JPH09199170A - Nonaqueous secondary battery - Google Patents
Nonaqueous secondary batteryInfo
- Publication number
- JPH09199170A JPH09199170A JP8008881A JP888196A JPH09199170A JP H09199170 A JPH09199170 A JP H09199170A JP 8008881 A JP8008881 A JP 8008881A JP 888196 A JP888196 A JP 888196A JP H09199170 A JPH09199170 A JP H09199170A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- compound
- electrolytic solution
- electrolyte
- secondary battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 20
- -1 aromatic azo compound Chemical class 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract 1
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical compound C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000009783 overcharge test Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006230 acetylene black 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
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- Y02E60/122—
Landscapes
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、負極にリチウムま
たはリチウムを吸蔵放出可能な物質、例えばリチウム合
金、炭素、遷移金属の酸化物やカルコゲン化合物を用
い、電解質に有機電解液や非水の固体電解質を用いる非
水電解質二次電池に関し、特に耐過充電性に優れた電池
を提供するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses lithium or a substance capable of occluding and releasing lithium, such as lithium alloy, carbon, oxides of transition metals or chalcogen compounds, as an anode, and an organic electrolyte or non-aqueous solid as an electrolyte. The present invention relates to a non-aqueous electrolyte secondary battery using an electrolyte, and particularly to a battery excellent in overcharge resistance.
【０００２】[0002]
【従来の技術】非水電解質電池が過充電された場合、電
解液の分解が起きる。分解された電解液の１部はガス化
し、電池内の内圧を高める。その結果電池が膨れるか、
安全弁が開く。電池が膨れたり安全弁が開くと、電池の
機能が失われてしまい、最悪の場合外気や水分との接触
により発熱を伴う負極の急激な酸化が起こり、電池の発
火や破裂の原因になる。また、ガス化しない場合でも電
解液の重合が起こり、電気抵抗の極めて高い物質が生成
し、電池の内部インピーダンスを増大させる為、電池の
機能が、失われてしまう。2. Description of the Related Art When a non-aqueous electrolyte battery is overcharged, decomposition of the electrolytic solution occurs. A part of the decomposed electrolytic solution is gasified to increase the internal pressure in the battery. As a result, the battery swells,
The safety valve opens. When the battery swells or the safety valve opens, the function of the battery is lost, and in the worst case, the negative electrode is rapidly oxidized by heat generation due to contact with outside air or moisture, which causes ignition or rupture of the battery. Further, even if it is not gasified, polymerization of the electrolytic solution occurs, a substance having extremely high electric resistance is generated, and the internal impedance of the battery is increased, so that the function of the battery is lost.
【０００３】従来、非水電解質電池に於て、過充電を受
けた時に生じる不具合を防止する為、電解液にレドック
ス試薬を添加することが、特開平５ー２０６５７１号公
報に提案されている。上記公報に提案されているレドッ
クス試薬はフェロセン、ニッケロセン、コバルトセンな
どのメタロセンである。本メタロセンの酸化還元電位
は、Ｌｉ／Ｌｉ+ に対し１．７Ｖ〜３．５Ｖである。従
って上記提案のメタロセンの場合、３Ｖ系の電池には適
用できるが、ＬｉＣｏＯ2 、ＬｉＮｉＯ2 やＬｉＭｎＯ
2 等を正極活物質に用いた作動電圧が３．５Ｖを越える
電池には、適用できなかった。Conventionally, in a non-aqueous electrolyte battery, it has been proposed in Japanese Patent Application Laid-Open No. 5-206571 to add a redox reagent to an electrolytic solution in order to prevent problems caused by overcharge. The redox reagents proposed in the above publications are metallocenes such as ferrocene, nickelocene and cobaltocene. The redox potential of this metallocene is 1.7 V to 3.5 V with respect to Li / Li + . Therefore, in the case of the above proposed metallocene, although it can be applied to 3V type batteries, LiCoO 2 , LiNiO 2 and LiMnO
It could not be applied to a battery in which 2 or the like was used as the positive electrode active material and the operating voltage exceeded 3.5V.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記従来技
術では達成されなかった作動電圧が３．５Ｖを越える非
水電解質電池が過充電をうけても、その機能が損なわれ
ず、また発火、破裂の危険性を低減した電池を提供しよ
うとするものである。SUMMARY OF THE INVENTION The present invention does not impair the function of a non-aqueous electrolyte battery whose operating voltage exceeds 3.5 V, which has not been achieved by the above-mentioned prior art, and does not impair its function. The present invention seeks to provide a battery with a reduced risk of bursting.
【０００５】[0005]
【課題を解決するための手段】本発明の第１は、正極の
作動電圧がＬi/Li+ 電極基準で３．５〜４．４ボルトで
あり、電解液または固体電解質中に芳香族アゾ化合物ま
たは芳香族アゾキシ化合物を含むことを特徴とする非水
二次電池である。本発明の第２は、電解質中に含まれる
芳香族アゾまたはアゾキシ化合物の濃度が、０．１〜
２．０Ｍ／ｌである請求項１記載の非水二次電池であ
る。The first aspect of the present invention is that the operating voltage of the positive electrode is 3.5 to 4.4 V based on the Li / Li + electrode, and the aromatic azo compound is contained in the electrolytic solution or the solid electrolyte. Alternatively, the non-aqueous secondary battery is characterized by containing an aromatic azoxy compound. The second aspect of the present invention is that the concentration of the aromatic azo or azoxy compound contained in the electrolyte is 0.1 to 0.1%.
The non-aqueous secondary battery according to claim 1, which has a capacity of 2.0 M / l.
【０００６】リチウムまたは、リチウム合金、炭素、酸
化物やカルコゲン化物を負極とする非水電解質電池が過
充電された場合、前記の如く電解液が分解してガス化
し、電池の内圧が上昇して安全弁が作動する。その時点
で電池の機能が失われてしまう。この問題の対策の１つ
として、前記の如く電解液中にメタロセンの如きレドッ
クス試薬を添加する方法が提案されている。しかし作動
電圧が３．５Ｖを越える電池に適用できるものがなかっ
たが、芳香族系のアゾまたはアゾキシ化合物をレドック
ス試薬として電解液中に添加することにより、作動電圧
が３．５Ｖを越える電池に対しても適用できる事を見い
出した。When a non-aqueous electrolyte battery having lithium, a lithium alloy, carbon, an oxide or a chalcogenide as a negative electrode is overcharged, the electrolytic solution is decomposed and gasified as described above, and the internal pressure of the battery increases. The safety valve is activated. At that point, the battery will lose its functionality. As one of the measures against this problem, a method of adding a redox reagent such as metallocene to the electrolytic solution has been proposed as described above. However, there was nothing applicable to a battery whose operating voltage exceeds 3.5V. However, by adding an aromatic azo or azoxy compound as a redox reagent to the electrolytic solution, a battery whose operating voltage exceeds 3.5V can be obtained. I also found that it can be applied.
【０００７】[0007]
【発明の実施の形態】電解液または高分子固体電解質に
アゾベンゼンやアゾキシベンゼン等の芳香族アゾ化合物
またはアゾキシ化合物を溶解させておく。電解液中に添
加されたアゾまたはアゾキシ化合物は、電解液中に溶解
する。電池が過充電された時、正極において電解酸化さ
れる。正極で電解酸化された同化合物は電解液中を拡散
し、負極に達してそこで電解還元され元の化合物に戻
る。同化合物は正極と負極の間を往復して電解酸化還元
を繰り返す。BEST MODE FOR CARRYING OUT THE INVENTION An aromatic azo compound or an azoxy compound such as azobenzene or azoxybenzene is dissolved in an electrolytic solution or a polymer solid electrolyte. The azo or azoxy compound added to the electrolytic solution dissolves in the electrolytic solution. When the battery is overcharged, it is electrolytically oxidized at the positive electrode. The same compound electrolytically oxidized at the positive electrode diffuses in the electrolytic solution, reaches the negative electrode, and is electrolytically reduced there to return to the original compound. The compound goes back and forth between the positive electrode and the negative electrode and repeats electrolytic redox.
【０００８】芳香族アゾまたはアゾキシ化合物の酸化還
元電位は、Ｌｉ／Ｌｉ+ に対し４．３Ｖ〜４．７Ｖであ
り、電解液が酸化分解される電位４．８〜５．０Ｖより
卑である。従って、過充電をされた場合でも電解液に変
化は生ぜず、添加したアゾまたはアゾキシ化合物の酸化
還元が繰り返されるだけである。The redox potential of the aromatic azo or azoxy compound is 4.3 V to 4.7 V with respect to Li / Li + , which is lower than the potential 4.8 to 5.0 V at which the electrolytic solution is oxidatively decomposed. . Therefore, even when overcharged, no change occurs in the electrolytic solution, and the redox of the added azo or azoxy compound is only repeated.
【０００９】添加した化合物の電解酸化還元反応が充電
電流の大きさに見合っていなければならない。電解質に
含まれる同化合物の濃度と電解電流の大きさを調べた結
果、濃度としては０．１〜２．０Ｍ／ｌが適当であるこ
とが分かった。The electrolytic redox reaction of the added compound must be commensurate with the magnitude of the charging current. As a result of examining the concentration of the same compound contained in the electrolyte and the magnitude of the electrolytic current, it was found that the appropriate concentration is 0.1 to 2.0 M / l.
【００１０】電解質に添加した芳香族アゾまたはアゾキ
シ化合物が、電池が過充電された場合、それ自身が電解
酸化還元反応を繰り返すだけで、電解質の酸化分解を防
止し、電池の機能停止や発火、破裂などの事故発生を防
止する効果が大きい。When the battery is overcharged, the aromatic azo or azoxy compound added to the electrolyte prevents the oxidative decomposition of the electrolyte by merely repeating the electrolytic redox reaction, thereby stopping the function of the battery or igniting the battery. It is highly effective in preventing accidents such as bursts.
【００１１】（実施例１）正極活物質であるＬｉＣo Ｏ
2 粉末９０重量部とアセチレンブラック粉末１０重量部
を混合する。該混合粉末９５重量部とポリフッカビニリ
デンの１０重量％ＮＭＰ溶液５０重量部を乳鉢にて混練
し、アルミ箔上に塗布した。乾燥してＮＭＰ（Ｎ−メチ
ル−ピロリトン）を除去した後、ロールプレスを行っ
た。プレス後の塗布層の厚みが１００ミクロンになるよ
う、塗布量を調節し、これを正極とした。(Example 1) LiCo 2 O 3 which is a positive electrode active material
2 90 parts by weight of powder and 10 parts by weight of acetylene black powder are mixed. 95 parts by weight of the mixed powder and 50 parts by weight of a 10% by weight NMP solution of poly (fuccavinylidene) were kneaded in a mortar and applied on an aluminum foil. After drying to remove NMP (N-methyl-pyrroliton), roll pressing was performed. The coating amount was adjusted so that the thickness of the coating layer after pressing was 100 μm, and this was used as the positive electrode.
【００１２】負極活物質である人造黒鉛粉末９５重量部
とポリフッカビニリデンの１０％ＮＭＰ溶液５０重量部
を乳鉢にて混練し、銅箔上に塗布した。乾燥してＮＭＰ
を除去した後、ロールプレスを行った。プレス後の塗布
層厚みが１００ミクロンになるよう、塗布量を調節し
た。セパレータには、微孔性ポリエチレンフィルムを用
いた。正極、セパレータ、負極を積層した後、電槽内に
収納し、電解液である１ＭのＬｉＰＦ6-ＥＣ／ＤＥＣ溶
液を注液した。電解液には予め０．５Ｍ／ｌのアゾキシ
ベンゼンを溶解させておいた。注液後常用の方法により
封口して電池とした。95 parts by weight of an artificial graphite powder as a negative electrode active material and 50 parts by weight of a 10% NMP solution of poly (fuccavinylidene) were kneaded in a mortar and applied on a copper foil. Dried and NMP
After removing, the roll was pressed. The coating amount was adjusted so that the thickness of the coating layer after pressing was 100 μm. A microporous polyethylene film was used as the separator. After stacking the positive electrode, the separator, and the negative electrode, the positive electrode, the separator, and the negative electrode were housed in a battery case, and a 1 M LiPF 6 -EC / DEC solution as an electrolytic solution was injected. 0.5 M / l azoxybenzene was dissolved in the electrolytic solution in advance. After the injection, the battery was sealed by a conventional method to obtain a battery.
【００１３】本電池を電流密度０．５Ｃの充電レートで
５時間の過充電を実施した。その結果を図１に示す。充
電を開始して２．５時間後に電圧が４．２Ｖに達し、そ
れ以降５時間まで電圧に変動が生じなかった。５時間後
に於いても電池に膨れは認められず、その後の放電で正
常な容量を示した。アゾキシベンゼンに換えてアゾベン
ゼンを添加した場合も同様の挙動を示した。This battery was overcharged for 5 hours at a charge rate of a current density of 0.5C. The result is shown in FIG. The voltage reached 4.2 V 2.5 hours after the start of charging, and the voltage did not fluctuate until 5 hours thereafter. No swelling was observed in the battery even after 5 hours, and a normal capacity was shown by the subsequent discharge. Similar behavior was observed when azobenzene was added instead of azoxybenzene.
【００１４】（比較例１）電解液にアゾキシベンゼンを
溶解させなかったこと以外は電池の構成を実施例１と同
一にした。又、過充電試験も実施例１と同様の条件にて
実施した。その結果を図１に示す。充電開始後３．８時
間で電池電圧は４．８Ｖに達し、それ以降一定の電圧を
示した。電池には膨れが認められた。又、電池のインピ
ーダンスが増大し、以降の放電、充電が不能になった。Comparative Example 1 The structure of the battery was the same as in Example 1 except that azoxybenzene was not dissolved in the electrolytic solution. The overcharge test was also performed under the same conditions as in Example 1. The result is shown in FIG. The battery voltage reached 4.8 V 3.8 hours after the start of charging, and showed a constant voltage thereafter. Swelling was observed in the battery. Also, the impedance of the battery increased, and subsequent discharge and charging became impossible.
【００１５】（実施例２）正極および負極は実施例１と
同様の方法で作製した。１Ｍのアゾキシベンゼンを溶解
させたＬｉＰＦ6 −ＥＣ（エチレンカーボネート）／Ｄ
ＥＣ（ジエチルカーボネイト）溶液を含有させたＰＥＯ
（ポリエチレンオキシド）から成る高分子固体電解質を
正極または負極のどちらか一方に厚み５０ミクロンにて
塗布した。このように作製した正極および負極を高分子
固体電解質の層が間に来るように積層した。本積層体を
電槽に収納した後、封口して電池とした。本電池を充電
レート０．２Ｃ，１０時間充電の過重電試験を実施し
た。充電開始７時間後に電池電圧が約４．４Ｖに達し、
それ以降は一定の電圧を示した。１０時間経過後も電池
に膨れは認められず、その後の放電でも正常な容量を示
した。Example 2 A positive electrode and a negative electrode were manufactured by the same method as in Example 1. LiPF 6 -EC (ethylene carbonate) / D in which 1M azoxybenzene was dissolved
PEO containing EC (diethyl carbonate) solution
A solid polymer electrolyte composed of (polyethylene oxide) was applied to either the positive electrode or the negative electrode at a thickness of 50 μm. The positive electrode and the negative electrode thus produced were laminated so that the layer of the solid polymer electrolyte was interposed therebetween. The laminated body was housed in a battery case and then sealed to obtain a battery. This battery was subjected to an overcharge test at a charge rate of 0.2 C for 10 hours. 7 hours after the start of charging, the battery voltage reaches about 4.4V,
After that, it showed a constant voltage. No swelling of the battery was observed even after 10 hours, and the battery showed normal capacity even after discharging.
【００１６】（比較例２）高分子固体電解質中にアゾキ
シベンゼンを含有させなかったこと以外は実施例２と同
一の電池構成にした。過充電試験も実施例２と同一の条
件で実施した。充電開始８時間経過後に電池電圧が４．
９Ｖに達し、以降は一定の電圧を示した。電池には膨れ
が認められた。又電池のインピーダンスが増大し、その
後の放電充電が不能になった。(Comparative Example 2) The same battery configuration as that of Example 2 was adopted except that azoxybenzene was not contained in the polymer solid electrolyte. The overcharge test was also performed under the same conditions as in Example 2. Battery voltage is 4. 8 hours after the start of charging.
It reached 9 V and showed a constant voltage thereafter. Swelling was observed in the battery. Moreover, the impedance of the battery increased, and the discharge charging after that became impossible.
【００１７】[0017]
【発明の効果】アゾベンゼンおよびアゾキシベンゼンに
代表される芳香族アゾ化合物およびアゾキシ化合物はＬ
ｉ／Ｌｉ+ 電極基準で約４．４Ｖに酸化電位をもつ、こ
れは３．６〜４．３Ｖで作動する正極より貴な電位であ
り充電に支障は生じない。又電解液の酸化分解電位４．
８〜５．０Ｖより卑である。従って電池が過充電された
ときには自らが酸化されて電解質の酸化を防止する。又
これらの物質は３．０Ｖ付近に還元電位を持つレドック
ス試薬であり、正極で酸化されたものは負極で還元され
てもとに戻り、繰り返し働く。実際の試作電池でも有効
に動作すると認められた。The aromatic azo compounds and azoxy compounds represented by azobenzene and azoxybenzene are L
It has an oxidation potential of about 4.4 V based on the i / Li + electrode, which is a nobler potential than the positive electrode operating at 3.6 to 4.3 V and does not hinder charging. In addition, the oxidative decomposition potential of the electrolyte 4.
It is more base than 8 to 5.0V. Therefore, when the battery is overcharged, it oxidizes itself to prevent oxidation of the electrolyte. Further, these substances are redox reagents having a reduction potential near 3.0 V, and those oxidized by the positive electrode return to the original state when reduced by the negative electrode, and work repeatedly. It was confirmed that the actual prototype battery would work effectively.
【００１８】リチウムイオン電池の過充電防止策は電池
外に設置した保護回路に頼っているのが現状である。し
かしこれにはスペースを必要とすること、高価であると
いう欠点がある。本発明は４Ｖ級電池を保護回路に依ら
ずに過充電から保護できる効果があり、スペース不要、
安価なことから工業的価値大なるものである。Under the present circumstances, overcharge prevention measures for lithium-ion batteries rely on a protection circuit installed outside the batteries. However, this has the disadvantages of requiring space and being expensive. INDUSTRIAL APPLICABILITY The present invention has an effect of protecting a 4V class battery from overcharging without relying on a protection circuit, and requires no space
It is of great industrial value because it is cheap.
【図１】本発明に係る非水二次電池と従来電池を過充電
した時の電圧挙動を比較した図である。FIG. 1 is a diagram comparing a voltage behavior when a non-aqueous secondary battery according to the present invention and a conventional battery are overcharged.
Claims (2)
３．５〜４．４ボルトであり、電解液または固体電解質
中に芳香族アゾ化合物または芳香族アゾキシ化合物を含
むことを特徴とする非水二次電池。1. The operating voltage of the positive electrode is 3.5 to 4.4 V based on the Li / Li + electrode, and the electrolytic solution or the solid electrolyte contains an aromatic azo compound or an aromatic azoxy compound. Non-aqueous rechargeable battery.
ゾキシ化合物の濃度が、０．１〜２．０Ｍ／ｌである請
求項１記載の非水二次電池。2. The non-aqueous secondary battery according to claim 1, wherein the concentration of the aromatic azo or azoxy compound contained in the electrolyte is 0.1 to 2.0 M / l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8008881A JPH09199170A (en) | 1996-01-23 | 1996-01-23 | Nonaqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8008881A JPH09199170A (en) | 1996-01-23 | 1996-01-23 | Nonaqueous secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09199170A true JPH09199170A (en) | 1997-07-31 |
Family
ID=11705028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8008881A Pending JPH09199170A (en) | 1996-01-23 | 1996-01-23 | Nonaqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09199170A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003030292A1 (en) * | 2001-09-27 | 2003-04-10 | Nisshinbo Industries, Inc., | Nonaqueous electrolyte secondary cell, power supply comprising the secondary cell, portable device, transportable or movable machine, electric apparatus for home use, and method for charging nonaqueous electrolyte secondary cell |
| US7425388B2 (en) | 2002-09-06 | 2008-09-16 | Samsung Sdi Co., Ltd. | Electrolyte for a lithium battery and a lithium battery comprising the same |
| US8252465B2 (en) | 2001-01-19 | 2012-08-28 | Samsung Sdi Co., Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| JP2014086185A (en) * | 2012-10-19 | 2014-05-12 | Toyota Motor Corp | Method of manufacturing nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN119481051A (en) * | 2024-11-05 | 2025-02-18 | 南开大学 | A diazene organic negative electrode material for aqueous alkaline batteries and its application |
-
1996
- 1996-01-23 JP JP8008881A patent/JPH09199170A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8252465B2 (en) | 2001-01-19 | 2012-08-28 | Samsung Sdi Co., Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| WO2003030292A1 (en) * | 2001-09-27 | 2003-04-10 | Nisshinbo Industries, Inc., | Nonaqueous electrolyte secondary cell, power supply comprising the secondary cell, portable device, transportable or movable machine, electric apparatus for home use, and method for charging nonaqueous electrolyte secondary cell |
| US7425388B2 (en) | 2002-09-06 | 2008-09-16 | Samsung Sdi Co., Ltd. | Electrolyte for a lithium battery and a lithium battery comprising the same |
| JP2014086185A (en) * | 2012-10-19 | 2014-05-12 | Toyota Motor Corp | Method of manufacturing nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN119481051A (en) * | 2024-11-05 | 2025-02-18 | 南开大学 | A diazene organic negative electrode material for aqueous alkaline batteries and its application |
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