JPH05190171A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH05190171A JPH05190171A JP4006737A JP673792A JPH05190171A JP H05190171 A JPH05190171 A JP H05190171A JP 4006737 A JP4006737 A JP 4006737A JP 673792 A JP673792 A JP 673792A JP H05190171 A JPH05190171 A JP H05190171A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- negative electrode
- electrolyte secondary
- secondary battery
- aqueous 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
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はリチウム等のアルカリ金
属、あるいはアルカリ土類金属を活物質とする負極と、
二酸化マンガン、三酸化モリブデン、五酸化バナジウ
ム、硫化チタンなどを活物質とする正極とを備えた非水
電解質二次電池に関する。FIELD OF THE INVENTION The present invention relates to a negative electrode using an alkali metal such as lithium or an alkaline earth metal as an active material,
The present invention relates to a non-aqueous electrolyte secondary battery provided with a positive electrode whose active material is manganese dioxide, molybdenum trioxide, vanadium pentoxide, titanium sulfide or the like.
【０００２】[0002]
【従来の技術】リチウム等のアルカリ金属、あるいはア
ルカリ土類金属を活物質とする負極と、二酸化マンガ
ン、三酸化モリブデン、五酸化バナジウム、硫化チタン
などを活物質とする正極とを備えた非水電解質二次電池
は、現在二次電池として多用されているニカド電池など
に比べ、電池容量が多いことが知られており、盛んにそ
の研究が成されており、一部実用化の域に達している。2. Description of the Related Art A non-aqueous material having a negative electrode whose active material is an alkali metal such as lithium or an alkaline earth metal and a positive electrode whose active material is manganese dioxide, molybdenum trioxide, vanadium pentoxide, titanium sulfide and the like. It is known that the electrolyte secondary battery has a larger battery capacity than the Ni-Cd battery, which is widely used as a secondary battery nowadays, and its research has been actively conducted, and it has reached the range of practical application. ing.
【０００３】ところがこの種電池の問題点としては、負
極活物質であるリチウムが、充電の際に負極表面に樹枝
状に成長して正極に接し、内部短絡を引き起こすために
充放電サイクルが極めて短いことが挙げられる。However, a problem with this type of battery is that the lithium, which is the negative electrode active material, grows in a dendritic manner on the surface of the negative electrode during charging and contacts the positive electrode, causing an internal short circuit, resulting in an extremely short charge / discharge cycle. It can be mentioned.
【０００４】このリチウムの負極表面への樹枝状成長に
対する対策として負極をリチウム合金で構成することが
提案されている。As a countermeasure against the dendritic growth of lithium on the surface of the negative electrode, it has been proposed to construct the negative electrode with a lithium alloy.
【０００５】これはリチウム単独の場合、放電によって
リチウムがイオンになって溶出すると負極表面が凹凸状
となり、その後の充電の際、リチウムが凸部に集中的に
電析して樹枝状に成長するのに対し、リチウム合金の場
合には充電時にリチウムが負極の基体となる金属と合金
を形成するように復元するため、リチウムの樹枝状成長
が抑制されるという利点を奏すためである。このような
基体となる金属としてはアルミニウム合金や、鉛、錫、
カドミウムなどの合金が提案されており、特にアルミニ
ウム中にマンガンを添加した合金を基体材料としたリチ
ウム合金を使用すればサイクル特性が優れた電池を作製
でき、実用化されている。This is because in the case of lithium alone, the surface of the negative electrode becomes uneven when lithium becomes ions and elutes by discharging, and during subsequent charging, lithium is electrodeposited intensively on the convex portion and grows in a dendritic form. On the other hand, in the case of a lithium alloy, lithium is restored so as to form an alloy with a metal serving as a base of the negative electrode during charging, and thus there is an advantage that dendritic growth of lithium is suppressed. Examples of such base metal include aluminum alloy, lead, tin,
Alloys such as cadmium have been proposed. In particular, if a lithium alloy containing an alloy in which manganese is added to aluminum as a base material is used, a battery having excellent cycle characteristics can be produced and put into practical use.
【０００６】[0006]
【発明が解決しようとする課題】然し乍らこの種のリチ
ウム合金を用いた電池では保存後のサイクル特性が劣化
するという新たな課題が存在することが判明した。これ
は保存によりリチウムとアルミニウムの合金が電解液と
反応してリチウム−アルミニウム合金表面に負活性皮膜
が生成し、充放電時リチウムの挿入、脱離反応を阻害す
るため負極反応が局在化し、その反応が集中して生じる
部分でリチウム−アルミニウム合金の微粉化が生じ、電
極の膨張や電極の脱落等が起きるためである。However, it has been found that batteries using this type of lithium alloy have a new problem that cycle characteristics after storage deteriorate. This is because the alloy of lithium and aluminum reacts with the electrolytic solution by storage to form a negative active film on the surface of the lithium-aluminum alloy, and the negative electrode reaction is localized because the lithium insertion and desorption reactions during charging and discharging are inhibited, This is because the lithium-aluminum alloy is pulverized at a portion where the reaction is concentrated and the electrodes expand or fall off.
【０００７】[0007]
【課題を解決するための手段】本発明はこのような新た
な課題に鑑みて為されたものであって、非水電解質二次
電池の負極として、アルミニウムとマンガンとから成る
合金に、アルミニウムよりも電気化学的に貴な金属から
選ばれる少なくとも一種を添加した合金から成る基体材
料と、活物質であるリチウムとの合金を用いている。The present invention has been made in view of such a new problem as described above, and a negative electrode of a non-aqueous electrolyte secondary battery has an alloy composed of aluminum and manganese, Also uses an alloy of a base material made of an alloy to which at least one kind selected from electrochemically noble metals is added and lithium as an active material.
【０００８】またこの基体材料となる合金中のマンガン
の添加量は、０．１ｗｔ％以上で、２．０ｗｔ％以下で
あり、且つバナジウム、クロム、チタンより選ばれる少
なくとも一種の添加量は、０．０１ｗｔ％以上、２．０
ｗｔ％以下、に選ばれている。The addition amount of manganese in the alloy which is the base material is 0.1 wt% or more and 2.0 wt% or less, and the addition amount of at least one selected from vanadium, chromium and titanium is 0. 0.01 wt% or more, 2.0
It is selected to be less than wt%.
【０００９】[0009]
【作用】本発明によれば、サイクル特性寿命が長く、し
かも保存後のサイクル特性にも優れた非水電解質二次電
池を得ることができる。According to the present invention, it is possible to obtain a non-aqueous electrolyte secondary battery having a long cycle characteristic life and excellent cycle characteristics after storage.
【００１０】この理由は基体材料としてアルミニウムと
マンガンとの合金を用いることによって、マンガンの添
加の効果により合金中にリチウムとの反応の活性点が増
加し、反応の局在化が抑制されサイクル特性が向上し、
更にバナジウム、クロム、チタン等の添加効果により保
存時に負極表面上に負活性皮膜が生成するすることを抑
制するため、保存後のサイクル特性の劣化を抑えること
ができたものと考えられる。またここでバナジウム、ク
ロム、チタンの添加が負活性皮膜の生成を抑制する理由
は定かではないが、これらの金属が電解液とリチウムと
の反応の被毒作用があるためではなかろうか。The reason for this is that the use of an alloy of aluminum and manganese as the base material increases the active sites of the reaction with lithium in the alloy due to the effect of the addition of manganese, and suppresses the localization of the reaction, resulting in cycle characteristics. Is improved,
Further, it is considered that the addition of vanadium, chromium, titanium, etc. suppresses the formation of a negative active film on the surface of the negative electrode during storage, so that deterioration of cycle characteristics after storage can be suppressed. Further, the reason why addition of vanadium, chromium, and titanium suppresses the formation of the negative active film is not clear, but it may be because these metals have a poisoning effect on the reaction between the electrolytic solution and lithium.
【００１１】[0011]
【実施例】図１は本発明に係る非水電解質二次電池の一
実施例を示す断面図であって、１は本発明の特徴とする
リチウム合金から成る負極であって、負極缶２の内底面
に固着した負極集電体３に圧着されている。４は正極で
あって、活物質としてのマンガン酸化物にアセチレンブ
ラック導電剤とフッ素樹脂結着剤とを８０：１０：１０
（重量比）の割合で混合した合剤を成型したものであ
り、正極缶５の内底面の正極集電体６に圧接されてい
る。1 is a sectional view showing an embodiment of a non-aqueous electrolyte secondary battery according to the present invention, in which 1 is a negative electrode made of a lithium alloy, which is a feature of the present invention, and a negative electrode can 2 It is pressure-bonded to the negative electrode current collector 3 fixed to the inner bottom surface. Numeral 4 is a positive electrode, in which acetylene black conductive agent and fluororesin binder are added to manganese oxide as an active material at 80:10:10.
The mixture is molded at a ratio of (weight ratio), and is pressed against the positive electrode current collector 6 on the inner bottom surface of the positive electrode can 5.
【００１２】７はポリプロピレン不織布よりなるセパレ
ータであって、このセパレータはプロピレンカーボネー
トと１．２ジメトキシエタンとの等体積混合溶媒に過塩
素酸リチウムを１モル／リットル溶解した非水電解液が
含浸されている。８は正、負極缶を電気絶縁する絶縁パ
ッキングである。尚、電池寸法は直径２５ｍｍφ、厚み
３．０ｍｍである。Reference numeral 7 is a separator made of polypropylene non-woven fabric, and this separator is impregnated with a non-aqueous electrolytic solution in which 1 mol / liter of lithium perchlorate is dissolved in an equal volume mixed solvent of propylene carbonate and 1.2 dimethoxyethane. ing. Reference numeral 8 is an insulating packing for electrically insulating the positive and negative electrode cans. The battery has a diameter of 25 mmφ and a thickness of 3.0 mm.
【００１３】次に本発明の特徴とする負極１の作成例に
ついて詳述する。Next, an example of producing the negative electrode 1 which is a feature of the present invention will be described in detail.
【００１４】［作成例 １］アルミニウム中にマンガン
１．０ｗｔ％と、バナジウムを表１に示す量になるよう
に添加して溶融して鋳造した後、冷却して得たアルミニ
ウムのインゴットを冷間圧延し厚み０．５ｍｍのＡｌ−
Ｍｎ−Ｖ合金の板を作製した。[Preparation Example 1] 1.0 wt% of manganese and vanadium were added to aluminum in amounts shown in Table 1, melted and cast, and then cooled to obtain an aluminum ingot. Al-rolled with a thickness of 0.5 mm
A Mn-V alloy plate was prepared.
【００１５】[0015]
【表１】 [Table 1]
【００１６】斯様にして作製したＡｌ−Ｍｎ−Ｖ合金板
を直径１９ｍｍの円盤上に打ち抜き、これを１モル／リ
ットルとなるようにＬｉＣｌＯ4を溶解した１．３ジオ
キソラン中で電解し、２００ｍＡｈの電気量に相当する
リチウムと反応させて合金化した。このようにして作製
した負極１を用いて作製した電池のうち、バナジウムＶ
の添加量が０．０１ｗｔ％〜２．０ｗｔ％のものをそれ
ぞれ本発明電池Ａ−１〜Ａ−８とし、バナジウムを添加
していなもの、並びに添加量３．０ｗｔ％のものを比較
電池Ｈ−１、Ｈ−２とする。The Al-Mn-V alloy plate thus prepared was punched out on a disk having a diameter of 19 mm, and this was electrolyzed in 1.3 dioxolane in which LiClO 4 was dissolved to a concentration of 1 mol / liter, and 200 mAh. And was alloyed by reacting with lithium corresponding to the amount of electricity. Among the batteries manufactured using the negative electrode 1 manufactured in this way, vanadium V
Of the present invention batteries A-1 to A-8 with the addition amount of 0.01 wt% to 2.0 wt% respectively, and those without addition of vanadium and the addition amount of 3.0 wt% are comparative batteries H -1, H-2.
【００１７】図２にバナジウム添加量を横軸にとり、縦
軸にサイクル数をとったサイクル特性図を示す。この図
において、実線は電池組立て直後の二次電池の特性、破
線は電池組立て後、室温で１年間保存したものの特性を
それぞれ示しており、バナジウムの添加量が０．０１ｗ
ｔ％〜２．０ｗｔ％のもの（Ａ−１〜Ａ−８）が優れた
サイクル特性を示すことがわかる。またバナジウムの添
加量が０．１ｗｔ％〜１．０ｗｔ％のもの（Ａ−２〜Ａ
−６）のものが特に優れた特性を示している。FIG. 2 shows a cycle characteristic diagram in which the horizontal axis represents the amount of vanadium added and the vertical axis represents the number of cycles. In this figure, the solid line shows the characteristics of the secondary battery immediately after the battery is assembled, and the broken line shows the characteristics of the battery stored for one year at room temperature after the battery is assembled.
It can be seen that those of t% to 2.0 wt% (A-1 to A-8) show excellent cycle characteristics. Moreover, the addition amount of vanadium is 0.1 wt% to 1.0 wt% (A-2 to A
-6) shows particularly excellent characteristics.
【００１８】尚、この時の試験条件は放電容量１２ｍＡ
ｈとし、充電は３ｍＡで３．２Ｖを終止としている。The test condition at this time was a discharge capacity of 12 mA.
It is set to h, and charging is 3 mA, and 3.2 V is terminated.
【００１９】［作成例 ２］バナジウムの代わりにクロ
ムを使用する他は作成例１と同様にして電池を作製し
た。ここで表２に本発明電池Ｂ−１〜Ｂ−８と比較電池
Ｈ−１、Ｈ−３の負極基体材料中のクロム添加量を示
す。[Preparation Example 2] A battery was prepared in the same manner as in Preparation Example 1 except that chromium was used instead of vanadium. Here, Table 2 shows the amount of chromium added to the negative electrode substrate materials of the present invention batteries B-1 to B-8 and the comparative batteries H-1 and H-3.
【００２０】[0020]
【表２】 [Table 2]
【００２１】図３にクロム添加量を横軸にとり、縦軸に
サイクル数をとったサイクル特性図を示す。この図にお
いて、実線は電池組立て直後の電池の特性、破線は室温
で１年間保存後の電池の特性をそれぞれ示しており、ク
ロムの添加量が０．０１ｗｔ％〜２．０ｗｔ％の電池
（Ｂ−１〜Ｂ−８）が優れたサイクル特性を示すことが
わかる。またクロムの添加量が０．１ｗｔ％〜１．０ｗ
ｔ％のもの（Ｂ−２〜Ｂ−６）のものが特に優れた特性
を示している。尚、この時の試験条件は、作成例１と同
様である。FIG. 3 shows a cycle characteristic diagram in which the horizontal axis represents the amount of chromium added and the vertical axis represents the number of cycles. In this figure, the solid line shows the characteristics of the battery immediately after assembling the battery, and the broken line shows the characteristics of the battery after storage at room temperature for 1 year, and the amount of chromium added is 0.01 wt% to 2.0 wt% (B It can be seen that -1 to B-8) show excellent cycle characteristics. The amount of chromium added is 0.1 wt% to 1.0 w
Those of t% (B-2 to B-6) show particularly excellent characteristics. The test conditions at this time are the same as those in the first creation example.
【００２２】［作成例 ３］バナジウムの代わりにチタ
ンを使用する他は作成例１と同様にして電池を作製し
た。ここで表３に本発明電池Ｃ−１〜Ｃ−８と比較電池
Ｈ−１、Ｈ−４の負極基体材料中のチタン添加量を示
す。[Preparation Example 3] A battery was prepared in the same manner as Preparation Example 1 except that titanium was used instead of vanadium. Here, Table 3 shows the amount of titanium added to the negative electrode base materials of the present invention batteries C-1 to C-8 and the comparative batteries H-1 and H-4.
【００２３】[0023]
【表３】 [Table 3]
【００２４】図４にチタン添加量を横軸にとり、縦軸に
サイクル数をとったサイクル特性図を示す。この図にお
いて、実線は電池組立て直後のものの特性、破線は室温
で１年間保存後のものの特性をそれぞれ示しており、チ
タンの添加量が０．０１ｗｔ％〜２．０ｗｔ％の電池
（Ｃ−１〜Ｃ−８）が優れたサイクル特性を示すことが
わかる。またチタンの添加量が０．１ｗｔ％〜１．０ｗ
ｔ％のもの（Ｃ−２〜Ｃ−６）のものが特に優れた特性
を示している。尚、この時の試験条件も、作成例１と同
様である。FIG. 4 shows a cycle characteristic diagram in which the horizontal axis represents the amount of titanium added and the vertical axis represents the number of cycles. In this figure, the solid line shows the characteristics immediately after battery assembly, and the broken line shows the characteristics after one year of storage at room temperature. The titanium addition amount was 0.01 wt% to 2.0 wt% (C-1 ~ C-8) shows excellent cycle characteristics. The amount of titanium added is 0.1 wt% to 1.0 w
Those of t% (C-2 to C-6) show particularly excellent characteristics. The test conditions at this time are the same as those in the first creation example.
【００２５】［作成例 ４］アルミニウム中にバナジウ
ム０．５ｗｔ％と、マンガンを表４に示す量になるよう
に添加して溶融して鋳造した後、冷却して得たアルミニ
ウムのインゴットを冷間圧延し厚み０．５ｍｍのＡｌ−
Ｍｎ−Ｖ合金の板を作製した。[Preparation Example 4] 0.5 wt% of vanadium and manganese were added to aluminum in amounts shown in Table 4, melted and cast, and cooled to obtain an aluminum ingot. Al-rolled with a thickness of 0.5 mm
A Mn-V alloy plate was prepared.
【００２６】[0026]
【表４】 [Table 4]
【００２７】斯様にして作製したＡｌ−Ｍｎ−Ｖ合金板
を直径１９ｍｍの円盤上に打ち抜き、これを１モル／リ
ットルとなるようにＬｉＣｌＯ4を溶解した１．３ジオ
キソラン中で電解し、２００ｍＡｈの電気量に相当する
リチウムと反応させて合金化した。このようにして作製
した負極１を用いて作製した電池のうち、マンガンＭｎ
の添加量が０．０１ｗｔ％〜２．０ｗｔ％のものをそれ
ぞれ本発明電池Ｄ−１〜Ｄ−８とし、マンガンを添加し
ていなもの、並びに添加量３．０ｗｔ％のものを比較電
池Ｈ−５、Ｈ−６とする。The Al-Mn-V alloy plate thus prepared was punched out on a disk having a diameter of 19 mm, and this was electrolyzed in 1.3 dioxolane in which LiClO 4 was dissolved to a concentration of 1 mol / liter, and 200 mAh. And was alloyed by reacting with lithium corresponding to the amount of electricity. Among the batteries manufactured using the negative electrode 1 manufactured in this way, manganese Mn
Comparative batteries H with addition amounts of 0.01 wt% to 2.0 wt% were designated as batteries D-1 to D-8 of the present invention, and those with no added manganese and addition amounts of 3.0 wt% -5 and H-6.
【００２８】図５にマンガン添加量を横軸にとり、縦軸
にサイクル数をとったサイクル特性図を示す。この図に
おいて、実線は電池組立て直後の二次電池の特性で、破
線は組立て後、室温で１年間保存した電池の特性をそれ
ぞれ示しており、マンガンの添加量が０．０１ｗｔ％〜
２．０ｗｔ％のもの（Ｄ−１〜Ｄ−８）が優れたサイク
ル特性を示すことがわかる。またマンガンの添加量が
０．１ｗｔ％〜２．０ｗｔ％の電池（Ｄ−２〜Ｄ−８）
が特に優れた特性を示している。尚、この時の試験条件
も、作成例１の場合と同じである。FIG. 5 is a cycle characteristic diagram in which the horizontal axis represents the amount of manganese added and the vertical axis represents the number of cycles. In this figure, the solid line shows the characteristics of the secondary battery immediately after the battery is assembled, and the broken line shows the characteristics of the battery stored for one year at room temperature after the assembly.
It can be seen that those of 2.0 wt% (D-1 to D-8) show excellent cycle characteristics. Batteries containing 0.1% to 2.0% by weight of manganese (D-2 to D-8)
Shows particularly excellent characteristics. The test conditions at this time are also the same as in the case of Preparation Example 1.
【００２９】[0029]
【発明の効果】本発明は以上の説明から明らかなよう
に、非水電解質二次電池の負極として、アルミニウムと
マンガンとから成る合金に、アルミニウムよりも電気化
学的に貴な金属から選ばれる少なくとも一種を添加した
合金から成る基体材料と、活物質であるリチウムとの合
金を用いているので、二次電池にとって重要なサイクル
特性が改善されており、特に電池組立てた後に保存状態
に置かれていた電池のサイクル特性が著しく改善され、
非水電解質二次電池に対する工業的価値は極めて高い。As is apparent from the above description, the present invention is an alloy of aluminum and manganese, which is used as a negative electrode of a non-aqueous electrolyte secondary battery, and at least a metal which is electrochemically more noble than aluminum. The use of an alloy of a base material consisting of an alloy with one type added and lithium, which is the active material, improves the cycle characteristics that are important for secondary batteries, and in particular, it is placed in a storage state after battery assembly. The battery cycle characteristics are significantly improved,
The industrial value of the non-aqueous electrolyte secondary battery is extremely high.
【図１】本発明に係る非水電解質二次電池の縦断面図で
ある。FIG. 1 is a vertical cross-sectional view of a non-aqueous electrolyte secondary battery according to the present invention.
【図２】本発明電池Ａ−１〜Ａ−８と比較電池Ｈ−１、
Ｈ−２とのサイクル特性図である。FIG. 2 shows the present invention batteries A-1 to A-8 and the comparative battery H-1.
It is a cycle characteristic view with H-2.
【図３】本発明電池Ｂ−１〜Ｂ−８と比較電池Ｈ−１、
Ｈ−３とのサイクル特性図である。FIG. 3 shows the present invention batteries B-1 to B-8 and the comparative battery H-1.
It is a cycle characteristic view with H-3.
【図４】本発明電池Ｃ−１〜Ｃ−８と比較電池Ｈ−１、
Ｈ−４とのサイクル特性図である。FIG. 4 shows the present invention batteries C-1 to C-8 and a comparative battery H-1.
It is a cycle characteristic view with H-4.
【図５】本発明電池Ｄ−１〜Ｄ−８と比較電池Ｈ−５、
Ｈ−６とのサイクル特性図である。FIG. 5 shows the present invention batteries D-1 to D-8 and the comparative battery H-5.
It is a cycle characteristic view with H-6.
１ 負極 ４ 正極 ７ セパレータ 1 Negative electrode 4 Positive electrode 7 Separator
Claims (9)
極と、を備え、前記負極は、アルミニウムとマンガンと
から成る合金に、アルミニウムよりも電気化学的に貴な
金属から選ばれる少なくとも一種を添加した合金から成
る基体材料と、活物質であるリチウムとの合金から成る
ことを特徴とした非水電解質二次電池。1. A chargeable / dischargeable positive electrode, a non-aqueous electrolyte, and a negative electrode, the negative electrode being an alloy of aluminum and manganese, and at least a metal electrochemically nobler than aluminum. A non-aqueous electrolyte secondary battery comprising an alloy of a base material made of an alloy to which one kind is added and lithium which is an active material.
るリチウムとを電気化学的に反応させて作製した合金か
ら成ることを特徴とした請求項１記載の非水電解質二次
電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode is made of an alloy produced by electrochemically reacting the base material and lithium as an active material.
金属は、バナジウム、クロム、チタンから選ばれる少な
くとも一種であることを特徴とする請求項１、または請
求項２記載の非水電解質二次電池。3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the metal electrochemically more noble than aluminum is at least one selected from vanadium, chromium and titanium. ..
ガン量は、０．１ｗｔ％以上で、２．０ｗｔ％以下であ
り、且つバナジウムの添加量は、０．０１ｗｔ％以上、
２．０ｗｔ％以下であることを特徴とした請求項３記載
の非水電解液二次電池。4. The amount of manganese in the alloy, which is the base material of the negative electrode, is 0.1 wt% or more and 2.0 wt% or less, and the addition amount of vanadium is 0.01 wt% or more,
The non-aqueous electrolyte secondary battery according to claim 3, wherein the content is 2.0 wt% or less.
ジウムの添加量は、０．１ｗｔ％で、以上１．０ｗｔ％
以下であることを特徴とする請求項４記載の非水電解質
二次電池。5. The addition amount of vanadium in the alloy, which is the base material of the negative electrode, is 0.1 wt% and is 1.0 wt% or more.
The non-aqueous electrolyte secondary battery according to claim 4, wherein:
ガン量は、０．１ｗｔ％以上で、２．０ｗｔ％以下であ
り、且つクロムの添加量は、０．０１ｗｔ％以上、２．
０ｗｔ％以下であることを特徴とした請求項３記載の非
水電解液二次電池。6. The amount of manganese in the alloy, which is the base material of the negative electrode, is 0.1 wt% or more and 2.0 wt% or less, and the amount of chromium added is 0.01 wt% or more, 2.
The non-aqueous electrolyte secondary battery according to claim 3, wherein the content is 0 wt% or less.
ムの添加量は、０．１ｗｔ％以上で、１．０ｗｔ％以下
であることを特徴とする請求項６記載の非水電解質二次
電池。7. The non-aqueous electrolyte secondary according to claim 6, wherein the amount of chromium added to the alloy as the base material of the negative electrode is 0.1 wt% or more and 1.0 wt% or less. battery.
ガン量は、０．１ｗｔ％以上で、２．０ｗｔ％以下であ
り、且つチタンの添加量は、０．０１ｗｔ％以上、２．
０ｗｔ％以下であることを特徴とした請求項３記載の非
水電解液二次電池。8. The amount of manganese in the alloy, which is the base material of the negative electrode, is 0.1 wt% or more and 2.0 wt% or less, and the amount of titanium added is 0.01 wt% or more, 2.
The non-aqueous electrolyte secondary battery according to claim 3, wherein the content is 0 wt% or less.
ンの添加量は、０．１ｗｔ％以上で、２．０ｗｔ％以下
であることを特徴とする請求項８記載の非水電解質二次
電池。9. The non-aqueous electrolyte secondary according to claim 8, wherein the addition amount of titanium in the alloy that is the base material of the negative electrode is 0.1 wt% or more and 2.0 wt% or less. battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04006737A JP3081336B2 (en) | 1992-01-17 | 1992-01-17 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04006737A JP3081336B2 (en) | 1992-01-17 | 1992-01-17 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05190171A true JPH05190171A (en) | 1993-07-30 |
| JP3081336B2 JP3081336B2 (en) | 2000-08-28 |
Family
ID=11646535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04006737A Expired - Fee Related JP3081336B2 (en) | 1992-01-17 | 1992-01-17 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3081336B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0690520A1 (en) | 1994-05-30 | 1996-01-03 | Canon Kabushiki Kaisha | Rechargeable batteries |
| EP0693792A1 (en) | 1994-07-19 | 1996-01-24 | Canon Kabushiki Kaisha | Rechargeable batteries having a specific anode and process for the production of them |
| US5658689A (en) * | 1995-09-06 | 1997-08-19 | Canon Kabushiki Kaisha | Rechargeable lithium battery having a specific electrolyte |
| US5698339A (en) * | 1994-10-21 | 1997-12-16 | Canon Kabushiki Kaisha | Anode with an anode active material-retaining body having a number of pores distributed therein, a rechargeable battery, provided with said anode, and the process for the production of said anode |
| US5728482A (en) * | 1995-12-22 | 1998-03-17 | Canon Kabushiki Kaisha | Secondary battery and method for manufacturing the same |
| US5998063A (en) * | 1994-12-02 | 1999-12-07 | Canon Kabushiki Kaisha | Lithium secondary cell |
| US6051340A (en) * | 1994-05-30 | 2000-04-18 | Canon Kabushiki Kaisha | Rechargeable lithium battery |
| US6063142A (en) * | 1994-12-01 | 2000-05-16 | Canon Kabushiki Kaisha | Process for producing a rechargeable lithium battery having an improved anode coated by a film containing a specific metal oxide material |
| US6432585B1 (en) | 1997-01-28 | 2002-08-13 | Canon Kabushiki Kaisha | Electrode structural body, rechargeable battery provided with said electrode structural body, and rechargeable battery |
| US6517974B1 (en) | 1998-01-30 | 2003-02-11 | Canon Kabushiki Kaisha | Lithium secondary battery and method of manufacturing the lithium secondary battery |
| US6730434B1 (en) | 1998-09-18 | 2004-05-04 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| US6835332B2 (en) | 2000-03-13 | 2004-12-28 | Canon Kabushiki Kaisha | Process for producing an electrode material for a rechargeable lithium battery, an electrode structural body for a rechargeable lithium battery, process for producing said electrode structural body, a rechargeable lithium battery in which said electrode structural body is used, and a process for producing said rechargeable lithium battery |
| US6949312B1 (en) | 1998-09-18 | 2005-09-27 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
-
1992
- 1992-01-17 JP JP04006737A patent/JP3081336B2/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6051340A (en) * | 1994-05-30 | 2000-04-18 | Canon Kabushiki Kaisha | Rechargeable lithium battery |
| US6596432B2 (en) | 1994-05-30 | 2003-07-22 | Canon Kabushiki Kaisha | Rechargeable batteries |
| EP0690520A1 (en) | 1994-05-30 | 1996-01-03 | Canon Kabushiki Kaisha | Rechargeable batteries |
| EP0693792A1 (en) | 1994-07-19 | 1996-01-24 | Canon Kabushiki Kaisha | Rechargeable batteries having a specific anode and process for the production of them |
| US5641591A (en) * | 1994-07-19 | 1997-06-24 | Canon Kabushiki Kaisha | Rechargeable batteries having a specific anode and process for the production of them |
| US5698339A (en) * | 1994-10-21 | 1997-12-16 | Canon Kabushiki Kaisha | Anode with an anode active material-retaining body having a number of pores distributed therein, a rechargeable battery, provided with said anode, and the process for the production of said anode |
| US6063142A (en) * | 1994-12-01 | 2000-05-16 | Canon Kabushiki Kaisha | Process for producing a rechargeable lithium battery having an improved anode coated by a film containing a specific metal oxide material |
| US5998063A (en) * | 1994-12-02 | 1999-12-07 | Canon Kabushiki Kaisha | Lithium secondary cell |
| US5658689A (en) * | 1995-09-06 | 1997-08-19 | Canon Kabushiki Kaisha | Rechargeable lithium battery having a specific electrolyte |
| US5728482A (en) * | 1995-12-22 | 1998-03-17 | Canon Kabushiki Kaisha | Secondary battery and method for manufacturing the same |
| US6432585B1 (en) | 1997-01-28 | 2002-08-13 | Canon Kabushiki Kaisha | Electrode structural body, rechargeable battery provided with said electrode structural body, and rechargeable battery |
| US6569568B2 (en) | 1998-01-30 | 2003-05-27 | Canon Kabushiki Kaisha | Lithium secondary battery and method of manufacturing the lithium secondary battery |
| US6517974B1 (en) | 1998-01-30 | 2003-02-11 | Canon Kabushiki Kaisha | Lithium secondary battery and method of manufacturing the lithium secondary battery |
| US6730434B1 (en) | 1998-09-18 | 2004-05-04 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| US6949312B1 (en) | 1998-09-18 | 2005-09-27 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| US7183018B2 (en) | 1998-09-18 | 2007-02-27 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| US7534528B2 (en) | 1998-09-18 | 2009-05-19 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| EP2219253A2 (en) | 1998-09-18 | 2010-08-18 | Canon Kabushiki Kaisha | Electrode material |
| US6835332B2 (en) | 2000-03-13 | 2004-12-28 | Canon Kabushiki Kaisha | Process for producing an electrode material for a rechargeable lithium battery, an electrode structural body for a rechargeable lithium battery, process for producing said electrode structural body, a rechargeable lithium battery in which said electrode structural body is used, and a process for producing said rechargeable lithium battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3081336B2 (en) | 2000-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5143852B2 (en) | Nonaqueous electrolyte secondary battery | |
| JPH05101846A (en) | Non-aqueous electrolytic secondary battery | |
| JPH0574486A (en) | Nonaqueous electrolyte battery | |
| JPH0750165A (en) | Non-aqueous electrolyte battery | |
| JP3081336B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH0896849A (en) | Nonaqueous electrolytic secondary battery | |
| EP0139756A1 (en) | Rechargeable electrochemical apparatus and negative pole therefor | |
| JPH01200572A (en) | Electrolyte for lithium storage battery | |
| JP3177257B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH0456079A (en) | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery thereof | |
| JPH0536401A (en) | Lithium secondary battery | |
| JPH0353743B2 (en) | ||
| JP2664469B2 (en) | Non-aqueous electrolyte battery | |
| JPH01274359A (en) | Nonaqueous electrolyte secondary battery | |
| JP4007636B2 (en) | Organic electrolyte secondary battery | |
| JP2989212B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP3025692B2 (en) | Rechargeable battery | |
| US6291108B1 (en) | Non-aqueous electrolyte cell | |
| JPH0864239A (en) | Nonaqueous electrolyte battery | |
| JP2714078B2 (en) | Non-aqueous electrolyte battery | |
| JP2840357B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH0935716A (en) | Lithium battery | |
| JP2656305B2 (en) | Organic electrolyte secondary battery | |
| JP2991758B2 (en) | Non-aqueous electrolyte for lithium secondary batteries | |
| JP2744061B2 (en) | Non-aqueous electrolyte secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080623 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090623 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |