JPH0541251A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH0541251A JPH0541251A JP3215900A JP21590091A JPH0541251A JP H0541251 A JPH0541251 A JP H0541251A JP 3215900 A JP3215900 A JP 3215900A JP 21590091 A JP21590091 A JP 21590091A JP H0541251 A JPH0541251 A JP H0541251A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- battery
- positive electrode
- lithium
- electrolyte
- 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]
【産業上の利用分野】本発明は、電子機器の駆動用電源
もしくはメモリ保持電源としての高エネルギー密度でか
つ高い安全性を有する非水電解質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 having high energy density and high safety as a power source for driving electronic equipment or a memory holding power source.
【０００２】[0002]
【従来の技術】電子機器の急激なる小形軽量化に伴い、
その電源である電池に対して小形で軽量かつ高エネルギ
ー密度で、更に繰り返し充放電が可能な二次電池の開発
への要求が高まっている。これら要求を満たす二次電池
として、リチウム二次電池が最も有望である。なぜな
ら、リチウム二次電池は、負極であるリチウムの電位が
極めて卑であるため、電池の電圧が高く、かつリチウム
の体積，重量エネルギー密度が高いため、高エネルギー
密度の二次電池を提供できるという利点を有しているか
らである。2. Description of the Related Art With the rapid reduction in size and weight of electronic devices,
There is an increasing demand for the development of secondary batteries that are small, lightweight, have high energy density, and can be repeatedly charged and discharged with respect to the battery that is the power source. A lithium secondary battery is most promising as a secondary battery that meets these requirements. This is because the lithium secondary battery has a high negative voltage, and thus has a high battery voltage, and has a high lithium volume and weight energy density. Therefore, a high energy density secondary battery can be provided. This is because it has advantages.
【０００３】リチウム二次電池の正極活物質は、研究の
結果より各種の材料が提案されている。その結果、たと
えばＴｉＳ2 ，ＭｎＯ2 ，Ｖ2 Ｏ5 ，ＬｉＣｏＯ2 ，Ｌ
ｉＭｎ2 Ｏ4 等の無機化合物系、あるいはポリアニリ
ン，ポリピロール等の有機化合物系活物質が優れた充放
電可逆性を有するものとして知られている。As a positive electrode active material for a lithium secondary battery, various materials have been proposed as a result of research. As a result, for example, TiS 2 , MnO 2 , V 2 O 5 , LiCoO 2 , L
Inorganic compound-based active materials such as iMn 2 O 4 or organic compound-based active materials such as polyaniline and polypyrrole are known to have excellent charge-discharge reversibility.
【０００４】それにも関わらず、現在リチウム二次電池
が本格的に実用化されない大きな理由として、リチウム
の樹枝状結晶の成長による内部短絡が挙げられる。短絡
時のジュール熱等により短絡部の温度がリチウムの融点
まで達すると、溶融リチウムと電池構成品間にて激しい
反応が起こり、電池温度が急上昇するとともに電池内圧
力も急激に上昇し、最終的には電池の破裂、最悪時には
電解液中の有機溶媒が燃えるなどして発火および爆発な
どの極めて危険な状態となる。そこで近年、負極に金属
リチウムを使わずに、リチウムの吸蔵放出が可能なＬｉ
−Ａｌ合金やカーボンを負極材料として用いた電池がさ
かんに研究されるようになった。Nonetheless, a major reason why lithium secondary batteries are not put into practical use at present is the internal short circuit due to the growth of lithium dendrites. When the temperature of the short circuit reaches the melting point of lithium due to Joule heat during a short circuit, a violent reaction occurs between the molten lithium and the battery components, causing a rapid increase in battery temperature and a rapid increase in battery internal pressure. If the battery is ruptured, or in the worst case, the organic solvent in the electrolyte is burned, it becomes extremely dangerous such as ignition or explosion. Therefore, in recent years, Li capable of inserting and extracting lithium without using metallic lithium for the negative electrode
-A battery using an Al alloy or carbon as a negative electrode material has been actively studied.
【０００５】[0005]
【発明が解決しようとする課題】しかし、これら負極材
料を用いた電池も複数セルを直列に接続し端子間に電圧
を印加して一括充電する場合に、各セル間の容量バラン
ス差等により一部セルが過充電状態となったときには、
正極活物質中のリチウムや電解質中のリチウムが、負極
容量を越えて負極上に電析するため、樹枝状結晶が成長
した電池が生じ上記に述べた危険が生じるという問題が
ある。However, even in the case of batteries using these negative electrode materials, when a plurality of cells are connected in series and a voltage is applied between the terminals to carry out batch charging, there is a difference in capacity balance between the cells. When the cell is overcharged,
Since lithium in the positive electrode active material and lithium in the electrolyte are deposited on the negative electrode beyond the negative electrode capacity, there is a problem that a battery in which dendrites grow and the above-mentioned danger occurs.
【０００６】[0006]
【課題を解決するための手段】本発明は、リチウムイオ
ンを吸蔵放出する物質からなる負極と、正極と、リチウ
ムイオンを含むイオン導電体を電解質とする二次電池に
おいて、負極の吸蔵可能なリチウムイオン量を、正極お
よび電解質から放出可能なリチウムイオン量以上とする
ことにより上記問題を解決した非水電解質二次電池を提
供するものである。DISCLOSURE OF THE INVENTION The present invention relates to a negative electrode composed of a substance capable of occluding and releasing lithium ions, a positive electrode, and a secondary battery having an ionic conductor containing lithium ions as an electrolyte. The present invention provides a non-aqueous electrolyte secondary battery that solves the above problems by making the amount of ions equal to or larger than the amount of lithium ions that can be released from the positive electrode and the electrolyte.
【０００７】[0007]
【作用】リチウムの吸蔵放出が可能なカーボンの充放電
機構を簡単に説明する。[Function] A carbon charging / discharging mechanism capable of inserting and extracting lithium will be briefly described.
【０００８】充電は、カーボン中のグラファイト層間へ
リチウムイオンがドープされることにより行われ、放電
はリチウムイオンのグラファイト層間からの脱ドープに
より起こる。カーボンが吸蔵可能なリチウムイオン量
は、理論的には炭素原子６個に対してリチウムイオン１
個であるといわれ、換言すればカーボン１ｇで約３７２
ｍＡｈのリチウムイオンが吸蔵できることになる。Charging is performed by doping lithium ions into graphite layers in carbon, and discharging is performed by dedoping lithium ions from the graphite layers. The theoretical amount of lithium ions that can be occluded by carbon is 1 lithium ion per 6 carbon atoms.
It is said to be individual, in other words, about 372 with 1 g of carbon.
The lithium ion of mAh can be stored.
【０００９】しかし、カーボンの吸蔵可能なリチウムイ
オン量を越えてリチウムイオンを吸蔵させようとする
と、吸蔵しきれないリチウムイオンは金属リチウムとし
てカーボン上に電析してしまう。However, if an attempt is made to occlude lithium ions in excess of the storable amount of lithium ions of carbon, the lithium ions that cannot be occluded will be electrodeposited on the carbon as metallic lithium.
【００１０】しかし、本発明の構成による電池において
は、負極の吸蔵可能なリチウムイオン量を、正極および
電解質から放出可能なリチウムイオン量以上としている
ためたとえ過充電状態となってもリチウムイオンは全て
負極に吸蔵されるため、負極上に金属リチウムが析出す
るという危険な状態が生ずることがない、高い安全性を
有する電池を提供することができる。However, in the battery having the structure of the present invention, the amount of lithium ions that can be occluded in the negative electrode is set to be equal to or more than the amount of lithium ions that can be released from the positive electrode and the electrolyte. Since it is occluded in the negative electrode, a dangerous state in which metallic lithium is deposited on the negative electrode does not occur, and a battery having high safety can be provided.
【００１１】[0011]
【実施例】以下に、好適な実施例を用いて本発明を説明
する。The present invention will be described below with reference to preferred embodiments.
【００１２】［実施例１］二酸化マンガンと炭酸リチウ
ムとをＬｉ／Ｍｎモル比で１／２にて混合・粉砕した
後、１トン／ｃｍ2 で直径２０ｍｍ、高さ２０ｍｍのペ
レットに成型した。Example 1 Manganese dioxide and lithium carbonate were mixed and pulverized at a Li / Mn molar ratio of 1/2, and then pulverized into pellets having a diameter of 20 mm and a height of 20 mm at 1 ton / cm 2 .
【００１３】この、ペレットを空気中において温度６５
０℃で６時間加熱焼成した。反応生成物は、暗青色粉末
でありＸ線回折パターンを調べたところそ、ＡＳＴＭ
No.35-782 のＬｉＭｎ2 Ｏ4 のデータと一致した。ま
た、３３°付近にＭｎ2 Ｏ3 （ＡＳＴＭNo.31-286 ）の
ピークが弱く確認された。The pellets are heated in air at a temperature of 65.
It was heated and calcined at 0 ° C. for 6 hours. The reaction product was a dark blue powder, and its X-ray diffraction pattern was examined.
It was in agreement with the data of LiMn 2 O 4 of No. 35-782. A weak peak of Mn 2 O 3 (ASTM No. 31-286) was confirmed around 33 °.
【００１４】このＬｉＭｎ2 Ｏ4 、１００重量部に対し
てアセチレンブラック（導電助剤）を５重量部、および
ポリ４フッ化エチレン（結着材）を２重量部添加してよ
く混練した後、温度２００℃で３時間真空乾燥して正極
合剤を調整した。そして、その正極合剤を１７３ｍｇず
つ秤量して３２５メッシュのＳＵＳ３１６製金網に包み
込んで、２トン／ｃｍ2 で加圧成形して正極とした。正
極の寸法は、直径１６．０ｍｍ厚み０．８ｍｍ程度で、
充電終止電位４．５Ｖ(Li/Li+ ) までの充電容量は約２
３ｍＡｈで、理論容量は約２４ｍＡｈである。After adding 5 parts by weight of acetylene black (conductive aid) and 2 parts by weight of polytetrafluoroethylene (binder) to 100 parts by weight of this LiMn 2 O 4 , and kneading well, The positive electrode mixture was prepared by vacuum drying at a temperature of 200 ° C. for 3 hours. Then, the positive electrode mixture was weighed in an amount of 173 mg each, wrapped in a 325 mesh SUS316 wire mesh, and pressure-molded at 2 ton / cm 2 to obtain a positive electrode. The size of the positive electrode is 16.0 mm in diameter and 0.8 mm in thickness,
The charge capacity up to a charge end potential of 4.5 V (Li / Li + ) is about 2
At 3 mAh, the theoretical capacity is about 24 mAh.
【００１５】負極には、Ｎｉ板上に生成析出させた熱分
解カーボン９０ｍｇを用いた。負極の寸法は、直径１
６．０ｍｍ厚み０．５ｍｍ程度である。リチウムの電析
に至る（０Ｖ(Li/Li+ ) ）までの充電容量は約２７ｍＡ
ｈで、理論容量は３３．５ｍＡｈである。For the negative electrode, 90 mg of pyrolytic carbon produced and deposited on a Ni plate was used. Negative electrode size is diameter 1
The thickness is about 6.0 mm and about 0.5 mm. The charging capacity up to the electrodeposition of lithium (0 V (Li / Li + )) is about 27 mA.
At h, the theoretical capacity is 33.5 mAh.
【００１６】セパレータにはポリプロピレンのマイクロ
ポーラスセパレータ（セルガードK274）及びポリプロピ
レンの不織布を重ねて用いて、外径20.0mm 高さ2.0mm
の電池を作成した。A polypropylene microporous separator (Celgard K274) and a polypropylene non-woven fabric are used as a separator, and the outer diameter is 20.0 mm and the height is 2.0 mm.
I made a battery.
【００１７】電解液には、スルホラン（Ｓ）とジメチル
カーボネイト（ＤＭＣ）とを体積比１：１で混合してな
る有機溶媒に電解質として過塩素酸リチウムを１モル／
リットル溶解したものを用いた。In the electrolytic solution, lithium perchlorate (1 mol / mol) was used as an electrolyte in an organic solvent prepared by mixing sulfolane (S) and dimethyl carbonate (DMC) at a volume ratio of 1: 1.
What was melt | dissolved in 1 liter was used.
【００１８】電池への注液量は、１００μｌ／セルとし
た。すなわち、電解質中のリチウムイオン量は１×１０
-4モルとなり、約２．７ｍＡｈの容量に相当する。The amount of liquid injected into the battery was 100 μl / cell. That is, the amount of lithium ions in the electrolyte is 1 × 10
-4 mol, which corresponds to a capacity of about 2.7 mAh.
【００１９】この本発明電池において、正極中から放出
可能なイオン量は２３ｍＡｈで電解質中から放出可能な
イオン量が２．７ｍＡｈであり、電池内の総イオン量は
２５．７ｍＡｈとなる。また過充電により、正極の理論
容量に相当する２４ｍＡｈのイオンが正極から放出され
たとした場合は電池内の総イオン量は２６．７ｍＡｈと
なる。In the battery of the present invention, the amount of ions that can be released from the positive electrode is 23 mAh, the amount of ions that can be released from the electrolyte is 2.7 mAh, and the total amount of ions in the battery is 25.7 mAh. If 24 mAh of ions corresponding to the theoretical capacity of the positive electrode are released from the positive electrode due to overcharge, the total amount of ions in the battery is 26.7 mAh.
【００２０】負極の充電可能な容量は、２７ｍＡｈであ
り電池内の総イオン量に対してそれぞれ約１０５％，１
０１％に当たり、電池を過充電したとしても負極上に金
属リチウムが析出することはない。The chargeable capacity of the negative electrode is 27 mAh, which is about 105% and 1% of the total amount of ions in the battery, respectively.
At 01%, metallic lithium does not deposit on the negative electrode even if the battery is overcharged.
【００２１】図１は、電池の縦断面図である。この図に
おいて１は、耐有機電解液性のステンレス鋼板をプレス
によって打ち抜き加工した正極端子を兼ねるケース、２
は同種の材料を打ち抜き加工した負極端子を兼ねる封口
板であり、その内壁には負極３が当接されている。５は
有機電解液を含浸したポリプロピレンからなるセパレー
ター、６は正極であり正極端子を兼ねるケース１の開口
端部を内方へかしめ、ガスケット４を介して負極端子を
兼ねる封口板２の内周を締め付けることにより密閉封口
している。この本発明の電池を電池（Ａ）とする。FIG. 1 is a vertical sectional view of a battery. In this figure, 1 is a case that also functions as a positive electrode terminal, which is formed by punching out a stainless steel plate having organic electrolyte resistance by a press, and 2
Is a sealing plate that also functions as a negative electrode terminal made by punching the same kind of material, and the negative electrode 3 is in contact with the inner wall thereof. 5 is a separator made of polypropylene impregnated with an organic electrolytic solution, 6 is a positive electrode, and the opening end of the case 1 also serving as a positive electrode terminal is caulked inward, and the inner periphery of the sealing plate 2 also serving as a negative electrode terminal is inserted through a gasket 4. It is closed and sealed by tightening. This battery of the present invention is referred to as battery (A).
【００２２】［比較例１］電池の負極活物質量を減じ、
負極の充電可能な容量が正極の充電終止電位４．５Ｖ(L
i/Li+ ) までの充電容量（２３ｍＡｈ）よりも若干大き
な２４ｍＡｈとなるようにした負極を用いることを除い
ては、電池構成が実施例１と同様な電池を作成した。こ
の正極制限の比較電池を電池（ア）とする。[Comparative Example 1] By reducing the amount of the negative electrode active material of the battery,
The chargeable capacity of the negative electrode is 4.5 V (L
A battery having the same battery configuration as in Example 1 was prepared except that the negative electrode was set to 24 mAh, which was slightly larger than the charging capacity (23 mAh) up to i / Li + ). This comparative battery with positive electrode restriction is referred to as battery (a).
【００２３】［比較例１］電池の負極活物質量をさらに
減じ、負極の充電可能な容量が正極の充電終止電位４．
５Ｖ(Li/Li+ ) までの充電容量（２３ｍＡｈ）よりも若
干少ない２２ｍＡｈとなるようにした負極を用いること
を除いては、電池構成が実施例１と同様な電池を作成し
た。この負極制限の比較電池を電池（イ）とする。。Comparative Example 1 The amount of the negative electrode active material of the battery was further reduced so that the chargeable capacity of the negative electrode was 4.
A battery having the same battery configuration as in Example 1 was prepared except that the negative electrode was set to 22 mAh, which was slightly smaller than the charge capacity (23 mAh) up to 5 V (Li / Li + ). This negative electrode limited comparative battery is referred to as battery (a). ..
【００２４】上記各種電池について、４．５Ｖ〜３．０
Ｖの間で１．８ｍＡの定電流で充放電を繰り返し、各サ
イクルにおける放電容量を測定した。その結果を図２に
示す。With respect to the above various batteries, 4.5 V to 3.0
Charge and discharge were repeated at a constant current of 1.8 mA between V and the discharge capacity in each cycle was measured. The result is shown in FIG.
【００２５】電池（Ａ），（ア），（イ）ともに良好な
充放電挙動を示し、１０サイクル経過後４．５Ｖまで充
電し電池を分解してたところ、本発明の電池（Ａ）およ
び正極制限の電池（ア）ともに金属リチウムの析出は認
められなかったが、負極制限の電池（イ）では、負極上
に金属リチウムの電析が認められた。これは、比較電池
（イ）において、負極の吸蔵可能な容量を越えて充電を
行ったためと思われる。The batteries (A), (A), and (B) all showed good charge and discharge behavior, and after 10 cycles, they were charged to 4.5 V and disassembled, and the batteries (A) and No deposition of metallic lithium was observed in the positive electrode limited battery (a), but metallic lithium deposition was observed on the negative electrode in the negative electrode limited battery (a). It is considered that this is because the comparative battery (a) was charged so as to exceed the storable capacity of the negative electrode.
【００２６】次に、電池が過充電された場合を想定し、
電池電圧４．５Ｖを越えてさらに１．８ｍＡの定電流で
強制的に１時間充電した。その後、電池を分解したとこ
ろ本発明電池（Ａ）では金属リチウムの析出が認められ
なかったが、正極制限の比較電池（ア）および負極制限
の比較電池（イ）では、金属リチウムが析出しているの
が認められた。この金属リチウムは、比較電池（ア）で
は電解液中のリチウムイオンが電析したものと思われ、
比較電池（イ）では、正極中および電解液中のリチウム
イオンが電析したものと思われる。Next, assuming that the battery is overcharged,
It was forcibly charged for 1 hour with a constant current of 1.8 mA exceeding the battery voltage of 4.5 V. After that, when the battery was disassembled, deposition of metallic lithium was not observed in the battery (A) of the present invention, but metallic lithium was deposited in the comparative battery (a) limited to the positive electrode and the comparative battery (a) limited to the negative electrode. Was found to exist. This metallic lithium is considered to be the electrodeposition of lithium ions in the electrolytic solution in the comparative battery (a),
In the comparative battery (a), it is considered that lithium ions in the positive electrode and the electrolytic solution were electrodeposited.
【００２７】今回の実験では、比較電池において金属リ
チウムの析出による電池内ショートや発火爆発などは認
められなかったものの、より対向面積の大きな電池もし
くはより大型の電池となれば危険性が大きくなる。In this experiment, although no battery short circuit or ignition explosion due to the deposition of metallic lithium was observed in the comparative battery, the risk becomes larger if the battery has a larger facing area or a larger battery.
【００２８】なお、上記実施例では負極活物質として熱
分解カーボンを用いたが、負極活物質は基本的に限定さ
れるず、リチウム合金やカーボン（たとえばピッチ系カ
ーボン，グラファイト，コークス）などのリチウムイオ
ンを吸蔵放出する物質を用いることができるが、安全性
および充放電可逆性の点でリチウム合金よりもカーボン
を用いた方が電池寿命が長く、より安全な電池を提供す
ることができると考えられる。Although pyrolytic carbon was used as the negative electrode active material in the above-mentioned examples, the negative electrode active material is not basically limited, and lithium such as lithium alloy or carbon (for example, pitch-based carbon, graphite, coke) is used. Although it is possible to use a substance that occludes and releases ions, it is thought that carbon is more durable than lithium alloy in terms of safety and charge-discharge reversibility, and a safer battery can be provided. Be done.
【００２９】正極活物質についても、特に限定されず従
来のリチウム二次電池で用いられている各種の材料を使
用することができる。たとえばＴｉＳ2 ，ＭｎＯ2 ，Ｖ
2 Ｏ5 ，ＬｉＣｏＯ2 ，ＬｉＭｎ2 Ｏ4 等の無機化合物
系、あるいはポリアニリン，ポリピロール等の有機化合
物系活物質を用いることができるが、エネルギー密度の
点からＬｉＣｏＯ2 およびＬｉＭｎ2 Ｏ4を用いるのが
好ましい。The positive electrode active material is not particularly limited, and various materials used in conventional lithium secondary batteries can be used. For example, TiS 2 , MnO 2 , V
An inorganic compound-based active material such as 2 O 5 , LiCoO 2 , or LiMn 2 O 4 or an organic compound-based active material such as polyaniline or polypyrrole can be used, but LiCoO 2 and LiMn 2 O 4 are used in terms of energy density. Is preferred.
【００３０】尚、ＬｉＣｏＯ2 を正極に用いた電池で
は、深い充放電を行うとＬｉＣｏＯ2 の劣化が大きいた
め、通常はＬｉＣｏＯ2からＬｉ(1-X) ＣｏＯ2 （０＜
Ｘ≦０．５）までの範囲で用いられる。[0030] In the battery using LiCoO 2 for the positive electrode, the deep for charging and discharging performed when deterioration of LiCoO 2 to large, usually from LiCoO 2 Li (1-X) CoO 2 (0 <
It is used in the range of X ≦ 0.5).
【００３１】過充電の際には０．５＜Ｘ≦１まで充電さ
れる可能性があるため、負極の吸蔵可能なリチウムイオ
ン量を、正極および電解質から放出可能なリチウムイオ
ン量以上とするためには、負極容量を正極の通常の充放
電容量の２倍以上としなければならないために電池エネ
ルギー密度が大きく低下する。Since there is a possibility of being charged to 0.5 <X ≦ 1 when overcharged, the amount of lithium ions that can be stored in the negative electrode is set to be equal to or more than the amount of lithium ions that can be released from the positive electrode and the electrolyte. In addition, since the negative electrode capacity must be twice or more the normal charge / discharge capacity of the positive electrode, the battery energy density is significantly reduced.
【００３２】一方、ＬｉＭｎ2 Ｏ4 はＬｉＭｎ2 Ｏ4 か
らＬｉ(1-X) Ｍｎ2 Ｏ4 （０＜Ｘ≦１）までの範囲で充
放電を行うため、負極容量は正極充放電容量と電解質中
のイオン量の和以上であればよく、正極活物質にＬｉＭ
ｎ2 Ｏ4 を用いることでエネルギー密度が高く、過充電
の際にも安全な非水電解質二次電池を提供できる。On the other hand, since LiMn 2 O 4 charges and discharges in the range from LiMn 2 O 4 to Li (1-X) Mn 2 O 4 (0 <X ≦ 1), the negative electrode capacity is the positive electrode charge / discharge capacity. The amount of ions in the electrolyte should be at least the sum, and LiM should be used as the positive electrode active material.
By using n 2 O 4 , it is possible to provide a non-aqueous electrolyte secondary battery that has a high energy density and is safe even when overcharged.
【００３３】また、リチウムイオン伝導性物質である有
機溶媒や固体のイオン導電体も基本的に限定されず、従
来の有機電解液二次電池に用いられているものを用いる
ことが出来る。たとえば、有機溶媒としては非プロトン
溶媒であるエチレンカーボネイトなどの環状エステル類
およびテトラハイドロフラン，ジオキソランなどのエー
テル類があげられ、これら単独もしくは２種以上を混合
した溶媒を用いることが出来る。固体のイオン導電体と
しては、リチウムイオン導電性を有するものであれば用
いることが出来る。その代表的なものとして、ポリエチ
レンオキサイドなどがあげられる。Further, the organic solvent which is a lithium ion conductive material and the solid ionic conductor are basically not limited, and those used in the conventional organic electrolyte secondary battery can be used. Examples of the organic solvent include cyclic esters such as ethylene carbonate which is an aprotic solvent and ethers such as tetrahydrofuran and dioxolane. These can be used alone or in a mixture of two or more kinds. As the solid ionic conductor, any substance having lithium ion conductivity can be used. A typical example thereof is polyethylene oxide.
【００３４】また、このような有機溶媒あるいは固体の
イオン導電体に溶解される支持電解質も基本的に限定さ
れるものではない。たとえば、 LiAsF6 ， LiClO4 ，Li
BF4 ，LiPF6 ，LiCF3 SO3 などの１種以上を用いること
ができる。Also, the supporting electrolyte dissolved in such an organic solvent or solid ionic conductor is not basically limited. For example, LiAsF 6 , LiClO 4 , Li
One or more of BF 4 , LiPF 6 and LiCF 3 SO 3 can be used.
【００３５】なお、前記の実施例に係る電池はいずれも
ボタン形電池であるが、円筒形、角形またはペーパー形
電池に本発明を適用しても同様の効果が得られる。Although the batteries according to the above-mentioned embodiments are all button type batteries, the same effect can be obtained by applying the present invention to cylindrical, prismatic or paper type batteries.
【００３６】[0036]
【発明の効果】以上詳述した如く、本発明によれば高い
安全性と優れたサイクル寿命性能を有する高エネルギー
密度の非水電解質二次電池を提供することができるもの
である。As described in detail above, according to the present invention, a high energy density non-aqueous electrolyte secondary battery having high safety and excellent cycle life performance can be provided.
【図１】非水電解質二次電池の一例であるボタン電池の
内部構造を示した図。FIG. 1 is a diagram showing an internal structure of a button battery which is an example of a non-aqueous electrolyte secondary battery.
【図２】試験電池のサイクルと放電容量を示した図。FIG. 2 is a diagram showing cycles and discharge capacities of test batteries.
１ 電池ケース ２ 封口板 ３ 負極 ４ ガスケット ５ セパレーター ６ 正極 1 Battery Case 2 Sealing Plate 3 Negative Electrode 4 Gasket 5 Separator 6 Positive Electrode
Claims (1)
なる負極と、正極と、リチウムイオンを含むイオン導電
体を電解質とする非水電解質二次電池において、負極の
吸蔵可能なリチウムイオン量は、正極および電解質から
放出可能なリチウムイオン量以上であることを特徴とす
る非水電解質二次電池。1. In a non-aqueous electrolyte secondary battery having a negative electrode made of a substance capable of occluding and releasing lithium ions, a positive electrode, and an ionic conductor containing lithium ions as an electrolyte, the storable amount of lithium ions in the negative electrode is And a non-aqueous electrolyte secondary battery in which the amount of lithium ions that can be released from the electrolyte is greater than or equal to the amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3215900A JP2734822B2 (en) | 1991-07-31 | 1991-07-31 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3215900A JP2734822B2 (en) | 1991-07-31 | 1991-07-31 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0541251A true JPH0541251A (en) | 1993-02-19 |
| JP2734822B2 JP2734822B2 (en) | 1998-04-02 |
Family
ID=16680116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3215900A Expired - Lifetime JP2734822B2 (en) | 1991-07-31 | 1991-07-31 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2734822B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5856043A (en) * | 1996-06-12 | 1999-01-05 | Nikkiso Company Ltd. | Non-aqueous electrolyte secondary battery |
| EP0954044A2 (en) * | 1998-03-23 | 1999-11-03 | Ngk Insulators, Ltd. | Lithium secondary battery |
| US6346995B1 (en) | 1993-06-29 | 2002-02-12 | Canon Kabushiki Kaisha | Communication apparatus with outgoing call limiting |
| CN100380714C (en) * | 2003-09-29 | 2008-04-09 | 新神户电机株式会社 | Battery pack and electric vehicle |
| US7648801B2 (en) * | 2004-04-01 | 2010-01-19 | 3M Innovative Properties Company | Redox shuttle for overdischarge protection in rechargeable lithium-ion batteries |
| US7811710B2 (en) | 2004-04-01 | 2010-10-12 | 3M Innovative Properties Company | Redox shuttle for rechargeable lithium-ion cell |
| WO2011074083A1 (en) | 2009-12-16 | 2011-06-23 | トヨタ自動車株式会社 | Lithium ion secondary battery |
| US8101302B2 (en) | 2008-02-12 | 2012-01-24 | 3M Innovative Properties Company | Redox shuttles for high voltage cathodes |
| WO2016121734A1 (en) * | 2015-01-30 | 2016-08-04 | Ｎｅｃエナジーデバイス株式会社 | Secondary battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0249364A (en) * | 1988-05-11 | 1990-02-19 | Matsushita Electric Ind Co Ltd | Lithium accumulator |
-
1991
- 1991-07-31 JP JP3215900A patent/JP2734822B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0249364A (en) * | 1988-05-11 | 1990-02-19 | Matsushita Electric Ind Co Ltd | Lithium accumulator |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6346995B1 (en) | 1993-06-29 | 2002-02-12 | Canon Kabushiki Kaisha | Communication apparatus with outgoing call limiting |
| US5856043A (en) * | 1996-06-12 | 1999-01-05 | Nikkiso Company Ltd. | Non-aqueous electrolyte secondary battery |
| EP0954044A2 (en) * | 1998-03-23 | 1999-11-03 | Ngk Insulators, Ltd. | Lithium secondary battery |
| US6506515B1 (en) | 1998-03-23 | 2003-01-14 | Ngk Insulators, Ltd. | Lithium secondary battery |
| EP0954044A3 (en) * | 1998-03-23 | 2003-04-16 | Ngk Insulators, Ltd. | Lithium secondary battery |
| US6616715B2 (en) | 1998-03-23 | 2003-09-09 | Ngk Insulators, Ltd. | Batteries having desired working volume ratios of positive and negative materials |
| US6800394B2 (en) | 1998-03-23 | 2004-10-05 | Ngk Insulators, Ltd. | Lithium secondary battery |
| CN100380714C (en) * | 2003-09-29 | 2008-04-09 | 新神户电机株式会社 | Battery pack and electric vehicle |
| US7648801B2 (en) * | 2004-04-01 | 2010-01-19 | 3M Innovative Properties Company | Redox shuttle for overdischarge protection in rechargeable lithium-ion batteries |
| US7811710B2 (en) | 2004-04-01 | 2010-10-12 | 3M Innovative Properties Company | Redox shuttle for rechargeable lithium-ion cell |
| US8101302B2 (en) | 2008-02-12 | 2012-01-24 | 3M Innovative Properties Company | Redox shuttles for high voltage cathodes |
| WO2011074083A1 (en) | 2009-12-16 | 2011-06-23 | トヨタ自動車株式会社 | Lithium ion secondary battery |
| US8936875B2 (en) | 2009-12-16 | 2015-01-20 | Toyota Jidosha Kabushiki Kaisha | Negative electrode containing graphite for lithium ion secondary battery |
| WO2016121734A1 (en) * | 2015-01-30 | 2016-08-04 | Ｎｅｃエナジーデバイス株式会社 | Secondary battery |
| CN107210494A (en) * | 2015-01-30 | 2017-09-26 | Nec 能源元器件株式会社 | Secondary cell |
| JPWO2016121734A1 (en) * | 2015-01-30 | 2017-11-16 | Ｎｅｃエナジーデバイス株式会社 | Secondary battery |
| EP3252862A4 (en) * | 2015-01-30 | 2018-08-08 | NEC Energy Devices, Inc. | Secondary battery |
| US10217988B2 (en) | 2015-01-30 | 2019-02-26 | Nec Energy Devices, Ltd. | Secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2734822B2 (en) | 1998-04-02 |
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