JPH06251764A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH06251764A JPH06251764A JP5031722A JP3172293A JPH06251764A JP H06251764 A JPH06251764 A JP H06251764A JP 5031722 A JP5031722 A JP 5031722A JP 3172293 A JP3172293 A JP 3172293A JP H06251764 A JPH06251764 A JP H06251764A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- negative electrode
- electrode plate
- secondary battery
- lithium secondary
- 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、サイクル特性の向上を
図ることができるリチウム二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery capable of improving cycle characteristics.
【０００２】[0002]
【従来の技術】正極活物質としてＬｉＣｏＯ2 等のリチ
ウム−金属複合酸化物を用い、負極としてＬｉイオンを
ドープ，脱ドープが可能な炭素質材料からなるリチウム
担持体を備えたいわゆるロッキングチェアー形のリチウ
ム二次電池は、放電時においてはＬｉイオンが正極側に
移行し、充電時においてはＬｉイオンが負極側に移行す
るもので、高い電池電圧および高エネルギー密度を得ら
れることから、コンピュータのメモリバックアップ用電
源など、種々の分野での利用が考えられている。 2. Description of the Related Art A lithium-metal composite oxide such as LiCoO 2 is used as a positive electrode active material, and a so-called rocking chair type having a lithium carrier made of a carbonaceous material capable of doping and dedoping Li ions as a negative electrode. In a lithium secondary battery, Li ions move to the positive electrode side during discharging and Li ions move to the negative electrode side during charging, and a high battery voltage and high energy density can be obtained. It is considered to be used in various fields such as backup power source.
【０００３】この種のリチウム二次電池としては、例え
ば特開平３−２２３６６号公報に開示されているものが
ある。An example of this type of lithium secondary battery is disclosed in Japanese Patent Application Laid-Open No. 3-22366.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、このよ
うなリチウム二次電池にあっては、本来の電池としての
電極反応以外にも、正負極表面上でＬｉイオンを消費し
ながら電解液の分解反応などの副次的な反応が進行する
ために、充放電サイクルを繰り返すにしたがって電極反
応に関与するＬｉイオンが減少し、放電容量が低下して
行くというサイクル特性劣化の問題があった。However, in such a lithium secondary battery, in addition to the electrode reaction as the original battery, the decomposition reaction of the electrolytic solution is consumed while consuming Li ions on the positive and negative electrode surfaces. Therefore, there is a problem of deterioration of cycle characteristics that Li ions involved in the electrode reaction decrease as the charge / discharge cycle is repeated and the discharge capacity decreases as the charge / discharge cycle is repeated.
【０００５】この発明は前記の問題点に鑑みてなされた
もので、その目的は、サイクル特性の劣化を抑制するこ
とができるリチウム二次電池を提供することにある。The present invention has been made in view of the above problems, and an object thereof is to provide a lithium secondary battery capable of suppressing deterioration of cycle characteristics.
【０００６】[0006]
【課題を解決するための手段】前記目的を達成するため
に本発明は、リチウム−金属複合酸化物を有する正極
と、セパレータと、リチウムのドープ，脱ドープが可能
である炭素質材料を有する負極とを順次重ね合わせた構
造を有する発電要素と非水電解液とを備えたリチウム二
次電池において、前記正極および負極の表面に該正極と
該負極との間の電極反応に関与しないイオン伝導性薄膜
が形成されていることを特徴とする。In order to achieve the above object, the present invention provides a positive electrode having a lithium-metal composite oxide, a separator, and a negative electrode having a carbonaceous material capable of lithium doping and dedoping. In a lithium secondary battery including a power generation element having a structure in which and are sequentially stacked and a non-aqueous electrolyte, ion conductivity not involved in an electrode reaction between the positive electrode and the negative electrode on the surfaces of the positive electrode and the negative electrode. It is characterized in that a thin film is formed.
【０００７】ここで、前記イオン伝導性薄膜は、ＲＦス
パッタ法を用いて形成されることが好ましい。Here, the ion conductive thin film is preferably formed by RF sputtering.
【０００８】[0008]
【作用】正極活物質および負極の表面に電池電極反応に
関与しないイオン伝導性薄膜が形成されているので、Ｌ
ｉイオンは正極活物質あるいは負極と副次的な反応を起
こして不活性化されることがなく、充放電サイクルを繰
り返してもサイクル特性は劣化しない。またこの薄膜は
イオン伝導性を有しておりＬｉイオンの通過を支障する
ことがないので、本来の電池電極反応を妨げることはな
い。[Function] Since the ion conductive thin film that does not participate in the battery electrode reaction is formed on the surfaces of the positive electrode active material and the negative electrode, L
The i-ion is not inactivated by causing a secondary reaction with the positive electrode active material or the negative electrode, and the cycle characteristics do not deteriorate even if the charge / discharge cycle is repeated. Further, since this thin film has ion conductivity and does not hinder passage of Li ions, it does not interfere with the original battery electrode reaction.
【０００９】なお、前記イオン伝導性薄膜をＲＦスパッ
タ法を用いて形成すれば、正極活物質または負極の表面
上の微細な凹凸部にも、均一に薄膜を生成させることが
できる。If the ion conductive thin film is formed by the RF sputtering method, the thin film can be uniformly formed on the fine irregularities on the surface of the positive electrode active material or the negative electrode.
【００１０】[0010]
【実施例】以下、本発明の好適実施例につき添付図面を
参照して詳細に説明する。ただし、本発明は以下の実施
例のみに限定されるものではない。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment of the present invention will now be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the following examples.
【００１１】《実施例１》図１に、本実施例の正極板の
模式的な断面図を示す。この正極板１の製造工程は次に
示すとおりである。正極活物質として、リチウム−金属
複合酸化物１０としてのＬｉＣｏＯ2 を８６重量％、導
電剤１２としての黒鉛およびアセチレンブラックをそれ
ぞれ４重量％、バインダー１４としてのポリフッ化ビニ
リデン（ＰＶＤＦ）を６重量％混合して作製した粉体
に、Ｎ−メチル−２−ピロリジノンを１００：１２０の
割合で混合し混練した。このようにして得られた正極活
物質のスラリーを、アルミニウム板３０（本実施例にあ
っては厚さ２０μｍ）に塗布し、８０℃で１時間熱風乾
燥炉内で乾燥させ、その後圧延して充填密度を高めて正
極板１を作製した。そして、この正極板１に塗布された
正極活物質の表面に、ＲＦスパッタ法を用いてＬｉ3.6
Ｓｉ0.6 Ｐ0.4 Ｏ4 なる組成を有するイオン伝導性非晶
質薄膜２０を生成して被覆した。Example 1 FIG. 1 is a schematic sectional view of the positive electrode plate of this example. The manufacturing process of the positive electrode plate 1 is as follows. As the positive electrode active material, 86 wt% of LiCoO 2 as the lithium-metal composite oxide 10, 4 wt% of graphite and acetylene black as the conductive agent 12, and 6 wt% of polyvinylidene fluoride (PVDF) as the binder 14 were used. N-methyl-2-pyrrolidinone was mixed with the powder produced by mixing in a ratio of 100: 120 and kneaded. The slurry of the positive electrode active material thus obtained was applied to an aluminum plate 30 (20 μm in thickness in this example), dried in a hot air drying oven at 80 ° C. for 1 hour, and then rolled. Positive electrode plate 1 was produced by increasing the packing density. Then, on the surface of the positive electrode active material applied to this positive electrode plate 1, Li 3.6 was used by RF sputtering.
An ion conductive amorphous thin film 20 having a composition of Si 0.6 P 0.4 O 4 was formed and coated.
【００１２】他方、図２に、本実施例の負極板２の模式
的な断面図を示す。この負極板２を作製するにあたり、
まずＬｉイオンのドープ，脱ドープが可能である炭素質
材料４０としてのピッチコークスを７０重量％、導電剤
４２としてのアセチレンブラックを１０重量％、フッ素
系バインダー４４を２０重量％混合して作製した粉体
に、Ｎ−メチル−２−ピロリジノンを１００：１２０の
割合で混合して混練した。このようにして得られた負極
合剤のスラリーを銅板６０（本実施例にあっては厚さ１
０μｍ）に塗布して、１５０℃，３０分間真空乾燥炉中
で乾燥させて負極板２を作製した。そして、この負極板
２にＲＦスパッタ法を用いてＬｉ3.6 Ｓｉ0.6 Ｐ0.4 Ｏ
4 なる組成を有するイオン伝導性非晶質薄膜５０を生成
して被覆した。On the other hand, FIG. 2 shows a schematic sectional view of the negative electrode plate 2 of this embodiment. In producing this negative electrode plate 2,
First, it was prepared by mixing 70% by weight of pitch coke as a carbonaceous material 40 capable of doping and dedoping with Li ions, 10% by weight of acetylene black as a conductive agent 42, and 20% by weight of a fluorine-based binder 44. N-methyl-2-pyrrolidinone was mixed with the powder at a ratio of 100: 120 and kneaded. The slurry of the negative electrode mixture thus obtained was applied to a copper plate 60 (thickness 1 in this embodiment).
0 μm) and dried in a vacuum drying oven at 150 ° C. for 30 minutes to prepare negative electrode plate 2. Then, Li 3.6 Si 0.6 P 0.4 O was applied to the negative electrode plate 2 by RF sputtering.
An ion conductive amorphous thin film 50 having a composition of 4 was produced and coated.
【００１３】以上のようにして得られた正極板１および
負極板２の間にポリプロピレン製マイクロポーラスフィ
ルムからなるセパレータ３を介装しスパイラル状に捲回
して発電要素とし、この発電要素を負極缶４に収装した
後エチレンカーボネートと炭酸ジエチルとの混合溶媒に
ＬｉＰＦ6 を１mol/l 溶解して得られた非水電解液を含
浸させて、図３に示すスパイラル形リチウム二次電池を
完成した。A separator 3 made of a polypropylene microporous film is interposed between the positive electrode plate 1 and the negative electrode plate 2 obtained as described above and spirally wound to form a power generating element. This power generating element is used as a negative electrode can. 4, and then impregnated with a non-aqueous electrolyte obtained by dissolving 1 mol / l of LiPF 6 in a mixed solvent of ethylene carbonate and diethyl carbonate to complete the spiral lithium secondary battery shown in FIG. .
【００１４】《実施例２》正極活物質として、リチウム
−金属複合酸化物１０としてのＬｉＮｉＯ2 を７０重量
％、導電剤１２としての黒鉛およびアセチレンブラック
をそれぞれ１０重量％、フッ素系バインダー１４を１０
重量％混合して作製した粉体に、Ｎ−メチル−２−ピロ
リジノンを１００：２００の割合で加えて混練した。こ
のようにして得られた正極活物質のスラリーを、アルミ
ニウム板３０（本実施例にあっては厚さ２０μｍ）に塗
布し、８０℃で１時間熱風乾燥炉内で乾燥させ、その後
圧延して充填密度を高めて正極板１を作製した。そし
て、この正極板１に塗布された正極活物質の表面に、Ｒ
Ｆスパッタ法を用いてＬｉ1.3 Ａｌ0.3 Ｔｉ1.7 （ＰＯ
4 ）3 なる組成を有するイオン伝導性非晶質薄膜２０を
生成して被覆した。Example 2 As the positive electrode active material, 70% by weight of LiNiO 2 as the lithium-metal composite oxide 10, 10% by weight of graphite and acetylene black as the conductive agent 12, and 10% by weight of the fluorine-based binder 14 were used.
N-methyl-2-pyrrolidinone was added at a ratio of 100: 200 to the powder prepared by mixing by weight% and kneaded. The slurry of the positive electrode active material thus obtained was applied to an aluminum plate 30 (20 μm in thickness in this example), dried in a hot air drying oven at 80 ° C. for 1 hour, and then rolled. Positive electrode plate 1 was produced by increasing the packing density. Then, on the surface of the positive electrode active material applied to the positive electrode plate 1, R
Li 1.3 Al 0.3 Ti 1.7 (PO
4 ) An ion conductive amorphous thin film 20 having a composition of 3 was produced and coated.
【００１５】他方、Ｌｉイオンのドープ，脱ドープが可
能である炭素質材料４０としての天然黒鉛を７０重量
％、導電剤４２としてのアセチレンブラックを１０重量
％、フッ素系バインダー４４を２０重量％混合して作製
した粉体に、Ｎ−メチル−２−ピロリジノンを１００：
１２０の割合で混合して混練した。このようにして得ら
れた負極合剤のスラリーを銅板６０（本実施例にあって
は厚さ１０μｍ）に塗布して、１５０℃，３０分間真空
乾燥炉中で乾燥させて負極板２を作製した。そして、こ
の負極板２にＲＦスパッタ法を用いてＬｉ1.3 Ａｌ0.3
Ｔｉ1.7 （ＰＯ4）3 なる組成を有するイオン伝導性非
晶質薄膜５０を生成して被覆した。On the other hand, 70% by weight of natural graphite as a carbonaceous material 40 capable of doping and dedoping with Li ions, 10% by weight of acetylene black as a conductive agent 42, and 20% by weight of a fluorine-based binder 44 are mixed. N-methyl-2-pyrrolidinone was added to the powder produced by 100:
The mixture was mixed and kneaded at a ratio of 120. The slurry of the negative electrode mixture thus obtained is applied to a copper plate 60 (thickness 10 μm in this embodiment) and dried in a vacuum drying oven at 150 ° C. for 30 minutes to prepare the negative electrode plate 2. did. Then, Li 1.3 Al 0.3 is applied to the negative electrode plate 2 by the RF sputtering method.
An ion conductive amorphous thin film 50 having a composition of Ti 1.7 (PO 4 ) 3 was produced and coated.
【００１６】以上のようにして得られた正極板１および
負極板２を用いて、前記実施例１と同様にスパイラル形
リチウム二次電池を完成した。Using the positive electrode plate 1 and the negative electrode plate 2 obtained as described above, a spiral type lithium secondary battery was completed in the same manner as in Example 1.
【００１７】《実施例３》正極活物質として、リチウム
−金属複合酸化物１０としてのＬｉＭｎ2 Ｏ4 を８５重
量％、導電剤１２としてのアセチレンブラックを７重量
％、フッ素系バインダー１４を８重量％混合して作製し
た粉体に、Ｎ−メチル−２−ピロリジノンを１００：１
２０の割合で加えて混練した。このようにして得られた
正極活物質のスラリーを、アルミニウム板３０（本実施
例にあっては厚さ２０μｍ）に塗布し、８０℃，１時間
熱風乾燥炉内で乾燥させ、その後圧延して充填密度を高
めて正極板１を作製した。そして、この正極板１に塗布
された正極活物質の表面に、ＲＦスパッタ法を用いてＬ
ｉ1.3 Ａｌ0.3 Ｚｒ1.9 （ＰＯ4 ）3 なる組成を有する
イオン伝導性非晶質薄膜２０を生成して被覆した。Example 3 As the positive electrode active material, 85 wt% of LiMn 2 O 4 as the lithium-metal composite oxide 10, 7 wt% of acetylene black as the conductive agent 12, and 8 wt% of the fluorine-based binder 14 were used. %, N-methyl-2-pyrrolidinone was added to the powder prepared by mixing 100%.
20 parts were added and kneaded. The positive electrode active material slurry thus obtained was applied to an aluminum plate 30 (thickness 20 μm in this example), dried in a hot air drying oven at 80 ° C. for 1 hour, and then rolled. Positive electrode plate 1 was produced by increasing the packing density. Then, on the surface of the positive electrode active material applied to this positive electrode plate 1, L
An ion conductive amorphous thin film 20 having a composition of i 1.3 Al 0.3 Zr 1.9 (PO 4 ) 3 was produced and coated.
【００１８】他方、Ｌｉイオンのドープ，脱ドープが可
能である炭素質材料４０としての天然黒鉛を７０重量
％、導電剤４２としてのアセチレンブラックを１０重量
％、フッ素系バインダー４４を２０重量％混合して作製
した粉体に、Ｎ−メチル−２−ピロリジノンを１００：
１２０の割合で混合して混練した。このようにして得ら
れた負極合剤のスラリーを、銅板６０（本実施例にあっ
ては厚さ１０μｍ）に塗布して、１５０℃，３０分間真
空乾燥炉中で乾燥させて負極板２を作製した。そして、
この負極板２にＲＦスパッタ法を用いてＬｉ1.3 Ａｌ
0.3 Ｚｒ1.9 （ＰＯ4 ）3 なる組成を有するイオン伝導
性非晶質薄膜５０を生成して被覆した。On the other hand, 70% by weight of natural graphite as a carbonaceous material 40 capable of doping and dedoping with Li ions, 10% by weight of acetylene black as a conductive agent 42, and 20% by weight of a fluorine-based binder 44 are mixed. N-methyl-2-pyrrolidinone was added to the powder produced by 100:
The mixture was mixed and kneaded at a ratio of 120. The slurry of the negative electrode mixture thus obtained was applied to a copper plate 60 (thickness 10 μm in this example) and dried in a vacuum drying oven at 150 ° C. for 30 minutes to form the negative electrode plate 2. It was made. And
This negative electrode plate 2 was coated with Li 1.3 Al by RF sputtering.
An ion conductive amorphous thin film 50 having a composition of 0.3 Zr 1.9 (PO 4 ) 3 was produced and coated.
【００１９】以上のようにして得られた正極板１および
負極板２を用いて、前記実施例１，２と同様にスパイラ
ル形リチウム二次電池を完成した。Using the positive electrode plate 1 and the negative electrode plate 2 obtained as described above, a spiral type lithium secondary battery was completed in the same manner as in Examples 1 and 2.
【００２０】次に、本実施例の作用について説明する。
図４〜図６は、前記実施例１〜３に係るスパイラル形リ
チウム二次電池のサイクル特性に対して従来の同形電池
のサイクル特性を比較例として示したグラフである。こ
こで比較例の電池とは、イオン伝導性非晶質薄膜２０，
５０がそれぞれ設けられていない正極板と負極板とを用
い、その他は実施例１〜３の電池と同様の仕様で完成さ
れたスパイラル形リチウム二次電池を示す。このグラフ
から明らかなように、本願発明の実施例１〜３に係る電
池は、比較例の従来電池と異なり充放電サイクルの反復
に伴う放電容量の減少、すなわちサイクル特性の劣化が
ほとんどないことが分かる。また、完成後の初期放電容
量自体も正極板および負極板にイオン伝導性非晶質薄膜
２０，５０が設けられていない比較例に比べて増加して
いる。Next, the operation of this embodiment will be described.
4 to 6 are graphs showing, as comparative examples, the cycle characteristics of the conventional same-type battery with respect to the cycle characteristics of the spiral type lithium secondary batteries according to Examples 1 to 3 above. Here, the battery of the comparative example means the ion conductive amorphous thin film 20,
A spiral type lithium secondary battery completed by using the same specifications as those of the batteries of Examples 1 to 3 except that a positive electrode plate and a negative electrode plate not provided with 50 are used. As is clear from this graph, the batteries according to Examples 1 to 3 of the invention of the present application, unlike the conventional battery of the comparative example, have almost no decrease in discharge capacity with repeated charge / discharge cycles, that is, almost no deterioration in cycle characteristics. I understand. Also, the initial discharge capacity itself after completion is increased as compared with the comparative example in which the ion conductive amorphous thin films 20 and 50 are not provided on the positive electrode plate and the negative electrode plate.
【００２１】これは、正極活物質および負極合剤の表面
を、電池電極反応とは直接関与しないイオン伝導性非晶
質薄膜で被覆したことによって、Ｌｉイオンの消費を伴
う電解液の分解反応や正極活物質および負極合剤表面上
でのＬｉイオンの不活性化を伴う副次的な反応が防止さ
れるためと推定される。This is because the surfaces of the positive electrode active material and the negative electrode mixture are coated with an ion conductive amorphous thin film that is not directly involved in the battery electrode reaction, so that the decomposition reaction of the electrolytic solution accompanied by the consumption of Li ions or It is presumed that this is because a side reaction accompanied by inactivation of Li ions on the surface of the positive electrode active material and the negative electrode mixture is prevented.
【００２２】[0022]
【発明の効果】以上詳細に説明したように、本発明によ
れば、正極活物質および負極合剤の表面に電池電極反応
に関与しないイオン伝導性薄膜が形成されているので、
Ｌｉイオンは正極活物質あるいは負極合剤と副次的な反
応を起こしていたずらに消費されたり不活性化されるこ
とがなく、サイクル特性の劣化を抑制することができ
る。As described in detail above, according to the present invention, since the ion conductive thin film that does not participate in the battery electrode reaction is formed on the surface of the positive electrode active material and the negative electrode mixture,
Li ions do not cause a secondary reaction with the positive electrode active material or the negative electrode mixture and are not consumed or deactivated without being mischievous, and deterioration of cycle characteristics can be suppressed.
【００２３】さらに、前記イオン伝導性薄膜をＲＦスパ
ッタ法を用いて形成すれば、正極活物質または負極合剤
表面上の微細な凹凸部にも、均一に薄膜を生成させるこ
とができ、サイクル特性の劣化をより確実に抑制するこ
とができる。Further, if the ion conductive thin film is formed by the RF sputtering method, the thin film can be uniformly formed on the fine irregularities on the surface of the positive electrode active material or the negative electrode mixture, and the cycle characteristics can be improved. Can be more reliably suppressed.
【図１】本願発明に係る正極板の一実施例の断面を示す
模式図である。FIG. 1 is a schematic view showing a cross section of an embodiment of a positive electrode plate according to the present invention.
【図２】本願発明の係る負極板の一実施例の断面を示す
模式図である。FIG. 2 is a schematic view showing a cross section of an embodiment of a negative electrode plate according to the present invention.
【図３】スパイラル形リチウム二次電池の断面図であ
る。FIG. 3 is a cross-sectional view of a spiral type lithium secondary battery.
【図４】本願第一実施例に係るスパイラル形リチウム二
次電池のサイクル特性と従来の同形電池のサイクル特性
とを比較して示すグラフである。FIG. 4 is a graph showing a comparison between the cycle characteristics of the spiral lithium secondary battery according to the first embodiment of the present application and the cycle characteristics of a conventional same-shaped battery.
【図５】本願第二実施例に係るスパイラル形リチウム二
次電池のサイクル特性と従来の同形電池のサイクル特性
とを比較して示すグラフである。FIG. 5 is a graph showing the cycle characteristics of the spiral type lithium secondary battery according to the second embodiment of the present application in comparison with the cycle characteristics of a conventional same-type battery.
【図６】本願第三実施例に係るスパイラル形リチウム二
次電池のサイクル特性と従来の同形電池のサイクル特性
とを比較して示すグラフである。FIG. 6 is a graph showing the cycle characteristics of the spiral type lithium secondary battery according to the third embodiment of the present application in comparison with the cycle characteristics of a conventional same-type battery.
１ 正極板 ２ 負極板 ３ セパレータ ４ 負極缶 １０ リチウム−金属複合酸化物 ４０ 炭素質材料（リチウムのドープ，脱ドープが可能
な）DESCRIPTION OF SYMBOLS 1 Positive electrode plate 2 Negative electrode plate 3 Separator 4 Negative electrode can 10 Lithium-metal composite oxide 40 Carbonaceous material (lithium can be doped and dedoped)
───────────────────────────────────────────────────── フロントページの続き (72)発明者 原田 吉郎 東京都港区新橋５丁目36番11号 富士電気 化学株式会社内 (72)発明者 名倉 秀哲 東京都港区新橋５丁目36番11号 富士電気 化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiro Harada 5-311, Shimbashi, Minato-ku, Tokyo Fuji Electric Chemical Co., Ltd. (72) Hidenori Nagura 5-36-11 Shinbashi, Minato-ku, Tokyo Fuji Electrochemical Co., Ltd.
Claims (2)
と、セパレータと、リチウムのドープ，脱ドープが可能
である炭素質材料を有する負極とを順次重ね合わせた構
造を有する発電要素と非水電解液とを備えたリチウム二
次電池において、 前記正極および負極の表面に該正極と該負極との間の電
極反応に関与しないイオン伝導性薄膜が形成されている
ことを特徴とするリチウム二次電池。1. A power generation element having a structure in which a positive electrode having a lithium-metal composite oxide, a separator, and a negative electrode having a carbonaceous material capable of lithium doping and dedoping are sequentially stacked, and a non-aqueous electrolysis. A lithium secondary battery including a liquid, wherein an ion conductive thin film that does not participate in an electrode reaction between the positive electrode and the negative electrode is formed on the surfaces of the positive electrode and the negative electrode. .
を用いて形成されることを特徴とする請求項１に記載の
リチウム二次電池。2. The lithium secondary battery according to claim 1, wherein the ion conductive thin film is formed by using an RF sputtering method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5031722A JPH06251764A (en) | 1993-02-22 | 1993-02-22 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5031722A JPH06251764A (en) | 1993-02-22 | 1993-02-22 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06251764A true JPH06251764A (en) | 1994-09-09 |
Family
ID=12338945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5031722A Pending JPH06251764A (en) | 1993-02-22 | 1993-02-22 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06251764A (en) |
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|---|---|---|---|---|
| JPH06290773A (en) * | 1993-03-30 | 1994-10-18 | Nippondenso Co Ltd | Lithium secondary battery |
| JPH09171813A (en) * | 1995-12-21 | 1997-06-30 | Sony Corp | Nonaqueous electrolyte battery |
| WO1998012761A1 (en) * | 1996-09-23 | 1998-03-26 | Valence Technology, Inc. | Lithium-containing, lithium-intercalating phosphates and their use as the positive or negative electrode material in a lithium secondary battery |
| JPH1196993A (en) * | 1997-09-22 | 1999-04-09 | Toyota Motor Corp | Negative electrode for lithium ion secondary battery |
| JP2000048810A (en) * | 1998-07-31 | 2000-02-18 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2004087251A (en) * | 2002-08-26 | 2004-03-18 | Nec Corp | Nonaqueous electrolytic solution secondary battery |
| US6720110B2 (en) | 1996-09-23 | 2004-04-13 | Valence Technology, Inc. | Lithium-containing phosphates, method of preparation, and uses thereof |
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| US6855462B2 (en) | 2000-04-27 | 2005-02-15 | Valence Technology, Inc. | Lithium metal fluorophosphate materials and preparation thereof |
| US6884544B2 (en) | 2000-01-18 | 2005-04-26 | Valence Technology, Inc. | Lithium-based active materials and preparation thereof |
| US6890686B1 (en) | 1999-03-23 | 2005-05-10 | Valence Technology, Inc. | Lithium-containing phosphate active materials |
| US6964827B2 (en) | 2000-04-27 | 2005-11-15 | Valence Technology, Inc. | Alkali/transition metal halo- and hydroxy-phosphates and related electrode active materials |
| US7482097B2 (en) | 2002-04-03 | 2009-01-27 | Valence Technology, Inc. | Alkali-transition metal phosphates having a +3 valence non-transition element and related electrode active materials |
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-
1993
- 1993-02-22 JP JP5031722A patent/JPH06251764A/en active Pending
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|---|---|---|---|---|
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| JPH09171813A (en) * | 1995-12-21 | 1997-06-30 | Sony Corp | Nonaqueous electrolyte battery |
| WO1998012761A1 (en) * | 1996-09-23 | 1998-03-26 | Valence Technology, Inc. | Lithium-containing, lithium-intercalating phosphates and their use as the positive or negative electrode material in a lithium secondary battery |
| US6720110B2 (en) | 1996-09-23 | 2004-04-13 | Valence Technology, Inc. | Lithium-containing phosphates, method of preparation, and uses thereof |
| JPH1196993A (en) * | 1997-09-22 | 1999-04-09 | Toyota Motor Corp | Negative electrode for lithium ion secondary battery |
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| US6890686B1 (en) | 1999-03-23 | 2005-05-10 | Valence Technology, Inc. | Lithium-containing phosphate active materials |
| US6884544B2 (en) | 2000-01-18 | 2005-04-26 | Valence Technology, Inc. | Lithium-based active materials and preparation thereof |
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| US6964827B2 (en) | 2000-04-27 | 2005-11-15 | Valence Technology, Inc. | Alkali/transition metal halo- and hydroxy-phosphates and related electrode active materials |
| US6855462B2 (en) | 2000-04-27 | 2005-02-15 | Valence Technology, Inc. | Lithium metal fluorophosphate materials and preparation thereof |
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| US7270915B2 (en) | 2000-04-27 | 2007-09-18 | Valence Technology, Inc. | Alkali/transition metal HALO-and hydroxy-phosphates and related electrode active materials |
| US7524584B2 (en) | 2000-04-27 | 2009-04-28 | Valence Technology, Inc. | Electrode active material for a secondary electrochemical cell |
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