ビニレンカーボネートは負極表面に安定な保護
皮膜を形成するため、電池の保存特性が良好であるとさ
れている。[0005] To solve the above-mentioned problems, Japanese Patent Laid-Open Nos. Hei 5-74486 and Hei 8-45545 have been proposed.
Japanese Patent Application Laid-Open Publication No. H11-163840 proposes to use a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent containing vinylene carbonate. Since vinylene carbonate forms a stable protective film on the surface of the negative electrode, it is said that the battery has excellent storage characteristics.
【０００６】ビニレンカーボネートの製法としては、最
も一般的なものとしてはクロロエチレンカーボネートの
脱塩化水素による方法が知られているが、本発明者らの
検討によれば、この方法により製造したビニレンカーボ
ネートを含む有機溶媒にリチウム塩を溶解した非水電解
液を用いた二次電池は、満足すべきサイクル特性を示さ
ない。本発明者らの検討によれば、その原因はビニレン
カーボネート中に含まれている原料由来の有機ハロゲン
化物が酸化分解することによるものと推定される。従っ
て本発明は、このようなビニレンカーボネートを溶媒の
一部とする非水電解液を用いても、サイクル特性の良い
リチウム二次電池を提供しようとするものである。As a method of producing vinylene carbonate, the most common method is the method of dechlorination of chloroethylene carbonate. According to the study of the present inventors, the vinylene carbonate produced by this method is known. A secondary battery using a non-aqueous electrolyte obtained by dissolving a lithium salt in an organic solvent containing is not satisfactory in cycle characteristics. According to the study of the present inventors, the cause is presumed to be due to the oxidative decomposition of the organic halide derived from the raw material contained in vinylene carbonate. Therefore, an object of the present invention is to provide a lithium secondary battery having good cycle characteristics even when such a non-aqueous electrolyte containing vinylene carbonate as a part of the solvent is used.
【０００７】[0007]
【課題を解決するための手段】本発明に係る非水電解液
二次電池は、リチウムを吸蔵・放出することが可能な負
極及び正極をセパレーターを介して対向させてなる電極
組立体、並びに非水電解液を容器に収容してなる非水電
解液二次電池において、非水電解液が有機ハロゲン化物
を含むビニレンカーボネートをその一部とする非水溶媒
にリチウム塩を溶解してなるものであり、かつ正極集電
体及びこれと電気的に接続されている部分のうち非水電
解液と接触する部分が、弁金属又はその合金で構成され
ていることを特徴とするものである。SUMMARY OF THE INVENTION A non-aqueous electrolyte secondary battery according to the present invention comprises an electrode assembly comprising a negative electrode capable of inserting and extracting lithium and a positive electrode opposed to each other with a separator interposed therebetween. In a non-aqueous electrolyte secondary battery containing a water electrolyte in a container, the non-aqueous electrolyte is obtained by dissolving a lithium salt in a non-aqueous solvent containing vinylene carbonate containing an organic halide as a part thereof. In addition, a portion of the positive electrode current collector and the portion electrically connected to the positive electrode current collector and the non-aqueous electrolyte solution are made of a valve metal or an alloy thereof.
【０００８】[0008]
【発明の実施の形態】本発明に係る非水電解液二次電池
に用いられる非水電解液は、ビニレンカーボネートを含
む非水溶媒にリチウム塩を溶解して調製される。ビニレ
ンカーボネートには通常、クロロエチレンカーボネー
ト、ジクロロエチレンカーボネート、クロロメチルメチ
ルカーボネート、クロロエタノール等の有機ハロゲン化
物が含まれている。最も一般的なビニレンカーボネート
の製法は、前述の如くクロロエチレンカーボネートの脱
塩化水素によるものなので、通常のビニレンカーボネー
トはこの原料由来のクロロエチレンカーボネートを含ん
でいる。ビニレンカーボネート中のこれらの有機ハロゲ
ン化物の含有率は、通常、１ｐｐｍ〜５０（重量）％で
ある。BEST MODE FOR CARRYING OUT THE INVENTION A non-aqueous electrolyte used for a non-aqueous electrolyte secondary battery according to the present invention is prepared by dissolving a lithium salt in a non-aqueous solvent containing vinylene carbonate. Vinylene carbonate usually contains organic halides such as chloroethylene carbonate, dichloroethylene carbonate, chloromethyl methyl carbonate, and chloroethanol. Since the most common method for producing vinylene carbonate is by dehydrochlorination of chloroethylene carbonate as described above, ordinary vinylene carbonate contains chloroethylene carbonate derived from this raw material. The content of these organic halides in vinylene carbonate is usually 1 ppm to 50 (weight)%.
【０００９】非水電解液を構成する非水溶媒は、この有
機ハロゲン化物を含むビニレンカーボネートと他の有機
溶媒とで構成される。非水溶媒に占めるビニレンカーボ
ネートの含有率は０．１〜３０重量％であるのが好まし
い。０．１重量％未満ではその効果が小さく、逆に３０
重量％を超える大量では電解液の低温特性が損なわれる
恐れがある。ビニレンカーボネートの好ましい含有率は
０．１〜２０重量％である。The non-aqueous solvent constituting the non-aqueous electrolyte is composed of vinylene carbonate containing this organic halide and another organic solvent. The content of vinylene carbonate in the non-aqueous solvent is preferably 0.1 to 30% by weight. If the content is less than 0.1% by weight, the effect is small.
If the amount exceeds the weight percentage, the low temperature characteristics of the electrolyte may be impaired. The preferred content of vinylene carbonate is 0.1 to 20% by weight.
【００１０】ビニレンカーボネートと併用する他の有機
溶媒としては、非水電解液の溶媒として知られているエ
チレンカーボネート、プロピレンカーボネート、ブチレ
ンカーボネート等の環状カーボネート、ジメチルカーボ
ネート、ジエチルカーボネート、ジ−ｎ−プロピルカー
ボネート、メチルエチルカーボネート、メチル−ｎ−プ
ロピルカーボネート、エチル−ｎ−プロピルカーボネー
ト等の鎖状カーボネート、γ−ブチロラクトン、γ−バ
レロラクトン等のラクトン、酢酸メチル、プロピオン酸
メチル等の鎖状カルボン酸エステル、テトラヒドロフラ
ン、２−メチルテトラヒドロフラン、テトラヒドロピラ
ン等の環状エーテル、ジメトキシエタン、ジエトキシエ
タン等の鎖状エーテル、スルフォラン、ジエチルスルホ
ン等の含硫黄化合物などが用いられる。これらのなかで
もカーボネートを用いるのが好ましい。通常は環状カー
ボネート及び鎖状カーボネートよりなる群から選ばれた
カーボネートとビニレンカーボネートとの合計量が７０
重量％以上を占める非水溶媒を用いる。この合計量が８
０重量％以上、特に９０重量％以上を占める非水溶媒を
用いるのが好ましい。Other organic solvents used in combination with vinylene carbonate include cyclic carbonates such as ethylene carbonate, propylene carbonate and butylene carbonate, dimethyl carbonate, diethyl carbonate, and di-n-propyl which are known as solvents for non-aqueous electrolytes. Chain carbonates such as carbonate, methyl ethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, lactones such as γ-butyrolactone and γ-valerolactone, chain carboxylic esters such as methyl acetate and methyl propionate , Tetrahydrofuran, cyclic ethers such as 2-methyltetrahydrofuran and tetrahydropyran, chain ethers such as dimethoxyethane and diethoxyethane, and sulfur-containing compounds such as sulfolane and diethylsulfone Are used. Among these, it is preferable to use carbonate. Usually, the total amount of carbonate and vinylene carbonate selected from the group consisting of cyclic carbonate and chain carbonate is 70%
A non-aqueous solvent occupying at least% by weight is used. This total amount is 8
It is preferable to use a non-aqueous solvent that accounts for 0% by weight or more, particularly 90% by weight or more.
【００１１】非水溶媒に溶解させる電解質のリチウム塩
としては、ＬｉＣｌＯ4 、ＬｉＰＦ 6 、ＬｉＢＦ4 、Ｌ
ｉＳｂＦ6 等の無機酸リチウム塩、又はＬｉＣＦ3 ＳＯ
3 、ＬｉＮ（ＣＦ3 ＳＯ2 ）2 、ＬｉＮ（Ｃ2 Ｆ5 ＳＯ
2 ）2 、ＬｉＮ（ＣＦ3 ＳＯ 2 ）（Ｃ4 Ｆ9 ＳＯ2 ）、
ＬｉＣ（ＣＦ3 ＳＯ2 ）3 等の有機酸リチウム塩など、
従来から非水電解液の電解質として用いられているもの
を用いればよい。これらは所望ならばいくつかを併用し
てもよい。非水電解液中のリチウム塩の濃度は通常０．
５〜２モル／リットルである。Lithium salt of electrolyte dissolved in non-aqueous solvent
As LiClOFour, LiPF 6, LiBFFour, L
iSbF6Or lithium salt of an inorganic acid such as LiCFThreeSO
Three, LiN (CFThreeSOTwo)Two, LiN (CTwoFFiveSO
Two)Two, LiN (CFThreeSO Two) (CFourF9SOTwo),
LiC (CFThreeSOTwo)ThreeSuch as lithium salts of organic acids, etc.
Conventionally used as electrolyte for non-aqueous electrolyte
May be used. These can be used in combination if desired.
You may. The concentration of the lithium salt in the non-aqueous electrolyte is usually 0.1.
It is 5 to 2 mol / l.
【００１２】本発明に係る非水電解液二次電池の正極及
び負極としては常用のものを用いることができる。正極
活物質としては、ＬｉＣｏＯ2 、ＬｉＮｉＯ2 、ＬｉＭ
ｎ2Ｏ4 等のリチウムを吸蔵・放出可能なリチウム遷移
金属複合酸化物が用いられる。正極用集電体としては、
アルミニウム、チタン、タンタル等の弁金属又はその合
金が用いられる。なかでもアルミニウム又はその合金を
用いるのが好ましい。ステンレス鋼などのような弁金属
以外の金属を用いると、これと接触する非水電解液中の
有機ハロゲン化物が酸化分解するので好ましくない。As the positive electrode and the negative electrode of the non-aqueous electrolyte secondary battery according to the present invention, conventional ones can be used. LiCoO 2 , LiNiO 2 , LiM
A lithium transition metal composite oxide capable of occluding and releasing lithium such as n 2 O 4 is used. As the current collector for the positive electrode,
Valve metals such as aluminum, titanium and tantalum or alloys thereof are used. Among them, it is preferable to use aluminum or its alloy. It is not preferable to use a metal other than the valve metal such as stainless steel, because the organic halide in the non-aqueous electrolyte that comes in contact with the metal is oxidatively decomposed.
【００１３】負極活物質としては、黒鉛を用いるのが好
ましい。黒鉛としては人造黒鉛及び精製天然黒鉛のいず
れをも用いることができる。また、これらの黒鉛にピッ
チなどで表面処理したものを用いるのも好ましい。黒鉛
のなかでも好ましいのは、学振法によるＸ線回折で求め
た格子面（００２面）のｄ値（層間距離）が０．３３５
〜０．３４ｎｍ、特に０．３３５〜０．３３７ｎｍのも
のである。なお、所望ならば、公知の他の負極活物質を
黒鉛の代りに用いたり、黒鉛と併用することもできる。
このような負極活物質としては、リチウム金属やその合
金、非黒鉛系炭素、酸化錫や酸化珪素等の金属酸化物な
どが挙げられる。負極用集電体としては、銅、ニッケ
ル、ステンレス鋼などが用いられる。なかでも銅を用い
るのが好ましい。It is preferable to use graphite as the negative electrode active material. As the graphite, either artificial graphite or purified natural graphite can be used. It is also preferable to use those obtained by subjecting these graphites to surface treatment with a pitch or the like. Among the graphites, the d value (interlayer distance) of the lattice plane (002 plane) obtained by X-ray diffraction by the Gakushin method is 0.335.
〜0.34 nm, especially 0.335 to 0.337 nm. If desired, another known negative electrode active material can be used instead of graphite, or can be used in combination with graphite.
Examples of such a negative electrode active material include lithium metal and its alloys, non-graphite carbon, and metal oxides such as tin oxide and silicon oxide. As the current collector for the negative electrode, copper, nickel, stainless steel, or the like is used. Among them, it is preferable to use copper.
【００１４】正極と負極とを隔てるセパレーターとして
は、ポリエチレン、ポリプロピレン等のポリオレフィン
の多孔性フイルム又は不織布などが用いられる。電池の
構造は、シート状の電極とセパレーターとを渦巻き状に
巻いたシリンダータイプ、薄片状の電極とセパレーター
とを積層したコインタイプなど、従来公知の任意の構造
とすることができる。As a separator for separating the positive electrode and the negative electrode, a porous film of a polyolefin such as polyethylene or polypropylene or a non-woven fabric is used. The structure of the battery can be any conventionally known structure such as a cylinder type in which a sheet-like electrode and a separator are spirally wound, and a coin type in which a flaky electrode and a separator are laminated.
【００１５】上記の正極、負極及びセパレーターから成
る電極組立体を収容する容器、すなわち電池の缶体とし
ては、常用のステンレス鋼製のものを用いることができ
る。しかし本発明においては、この缶体及び缶体内に収
容されるリード線や安全弁などのうち正極と電気的に接
続されていて、かつ非水電解液と接触する部分は、弁金
属又はその合金で構成する。従って常用のステンレス鋼
製の缶体を用いる場合には、その正極側の内面を弁金属
で被覆する。このようにすることにより、これと接触す
る非水電解液中のビニレンカーボネートに同伴している
有機ハロゲン化物の酸化分解を防止することができる。
また、アルミニウムやアルミニウム合金等の弁金属で缶
体を構成してもよい。As a container for accommodating the above-mentioned electrode assembly comprising the positive electrode, the negative electrode and the separator, that is, a battery can, a conventional stainless steel can be used. However, in the present invention, a portion of the can body and the lead wire and the safety valve housed in the can body that are electrically connected to the positive electrode and that come into contact with the nonaqueous electrolyte are made of valve metal or an alloy thereof. Constitute. Therefore, when a normal stainless steel can is used, its inner surface on the positive electrode side is coated with a valve metal. By doing so, it is possible to prevent the oxidative decomposition of the organic halide accompanying the vinylene carbonate in the non-aqueous electrolyte that comes into contact therewith.
Moreover, you may comprise a can body with valve metals, such as aluminum and an aluminum alloy.
【００１６】本発明に係る非水電解液二次電池は上記し
たような構成を有しているので、非水電解液の分解が抑
制され、長期間に亘り安定した性能を発揮することがで
きる。これは非水電解液中のビニレンカーボネートが負
極上に安定な保護皮膜を形成して、負極上での非水電解
液の分解を抑制することと、正極集電体やこれと電気的
に接続されていてかつ非水電解液と接触する部分が弁金
属で構成されていてその表面が酸化皮膜で覆われている
ので、これらと接触する非水電解液中の有機ハロゲン化
物の酸化分解が抑制されることによるものと考えられ
る。Since the non-aqueous electrolyte secondary battery according to the present invention has the above-described structure, decomposition of the non-aqueous electrolyte is suppressed, and stable performance can be exhibited over a long period of time. . This is because vinylene carbonate in the non-aqueous electrolyte forms a stable protective film on the negative electrode to suppress the decomposition of the non-aqueous electrolyte on the negative electrode, and to connect the positive electrode current collector and And the part that comes in contact with the non-aqueous electrolyte is made of valve metal, and its surface is covered with an oxide film, which suppresses the oxidative decomposition of organic halides in the non-aqueous electrolyte that comes into contact with them. It is thought that it is due to being done.
【００１７】[0017]
【実施例】以下に実施例により本発明を更に具体的に説
明するが、本発明はこれらの実施例に限定されるもので
はない。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００１８】ビニレンカーボネートの調製；ジムロート
及び滴下ロートを備えた２００ｍｌのガラス製四つ口フ
ラスコに、クロロエチレンカーボネート５２ｇ（４２４
ｍｍｏｌ）及びエチルエーテル５２ｇを仕込んだ。窒素
雰囲気下でこの混合液を攪拌しながら、滴下ロートから
トリエチルアミン４９ｇ（４８４ｍｍｏｌ）を約３０分
間かけて滴下した。次いで液温を３０℃として、反応液
をガスクロマトグラフィーで分析することにより反応の
進行を追跡しながら、３５時間反応させた。得られたビ
ニレンカーボネートには、３３重量％のクロロエチレン
カーボネートが含まれていた。Preparation of vinylene carbonate: In a 200 ml glass four-necked flask equipped with a Dim funnel and a dropping funnel, 52 g (424) of chloroethylene carbonate was added.
mmol) and 52 g of ethyl ether. While stirring this mixture under a nitrogen atmosphere, 49 g (484 mmol) of triethylamine was dropped from the dropping funnel over about 30 minutes. Next, the reaction temperature was set at 30 ° C., and the reaction was performed for 35 hours while analyzing the reaction liquid by gas chromatography to monitor the progress of the reaction. The resulting vinylene carbonate contained 33% by weight of chloroethylene carbonate.
【００１９】正極の調製；ＬｉＣｏＯ2 ８５重量部にカ
ーボンブラック６重量部及びポリフッ化ビニリデン９重
量部を配合してよく混合した。これにＮ−メチル−２−
ピロリドンを加えてスラリーとし、これを厚さ２０μｍ
のアルミニウム箔上に均一に塗布した。乾燥後、直径１
２．５ｍｍの円板状に打抜いて正極とした。Preparation of positive electrode: 85 parts by weight of LiCoO 2 were mixed with 6 parts by weight of carbon black and 9 parts by weight of polyvinylidene fluoride and mixed well. N-methyl-2-
Pyrrolidone was added to form a slurry, which was 20 μm thick.
Was uniformly applied on the aluminum foil. After drying, diameter 1
A 2.5 mm disk was punched out to obtain a positive electrode.
【００２０】負極の調製；Ｘ線回折における格子面（０
０２面）のｄ値が０．３３６ｎｍである人造黒鉛粉末Ｋ
Ｓ−４４（ティムカル社製品）９４重量部に、ポリフッ
化ビニリデン６重量部を配合してよく混合した。これに
Ｎ−メチル−２−ピロリドンを加えてスラリーとし、こ
れを厚さ１８μｍの銅箔上に均一に塗布した。乾燥後、
直径１２．５ｍｍの円板状に打抜いて負極とした。Preparation of negative electrode; lattice plane (0
02) artificial graphite powder K having a d value of 0.336 nm
94 parts by weight of S-44 (manufactured by Timcal) were mixed with 6 parts by weight of polyvinylidene fluoride and mixed well. N-methyl-2-pyrrolidone was added to this to form a slurry, which was uniformly applied on a copper foil having a thickness of 18 μm. After drying,
A negative electrode was punched out into a disk having a diameter of 12.5 mm.
【００２１】非水電解液の調製；六フッ化リン酸リチウ
ム（ＬｉＰＦ6 ）を乾燥アルゴン雰囲気中でよく乾燥し
た。プロピレンカーボネートと上記で調製したビニレン
カーボネートとの９：１（重量比）の混合溶媒中に、こ
の六フッ化リン酸リチウムを１モル／リットルの濃度と
なるように溶解して非水電解液とした。Preparation of non-aqueous electrolyte: Lithium hexafluorophosphate (LiPF 6 ) was thoroughly dried in a dry argon atmosphere. This lithium hexafluorophosphate was dissolved in a 9: 1 (weight ratio) mixed solvent of propylene carbonate and the above-prepared vinylene carbonate so as to have a concentration of 1 mol / liter, and the solution was mixed with a non-aqueous electrolyte. did.
【００２２】電池の製作；ステンレス鋼製の正極缶に正
極を収容し、その上に非水電解液を含浸させたセパレー
ター（ポリプロピレンの微孔フイルム）及び負極を順次
載置した。この正極缶とステンレス鋼製の封孔板とを、
絶縁性のガスケットを介してかしめて密封し、コイン型
電池を製作した。なお、実施例では正極を収容する前に
ステンレス鋼製の正極缶の内面をアルミニウム箔で被覆
して、非水電解液が正極缶に接触しないようにした。Production of Battery: The positive electrode was accommodated in a stainless steel positive electrode can, on which a separator (polypropylene microporous film) impregnated with a non-aqueous electrolyte and a negative electrode were sequentially placed. This positive electrode can and a stainless steel sealing plate
It was caulked and sealed via an insulating gasket to produce a coin-type battery. In the examples, the inner surface of the stainless steel positive electrode can was covered with aluminum foil before accommodating the positive electrode so that the nonaqueous electrolyte did not come into contact with the positive electrode can.
【００２３】充放電試験；上記で製作した電池を用い
て、２５℃、０．５ｍＡの定電流で充電終止電圧４．２
Ｖ、放電終止電圧２．５Ｖで充放電試験を行った。結果
を図−１に示す。ステンレス鋼製の正極缶の内面をアル
ミニウム箔で被覆して非水電解液が正極缶に接触しない
ようにした実施例の電池では、安定して充放電を反復す
ることができた。これに対し、ステンレス鋼製の正極缶
に非水電解液が接触する比較例の電池では、２サイクル
目までしか充放電できなかった。Charge / discharge test: Using the battery prepared above, a charge end voltage of 4.2 at a constant current of 0.5 mA at 25 ° C.
A charge / discharge test was performed at V and a discharge end voltage of 2.5 V. The results are shown in FIG. In the battery of the example in which the inner surface of the stainless steel positive electrode can was covered with an aluminum foil so that the nonaqueous electrolyte did not come into contact with the positive electrode can, charging and discharging could be stably repeated. On the other hand, in the battery of the comparative example in which the nonaqueous electrolyte contacted the stainless steel positive electrode can, charging and discharging could only be performed up to the second cycle.
【図１】図−１は正極集電体としてアルミニウムを用
い、かつステンレス鋼製の正極缶の内面をアルミニウム
箔で被覆した本発明に係る電池と、正極缶の内面をアル
ミニウム箔で被覆しなかった以外は、全く同様にして製
作した電池との充放電試験の結果を示すグラフである。FIG. 1 shows a battery according to the present invention in which aluminum is used as a positive electrode current collector and the inner surface of a stainless steel positive electrode can is coated with aluminum foil, and the inner surface of the positive electrode can is not coated with aluminum foil. 7 is a graph showing the results of a charge / discharge test with a battery manufactured in exactly the same manner as above.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H003 BB01 BB02 BB05 BB12 BD03 BD04 5H014 AA04 AA06 EE01 EE05 EE08 EE10 HH01 HH08 5H017 AA03 AS01 AS06 AS10 EE01 EE08 HH05 5H029 AJ05 AK03 AL07 AM03 AM07 BJ03 BJ16 DJ02 DJ05 DJ07 EJ01 HJ01 HJ10 HJ12 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) HJ12
Claims (9)
負極及び正極をセパレーターを介して対向させてなる電
極組立体、並びに非水電解液を容器に収容してなる非水
電解液二次電池において、非水電解液が有機ハロゲン化
物を含むビニレンカーボネートをその一部とする非水溶
媒にリチウム塩を溶解して成るものであり、かつ正極集
電体及びこれと電気的に接続されている部分のうち非水
電解液と接触する部分が、弁金属又はその合金で構成さ
れていることを特徴とする二次電池。1. An electrode assembly comprising a negative electrode and a positive electrode capable of inserting and extracting lithium facing each other via a separator, and a non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte contained in a container. Wherein the non-aqueous electrolyte is obtained by dissolving a lithium salt in a non-aqueous solvent containing vinylene carbonate containing an organic halide as a part thereof, and is electrically connected to the positive electrode current collector A secondary battery, wherein a portion of the portion that contacts the nonaqueous electrolyte is made of a valve metal or an alloy thereof.
有率が０．１〜３０重量％であることを特徴とする請求
項１に記載の二次電池。2. The secondary battery according to claim 1, wherein the content of vinylene carbonate in the non-aqueous solvent is 0.1 to 30% by weight.
キレンカーボネートを含んでおり、かつその含有率が１
ｐｐｍ以上で５０重量％以下であることを特徴とする請
求項１又は２に記載の二次電池。3. The vinylene carbonate contains a halogenated alkylene carbonate, and the content thereof is 1
The secondary battery according to claim 1, wherein the content of the secondary battery is not less than 50 ppm by weight in the range of not less than ppm.
キレンカーボネートとして少くともクロロエチレンカー
ボネートを含むことを特徴とする請求項１ないし３のい
ずれかに記載の二次電池。4. The secondary battery according to claim 1, wherein the vinylene carbonate contains at least chloroethylene carbonate as a halogenated alkylene carbonate.
ジアルキルカーボネートよりなる群から選ばれた少くと
も１種のカーボネートを含有しており、かつこのカーボ
ネートと有機ハロゲン化物を含むビニレンカーボネート
の合計量が、非水溶媒の７０重量％以上を占めることを
特徴とする請求項１ないし４のいずれかに記載の二次電
池。5. The non-aqueous solvent contains at least one carbonate selected from the group consisting of an alkylene carbonate and a dialkyl carbonate, and the total amount of the carbonate and vinylene carbonate containing an organic halide is non-aqueous. The secondary battery according to any one of claims 1 to 4, wherein the secondary battery accounts for 70% by weight or more of the water solvent.
アルミニウム合金であることを特徴とする請求項１ない
し５のいずれかに記載の二次電池。6. The secondary battery according to claim 1, wherein the valve metal or its alloy is aluminum or an aluminum alloy.
可能な炭素材料を活物質とするものであることを特徴と
する請求項１ないし６のいずれかに記載の二次電池。7. The secondary battery according to claim 1, wherein the negative electrode uses a carbon material capable of occluding and releasing lithium as an active material.
可能なリチウム遷移金属複合酸化物を活物質とするもの
であることを特徴とする請求項１ないし７のいずれかに
記載の二次電池。8. The secondary battery according to claim 1, wherein the positive electrode uses a lithium transition metal composite oxide capable of inserting and extracting lithium as an active material. .
Ｆ6 、ＬｉＢＦ4 及びＬｉＳｂＦ6 よりなる群から選ば
れる無機酸リチウム塩、又はＬｉＣＦ3 ＳＯ3 、ＬｉＮ
（ＣＦ3 ＳＯ2 ）2 、ＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）2 、Ｌ
ｉＮ（ＣＦ3 ＳＯ 2 ）（Ｃ4 Ｆ9 ＳＯ2 ）、及びＬｉＣ
（ＣＦ3 ＳＯ2 ）3 よりなる群から選ばれる有機酸リチ
ウム塩であることを特徴とする請求項１ないし８のいず
れかに記載の二次電池。9. The lithium salt is LiClO.Four, LiP
F6, LiBFFourAnd LiSbF6Selected from the group consisting of
Inorganic acid lithium salt, or LiCFThreeSOThree, LiN
(CFThreeSOTwo)Two, LiN (CTwoFFiveSOTwo)Two, L
iN (CFThreeSO Two) (CFourF9SOTwo) And LiC
(CFThreeSOTwo)ThreeOrganic acid selected from the group consisting of
A salt according to any one of claims 1 to 8, wherein the salt is
The secondary battery according to any one of the claims.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00869599A JP4568920B2 (en) | 1999-01-18 | 1999-01-18 | Non-aqueous electrolyte secondary battery and non-aqueous electrolyte used therefor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00869599A JP4568920B2 (en) | 1999-01-18 | 1999-01-18 | Non-aqueous electrolyte secondary battery and non-aqueous electrolyte used therefor |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000208169A true JP2000208169A (en) | 2000-07-28 |
| JP2000208169A5 JP2000208169A5 (en) | 2005-05-19 |
| JP4568920B2 JP4568920B2 (en) | 2010-10-27 |
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|---|---|---|---|
| JP00869599A Expired - Fee Related JP4568920B2 (en) | 1999-01-18 | 1999-01-18 | Non-aqueous electrolyte secondary battery and non-aqueous electrolyte used therefor |
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| Country | Link |
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| WO2001080345A1 (en) * | 2000-04-17 | 2001-10-25 | Ube Industries, Ltd. | Non-aqueous electrolyte and lithium secondary battery |
| US7419747B2 (en) | 2002-06-11 | 2008-09-02 | Nec Corporation | Electrolyte for secondary battery and secondary battery using same |
| JP2009187698A (en) * | 2008-02-04 | 2009-08-20 | Gs Yuasa Corporation | Nonaqueous electrolyte battery, and its manufacturing method |
| EP2109177A1 (en) | 2008-04-07 | 2009-10-14 | NEC TOKIN Corporation | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the same |
| JP2010205742A (en) * | 2002-07-15 | 2010-09-16 | Ube Ind Ltd | Nonaqueous electrolyte and lithium battery using the same |
| CN113903997A (en) * | 2016-07-22 | 2022-01-07 | 大金工业株式会社 | Electrolyte solution, electrochemical device, secondary battery, and module |
| US11322780B2 (en) | 2016-07-22 | 2022-05-03 | Daikin Industries, Ltd. | Electrolyte solution, electrochemical device, secondary battery, and module |
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|---|---|
| JP4568920B2 (en) | 2010-10-27 |
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