JPH05101846A - Non-aqueous electrolytic secondary battery - Google Patents
Non-aqueous electrolytic secondary batteryInfo
- Publication number
- JPH05101846A JPH05101846A JP3260744A JP26074491A JPH05101846A JP H05101846 A JPH05101846 A JP H05101846A JP 3260744 A JP3260744 A JP 3260744A JP 26074491 A JP26074491 A JP 26074491A JP H05101846 A JPH05101846 A JP H05101846A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- electrolytic solution
- metal
- battery
- additive
- 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、充放電可能な正極と、
非水電解液と、リチウム、リチウム合金、或はリチウム
と炭素との化合物から成る負極と、から構成され、前記
電解液はリチウム金属より電気化学的に貴な金属の硝酸
塩、或は亜硝酸塩を含むことを特徴とする非水電解液二
次電池に関する。The present invention relates to a chargeable / dischargeable positive electrode,
It comprises a non-aqueous electrolyte and a negative electrode made of lithium, a lithium alloy, or a compound of lithium and carbon, and the electrolyte contains a nitrate or nitrite of a metal electrochemically more noble than lithium metal. The present invention relates to a non-aqueous electrolyte secondary battery containing the same.
【０００２】[0002]
【従来の技術】リチウムを主体とする負極を有する非水
系電解液二次電池はエネルギー密度が高いことから注目
され、実用に供されつつある。2. Description of the Related Art A non-aqueous electrolyte secondary battery having a negative electrode containing lithium as a main component is attracting attention because of its high energy density and is being put to practical use.
【０００３】ところがこの種の非水系電解質二次電池に
は次のような問題点がある。それは負極活物質であるリ
チウムが放電、充電の際にリチウムの溶解、析出が均一
に生じないため、電流の局在化が生じ、その結果放電時
には負極表面が凹凸状になったり、また充電時にはリチ
ウムが樹枝状に成長して正極に接し、内部短絡を引き起
こしたり、或は充電によって電析した活性なリチウムと
電解液が反応してリチウムの充放電効率が低下するた
め、充放電サイクルが極めて短いことである。However, this type of non-aqueous electrolyte secondary battery has the following problems. This is because lithium, which is the negative electrode active material, does not uniformly dissolve and precipitate lithium during discharging and charging, resulting in localization of current, resulting in uneven surface of the negative electrode during discharging, and during charging. Lithium grows in a dendritic manner and contacts the positive electrode, causing an internal short circuit, or the active lithium that has been electrodeposited by charging reacts with the electrolytic solution to reduce the lithium charge / discharge efficiency. It's short.
【０００４】この対策として、電解液中にエチレングリ
コールを添加したり（特開昭５９−１３００９３号公報
参照）、同じくエタノールや２−メトキシアルコール、
ジエチレングリコールモノメチルエーテル等のアルコー
ル系化合物を添加する提案（特開昭５７−６３７７４号
公報、特開昭６０−８９０７５号公報）等が為されてい
る。As measures against this, ethylene glycol is added to the electrolytic solution (see JP-A-59-130093), ethanol, 2-methoxy alcohol,
Proposals for adding alcohol compounds such as diethylene glycol monomethyl ether (JP-A-57-63774 and JP-A-60-89075) have been made.
【０００５】[0005]
【発明が解決しようとする課題】然し乍ら何れの方法も
特性の改善は見られるものの、二次電池として満足でき
る充分な効果は得られていない。However, although any of the methods has been found to have improved characteristics, it has not been sufficiently effective as a secondary battery.
【０００６】[0006]
【課題を解決するための手段】本発明はこのような課題
に鑑みて為されたものであって、充放電可能な正極と、
非水電解液と、リチウム、リチウム合金、或はリチウム
と炭素との化合物から成る負極と、から構成され、前記
電解液として電気化学的にリチウム金属より電気化学的
に貴な金属の硝酸塩、或は亜硝酸塩を含ませたものであ
り、そのリチウム金属より電気化学的に貴な金属として
は、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ａｌ、Ｃｒ、Ｍｎ、Ｆ
ｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ａｇ、Ｃｄ、Ｉ
ｎ、Ｓｎ、Ｓｂ、Ｔｌ、Ｐｂ、Ｂｉから選ばれる金属の
一種であり、更に前記リチウム金属より電気化学的に貴
な金属の硝酸塩、或は亜硝酸塩の添加量が１０-6ｍｏｌ
／ｌ以上、１０-1ｍｏｌ／ｌ以下であることを特徴とし
ている。The present invention has been made in view of the above problems, and includes a chargeable / dischargeable positive electrode,
A non-aqueous electrolyte solution and a negative electrode composed of lithium, a lithium alloy, or a compound of lithium and carbon, and the electrolyte solution is a nitrate of a metal electrochemically more noble than lithium metal electrochemically, or Contains nitrite, and as the metal electrochemically more noble than the lithium metal, Mg, Ca, Sr, Ba, Al, Cr, Mn, F
e, Co, Ni, Cu, Zn, Ga, Ag, Cd, I
n, Sn, Sb, Tl, Pb, Bi, which is one of the metals, and the amount of the nitrate or nitrite of the metal electrochemically noble than the lithium metal is 10 -6 mol.
/ L or more and 10 -1 mol / l or less.
【０００７】（ホ） 作用 本発明は電解液中にリチウムより貴な金属の硝酸塩、も
しくは亜硝酸塩を添加しているので、電解液中のこれら
の金属イオンの一部と負極表面のリチウム金属とがイオ
ン交換し、その結果、リチウム表面の不活性被膜が除去
され、更にリチウムより貴な金属が析出する。この反応
によりリチウム表面の不活性被膜が除去されるため、リ
チウムの充放電の活性点が増加するため、放電時にはリ
チウム面の均一な溶解が生じ、また充電時には電流の集
中が抑制されるのでリチウムの樹枝状成長が生じにくく
なる。またリチウムより貴な金属がリチウム面に析出す
るが、これが電解液溶媒と活性リチウムとの反応を妨害
するためリチウムの充放電効率も向上する。これらの理
由によりリチウム二次電池のサイクル特性が向上する。(E) Action Since the present invention adds a nitrate or nitrite of a metal that is more noble than lithium to the electrolytic solution, some of these metal ions in the electrolytic solution and lithium metal on the surface of the negative electrode Are ion-exchanged, and as a result, the inactive coating film on the lithium surface is removed, and a metal nobler than lithium is deposited. This reaction removes the inactive coating on the lithium surface, increasing the number of active sites for charging / discharging lithium, so that the lithium surface is uniformly dissolved during discharging and current concentration is suppressed during charging. The dendritic growth of is less likely to occur. Further, a metal nobler than lithium is deposited on the lithium surface, but this interferes with the reaction between the electrolytic solution solvent and active lithium, so that the charge / discharge efficiency of lithium is also improved. For these reasons, the cycle characteristics of the lithium secondary battery are improved.
【０００８】[0008]
【実施例】第１図は本発明の１実施例による電池の縦断
面図を示し、図において１はリチウム金属よりなる負極
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の内底面に固着し
た正極集電体６に圧着されている。1 is a vertical cross-sectional view of a battery according to an embodiment of the present invention, in which 1 is a negative electrode made of lithium metal, and a negative electrode current collector 3 fixed to the inner bottom surface of a negative electrode can 2. Is crimped to. Reference numeral 4 denotes a positive electrode, which is formed by molding a mixture of manganese oxide as an active material and an acetylene black conductive agent and a fluororesin binder at a ratio of 80:10:10 (weight ratio). It is pressure-bonded to the positive electrode current collector 6 fixed to the inner bottom surface of the can 5.
【０００９】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、このセパレータに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／ｌ溶解し、更に本発明の要旨
とする添加剤（詳細は後述）を添加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、この電池寸法は直径２５ｍｍφ、厚み３．０
ｍｍである。Reference numeral 7 is a separator made of polypropylene nonwoven fabric, in which 1 mol / l of lithium perchlorate is dissolved in an equal volume mixed solvent of propylene carbonate and 1.2 dimethoxyethane. Is impregnated with a non-aqueous electrolytic solution containing an additive (details will be described later). 8 is an insulating packing that electrically insulates the positive and negative electrode cans.
mm.
【００１０】作成例 １ 表１に、リチウム金属より電気化学的に貴な金属、具体
的には、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ａｌ、Ｃｒ、Ｍｎ、
Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ａｇ、Ｃｄ、Ｉ
ｎ、Ｓｎ、Ｓｂ、Ｔｌ、Ｐｂ、Ｂｉのうちから選ばれた
硝酸塩を前記電解液に含浸させ、更にその添加濃度（ｍ
ｏｌ／ｌ）を種々変化させた場合の組み合わせが示され
ており、この表１中の大文字で表した電池（Ａ、Ｂ、
Ｃ、Ｄ、Ｅ、Ｆ、Ｇ、Ｈ、Ｉ、Ｊ、Ｋ、Ｌ、Ｍ、Ｎ、
Ｏ、Ｐ、Ｑ、Ｒ、Ｓ、Ｔ）が本発明電池であり、小文字
で表した電池（ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、ｉ、
ｊ、ｋ、ｌ、ｍ、ｎ、ｏ、ｐ、ｑ、ｒ、ｓ、ｔ）が比較
電池である。Preparation Example 1 Table 1 shows metals that are electrochemically more noble than lithium metal, specifically Mg, Ca, Sr, Ba, Al, Cr, Mn,
Fe, Co, Ni, Cu, Zn, Ga, Ag, Cd, I
The electrolyte solution is impregnated with a nitrate selected from n, Sn, Sb, Tl, Pb and Bi, and the concentration added (m
ol / l) are shown in various combinations and the capitalized cells (A, B,
C, D, E, F, G, H, I, J, K, L, M, N,
O, P, Q, R, S, T) are the batteries of the present invention, and the batteries represented by lowercase letters (a, b, c, d, e, f, g, h, i,
j, k, l, m, n, o, p, q, r, s, t) are comparative batteries.
【００１１】[0011]
【表１】 [Table 1]
【００１２】そして電解液に添加したリチウム金属より
電気化学的に貴な各金属の硝酸塩の添加濃度を変化させ
た場合のサイクル特性を図２から図２１に示す。これら
の図において、それぞれ縦軸には各電池のサイクル寿命
を、横軸には各添加剤の濃度をプロットした。また試験
条件は放電容量２０ｍＡｈとし、充電は３ｍＡで３．５
Ｖを終止とした。2 to 21 show the cycle characteristics when the concentration of the nitrate of each metal electrochemically more noble than the lithium metal added to the electrolytic solution is changed. In these figures, the vertical axis represents the cycle life of each battery and the horizontal axis represents the concentration of each additive. The test conditions were a discharge capacity of 20 mAh and a charge of 3 mA at 3.5.
V was terminated.
【００１３】図２は添加剤として、Ａｌ（ＮＯ3）3を電
解液に種々の添加量で添加した場合の添加量とサイクル
特性であり、添加剤の添加量が１０-6ｍｏｌ〜１０-1ｍ
ｏｌの場合の電池（Ａ1）、（Ａ2）、（Ａ3）、（Ａ
4）、（Ａ5）、（Ａ6）は２００サイクル以上の充放電
特性を示すのに対し、添加量が１０-6ｍｏｌ〜１０-1ｍ
ｏｌより外れた電池（ａ1）、（ａ2）、（ａ3）のサイ
クル特性は極端に低下していることがわかる。このよう
に添加剤の添加量としては１０-6ｍｏｌ〜１０-1ｍｏｌ
の範囲が適していることがわかる。以下同様に、図３は
添加剤としてＣｒ（ＮＯ3）3を用いた電池のサイクル特
性図、図４は添加剤としてＭｎ（ＮＯ3）2を用いた電池
のサイクル特性図、図５は添加剤としてＦｅ（ＮＯ3）3
を用いた電池のサイクル特性図、図６は添加剤としてＣ
ｏ（ＮＯ3）2を用いた電池のサイクル特性図、図７は添
加剤としてＮｉ（ＮＯ3）2を用いた電池のサイクル特性
図、図８は添加剤としてＣｕ（ＮＯ3）2を用いた電池の
サイクル特性図、図９は添加剤としてＺｎ（ＮＯ3）2を
用いた電池のサイクル特性図、図１０は添加剤としてＧ
ａ（ＮＯ3）2を用いた電池のサイクル特性図、図１１は
添加剤としてＡｇＮＯ3を用いた電池のサイクル特性
図、図１２は添加剤としてＣｄ（ＮＯ3）2を用いた電池
のサイクル特性図、図１３は添加剤としてＩｎ（Ｎ
Ｏ3）3を用いた電池のサイクル特性図、図１４は添加剤
としてＳｎ（ＮＯ3）2を用いた電池のサイクル特性図、
図１５は添加剤としてＳｂ（ＮＯ3）3を用いた電池のサ
イクル特性図、図１６は添加剤としてＴｌＮＯ3を用い
た電池のサイクル特性図、図１７は添加剤としてＰｂ
（ＮＯ3）2を用いた電池のサイクル特性図、図１８は添
加剤としてＢｉ（ＮＯ3）3を用いた電池のサイクル特性
図、図１９は添加剤としてＭｇ（ＮＯ 3）2を用いた電池
のサイクル特性図、図２０は添加剤としてＳｒ（Ｎ
Ｏ3）2を用いた電池のサイクル特性図、図２１は添加剤
としてＢａ（ＮＯ3）2を用いた電池のサイクル特性図で
ある。FIG. 2 shows Al (NO3)3The electric
Addition amount and cycle when adding various amounts to the solution
It is a characteristic that the additive amount is 10-6mol-10-1m
batteries (A1), (A2), (A3), (A
4), (A5), and (A6) charge and discharge for 200 cycles or more
While showing characteristics, the addition amount is 10-6mol-10-1m
batteries (a1), (a2), (a3) that are out of ol
It can be seen that the crew characteristics are extremely deteriorated. like this
The additive amount of 10 is-6mol-10-1mol
It turns out that the range of is suitable. Similarly,
Cr (NO as an additive3)3Battery cycle characteristics using
Fig. 4 shows Mn (NO3)2Battery using
Fig. 5 shows the cycle characteristics of Fe (NO3)3
Fig. 6 shows the cycle characteristics of the battery using
o (NO3)2Fig. 7 shows the cycle characteristics of the battery using
Ni (NO as additive)3)2Characteristics of batteries using
Figures and 8 show Cu (NO3)2Of the battery using
Cycle characteristic diagram, Figure 9 shows Zn (NO3)2To
Fig. 10 shows the cycle characteristics of the battery used.
a (NO3)2Fig. 11 shows the cycle characteristics of a battery using
AgNO as an additive3Characteristics of batteries using
Figures and 12 show Cd (NO3)2Battery using
Fig. 13 shows the cycle characteristics of In (N
O3)3Fig. 14 shows the cycle characteristics of the battery using
As Sn (NO3)2Cycle characteristic diagram of the battery using
FIG. 15 shows that Sb (NO3)3Of the battery using
Eggle characteristics diagram, Figure 16 shows TlNO as an additive3Using
Fig. 17 shows the cycle characteristics of the battery
(NO3)2Fig. 18 shows the cycle characteristics of the battery using
Bi (NO as an additive3)3Characteristics of batteries using
Figure 19 shows Mg (NO) as an additive. 3)2Battery using
Fig. 20 shows the cycle characteristics of Sr (N
O3)2Fig. 21 shows the cycle characteristics of the battery using
As Ba (NO3)2In the cycle characteristic diagram of the battery using
is there.
【００１４】作成例 ２ 表２に、リチウム金属より電気化学的に貴な金属である
Ｃａ、Ａｇの亜硝酸塩を前記電解液に含浸させ、更にそ
の添加濃度（ｍｏｌ／ｌ）を種々変化させた場合の組み
合わせが示されており、この表２中の大文字で表した電
池（Ｕ、Ｖ）が本発明電池であり、小文字で表した電池
（ｕ、ｖ）が比較電池である。Preparation Example 2 In Table 2, the nitrites of Ca and Ag, which are electrochemically more noble metals than lithium metal, were impregnated into the electrolytic solution, and the addition concentration (mol / l) was variously changed. The combination of cases is shown, and the batteries (U, V) shown in uppercase letters in Table 2 are the batteries of the present invention, and the batteries (u, v) shown in lowercase letters are comparative batteries.
【００１５】[0015]
【表２】 [Table 2]
【００１６】そして電解液に添加したＣａ、Ａｇの亜硝
酸塩Ｃａ（ＮＯ2）2、ＡｇＮＯ2の添加濃度を変化させ
た場合のサイクル特性を図２２、並びに図２３に示す。
これらの図においても先の硝酸塩の場合と同様に、それ
ぞれ縦軸には各電池のサイクル寿命を、横軸には各添加
剤の濃度をプロットした。また試験条件は放電容量２０
ｍＡｈとし、充電は３ｍＡで３．５Ｖを終止とした。22 and 23 show the cycle characteristics when the addition concentrations of Ca, Ag nitrite Ca (NO 2 ) 2 and AgNO 2 added to the electrolytic solution were changed.
In these figures, the cycle life of each battery is plotted on the vertical axis, and the concentration of each additive is plotted on the horizontal axis, as in the case of the nitrate. The test condition is discharge capacity 20
It was set to mAh, and charging was terminated at 3.5 mA at 3 mA.
【００１７】これらのサイクル特性図から明らかなよう
に、電解液に電気化学的にリチウム金属より電気化学的
に貴な金属の硝酸塩、或は亜硝酸塩を１０-6ｍｏｌ〜１
０-1ｍｏｌの範囲で添加することによってサイクル特性
が極めて向上していることが理解できる。As is clear from these cycle characteristic diagrams, a nitrate or nitrite of a metal that is electrochemically more electrochemically electrochemical than lithium metal is added to the electrolytic solution at 10 -6 mol to 1 mol.
It can be understood that the cycle characteristics are extremely improved by adding in the range of 0 -1 mol.
【００１８】このように電解液に電気化学的にリチウム
金属より電気化学的に貴な金属の硝酸塩、或は亜硝酸塩
を添加することによってサイクル特性が極めて向上する
のは次の理由によるものと考えられる。The reason why the cycle characteristics are remarkably improved by adding a nitrate or nitrite of a metal electrochemically more noble than lithium metal to the electrolyte is considered to be for the following reason. Be done.
【００１９】電解液にリチウムより貴な金属の硝酸塩、
もしくは亜硝酸塩を添加することによって、電解液中の
これらの金属イオンの一部と負極表面のリチウム金属と
がイオン交換し、従ってリチウム表面の負活性被膜が除
去され、更にりチウムより貴な金属が析出する。即ち、
リチウム表面の負活性被膜が除去されることによりリチ
ウムの充放電の活性点が増加する。その結果、放電時に
はリチウム面の均一な溶解が生じ、また充電時には電流
の集中が抑制されるためリチウムの樹枝状成長が生じに
くくなりサイクル特性が向上するものと考えられる。ま
た更にこれらの金属の硝酸塩、亜硝酸塩を添加すること
によりリチウムより貴な金属の少なくとも一部がリチウ
ム面に析出するが、これが電解液溶媒と活性リチウムと
が反応してリチウム表面に不活性被膜の生成を妨害する
ため、リチウムの電気化学的な不活性化を抑制し充放電
効率も向上する。A nitrate of a metal nobler than lithium is used as an electrolyte.
Alternatively, by adding nitrite, a part of these metal ions in the electrolytic solution and the lithium metal on the surface of the negative electrode are ion-exchanged, so that the negative active film on the surface of lithium is removed, and a metal more noble than lithium is added. Is deposited. That is,
Removal of the negatively active coating on the surface of lithium increases the active sites for charging and discharging lithium. As a result, it is considered that uniform dissolution of the lithium surface occurs during discharging, and current concentration is suppressed during charging, so that dendritic growth of lithium is less likely to occur and cycle characteristics are improved. Further, by adding nitrates or nitrites of these metals, at least a part of the metals nobler than lithium is deposited on the lithium surface, which reacts with the electrolytic solution solvent and active lithium to form an inactive film on the lithium surface. Therefore, the electrochemical deactivation of lithium is suppressed and the charging / discharging efficiency is also improved.
【００２０】このように本発明によればサイクル特性に
優れた非水電解質二次電池を作成できるため、その工業
的価値は極めて高い。As described above, according to the present invention, a non-aqueous electrolyte secondary battery having excellent cycle characteristics can be prepared, so that its industrial value is extremely high.
【００２１】また本実施例においては活物質としてリチ
ウムを例示したが、Ｌｉ−Ａｌ合金やＬｉ−Ｐｂ合金、
Ｌｉ−易融合金、Ｌｉ−ウッド合金、Ｌｉ−Ｂ合金等の
Ｌｉ合金、Ｌｉ−カーボン化合物、あるいは他のアルカ
リ金属、アルカリ土類金属及びその合金でもよい。In this embodiment, lithium is used as the active material, but Li--Al alloy, Li--Pb alloy,
Li-easy fusion alloy, Li-wood alloy, Li-alloy such as Li-B alloy, Li-carbon compound, or other alkali metal, alkaline earth metal and alloy thereof may be used.
【００２２】また本発明は固体電解質二次電池への応用
も可能である。The present invention can also be applied to a solid electrolyte secondary battery.
【００２３】[0023]
【発明の効果】本発明は以上の説明から明らかなよう
に、充放電可能な正極と、非水電解液と、リチウム、リ
チウム合金、或はリチウムと炭素との化合物を負極と、
から成るり、前記電解液としてリチウム金属より電気化
学的に貴な金属の硝酸塩、或は亜硝酸塩を含ませている
ので、非水電解液電池のサイクル特性が改善される。As is apparent from the above description, the present invention provides a chargeable / dischargeable positive electrode, a non-aqueous electrolyte solution, and a negative electrode containing lithium, a lithium alloy, or a compound of lithium and carbon.
Since the electrolyte contains a nitrate or nitrite of a metal electrochemically more noble than lithium metal, the cycle characteristics of the non-aqueous electrolyte battery are improved.
【図１】本発明電池の縦断面図である。FIG. 1 is a vertical sectional view of a battery of the present invention.
【図２】電解液に添加剤としてＡｌ（ＮＯ3）3を用いた
電池のサイクル特性図である。FIG. 2 is a cycle characteristic diagram of a battery using Al (NO 3 ) 3 as an additive in an electrolytic solution.
【図３】電解液に添加剤としてＣｒ（ＮＯ3）3を用いた
電池のサイクル特性図である。FIG. 3 is a cycle characteristic diagram of a battery using Cr (NO 3 ) 3 as an additive in an electrolytic solution.
【図４】電解液に添加剤としてＭｎ（ＮＯ3）2を用いた
電池のサイクル特性図である。FIG. 4 is a cycle characteristic diagram of a battery using Mn (NO 3 ) 2 as an additive in an electrolytic solution.
【図５】電解液に添加剤としてＦｅ（ＮＯ3）3を用いた
電池のサイクル特性図である。FIG. 5 is a cycle characteristic diagram of a battery using Fe (NO 3 ) 3 as an additive in an electrolytic solution.
【図６】電解液に添加剤としてＣｏ（ＮＯ3）2を用いた
電池のサイクル特性図である。FIG. 6 is a cycle characteristic diagram of a battery using Co (NO 3 ) 2 as an additive in an electrolytic solution.
【図７】電解液に添加剤としてＮｉ（ＮＯ3）2を用いた
電池のサイクル特性図である。FIG. 7 is a cycle characteristic diagram of a battery using Ni (NO 3 ) 2 as an additive in an electrolytic solution.
【図８】電解液に添加剤としてＣｕ（ＮＯ3）2を用いた
電池のサイクル特性図である。FIG. 8 is a cycle characteristic diagram of a battery using Cu (NO 3 ) 2 as an additive in an electrolytic solution.
【図９】電解液に添加剤としてＺｎ（ＮＯ3）2を用いた
電池のサイクル特性図である。FIG. 9 is a cycle characteristic diagram of a battery using Zn (NO 3 ) 2 as an additive in an electrolytic solution.
【図１０】電解液に添加剤としてＧａ（ＮＯ3）2を用い
た電池のサイクル特性図である。FIG. 10 is a cycle characteristic diagram of a battery using Ga (NO 3 ) 2 as an additive in an electrolytic solution.
【図１１】電解液に添加剤としてＡｇＮＯ3を用いた電
池のサイクル特性図である。FIG. 11 is a cycle characteristic diagram of a battery using AgNO 3 as an additive in an electrolytic solution.
【図１２】電解液に添加剤としてＣｄ（ＮＯ3）2を用い
た電池のサイクル特性図である。FIG. 12 is a cycle characteristic diagram of a battery using Cd (NO 3 ) 2 as an additive in an electrolytic solution.
【図１３】電解液に添加剤としてＩｎ（ＮＯ3）3を用い
た電池のサイクル特性図である。FIG. 13 is a cycle characteristic diagram of a battery using In (NO 3 ) 3 as an additive in an electrolytic solution.
【図１４】電解液に添加剤としてＳｎ（ＮＯ3）2を用い
た電池のサイクル特性図である。FIG. 14 is a cycle characteristic diagram of a battery using Sn (NO 3 ) 2 as an additive in an electrolytic solution.
【図１５】電解液に添加剤としてＳｂ（ＮＯ3）3を用い
た電池のサイクル特性図である。FIG. 15 is a cycle characteristic diagram of a battery using Sb (NO 3 ) 3 as an additive in an electrolytic solution.
【図１６】電解液に添加剤としてＴｌＮＯ3を用いた電
池のサイクル特性図である。FIG. 16 is a cycle characteristic diagram of a battery using TlNO 3 as an additive in an electrolytic solution.
【図１７】電解液に添加剤としてＰｂ（ＮＯ3）2を用い
た電池のサイクル特性図である。FIG. 17 is a cycle characteristic diagram of a battery using Pb (NO 3 ) 2 as an additive in an electrolytic solution.
【図１８】電解液に添加剤としてＢｉ（ＮＯ3）3を用い
た電池のサイクル特性図である。FIG. 18 is a cycle characteristic diagram of a battery using Bi (NO 3 ) 3 as an additive in an electrolytic solution.
【図１９】電解液に添加剤としてＭｇ（ＮＯ3）2を用い
た電池のサイクル特性図である。FIG. 19 is a cycle characteristic diagram of a battery using Mg (NO 3 ) 2 as an additive in an electrolytic solution.
【図２０】電解液に添加剤としてＳｒ（ＮＯ3）2を用い
た電池のサイクル特性図である。FIG. 20 is a cycle characteristic diagram of a battery using Sr (NO 3 ) 2 as an additive in an electrolytic solution.
【図２１】電解液に添加剤としてＢａ（ＮＯ3）2を用い
た電池のサイクル特性図である。FIG. 21 is a cycle characteristic diagram of a battery using Ba (NO 3 ) 2 as an additive in an electrolytic solution.
【図２２】電解液に添加剤としてＣａ（ＮＯ2）2を用い
た電池のサイクル特性図である。FIG. 22 is a cycle characteristic diagram of a battery using Ca (NO 2 ) 2 as an additive in an electrolytic solution.
【図２３】電解液に添加剤としてＡｇＮＯ2を用いた電
池のサイクル特性図である。FIG. 23 is a cycle characteristic diagram of a battery using AgNO 2 as an additive in an electrolytic solution.
１ 負極 ４ 正極 ７ セパレータ 1 Negative electrode 4 Positive electrode 7 Separator
Claims (3)
チウム、リチウム合金、或はリチウムと炭素との化合物
から成る負極と、から構成された非水電解質二次電池に
おいて、前記電解液はリチウム金属より電気化学的に貴
な金属の硝酸塩、或は亜硝酸塩を含むことを特徴とする
非水電解液二次電池。1. A non-aqueous electrolyte secondary battery comprising a chargeable / dischargeable positive electrode, a non-aqueous electrolytic solution, and a negative electrode composed of lithium, a lithium alloy, or a compound of lithium and carbon. A non-aqueous electrolyte secondary battery characterized in that the liquid contains a nitrate or nitrite of a metal electrochemically more precious than lithium metal.
金属として、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ａｌ、Ｃｒ、Ｍ
ｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ａｇ、Ｃ
ｄ、Ｉｎ、Ｓｎ、Ｓｂ、Ｔｌ、Ｐｂ、Ｂｉから選ばれる
金属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. A metal that is electrochemically more noble than the lithium metal, such as Mg, Ca, Sr, Ba, Al, Cr, and M.
n, Fe, Co, Ni, Cu, Zn, Ga, Ag, C
The non-aqueous electrolyte secondary battery according to claim 1, which is a metal selected from d, In, Sn, Sb, Tl, Pb, and Bi.
金属の硝酸塩、或は亜硝酸塩の添加量が１０-6ｍｏｌ／
ｌ以上、１０-1ｍｏｌ／ｌ以下であることを特徴とする
請求項１、或は請求項２記載の非水電解液二次電池。3. The amount of nitrate or nitrite of a metal electrochemically more noble than lithium metal is 10 −6 mol / mol.
It is 1 or more and 10 -1 mol / l or less, The non-aqueous electrolyte secondary battery according to claim 1 or 2, characterized in that
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3260744A JPH05101846A (en) | 1991-10-08 | 1991-10-08 | Non-aqueous electrolytic secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3260744A JPH05101846A (en) | 1991-10-08 | 1991-10-08 | Non-aqueous electrolytic secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05101846A true JPH05101846A (en) | 1993-04-23 |
Family
ID=17352145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3260744A Pending JPH05101846A (en) | 1991-10-08 | 1991-10-08 | Non-aqueous electrolytic secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05101846A (en) |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0778633A (en) * | 1993-09-07 | 1995-03-20 | Toshiba Corp | Secondary battery with nonaqueous electrolytic solution |
| JPH08171936A (en) * | 1994-12-16 | 1996-07-02 | Sanyo Electric Co Ltd | Lithium secondary battery |
| EP0969539A1 (en) * | 1998-06-30 | 2000-01-05 | Wilson Greatbatch Ltd. | Organic nitrite additives for nonaqueous electrolyte in alkali metal electrochemical cells |
| US6060184A (en) * | 1998-07-09 | 2000-05-09 | Wilson Greatbatch Ltd. | Inorganic and organic nitrate additives for nonaqueous electrolyte in alkali metal electrochemical cells |
| US6136477A (en) * | 1998-10-22 | 2000-10-24 | Wilson Greatbatch Ltd. | Nitrate additives for nonaqueous electrolyte rechargeable cells |
| US6210839B1 (en) * | 1999-01-25 | 2001-04-03 | Wilson Greatbatch Ltd. | Nitrite additives for nonaqueous electrolyte rechargeable electrochemical cells |
| US6528207B2 (en) | 2001-01-18 | 2003-03-04 | Wilson Greatbatch Ltd. | Electrochemical cell having an electrode with a nitrite additive in the electrode active mixture |
| US6562515B2 (en) | 2001-03-21 | 2003-05-13 | Wilson Greatbatch Ltd. | Electrochemical cell having an electrode with a nitrate additive in the electrode active mixture |
| JP2007123246A (en) * | 2005-09-28 | 2007-05-17 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2007165294A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte solution for lithium secondary battery and lithium secondary battery using it |
| JP2007165296A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Lithium secondary battery |
| JP2007165297A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Lithium secondary battery |
| JP2007165298A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Lithium secondary battery |
| JP2007165301A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Lithium secondary battery |
| JP2007165299A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Lithium secondary battery |
| JP2007173222A (en) * | 2005-11-25 | 2007-07-05 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007180016A (en) * | 2005-11-29 | 2007-07-12 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution for secondary battery, and nonaqueous electrolyte secondary battery using it |
| JP2007180025A (en) * | 2005-12-02 | 2007-07-12 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007180015A (en) * | 2005-11-29 | 2007-07-12 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution for lithium secondary battery, and lithium secondary battery using it |
| JP2007184257A (en) * | 2005-12-07 | 2007-07-19 | Mitsubishi Chemicals Corp | Non-aqueous electrolyte solution for secondary cell and non-aqueous electrolyte secondary battery employing the same |
| JP2007188871A (en) * | 2005-12-13 | 2007-07-26 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007194208A (en) * | 2005-12-22 | 2007-08-02 | Mitsubishi Chemicals Corp | Lithium secondary cell, and battery pack formed by connecting the plurality of it |
| JP2007194207A (en) * | 2005-12-21 | 2007-08-02 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007194209A (en) * | 2005-12-22 | 2007-08-02 | Mitsubishi Chemicals Corp | Lithium secondary cell, and battery pack formed by connecting the plurality of it |
| JP2007200871A (en) * | 2005-12-28 | 2007-08-09 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007214120A (en) * | 2006-01-13 | 2007-08-23 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007227368A (en) * | 2006-01-27 | 2007-09-06 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2012109048A (en) * | 2010-11-15 | 2012-06-07 | Toyota Motor Corp | Regeneration method of nonaqueous electrolyte secondary battery |
| JP2013138012A (en) * | 2005-12-22 | 2013-07-11 | Mitsubishi Chemicals Corp | Lithium secondary battery and battery pack formed by connecting lithium secondary batteries together |
| US9029022B2 (en) | 2005-10-20 | 2015-05-12 | Mitsubishi Chemical Corporation | Lithium secondary batteries and nonaqueous electrolyte for use in the same |
| JP2018190493A (en) * | 2017-04-28 | 2018-11-29 | プライムアースＥｖエナジー株式会社 | Nonaqueous electrolyte secondary battery and method for manufacturing the same |
| KR20200143269A (en) * | 2019-06-13 | 2020-12-23 | 한양대학교 산학협력단 | Electrolyte solution composition for lithium secondary battery and lithium secondary battery comprising the same |
-
1991
- 1991-10-08 JP JP3260744A patent/JPH05101846A/en active Pending
Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0778633A (en) * | 1993-09-07 | 1995-03-20 | Toshiba Corp | Secondary battery with nonaqueous electrolytic solution |
| JPH08171936A (en) * | 1994-12-16 | 1996-07-02 | Sanyo Electric Co Ltd | Lithium secondary battery |
| EP0969539A1 (en) * | 1998-06-30 | 2000-01-05 | Wilson Greatbatch Ltd. | Organic nitrite additives for nonaqueous electrolyte in alkali metal electrochemical cells |
| US6060184A (en) * | 1998-07-09 | 2000-05-09 | Wilson Greatbatch Ltd. | Inorganic and organic nitrate additives for nonaqueous electrolyte in alkali metal electrochemical cells |
| US6136477A (en) * | 1998-10-22 | 2000-10-24 | Wilson Greatbatch Ltd. | Nitrate additives for nonaqueous electrolyte rechargeable cells |
| US6210839B1 (en) * | 1999-01-25 | 2001-04-03 | Wilson Greatbatch Ltd. | Nitrite additives for nonaqueous electrolyte rechargeable electrochemical cells |
| US6528207B2 (en) | 2001-01-18 | 2003-03-04 | Wilson Greatbatch Ltd. | Electrochemical cell having an electrode with a nitrite additive in the electrode active mixture |
| US6562515B2 (en) | 2001-03-21 | 2003-05-13 | Wilson Greatbatch Ltd. | Electrochemical cell having an electrode with a nitrate additive in the electrode active mixture |
| JP2007123246A (en) * | 2005-09-28 | 2007-05-17 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| US9029022B2 (en) | 2005-10-20 | 2015-05-12 | Mitsubishi Chemical Corporation | Lithium secondary batteries and nonaqueous electrolyte for use in the same |
| US11769871B2 (en) | 2005-10-20 | 2023-09-26 | Mitsubishi Chemical Corporation | Lithium secondary batteries and nonaqueous electrolyte for use in the same |
| US9112236B2 (en) | 2005-10-20 | 2015-08-18 | Mitsubishi Chemical Corporation | Lithium secondary batteries and nonaqueous electrolyte for use in the same |
| JP2007165294A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte solution for lithium secondary battery and lithium secondary battery using it |
| JP2007165296A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Lithium secondary battery |
| JP2007165297A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Lithium secondary battery |
| JP2007165298A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Lithium secondary battery |
| JP2007165301A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Lithium secondary battery |
| JP2007165299A (en) * | 2005-11-16 | 2007-06-28 | Mitsubishi Chemicals Corp | Lithium secondary battery |
| JP2007173222A (en) * | 2005-11-25 | 2007-07-05 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007180016A (en) * | 2005-11-29 | 2007-07-12 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution for secondary battery, and nonaqueous electrolyte secondary battery using it |
| JP2007180015A (en) * | 2005-11-29 | 2007-07-12 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution for lithium secondary battery, and lithium secondary battery using it |
| JP2007180025A (en) * | 2005-12-02 | 2007-07-12 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007184257A (en) * | 2005-12-07 | 2007-07-19 | Mitsubishi Chemicals Corp | Non-aqueous electrolyte solution for secondary cell and non-aqueous electrolyte secondary battery employing the same |
| JP2007188871A (en) * | 2005-12-13 | 2007-07-26 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007194207A (en) * | 2005-12-21 | 2007-08-02 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007194209A (en) * | 2005-12-22 | 2007-08-02 | Mitsubishi Chemicals Corp | Lithium secondary cell, and battery pack formed by connecting the plurality of it |
| JP2013138012A (en) * | 2005-12-22 | 2013-07-11 | Mitsubishi Chemicals Corp | Lithium secondary battery and battery pack formed by connecting lithium secondary batteries together |
| JP2007194208A (en) * | 2005-12-22 | 2007-08-02 | Mitsubishi Chemicals Corp | Lithium secondary cell, and battery pack formed by connecting the plurality of it |
| JP2007200871A (en) * | 2005-12-28 | 2007-08-09 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007214120A (en) * | 2006-01-13 | 2007-08-23 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2007227368A (en) * | 2006-01-27 | 2007-09-06 | Mitsubishi Chemicals Corp | Lithium ion secondary battery |
| JP2012109048A (en) * | 2010-11-15 | 2012-06-07 | Toyota Motor Corp | Regeneration method of nonaqueous electrolyte secondary battery |
| JP2018190493A (en) * | 2017-04-28 | 2018-11-29 | プライムアースＥｖエナジー株式会社 | Nonaqueous electrolyte secondary battery and method for manufacturing the same |
| KR20200143269A (en) * | 2019-06-13 | 2020-12-23 | 한양대학교 산학협력단 | Electrolyte solution composition for lithium secondary battery and lithium secondary battery comprising the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH05101846A (en) | Non-aqueous electrolytic secondary battery | |
| EP0974169B1 (en) | An iron-based storage battery | |
| JP5143852B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP3148293B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPS6079678A (en) | Rechargeable manganese dioxide/zinc battery | |
| JPH05234621A (en) | Nonaqueous electrolyte secondary battery and its manufacture | |
| JPH06325764A (en) | Nonaqeous electrolytic secondary battery | |
| GB2060242A (en) | Rechargeable nonaqueous silver alloy anode cell | |
| JP3081336B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP2735842B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH0896849A (en) | Nonaqueous electrolytic secondary battery | |
| JPH0582168A (en) | Nonaqueous electrolyte battery | |
| JP3565478B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP3177257B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP2709303B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH06310125A (en) | Negative electrode for lithium secondary battery | |
| JP3404929B2 (en) | Non-aqueous electrolyte battery | |
| JP3223035B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH0652848A (en) | Nonaqueous electrolytic secondary battery | |
| JP3017756B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP3157209B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP2000058120A (en) | Electrolyte for lithium secondary battery | |
| JP3048953B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH10125317A (en) | Monaqueous electrolyte secondary battery | |
| JPH0554912A (en) | Nonaqueous electrolytic secondary battery and manufacture thereof |