JPH04220961A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH04220961A JPH04220961A JP2412061A JP41206190A JPH04220961A JP H04220961 A JPH04220961 A JP H04220961A JP 2412061 A JP2412061 A JP 2412061A JP 41206190 A JP41206190 A JP 41206190A JP H04220961 A JPH04220961 A JP H04220961A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- lithium
- battery
- sealing plate
- batteries
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 238000007789 sealing Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000005486 organic electrolyte Substances 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 238000004080 punching Methods 0.000 abstract description 3
- 239000010935 stainless steel Substances 0.000 abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910014135 LiMn2 O4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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、リチウム二次電池の負
極に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative electrode for a lithium secondary battery.
【０００２】0002
【従来の技術とその課題】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。[Prior art and its problems] Lithium secondary batteries have a high energy density secondary battery because the potential of lithium, which is the negative electrode, is extremely base, so the voltage of the battery is high, and the volume and weight energy density of lithium are high. It has the advantage of being able to provide secondary batteries.
【０００３】しかし、従来のリチウム二次電池は、負極
であるリチウムの充放電効率が低いために電池のサイク
ル寿命が短いという問題があった。この、原因として電
析リチウムと有機電解液との反応によるリチウムの消耗
、デンドライトリチウムの脱落にともなうリチウムの消
耗などが考えられている。However, conventional lithium secondary batteries have a problem in that the cycle life of the battery is short because the charging and discharging efficiency of lithium, which is the negative electrode, is low. The causes of this are thought to be lithium consumption due to the reaction between the electrodeposited lithium and the organic electrolyte, and lithium consumption due to shedding of dendrite lithium.
【０００４】そこで、負極のサイクル寿命をのばすため
に、カーボンやアルミニウム合金およびウッド合金をリ
チウムのホストとして用いることが検討されている。確
かに、これらの負極はリチウムの電析をともなわず、リ
チウムイオンを吸蔵放出する事ができるため、電析リチ
ウムと電解液との反応やデンドライトリチウムの発生な
どの問題を解決することができ、負極サイクル寿命を大
きく向上させることができる。[0004] Therefore, in order to extend the cycle life of the negative electrode, the use of carbon, aluminum alloy, and wood alloy as a host for lithium is being considered. It is true that these negative electrodes can absorb and release lithium ions without electrodeposition of lithium, so they can solve problems such as the reaction between electrodeposited lithium and electrolyte and the generation of dendrite lithium. The cycle life of the negative electrode can be greatly improved.
【０００５】しかし、これらホスト化合物はリチウムに
比べ電位が５０〜５００ｍＶ程度貴になること、および
負極の体積エネルギー密度で約１／５以下，重量エネル
ギー密度で約１／１０以下へと大きく低下するという問
題を有する。[0005] However, the potential of these host compounds is about 50 to 500 mV nobler than that of lithium, and the volume energy density of the negative electrode is approximately 1/5 or less, and the gravimetric energy density is significantly reduced to approximately 1/10 or less. There is a problem.
【０００６】したがって、従来の負極に代わって、サイ
クル寿命が長く、かつリチウムと同等の電位および体積
，重量エネルギー密度を有するリチウム二次電池用の負
極が強く望まれていた。[0006] Therefore, in place of conventional negative electrodes, there has been a strong desire for a negative electrode for lithium secondary batteries that has a long cycle life and has a potential, volume, and weight energy density equivalent to that of lithium.
【０００７】[0007]
【課題を解決するための手段】本発明は、リチウムを負
極に備えた二次電池において、該負極がビスマスを含有
しており、その含有量が重量百分率で５％以下であるこ
とを特徴とするリチウム二次電池の負極を提供し前記の
課題を解決するものである。[Means for Solving the Problems] The present invention provides a secondary battery having a lithium negative electrode, characterized in that the negative electrode contains bismuth, and the content thereof is 5% or less in weight percentage. The present invention provides a negative electrode for a lithium secondary battery that solves the above problems.
【０００８】[0008]
【実施例】以下に、好適な実施例を用いて本発明を説明
する。EXAMPLES The present invention will be explained below using preferred examples.
【０００９】［実施例１］正極活物質として、５０ｍｍ
Ｈｇ以下の減圧下において３７５℃で５時間減圧乾燥処
理した後、電気炉で空気中において３７５℃で２０時間
追加熱処理して調製した二酸化マンガンを用いた。[Example 1] As a positive electrode active material, 50 mm
Manganese dioxide prepared by drying under reduced pressure at 375° C. for 5 hours under a reduced pressure of Hg or less and then additionally heat-treating at 375° C. for 20 hours in air in an electric furnace was used.
【００１０】この二酸化マンガン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、１２０℃で４時間熱風乾燥して正極合剤を
調整した。そして、その正極合剤を１０８ｍｇ 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１５．０ｍｍ厚み０．６ｍｍ 程度で
ある。この正極を電池に組み込むまえに再度、１２０℃
で３時間熱風乾燥処理を行った。To 100 parts by weight of this manganese dioxide, 5 parts by weight of acetylene black (conductivity aid) and 2 parts by weight of polytetrafluoroethylene (binder) were added and kneaded well, and then heated at 120°C. A positive electrode mixture was prepared by drying with hot air for 4 hours. Then, 108 mg of each of the positive electrode mixtures was weighed out, wrapped in a 325-mesh SUS316 wire gauze, and press-molded at 2 tons/cm2 to obtain a positive electrode. The dimensions of the positive electrode are approximately 15.0 mm in diameter and 0.6 mm in thickness. Before assembling this positive electrode into a battery, it was heated to 120℃ again.
A hot air drying process was performed for 3 hours.
【００１１】負極には、本発明のビスマスを含有したリ
チウムを用いた。負極中のビスマスの含有量は重量百分
率で１％（１ｗｔ％）である。負極のサイズは直径１６
ｍｍ、厚み０．１ｍｍ 程度で、理論容量は４０ｍＡｈ
である。[0011] Lithium containing bismuth of the present invention was used for the negative electrode. The content of bismuth in the negative electrode is 1% by weight (1 wt%). The size of the negative electrode is 16 in diameter.
mm, thickness is about 0.1mm, theoretical capacity is 40mAh
It is.
【００１２】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。[0012] A polypropylene microporous separator (Celgard K274) and a polypropylene nonwoven fabric were used for the separator, and the outer diameter was 20.0 mm.
A battery with a height of 2.0 mm was created.
【００１３】電解液には、ＥＣ＋４−ＭｅＤＯＬ＋ＤＯ
Ｌ（５：３：２．７）混合溶媒に ＬｉＣｌＯ４ を１
ｍｏｌ／ｌ溶解したものを用いた。[0013] The electrolyte contains EC+4-MeDOL+DO
1 LiClO4 in L (5:3:2.7) mixed solvent
A mol/l solution was used.
【００１４】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、その内壁には負極活物質３が圧着されている
。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は正極合剤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。FIG. 1 is a longitudinal sectional view of the battery. In this figure, 1 is a case that also serves as a positive terminal, which is made by punching an organic electrolyte-resistant stainless steel plate using a press, and 2
is a sealing plate that also serves as a negative electrode terminal, which is made by punching out the same material, and the negative electrode active material 3 is crimped onto the inner wall of the sealing plate. 5 is a separator made of polypropylene impregnated with an organic electrolyte, and 6 is a positive electrode mixture.The open end of the case 1, which also serves as a positive electrode terminal, is caulked inward, and the inside of the sealing plate 2, which also serves as a negative electrode terminal, is inserted through a gasket 4. It is sealed tightly by tightening the circumference.
【００１５】この本発明の負極を用いた電池を電池（Ａ
）とする。A battery using the negative electrode of the present invention is a battery (A
).
【００１６】［実施例２］電池の負極として、ビスマス
を２ｗｔ％含有したリチウムを用いることを除いて他は
、負極のサイズと理論容量および電池構成が実施例１と
同様な電池を作成した。この本発明の負極を用いた電池
を電池（Ｂ）とする。[Example 2] A battery was prepared having the same negative electrode size, theoretical capacity, and battery configuration as in Example 1, except that lithium containing 2 wt % bismuth was used as the battery negative electrode. A battery using this negative electrode of the present invention is referred to as battery (B).
【００１７】［実施例３］電池の負極として、ビスマス
を５ｗｔ％含有したリチウムを用いることを除いて他は
、負極のサイズと理論容量および電池構成が実施例１と
同様の電池を作成した。この本発明の負極を用いた電池
を電池（Ｃ）とする。[Example 3] A battery was prepared having the same negative electrode size, theoretical capacity, and battery configuration as in Example 1, except that lithium containing 5 wt % bismuth was used as the negative electrode. A battery using this negative electrode of the present invention is referred to as battery (C).
【００１８】［比較例１］電池の負極として、リチウム
を用いることを除いて他は、負極のサイズと理論容量お
よび電池構成が実施例１と同様の電池を作成した。この
負極を用いた電池を電池（ア）とする。[Comparative Example 1] A battery was prepared in which the size of the negative electrode, the theoretical capacity, and the battery configuration were the same as in Example 1, except that lithium was used as the negative electrode of the battery. A battery using this negative electrode is referred to as a battery (A).
【００１９】［比較例２］電池の負極として、アルミニ
ウムを２０ｗｔ％含有したリチウムを用いることを除い
て他は、負極のサイズと理論容量および電池構成が実施
例１と同様の電池を作成した。この負極を用いた電池を
電池（イ）とする。[Comparative Example 2] A battery was prepared in which the size of the negative electrode, the theoretical capacity, and the battery configuration were the same as in Example 1, except that lithium containing 20 wt % of aluminum was used as the negative electrode of the battery. A battery using this negative electrode is called a battery (A).
【００２０】電池の種類とその充放電サイクルの進行に
ともなう放電容量変化を図２に示す。 本発明の電池
（Ａ），（Ｂ）および（Ｃ）は、比較電池（ア）および
（イ）に比較して長いサイクル寿命を有する。FIG. 2 shows the types of batteries and changes in discharge capacity as the charge/discharge cycle progresses. Batteries (A), (B), and (C) of the present invention have longer cycle lives than comparative batteries (A) and (B).
【００２１】本発明の負極を備えた電池が、長いサイク
ル寿命を有する理由は明かではないが、以下のように考
えられる。The reason why the battery equipped with the negative electrode of the present invention has a long cycle life is not clear, but it is thought to be as follows.
【００２２】これら試験終了電池を分解したところ、本
発明の電池を除いた全ての電池において、負極が微粉化
しているのがみられた。これら電池の正極をそのまま用
いて再度電池を組み立て充放電試験を行ったところ、放
電容量が初期容量まで回復した。これら事実より、これ
ら電池の寿命は、全て負極により制限されていることが
わかった。本発明の負極のサイクル寿命が長くなった理
由は明確ではないが、リチウムに含有されているビスマ
スが、デンドライトリチウムの発生とリチウムと有機電
解液との反応を抑制するためであると思われる。When these test-completed batteries were disassembled, it was found that the negative electrodes of all the batteries except the battery of the present invention had been pulverized. When the batteries were reassembled using the positive electrodes of these batteries and subjected to a charge/discharge test, the discharge capacity recovered to the initial capacity. From these facts, it has been found that the lifespan of these batteries is all limited by the negative electrode. The reason why the cycle life of the negative electrode of the present invention is longer is not clear, but it is thought that bismuth contained in lithium suppresses the generation of dendrite lithium and the reaction between lithium and the organic electrolyte.
【００２３】また、本発明の負極は、ビスマスの含有量
が少量のため、電位および体積，重量エネルギー密度が
リチウムとほとんど変わらないという優れた特徴を有し
ている。Further, the negative electrode of the present invention has excellent characteristics in that the potential, volume, and weight energy density are almost the same as those of lithium because the content of bismuth is small.
【００２４】本発明によるリチウム二次電池に用いられ
る正極活物質は、実施例に用いたものに限定されるもの
ではなく、従来のリチウム二次電池に用いられている正
極活物質、すなわちリチウムイオンあるいはアニオンと
電気化学的に可逆反応を行う物質を用いることができる
。たとえば、 ＭｎＯ２ ，ＬｉＭｎ２ Ｏ４ ，Ｌ
ｉＣｏＸ Ｍｎ２−Ｘ Ｏ２，ＬｉＣｏＸ Ｎｉ１−
Ｘ Ｏ２ ， ＣｏＯ２ ， ＴｉＳ２ ， Ｖ２
Ｏ５ およびポリアニリンなどがあげられる。[0024] The positive electrode active material used in the lithium secondary battery according to the present invention is not limited to that used in the examples, but can be any positive electrode active material used in conventional lithium secondary batteries, that is, lithium ion. Alternatively, a substance that electrochemically undergoes a reversible reaction with anions can be used. For example, MnO2, LiMn2 O4, L
iCoX Mn2-X O2, LiCoX Ni1-
XO2, CoO2, TiS2, V2
Examples include O5 and polyaniline.
【００２５】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、実施例に用いたもの限
定されず、従来のリチウム二次電池に用いられているも
のを用いることができる。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 and solid ion conductor which are lithium ion conductive substances are not limited to those used in the examples, and those used in conventional lithium secondary batteries can be used. For example, organic solvents include cyclic esters such as ethylene carbonate, which are aprotic solvents, and ethers such as tetrahydrofuran and dioxolane, and these solvents may be used alone or in combination of two or more thereof. As the solid ion conductor, any material having lithium ion conductivity can be used. A typical example thereof is polyethylene oxide.
【００２６】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同様に実施例に
限定されるものではない。たとえば、 ＬｉＡｓＦ６
， ＬｉＣｌＯ４ ，ＬｉＢＦ４ ，ＬｉＰＦ６ ，Ｌ
ｉＣＦ３ ＳＯ３ などの１種以上を用いることができ
る。[0026] Similarly, the supporting electrolyte dissolved in such an organic solvent or solid ionic conductor is not limited to the examples. For example, LiAsF6
, LiClO4 , LiBF4 , LiPF6 , L
One or more types such as iCF3 SO3 can be used.
【００２７】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 all of the batteries according to the above embodiments are button-shaped batteries, similar effects can be obtained even if the present invention is applied to cylindrical, prismatic, or paper-shaped batteries.
【００２８】[0028]
【発明の効果】本発明により従来の電池に比較して優れ
たサイクル寿命性能を有する高エネルギー密度のリチウ
ム二次電池を提供することができるものである。According to the present invention, it is possible to provide a high energy density lithium secondary battery which has superior cycle life performance compared to conventional batteries.
【図１】リチウム二次電池の一例であるボタン電池の内
部構造を示した図である。FIG. 1 is a diagram showing the internal structure of a button battery, which is an example of a lithium secondary battery.
【図２】本発明の効果を示した図である。FIG. 2 is a diagram showing the effects of the present invention.
１ 電池ケース ２ 封口板 ３ リチウム ４ ガスケット ５ セパレーター ６ 正極合剤 1 Battery case 2 Sealing plate 3 Lithium 4 Gasket 5 Separator 6 Positive electrode mixture
Claims (1)
いて、該負極がビスマスを含有しており、その含有量が
重量百分率で５％以下であることを特徴とするリチウム
二次電池の負極。1. A negative electrode for a lithium secondary battery comprising lithium as a negative electrode, wherein the negative electrode contains bismuth, and the content thereof is 5% or less by weight percentage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41206190A JP3163444B2 (en) | 1990-12-19 | 1990-12-19 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41206190A JP3163444B2 (en) | 1990-12-19 | 1990-12-19 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04220961A true JPH04220961A (en) | 1992-08-11 |
| JP3163444B2 JP3163444B2 (en) | 2001-05-08 |
Family
ID=18520950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP41206190A Expired - Fee Related JP3163444B2 (en) | 1990-12-19 | 1990-12-19 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3163444B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100603267B1 (en) * | 1999-10-27 | 2006-07-20 | 삼성에스디아이 주식회사 | Secondary battery |
-
1990
- 1990-12-19 JP JP41206190A patent/JP3163444B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100603267B1 (en) * | 1999-10-27 | 2006-07-20 | 삼성에스디아이 주식회사 | Secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3163444B2 (en) | 2001-05-08 |
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