JP2962782B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JP2962782B2 JP2962782B2 JP2199519A JP19951990A JP2962782B2 JP 2962782 B2 JP2962782 B2 JP 2962782B2 JP 2199519 A JP2199519 A JP 2199519A JP 19951990 A JP19951990 A JP 19951990A JP 2962782 B2 JP2962782 B2 JP 2962782B2
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- JP
- Japan
- Prior art keywords
- battery
- present
- negative electrode
- solvent
- lithium
- 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.)
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Classifications
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- 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
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- Primary Cells (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は、リチウム或るいはリチウムを含む合金から
なる負極と、正極と、溶質、及び溶媒からなる電解液
と、を備えた非水系電解液電池に関する。The present invention relates to a nonaqueous system comprising a negative electrode made of lithium or an alloy containing lithium, a positive electrode, and an electrolytic solution consisting of a solute and a solvent. The present invention relates to an electrolyte battery.
（ロ）従来の技術 非水系電解液電池は、単位体積当りのエネルギ密度が
高く、且つ自己放電率が低いという利点を有している。(B) Conventional technology Non-aqueous electrolyte batteries have the advantages of high energy density per unit volume and low self-discharge rate.
ところで電解液を構成する溶質としては一般に過塩素
酸リチウムが用いられているが、この過塩素酸リチウム
を用いた場合には電池の低温放電特性に難があり、また
過塩素酸リチウムは非常に酸化力が大であるため有機溶
媒を酸化してしまうという欠点があった。By the way, lithium perchlorate is generally used as a solute constituting the electrolytic solution. However, when this lithium perchlorate is used, the low-temperature discharge characteristics of the battery are difficult, and lithium perchlorate is very poor. There is a disadvantage that the organic solvent is oxidized because of its high oxidizing power.
これを解決する手段として、例えば特開昭58−66264
号公報や特開昭58−163176号公報に示されているよう
に、フッ素を含むリチウム塩を溶質として用い、前記低
温放電特性を改善するとともに、有機溶媒の酸化を抑制
する技術があった。As means for solving this, for example, Japanese Patent Application Laid-Open No. 58-66264
As disclosed in Japanese Patent Application Laid-Open No. 58-163176 and Japanese Patent Application Laid-Open No. 58-163176, there has been a technique using a lithium salt containing fluorine as a solute to improve the low-temperature discharge characteristics and suppress the oxidation of an organic solvent.
しかしながらフッ素を含むリチウム塩を溶質に用いた
場合、電池缶材料が腐食し、電解液中に溶解した電池缶
材料が負極表面に析出するので、電圧降下、放電容量の
減少等を引き起こし、電池の保存特性を劣化させるとい
う問題点があった。However, when a lithium salt containing fluorine is used as a solute, the battery can material is corroded, and the battery can material dissolved in the electrolytic solution is deposited on the negative electrode surface. There was a problem that storage characteristics deteriorated.
これを解決する方法として電解液に硝酸リチウムを添
加させるという技術を本発明者等は先に提案した。The present inventors have previously proposed a technique of adding lithium nitrate to an electrolytic solution as a method for solving this.
（ハ）発明が解決しようとする課題 このように溶質側の改良によって溶媒、及び電池缶の
酸化、腐食を抑制し、放電特性、及び保存特性を向上さ
せる技術が従来から種々提案されてきたが、一方の自己
放電率の低下を目的とした技術改良は余り成されていな
い。(C) Problems to be Solved by the Invention As described above, various techniques for suppressing oxidation and corrosion of a solvent and a battery can by improving the solute side and improving discharge characteristics and storage characteristics have been conventionally proposed. On the other hand, there have been few technical improvements aimed at lowering the self-discharge rate.
そこで、本発明者等は、自己放電の原因は負極リチウ
ムと溶媒との反応に起因することを見出した。Then, the present inventors have found that the cause of the self-discharge is caused by the reaction between the negative electrode lithium and the solvent.
本発明はかかる原因に鑑み、溶媒としてリチウムと反
応しにくい不飽和の炭素−炭素結合を鎖式に有する化合
物を用いて、自己放電特性を改善することを目的とす
る。In view of the above, an object of the present invention is to improve the self-discharge characteristics by using a compound having an unsaturated carbon-carbon bond in a chain system that is difficult to react with lithium as a solvent.
（ニ）課題を解決するための手段 本発明は、リチウム或るいはリチウムを含む合金から
なる負極と、正極と、溶質と溶媒からなる電解液とを備
え、前記溶媒として、不飽和の炭素−炭素結合を鎖式に
有するビニルエチレンカーボネート、２−ビニル−1,3
−ジオキソラン、1,2−ジメトキシエチレン、ジビニル
エーテル、Ｎ−ビニルイミダゾール、ビニルアミン、ビ
ニルシクロヘキサンの群から選ばれた少なくとも一つの
化合物からなる溶媒を用いたものである。(D) Means for Solving the Problems The present invention comprises a negative electrode made of lithium or an alloy containing lithium, a positive electrode, and an electrolytic solution consisting of a solute and a solvent. Vinyl ethylene carbonate having a carbon bond in a chain formula, 2-vinyl-1,3
A solvent comprising at least one compound selected from the group consisting of dioxolane, 1,2-dimethoxyethylene, divinyl ether, N-vinylimidazole, vinylamine and vinylcyclohexane.
（ホ）作用 上記の如く溶媒として不飽和の炭素−炭素結合を鎖式
に有する化合物を用いたことにより、該溶媒と負極リチ
ウムとの反応が極めて少なくなった。(E) Action As described above, by using a compound having an unsaturated carbon-carbon bond in a chain formula as a solvent, the reaction between the solvent and the negative electrode lithium was extremely reduced.
（ヘ）実施例 ○実施例１ 第１図は本発明による扁平型非水系電解液一次電池の
断面図を示し、リチウム金属からなる負極１は負極集電
体２の内面に圧着されており、この負極集電体２はフェ
ライト系ステンレス鋼（SUS430）からなる断面略コ字状
の負極缶３の内底面に固着されている。上記負極缶３の
周端はポリプロピレン性の絶縁パッキング４の内部に固
定されており、絶縁パッキング４の外周には、ステンレ
スからなり上記負極缶３とは反対方向に断面略コ字状を
成す正極缶５が固定されている。この正極缶５の内底面
には正極集電体６が固着されており、この正極集電体６
の内面には正極７が固定されている。さらにこの正極７
と前記負極１との間には、電解液が含浸されたセパレー
タ８が介挿されている。(F) Examples Example 1 FIG. 1 is a cross-sectional view of a flat type nonaqueous electrolyte primary battery according to the present invention, in which a negative electrode 1 made of lithium metal is pressed on the inner surface of a negative electrode current collector 2, The negative electrode current collector 2 is fixed to an inner bottom surface of a negative electrode can 3 made of ferritic stainless steel (SUS430) and having a substantially U-shaped cross section. A peripheral end of the negative electrode can 3 is fixed inside a polypropylene insulating packing 4. A positive electrode made of stainless steel and having a substantially U-shaped cross section in a direction opposite to the negative electrode can 3 is provided on the outer periphery of the insulating packing 4. The can 5 is fixed. A positive electrode current collector 6 is fixed to the inner bottom surface of the positive electrode can 5.
The positive electrode 7 is fixed to the inner surface of the. Furthermore, this positive electrode 7
A separator 8 impregnated with an electrolyte is interposed between the anode and the negative electrode 1.
ところで、前記正極７は350〜430℃の温度範囲で熱処
理した二酸化マンガンを活物質として用い、この二酸化
マンガンと、導電剤としてのカーボン粉末と、結着剤と
してのフッ素樹脂粉末とを8:10:5の重量比で混合し、次
にこの混合物を加圧成形した後、250〜350℃で熱処理し
て作製した。By the way, the positive electrode 7 uses manganese dioxide heat-treated at a temperature range of 350 to 430 ° C. as an active material. : 5, and then press-molded this mixture, followed by heat treatment at 250-350 ° C.
また前記負極１は、リチウム圧延板を所定寸法に打ち
抜くことにより作製した。The negative electrode 1 was manufactured by stamping a rolled lithium plate into a predetermined size.
そして電解液としては、不飽和の炭素−炭素結合を鎖
式に有するビニルエチレンカーボネートと、1,2−ジメ
トキシエタンとの等体積の混合溶媒に、溶質としてのト
リフルオロメタンスルホン酸リチウム（LiCF3SO3）を1m
ol/溶解したものを用いた。As the electrolytic solution, lithium trifluoromethanesulfonate (LiCF 3 SO 4) as a solute is mixed with an equal volume of a mixed solvent of vinylethylene carbonate having an unsaturated carbon-carbon bond in a chain formula and 1,2-dimethoxyethane. 3 ) 1m
ol / dissolved was used.
これら正負極7,1、及び電解液を、セパレータ８を介
して正負極缶5,3内に納め、組み立てた電池を、以下本
発明電池Ａと称する。尚、組み立てられた電池の電池径
は20nm、電池厚は2.5mm、電池容量は130mAHとした。The battery assembled by placing the positive and negative electrodes 7, 1 and the electrolyte solution in the positive and negative electrode cans 5, 3 via the separator 8 is hereinafter referred to as Battery A of the present invention. The battery diameter of the assembled battery was 20 nm, the battery thickness was 2.5 mm, and the battery capacity was 130 mAH.
○比較例１ 上記ビニルエチレンカーボネートの代わりに鎖式の炭
素−炭素結合を持たないエチレンカーボネートを用いた
他は上記実施例１と同様にして電池を作製した。このよ
うにして作製した電池を比較電池Ｘと称する。Comparative Example 1 A battery was prepared in the same manner as in Example 1 except that a chain-type ethylene carbonate having no carbon-carbon bond was used in place of the vinyl ethylene carbonate. The battery fabricated in this manner is referred to as Comparative Battery X.
○試験１ 上記本発明電池Ａと、比較電池Ｘにおいて、初期の放
電特性を調べた。その結果を第２図、及び第３図に示
す。なお、第２図は電池組立て後、直ちに温度25℃、負
荷3klで放電したときの放電特性図であり、第３図は電
池組立て後、温度60℃で３ケ月間保存（室温で４〜５年
間保存した場合に相当）した後、温度25℃、負荷3klで
放電したときの放電特性図である。Test 1 Initial discharge characteristics of the battery A of the present invention and the comparative battery X were examined. The results are shown in FIG. 2 and FIG. FIG. 2 is a discharge characteristic diagram when the battery was immediately discharged at a temperature of 25 ° C. and a load of 3 kl after assembling the battery, and FIG. FIG. 7 is a discharge characteristic diagram when the battery is discharged at a temperature of 25 ° C. and a load of 3 kl after storage for a year).
上記第2,3図から明らかなように、本発明電池Ａと比
較電池Ｘとは初期の放電特性では同等の値を示してい
る。しかしながら、保存後の放電特性を比較すると、本
発明電池Ａの方が比較電池Ｘより長時間（略10hの差）
高い放電電圧を示し、長期保存後でも内部インピーダン
スの増加が抑制されていることが分かる。As is clear from FIGS. 2 and 3, the battery A of the present invention and the comparative battery X show equivalent values in the initial discharge characteristics. However, comparing the discharge characteristics after storage, the battery A of the present invention has a longer time (a difference of approximately 10 hours) than the comparative battery X.
It shows a high discharge voltage, indicating that the increase in internal impedance is suppressed even after long-term storage.
また、長期保存後の前記両電池A,Xを分解したとこ
ろ、比較電池Ｘでは負極リチウム表面が黒く変色してい
たのに対し、本発明電池Ａではそのような現象は見られ
なかった。When the batteries A and X were disassembled after long-term storage, the lithium battery surface of the comparative battery X was discolored to black, whereas the battery A of the present invention did not show such a phenomenon.
この結果より、比較電池Ｘでは保存中にエチレンカー
ボネートがリチウム負極と反応し、この結果保存後の放
電特性が低下したものと考えられる。From these results, it is considered that in the comparative battery X, ethylene carbonate reacted with the lithium negative electrode during storage, and as a result, the discharge characteristics after storage decreased.
一方、本発明電池Ａのように電解液の溶媒としてビニ
ルエチレンカーボネートを用いると、電子供与性のビニ
ル基がエチレンカーボネートと負極リチウムとの反応を
抑制し、この結果、保存後の放電特性の低下を防止でき
たものと考えられる。On the other hand, when vinyl ethylene carbonate is used as the solvent of the electrolytic solution as in the battery A of the present invention, the electron-donating vinyl group suppresses the reaction between ethylene carbonate and the negative electrode lithium, and as a result, the discharge characteristics after storage deteriorate. It is probable that this was prevented.
○実施例２ 電解液の溶質としてLiPF6を用い、溶媒として不飽和
の炭素−炭素結合を鎖式に有する２−ビニル−1,3−ジ
オキソランとプロピレンカーボネートとの等体積の混合
溶媒を用いた他は、上記実施例１と同様にして電池を作
製した。Example 2 LiPF 6 was used as the solute of the electrolytic solution, and an equal volume mixed solvent of 2-vinyl-1,3-dioxolane having an unsaturated carbon-carbon bond in a chain formula and propylene carbonate was used as a solvent. Otherwise, a battery was fabricated in the same manner as in Example 1.
このようにして作製した電池を、以下本発明電池Ｂと
称す。The battery fabricated in this manner is hereinafter referred to as Battery B of the invention.
○比較例２ 次に、２−ビニル−1,3−ジオキソランの代わりに鎖
式の炭素−炭素結合を持たない1,3−ジオキソランを用
いる他は上記実施例２と同様にして電池を作製した。Comparative Example 2 Next, a battery was fabricated in the same manner as in Example 2 except that 1,3-dioxolane having no chain-type carbon-carbon bond was used instead of 2-vinyl-1,3-dioxolane. .
このようにして作製した電池を以下比較電池Ｙと称す
る。The battery fabricated in this manner is hereinafter referred to as Comparative Battery Y.
○試験２ 上記本発明電池Ｂ、及び比較電池Ｙの初期の放電特性
と、保存後の放電特性とを、前記試験１と同様の条件で
調べた。その結果を夫々第４図、及び第５図に示す。こ
れら第4,5図から明らかなように初期の放電特性は両電
池B,Y共に同等であるが、保存後の放電特性は、比較電
池Ｙより本発明電池Ｂの方が優れている（略15hの差）
ことが分かる。Test 2 The initial discharge characteristics and the discharge characteristics after storage of the battery B of the present invention and the comparative battery Y were examined under the same conditions as in the test 1. The results are shown in FIGS. 4 and 5, respectively. As is clear from FIGS. 4 and 5, the initial discharge characteristics of both batteries B and Y are equivalent, but the discharge characteristics after storage of the battery B of the present invention are superior to those of the comparative battery Y (approximately). 15h difference)
You can see that.
○実施例３ 前記実施例１、及び実施例２では非水系の一次電池に
ついて本発明電池を説明したが、次に非水系二次電池に
適用した実施例３について説明する。Third Embodiment In the first and second embodiments, the battery of the present invention has been described for a non-aqueous primary battery. Next, a third embodiment in which the present invention is applied to a non-aqueous secondary battery will be described.
この非水系二次電池の構造は前記第１図に示す扁平型
一次電池と同じであるが、正極７の活物質として充電可
能なマンガン酸化物を用いた点が異なっており、また、
その電解液としては、不飽和の炭素−炭素結合を鎖式に
有するビニルエチレンカーボネートと、1,2−ジメトキ
シエタンとの等体積の混合溶媒に、溶質としてのトリフ
ルオロメタンスルホン酸リチウムを1mol/溶解したも
のを用いた点が異なっている。The structure of this non-aqueous secondary battery is the same as that of the flat primary battery shown in FIG. 1, except that a chargeable manganese oxide is used as the active material of the positive electrode 7.
As the electrolytic solution, 1 mol / dissolved lithium trifluoromethanesulfonate as a solute in an equal volume mixed solvent of vinylethylene carbonate having an unsaturated carbon-carbon bond in a chain formula and 1,2-dimethoxyethane. The difference is that they are used.
このようにして作製した電池を本発明電池Ｃと称す
る。The battery fabricated in this manner is referred to as Battery C of the invention.
○比較例３ 上記実施例３のビニルエチレンカーボネートの代わり
に鎖式の炭素−炭素結合を持たないエチレンカーボネー
トを用いた他は本発明電池Ｃと同様にして比較電池Ｚを
得た。Comparative Example 3 A comparative battery Z was obtained in the same manner as the battery C of the present invention, except that the ethylene carbonate having no chain carbon-carbon bond was used in place of the vinyl ethylene carbonate of the above-mentioned Example 3.
○試験３ 前記本発明電池Ｃと、比較電池Ｚとの充放電サイクル
試験を行ってその特性を調べた。ここでは、充放電電流
を2mA、充電時間を３時間とし、充放電の繰り返しによ
り端子電圧が2.0Vに達するまでの放電サイクル数を取っ
た。電池組立て直後にサイクル試験を行った結果を第６
図に示し、60℃で３ケ月保存後にサイクル試験を行った
結果を第７図に夫々示す。Test 3 A charge-discharge cycle test was performed on the battery C of the present invention and the comparative battery Z, and the characteristics were examined. Here, the charging / discharging current was 2 mA, the charging time was 3 hours, and the number of discharge cycles until the terminal voltage reached 2.0 V by repeating the charging / discharging was taken. The results of the cycle test performed immediately after battery assembly
FIG. 7 shows the results of the cycle test after storage at 60 ° C. for 3 months.
上記第6,7図から初期のサイクル特性は両電池C,Zとも
同等であるが、本発明電池Ｃは保存後のサイクル特性に
関して、比較電池Ｚよりも優れている（略25回の差）こ
とが分かる。From FIGS. 6 and 7, the initial cycle characteristics are the same for both batteries C and Z, but the battery C of the present invention is superior to the comparative battery Z in the cycle characteristics after storage (approximately 25 times difference). You can see that.
本発明は上記溶媒材料の他、1,2−ジメトキシエチレ
ン、ジビニルエーテル、Ｎ−ビニルイミダゾール、ビニ
ルアミン、ビニルシクロヘキサンも同様の効果を生じる
ことを確認した。In the present invention, it has been confirmed that, in addition to the above solvent materials, 1,2-dimethoxyethylene, divinyl ether, N-vinylimidazole, vinylamine, and vinylcyclohexane also produce similar effects.
（ト）発明の効果 以上説明したように本発明によれば、電池の保存中に
溶媒が負極と反応することを抑制することができるの
で、初期の放電特性のみならず、保存後の放電特性を改
善することができる。この結果、非水系電解液電池の性
能を飛躍的に向上させることができ、その工業的価値は
極めて大きい。(G) Effects of the Invention As described above, according to the present invention, it is possible to suppress the reaction of the solvent with the negative electrode during storage of the battery, so that not only the initial discharge characteristics but also the discharge characteristics after storage. Can be improved. As a result, the performance of the non-aqueous electrolyte battery can be dramatically improved, and its industrial value is extremely large.
第１図は本発明電池の縦断面図、第２図は本発明電池Ａ
及び比較電池Ｘにおける初期の放電特性を示す図、第３
図は本発明電池Ａ及び比較電池Ｘにおける保存後の放電
特性を示す図、第４図は本発明電池Ｂ及び比較電池Ｙに
おける初期の放電特性を示す図、第５図は本発明電池Ｂ
及び比較電池Ｙにおける保存後の放電特性を示す図、第
６図は本発明電池Ｃ及び比較電池Ｚにおける初期のサイ
クル特性を示す図、第７図は本発明電池Ｃ及び比較電池
Ｚにおける保存後のサイクル特性を示す図である。 A,B,C……本発明電池、 X,Y,Z……比較電池、 １……負極、 ２……負極集電体、 ３……負極缶、 ４……絶縁パッキング、 ５……正極缶、 ６……負極集電体、 ７……負極、 ８……セパレータ。FIG. 1 is a longitudinal sectional view of the battery of the present invention, and FIG.
And FIG. 3 shows an initial discharge characteristic of the comparative battery X.
The figure shows the discharge characteristics of the battery A of the present invention and the comparative battery X after storage, FIG. 4 shows the initial discharge characteristics of the battery B of the present invention and the comparative battery Y, and FIG. 5 shows the battery B of the present invention.
FIG. 6 is a diagram showing discharge characteristics after storage in the comparative battery Y, FIG. 6 is a diagram showing initial cycle characteristics in the battery C of the present invention and the comparative battery Z, and FIG. FIG. 4 is a diagram showing cycle characteristics of the present invention. A, B, C ... battery of the present invention, X, Y, Z ... comparative battery, 1 ... negative electrode, 2 ... negative electrode current collector, 3 ... negative electrode can, 4 ... insulating packing, 5 ... positive electrode Can, 6: Negative electrode current collector, 7: Negative electrode, 8: Separator.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 6/16 H01M 10/40 Continuation of front page (58) Field surveyed (Int.Cl. 6 , DB name) H01M 6/16 H01M 10/40
Claims (1)
なる負極と、正極と、溶質と溶媒からなる電解液とを備
え、前記溶媒として、不飽和の炭素−炭素結合を鎖式に
有するビニルエチレンカーボネート、２−ビニル−1,3
−ジオキソラン、1,2−ジメトキシエチレン、ジビニル
エーテル、Ｎ−ビニルイミダゾール、ビニルアミン、ビ
ニルシクロヘキサンの群から選ばれた少なくとも一つの
化合物からなる溶媒を用いたことを特徴とする非水系電
解液電池。1. A negative electrode comprising lithium or an alloy containing lithium, a positive electrode, and an electrolytic solution comprising a solute and a solvent, wherein the solvent is a vinylethylene having an unsaturated carbon-carbon bond in a chain system. Carbonate, 2-vinyl-1,3
A non-aqueous electrolyte battery using a solvent comprising at least one compound selected from the group consisting of dioxolane, 1,2-dimethoxyethylene, divinyl ether, N-vinylimidazole, vinylamine, and vinylcyclohexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2199519A JP2962782B2 (en) | 1990-07-26 | 1990-07-26 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2199519A JP2962782B2 (en) | 1990-07-26 | 1990-07-26 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0487156A JPH0487156A (en) | 1992-03-19 |
| JP2962782B2 true JP2962782B2 (en) | 1999-10-12 |
Family
ID=16409178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2199519A Expired - Fee Related JP2962782B2 (en) | 1990-07-26 | 1990-07-26 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2962782B2 (en) |
Cited By (1)
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|---|---|---|---|---|
| US8697291B2 (en) | 2010-10-07 | 2014-04-15 | Uchicago Argonne, Llc | Non-aqueous electrolyte for lithium-ion battery |
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1990
- 1990-07-26 JP JP2199519A patent/JP2962782B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8697291B2 (en) | 2010-10-07 | 2014-04-15 | Uchicago Argonne, Llc | Non-aqueous electrolyte for lithium-ion battery |
| US9218915B2 (en) | 2010-10-07 | 2015-12-22 | Uchicago Argonne, Llc | Non-aqueous electrolyte for lithium-ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0487156A (en) | 1992-03-19 |
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