JPH08138743A - Nonaqeuous electrolyte secondary battery - Google Patents
Nonaqeuous electrolyte secondary batteryInfo
- Publication number
- JPH08138743A JPH08138743A JP6279120A JP27912094A JPH08138743A JP H08138743 A JPH08138743 A JP H08138743A JP 6279120 A JP6279120 A JP 6279120A JP 27912094 A JP27912094 A JP 27912094A JP H08138743 A JPH08138743 A JP H08138743A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- lithium
- carbonate
- battery
- 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.)
- Pending
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、非水電解液二次電池
の、とくにその極板上に析出したリチウムの発火を防止
できる負極を提供するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a negative electrode which can prevent ignition of lithium deposited on a non-aqueous electrolyte secondary battery, especially on its electrode plate.
【０００２】[0002]
【従来の技術】近年、ＡＶ機器あるいはパソコン等の電
子機器のポータブル化、コードレス化が急速に進んでお
り、これらの駆動用電源として小型、軽量で高エネルギ
ー密度を有する二次電池への要求が高い。この中でリチ
ウムを活物質とする負極を用いた非水電解液二次電池は
とりわけ高電圧、高エネルギー密度を有する電池として
期待が大きい。従来、この電池には負極にリチウム金
属、正極に二酸化マンガンや五酸化バナジウムが用いら
れ、３Ｖ級の電池が実現されていた。2. Description of the Related Art In recent years, portable and cordless AV devices or electronic devices such as personal computers have been rapidly developed, and there has been a demand for a small size, lightweight secondary battery having a high energy density as a power source for driving these devices. high. Among them, non-aqueous electrolyte secondary batteries using a negative electrode containing lithium as an active material are particularly expected as batteries having high voltage and high energy density. Conventionally, a lithium metal is used for the negative electrode and manganese dioxide or vanadium pentoxide is used for the positive electrode in this battery, and a 3V class battery has been realized.
【０００３】ところが、負極にリチウム金属を用いた場
合には、充電時に負極上にリチウムが樹枝状（デンドラ
イト状）に析出し、このデンドライト状リチウムによっ
て電池の内部短絡が発生して電池の発熱、発火が起こっ
ていた。However, when lithium metal is used for the negative electrode, lithium is deposited in a dendritic form (dendritic form) on the negative electrode during charging, and this dendrite-like lithium causes an internal short circuit in the battery, resulting in heat generation of the battery. There was a fire.
【０００４】また、電池が高温下に置かれた場合にはリ
チウムがデンドライト状に析出した負極と電解液とが化
学反応を起こして電池が発熱し、熱暴走状態となって発
火に至る可能性があり、電池の安全性確保に問題があっ
た。Further, when the battery is placed at a high temperature, there is a possibility that the negative electrode on which lithium is deposited in the form of dendrite and the electrolytic solution cause a chemical reaction to heat the battery, resulting in a thermal runaway state and ignition. There was a problem in ensuring the safety of the battery.
【０００５】リチウムが負極上でデンドライト状に析出
することを防止するために、負極に炭素材料を用いこの
炭素材料の層間にインターカレートおよびデインターカ
レートさせるものが提案されている。In order to prevent lithium from dendrite-like deposition on the negative electrode, it has been proposed to use a carbon material for the negative electrode and intercalate and deintercalate between the layers of this carbon material.
【０００６】この負極では充電時にリチウムが炭素の層
間にインターカレートされるために、極板上でリチウム
がデンドライト状に析出することは原理的に起こらず、
デンドライト状の金属リチウムと電解液との化学反応に
よる発熱は生じない。In this negative electrode, lithium is intercalated between carbon layers during charging, so that lithium is not dendrite-like deposited on the electrode plate in principle.
No heat is generated by the chemical reaction between the dendrite-like metallic lithium and the electrolytic solution.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、リチウ
ムを可逆的にインターカレートおよびデインターカレー
トし得る炭素材料を負極に用いた場合でも、充放電サイ
クルを繰り返すにつれ徐々に負極の劣化が始まるので充
電時における負極のリチウム受入れ性は低下してくる。
つまり、サイクル寿命末期においては負極の炭素材料の
層間にリチウムが容易にインターカレートしなくなるの
で、負極表面上で金属リチウムがデンドライト状に析出
するようになる。そして、このようなサイクル寿命末期
の電池が高温下に置かれた場合にはデンドライト状に析
出したリチウム金属と電解液とが化学反応を起こして電
池が発熱し、さらに熱暴走状態となって電池が発火して
いた。However, even when a carbon material capable of reversibly intercalating and deintercalating lithium is used for the negative electrode, the deterioration of the negative electrode gradually begins as the charging / discharging cycle is repeated. The lithium acceptability of the negative electrode during charging decreases.
That is, at the end of the cycle life, lithium is not easily intercalated between the layers of the carbon material of the negative electrode, so that metallic lithium is deposited in the form of dendrite on the surface of the negative electrode. When such a battery at the end of the cycle life is placed under high temperature, the lithium metal deposited in the dendrite state and the electrolytic solution cause a chemical reaction to generate heat in the battery, which further causes a thermal runaway condition. Was ignited.
【０００８】本発明はこのような課題を解決するもので
あり、負極上でデンドライト状に析出したリチウムが高
温時などに電解液と化学反応を起こして発熱することを
防止することができ、安全性に優れた非水電解液二次電
池を提供するものである。The present invention is intended to solve such a problem, and it is possible to prevent lithium dendrite-like deposited on the negative electrode from causing a chemical reaction with the electrolytic solution at a high temperature to generate heat. A non-aqueous electrolyte secondary battery having excellent properties is provided.
【０００９】[0009]
【課題を解決するための手段】本発明はリチウムイオン
を活物質とする負極と、非水電解液と、リチウム含有金
属酸化物からなる正極とを備えた非水電解液二次電池に
おいて、上記負極にアルカリ金属炭酸塩、アルカリ土類
金属炭酸塩、遷移金属炭酸塩よりなる群から選ばれる少
なくとも一種の炭酸塩を添加したことを特徴とする。さ
らには、上記炭酸塩を負極の重量に対して１％から１０
％の割合で添加したものである。さらには、負極にＮａ
2ＣＯ3、Ｌｉ2ＣＯ3のうち少なくとも一種を添加したこ
とを特徴とする。さらには、負極に添加するＮａ2Ｃ
Ｏ3、Ｌｉ2ＣＯ3のうち少なくとも一種が負極の重量に
対して１％〜１０％としたものである。The present invention provides a non-aqueous electrolyte secondary battery comprising a negative electrode using lithium ions as an active material, a non-aqueous electrolyte, and a positive electrode comprising a lithium-containing metal oxide. At least one carbonate selected from the group consisting of alkali metal carbonates, alkaline earth metal carbonates and transition metal carbonates is added to the negative electrode. Furthermore, the above-mentioned carbonate is used in an amount of 1% to 10% based on the weight of the negative electrode.
% Added. Furthermore, Na is used for the negative electrode.
At least one of 2 CO 3 and Li 2 CO 3 is added. Furthermore, Na 2 C added to the negative electrode
At least one of O 3 and Li 2 CO 3 is 1% to 10% of the weight of the negative electrode.
【００１０】負極には、リチウムイオンを活物質とする
材料、例えば、リチウムを可逆的にインターカレート／
デインターカレートすることが可能な炭素材料などが用
いられる。For the negative electrode, a material having lithium ions as an active material, such as lithium, is reversibly intercalated /
A carbon material that can be deintercalated is used.
【００１１】[0011]
【作用】デンドライト状に析出した金属リチウムは、電
解液に接している表面が電解液に対して化学的に活性な
状態であり、高温下では電解液と容易に発熱反応する。
これに対して本発明では負極に炭酸塩を添加しているの
でデンドライト状に析出した金属リチウムの表面は前記
炭酸塩の炭酸イオン（ＣＯ3 2-）と反応し、デンドライ
ト状リチウムの表面にＬｉ2ＣＯ3の被膜が形成される。
このＬｉ2ＣＯ3は電解液に対してほとんど不溶であり、
また熱安定性も高いことから、リチウムと電解液との反
応を抑制する被膜として機能し、電池の安全性を高める
ことができる。析出した金属リチウムと炭酸塩との反応
はイオン交換反応であり、リチウムの酸化還元電位は最
も低いことから、リチウムイオン以外の陽イオンを含む
炭酸塩、例えばＮａ2ＣＯ3とは容易にイオン交換反応す
る。また、Ｌｉ2ＣＯ3の場合には、濃度勾配によって炭
酸イオンは容易に金属リチウム中に拡散し、表面にＬｉ
2ＣＯ3の被膜が形成される。The metal lithium deposited in the dendrite form has a surface in contact with the electrolytic solution that is chemically active with respect to the electrolytic solution, and easily reacts exothermically with the electrolytic solution at high temperatures.
On the other hand, in the present invention, since the carbonate is added to the negative electrode, the surface of the metallic lithium deposited in the dendrite form reacts with the carbonate ion (CO 3 2− ) of the carbonate, and the surface of the dendrite-like lithium becomes Li. A film of 2 CO 3 is formed.
This Li 2 CO 3 is almost insoluble in the electrolytic solution,
Further, since it has high thermal stability, it can function as a film that suppresses the reaction between lithium and the electrolytic solution, and can enhance the safety of the battery. The reaction between the precipitated metal lithium and the carbonate is an ion exchange reaction, and since the redox potential of lithium is the lowest, it is easy to perform an ion exchange with a carbonate containing a cation other than lithium ion, for example, Na 2 CO 3. react. Further, in the case of Li 2 CO 3, the carbonate ion easily diffuses into metallic lithium due to the concentration gradient, and Li 2 CO 3 is deposited on the surface.
A film of 2 CO 3 is formed.
【００１２】非水電解液二次電池の内部にＬｉ2ＣＯ3を
添加する技術は、特開平１−２８６２６３号公報、特開
平４−３２９２６８号公報に記載されている。Techniques for adding Li 2 CO 3 to the inside of a non-aqueous electrolyte secondary battery are described in JP-A-1-286263 and JP-A-4-329268.
【００１３】特開平１−２８６２６３号公報には、電解
液中にＬｉ2ＣＯ3を添加することが示されているが、電
解液中に溶解できるＬｉ2ＣＯ3の量は極めて微量である
ために本発明の目的である負極を覆うのに充分なＬｉ2
ＣＯ3の被膜を形成することができない。Japanese Patent Laid-Open No. 1-286263 discloses adding Li 2 CO 3 to the electrolytic solution, but the amount of Li 2 CO 3 that can be dissolved in the electrolytic solution is extremely small. Sufficient Li 2 to cover the negative electrode which is the object of the present invention.
A CO 3 film cannot be formed.
【００１４】また、特開平４−３２９２６８号公報には
安全弁を備えた非水電解液二次電池において正極にＬｉ
2ＣＯ3を添加して電池の過充電時に正極の電位が高くな
った際に正極に添加したＬｉ2ＣＯ3を電気化学的に分解
して炭酸ガスを放出することによって電池内圧を高くし
て安全性を作動させて電池が過充電されることを防ぐも
のである。したがって、本発明のようにサイクル寿命末
期に負極に析出するリチウムの表面に被膜を形成させる
という作用はないものである。Further, in Japanese Patent Application Laid-Open No. 4-329268, in a non-aqueous electrolyte secondary battery equipped with a safety valve, Li is used as a positive electrode.
By increasing the internal pressure of the battery by releasing Li 2 CO 3 was added to the positive electrode when the potential of the positive electrode is increased during overcharging of the battery by adding 2 CO 3 electrochemically decomposed to carbon dioxide The safety is activated to prevent the battery from being overcharged. Therefore, unlike the present invention, there is no action of forming a film on the surface of lithium deposited on the negative electrode at the end of the cycle life.
【００１５】[0015]
【実施例】以下、本発明の実施例を図面を参照しながら
説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００１６】（実施例１）図１に本実施例で用いた円筒
形電池の縦断面図を示す。図において、１は耐有機電解
液性のステンレス鋼板を加工した電池ケース、２は安全
弁を設けた封口板、３は絶縁パッキングを示す。４は極
板群であり、正極および負極がセパレータを介して渦巻
状に巻回されたものでケース１内に収納されている。そ
して上記正極からは正極リード５が引き出されて封口板
２に接続され、負極からは負極リード６が引き出されて
電池ケース１の底部に接続されている。７は絶縁リング
で極板群４の上下部にそれぞれ設けられている。以下
正、負極板等について詳しく説明する。(Embodiment 1) FIG. 1 is a vertical sectional view of a cylindrical battery used in this embodiment. In the figure, 1 is a battery case formed by processing an organic electrolyte resistant stainless steel plate, 2 is a sealing plate provided with a safety valve, and 3 is an insulating packing. Reference numeral 4 denotes an electrode plate group, which is formed by spirally winding a positive electrode and a negative electrode via a separator and is housed in the case 1. A positive electrode lead 5 is drawn out from the positive electrode and connected to the sealing plate 2, and a negative electrode lead 6 is drawn out from the negative electrode and connected to the bottom of the battery case 1. Insulating rings 7 are provided on the upper and lower portions of the electrode plate group 4, respectively. The positive and negative electrode plates will be described in detail below.
【００１７】正極は、Ｌｉ2ＣＯ3とＣｏ3Ｏ4とを混合
し、９００℃で１０時間焼成して合成したＬｉＣｏＯ2
の粉末１００重量部に、アセチレンブラック３重量部、
フッ素樹脂系結着剤７重量部を混合し、カルボキシメチ
ルセルロース水溶液に懸濁させてペースト状にした。こ
のペーストを厚さ０．０３ｍｍのアルミ箔の両面に塗着
し、乾燥後圧延して厚さ０．１８ｍｍ、幅３７ｍｍ、長
さ２４０ｍｍの正極板とした。The positive electrode was prepared by mixing Li 2 CO 3 and Co 3 O 4 and firing at 900 ° C. for 10 hours to synthesize LiCoO 2.
3 parts by weight of acetylene black,
7 parts by weight of a fluororesin binder was mixed and suspended in a carboxymethyl cellulose aqueous solution to form a paste. This paste was applied on both sides of an aluminum foil having a thickness of 0.03 mm, dried and rolled to obtain a positive electrode plate having a thickness of 0.18 mm, a width of 37 mm and a length of 240 mm.
【００１８】負極はメソフェーズ小球体を２８００℃の
高温で黒鉛化したもの（以下メソフェーズ黒鉛と称す）
を用いた。このメソフェーズ黒鉛１００重量部にスチレ
ン／ブタジエンゴム３重量部を混合した後、Ｎａ2ＣＯ3
をメソフェーズ黒鉛の重量に対して０．５％、１％、５
％、１０％、１５％混合し、カルボキシメチルセルロー
ス水溶液に懸濁させてペースト状にした。そしてこのペ
ーストを厚さ０．０２ｍｍの銅箔の両面に塗着し、乾燥
後圧延して、厚さ０．２０ｍｍ、幅３９ｍｍ、長さ２６
０ｍｍの負極板とした。The negative electrode is obtained by graphitizing mesophase spheres at a high temperature of 2800 ° C. (hereinafter referred to as mesophase graphite).
Was used. After mixing 3 parts by weight of styrene / butadiene rubber with 100 parts by weight of this mesophase graphite, Na 2 CO 3
0.5%, 1%, 5 with respect to the weight of mesophase graphite
%, 10% and 15% were mixed and suspended in a carboxymethylcellulose aqueous solution to form a paste. Then, this paste is applied to both sides of a copper foil having a thickness of 0.02 mm, dried and rolled to have a thickness of 0.20 mm, a width of 39 mm, and a length of 26.
The negative electrode plate was 0 mm.
【００１９】そして、正極板にはアルミニウム製、負極
板にはニッケル製のリードをそれぞれ取り付け、厚さ
０．０２５ｍｍ、幅４５ｍｍ、長さ７３０ｍｍのポリプ
ロピレン製セパレータを介して渦巻状に巻回して極板群
を構成し、これを直径１４．０ｍｍ、高さ５０ｍｍの電
池ケースに納入した。電解液にはＥＣとＤＥＣとＭＰと
を３０：５０：２０の体積比で混合した溶媒に１モル／
リットルのＬｉＰＦ6を溶解したものを用い、これを注
液した後封口し、本発明の電池Ａとした。Then, a lead made of aluminum is attached to the positive electrode plate and a lead made of nickel is attached to the negative electrode plate, and the electrode is wound in a spiral shape through a polypropylene separator having a thickness of 0.025 mm, a width of 45 mm and a length of 730 mm. A plate group was constructed and delivered to a battery case having a diameter of 14.0 mm and a height of 50 mm. The electrolytic solution was prepared by mixing EC, DEC and MP in a volume ratio of 30:50:20 in a solvent of 1 mol / mol.
A solution prepared by dissolving 1 liter of LiPF 6 was used, which was poured and then sealed to obtain a battery A of the invention.
【００２０】（実施例２）メソフェーズ黒鉛１００重量
部にスチレン／ブタジエンゴム３重量部を混合した後、
Ｌｉ2ＣＯ3をメソフェーズ黒鉛の重量に対して０．５
％、１％、５％、１０％、１５％混合し、カルボキシメ
チルセルロース水溶液に懸濁させてペースト状にした以
外は（実施例１）と同様の電池を構成し、これを本発明
の電池Ｂとした。Example 2 After mixing 3 parts by weight of styrene / butadiene rubber with 100 parts by weight of mesophase graphite,
Li 2 CO 3 is 0.5 based on the weight of the mesophase graphite.
%, 1%, 5%, 10%, 15% were mixed, and a battery similar to that of (Example 1) was constructed except that it was suspended in an aqueous solution of carboxymethyl cellulose to form a paste. And
【００２１】（比較例）メソフェーズ黒鉛１００重量部
にスチレン／ブタジエンゴム３重量部を混合し、カルボ
キシメチルセルロース水溶液に懸濁させてペースト状に
した。そして、このペーストを厚さ０．０２ｍｍの銅箔
の両面に塗着し、乾燥後圧延して、厚さ０．２０ｍｍ、
幅３９ｍｍ、長さ２６０ｍｍの負極板とした以外は（実
施例１）と同様の電池を構成し、これを比較の電池Ｃと
した。Comparative Example 100 parts by weight of mesophase graphite was mixed with 3 parts by weight of styrene / butadiene rubber, and the mixture was suspended in an aqueous carboxymethylcellulose solution to form a paste. Then, this paste is applied to both surfaces of a copper foil having a thickness of 0.02 mm, dried and rolled to a thickness of 0.20 mm,
A battery similar to that of (Example 1) was constructed except that a negative electrode plate having a width of 39 mm and a length of 260 mm was used, and this was used as a comparative battery C.
【００２２】次に、本発明の電池Ａ、Ｂと比較の電池Ｃ
を各２セルずつ用意して充放電サイクル寿命試験を行っ
た。充放電条件は２０℃において充電は充電電圧４．１
Ｖ、充電時間２時間の定電圧充電を行い、制限電流を３
５０ｍＡとし、放電は放電電流５００ｍＡ、放電終止電
圧３．０Ｖの定電流放電を行った。そして、それぞれ１
０サイクル目の放電容量を初期容量とし、初期容量の半
分以下の容量に劣化した時点をサイクル寿命末期として
充電状態でサイクル試験を中止した。サイクル寿命末期
の電池の２個のうち１セルは分解し、負極板の表面状態
を観察して、金属リチウムの析出の有無を調べた。もう
一方の電池はＵＬ規格による加熱試験（室温から毎分５
℃で１６５℃まで昇温し、１６５℃で１０分間維持）を
行い、発火の有無を調べた。初期容量、サイクル寿命末
期における電池の負極上への金属リチウムの析出の有
無、加熱試験による発火の有無の結果を（表１）に示
す。Next, the batteries A and B of the present invention and the comparative battery C
Each 2 cells were prepared and a charge / discharge cycle life test was conducted. Charge / discharge conditions are 20 ° C and charge is 4.1
V, charging time 2 hours constant voltage charging, limit current 3
The discharge was carried out at a constant current of 50 mA and a discharge current of 500 mA and a discharge end voltage of 3.0 V. And each one
The discharge capacity at the 0th cycle was defined as the initial capacity, and the point at which the capacity deteriorated to half or less of the initial capacity was regarded as the end of cycle life, and the cycle test was stopped in the charged state. One of two cells at the end of the cycle life was disassembled, and the surface condition of the negative electrode plate was observed to examine whether metal lithium was deposited. The other battery is a UL standard heating test (5 minutes from room temperature
The temperature was raised to 165 ° C. at a temperature of 165 ° C. and the temperature was maintained at 165 ° C. for 10 minutes), and the presence or absence of ignition was examined. The results of the initial capacity, the presence or absence of metal lithium deposition on the negative electrode of the battery at the end of the cycle life, and the presence or absence of ignition in the heating test are shown in (Table 1).
【００２３】[0023]
【表１】 [Table 1]
【００２４】（表１）に示したように、各電池のサイク
ル寿命末期には負極上への金属リチウムの析出が確認さ
れた。加熱試験の結果、比較の電池Ｃは金属リチウムと
電解液が反応して発火したが、本発明の電池Ａにおいて
Ｎａ2ＣＯ3を１％、５％、１０％、１５％添加した場合
には前記反応を防止することができ発火しなかった。し
かし、Ｎａ2ＣＯ3を１５％添加した場合には初期容量は
低下した。As shown in (Table 1), it was confirmed that metallic lithium was deposited on the negative electrode at the end of the cycle life of each battery. As a result of the heating test, the comparative battery C ignited due to the reaction between the lithium metal and the electrolytic solution, but when Na 2 CO 3 was added at 1%, 5%, 10% and 15% in the battery A of the present invention, The reaction could be prevented and no ignition occurred. However, when Na 2 CO 3 was added by 15%, the initial capacity decreased.
【００２５】以上の結果より、負極にＮａ2ＣＯ3を１％
以上１０％以下添加することによって、電池容量を低下
させることなくサイクル寿命末期における電池の熱安定
性を向上させることができた。From the above results, 1% of Na 2 CO 3 was added to the negative electrode.
By adding 10% or less, the thermal stability of the battery at the end of the cycle life could be improved without reducing the battery capacity.
【００２６】同様に負極にＬｉ2ＣＯ３を１％以上１０
％以下添加することによって電池容量を低下させること
なくサイクル寿命末期における電池の熱安定性を向上さ
せることができた。Similarly, 1% or more of Li 2 CO 3 is added to the negative electrode 10
%, It was possible to improve the thermal stability of the battery at the end of the cycle life without reducing the battery capacity.
【００２７】なお、本実施例では炭酸イオンの供給源と
してＮａ2ＣＯ3、Ｌｉ2ＣＯ3を用いた場合について説明
したが、他のアルカリ金属炭酸塩、アルカリ土類金属炭
酸塩、遷移金属炭酸塩の少なくとも一種の炭酸塩を用い
ても同様な結果が得られた。In this embodiment, the case where Na 2 CO 3 and Li 2 CO 3 are used as the carbonate ion supply source has been described, but other alkali metal carbonates, alkaline earth metal carbonates, transition metal carbonates are used. Similar results were obtained with at least one carbonate salt.
【００２８】また、本実施例では正極にはＬｉＣｏＯ2
を用いたが、他のリチウム含有金属酸化物を用いた場合
も同様な効果が得られた。In this embodiment, the positive electrode is made of LiCoO 2
However, similar effects were obtained when other lithium-containing metal oxides were used.
【００２９】[0029]
【発明の効果】以上のように本発明では、負極にアルカ
リ金属炭酸塩、アルカリ土類金属炭酸塩、遷移金属炭酸
塩のうちの少なくとも一種の炭酸塩を用いているので、
負極上に析出した金属リチウムと炭酸イオンが反応して
被膜を形成し、金属リチウムと電解液との反応を防止し
て電池の安全性を高めることができる。As described above, in the present invention, at least one carbonate selected from the group consisting of alkali metal carbonates, alkaline earth metal carbonates and transition metal carbonates is used for the negative electrode.
Metal lithium deposited on the negative electrode reacts with carbonate ions to form a film, which prevents the reaction between the metal lithium and the electrolytic solution to enhance the safety of the battery.
【図１】本発明の円筒形電池の縦断面図FIG. 1 is a longitudinal sectional view of a cylindrical battery of the present invention.
１ 電池ケース ２ 封口板 ３ 絶縁パッキング ４ 極板群 ５ 正極リード ６ 負極リード ７ 絶縁リング 1 Battery Case 2 Sealing Plate 3 Insulation Packing 4 Electrode Plate Group 5 Positive Electrode Lead 6 Negative Electrode Lead 7 Insulation Ring
───────────────────────────────────────────────────── フロントページの続き (72)発明者 守田 彰克 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akikatsu Morita 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (4)
極と、非水電解液を用いる非水電解液二次電池におい
て、負極にアルカリ金属炭酸塩、アルカリ土類金属炭酸
塩、遷移金属炭酸塩よりなる群から選ばれる少なくとも
一種の炭酸塩を添加したことを特徴とする非水電解液二
次電池。1. A non-aqueous electrolyte secondary battery using a positive electrode, a negative electrode using lithium ions as an active material, and a non-aqueous electrolyte, wherein the negative electrode is an alkali metal carbonate, an alkaline earth metal carbonate, or a transition metal carbonate. A non-aqueous electrolyte secondary battery comprising at least one carbonate selected from the group consisting of salts.
して１％〜１０％であることを特徴とする請求項１記載
の非水電解液二次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the carbonate added to the negative electrode is 1% to 10% with respect to the weight of the negative electrode.
極と、非水電解液を用いる非水電解液二次電池におい
て、負極にＮａ2ＣＯ3、Ｌｉ2ＣＯ3のうち少なくとも１
種を添加したことを特徴とする非水電解液二次電池。3. A non-aqueous electrolyte secondary battery using a positive electrode, a negative electrode using lithium ions as an active material, and a non-aqueous electrolyte, wherein at least one of Na 2 CO 3 and Li 2 CO 3 is used as the negative electrode.
A non-aqueous electrolyte secondary battery comprising a seed.
うち少なくとも１種が負極の重量に対して１％〜１０％
であることを特徴とする請求項３記載の非水電解液二次
電池。4. At least one of Na 2 CO 3 and Li 2 CO 3 added to the negative electrode is 1% to 10% with respect to the weight of the negative electrode.
The non-aqueous electrolyte secondary battery according to claim 3, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6279120A JPH08138743A (en) | 1994-11-14 | 1994-11-14 | Nonaqeuous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6279120A JPH08138743A (en) | 1994-11-14 | 1994-11-14 | Nonaqeuous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08138743A true JPH08138743A (en) | 1996-05-31 |
Family
ID=17606715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6279120A Pending JPH08138743A (en) | 1994-11-14 | 1994-11-14 | Nonaqeuous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08138743A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10233208A (en) * | 1996-12-20 | 1998-09-02 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2001176500A (en) * | 1999-12-08 | 2001-06-29 | Samsung Sdi Co Ltd | Negative electrode active material slurry composition for lithium secondary battery, and method of manufacturing negative electrode using the same |
| JP2009170287A (en) * | 2008-01-17 | 2009-07-30 | Mitsubishi Chemicals Corp | Electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery using the same |
| WO2015025417A1 (en) * | 2013-08-23 | 2015-02-26 | 株式会社日立製作所 | Negative electrode material and lithium ion secondary battery using same |
| JP2018060692A (en) * | 2016-10-05 | 2018-04-12 | 旭化成株式会社 | Nonaqueous secondary battery |
| WO2020175362A1 (en) | 2019-02-28 | 2020-09-03 | パナソニック株式会社 | Slurry for non-aqueous electrolyte secondary cell, method for manufacturing slurry for non-aqueous electrolyte secondary cell, electrode for non-aqueous electrolyte secondary cell, and non-aqueous electrolyte secondary cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06140077A (en) * | 1992-09-11 | 1994-05-20 | Mitsubishi Electric Corp | Electrochemical element, lithium secondary battery and set battery and manufacture thereof |
| JPH07235297A (en) * | 1993-12-27 | 1995-09-05 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
-
1994
- 1994-11-14 JP JP6279120A patent/JPH08138743A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06140077A (en) * | 1992-09-11 | 1994-05-20 | Mitsubishi Electric Corp | Electrochemical element, lithium secondary battery and set battery and manufacture thereof |
| JPH07235297A (en) * | 1993-12-27 | 1995-09-05 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10233208A (en) * | 1996-12-20 | 1998-09-02 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2001176500A (en) * | 1999-12-08 | 2001-06-29 | Samsung Sdi Co Ltd | Negative electrode active material slurry composition for lithium secondary battery, and method of manufacturing negative electrode using the same |
| JP2009170287A (en) * | 2008-01-17 | 2009-07-30 | Mitsubishi Chemicals Corp | Electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery using the same |
| WO2015025417A1 (en) * | 2013-08-23 | 2015-02-26 | 株式会社日立製作所 | Negative electrode material and lithium ion secondary battery using same |
| JP2018060692A (en) * | 2016-10-05 | 2018-04-12 | 旭化成株式会社 | Nonaqueous secondary battery |
| WO2020175362A1 (en) | 2019-02-28 | 2020-09-03 | パナソニック株式会社 | Slurry for non-aqueous electrolyte secondary cell, method for manufacturing slurry for non-aqueous electrolyte secondary cell, electrode for non-aqueous electrolyte secondary cell, and non-aqueous electrolyte secondary cell |
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