JPH0684525A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH0684525A JPH0684525A JP26075592A JP26075592A JPH0684525A JP H0684525 A JPH0684525 A JP H0684525A JP 26075592 A JP26075592 A JP 26075592A JP 26075592 A JP26075592 A JP 26075592A JP H0684525 A JPH0684525 A JP H0684525A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- aqueous electrolyte
- ester
- battery
- present
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 38
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 claims abstract description 15
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 protocatechuic acid ester Chemical class 0.000 claims description 11
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims description 5
- LNTHITQWFMADLM-UHFFFAOYSA-N anhydrous gallic acid Natural products OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 abstract description 10
- 230000006866 deterioration Effects 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 4
- 238000004321 preservation Methods 0.000 abstract 2
- 229940021013 electrolyte solution Drugs 0.000 description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- CUFLZUDASVUNOE-UHFFFAOYSA-N methyl 3,4-dihydroxybenzoate Chemical compound COC(=O)C1=CC=C(O)C(O)=C1 CUFLZUDASVUNOE-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910003174 MnOOH Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- KBPUBCVJHFXPOC-UHFFFAOYSA-N ethyl 3,4-dihydroxybenzoate Chemical compound CCOC(=O)C1=CC=C(O)C(O)=C1 KBPUBCVJHFXPOC-UHFFFAOYSA-N 0.000 description 2
- VFPFQHQNJCMNBZ-UHFFFAOYSA-N ethyl gallate Chemical compound CCOC(=O)C1=CC(O)=C(O)C(O)=C1 VFPFQHQNJCMNBZ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- YBMTWYWCLVMFFD-UHFFFAOYSA-N 3-methylbutyl 3,4,5-trihydroxybenzoate Chemical compound CC(C)CCOC(=O)C1=CC(O)=C(O)C(O)=C1 YBMTWYWCLVMFFD-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 235000019277 ethyl gallate Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- DZPQPQLYRIVMGC-UHFFFAOYSA-N propyl 3,4-dihydroxybenzoate Chemical compound CCCOC(=O)C1=CC=C(O)C(O)=C1 DZPQPQLYRIVMGC-UHFFFAOYSA-N 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- Y02E60/12—
Landscapes
- Primary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非水系電解液電池に係
わり、特に保存特性の向上を目的とした非水系電解液の
改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte battery, and more particularly to improvement of a non-aqueous electrolyte solution for the purpose of improving storage characteristics.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
非水系電解液電池の電解液溶媒として、プロピレンカー
ボネート、ジメチルカーボネートなどの有機溶媒が一般
的に使用されている。2. Description of the Related Art Conventionally, the problems to be solved by the invention
An organic solvent such as propylene carbonate or dimethyl carbonate is generally used as an electrolytic solution solvent for a non-aqueous electrolytic solution battery.
【０００３】この種の従来の非水系電解液電池には、高
電位の正極側において非水系電解液中の溶媒分子が二酸
化マンガン等の正極活物質の表面に存在する官能基と反
応して分解し易いため、保存特性が良くないという問題
があった。In this type of conventional non-aqueous electrolyte battery, solvent molecules in the non-aqueous electrolyte on the high potential positive electrode side react with functional groups present on the surface of the positive electrode active material such as manganese dioxide to decompose. Therefore, there is a problem that the storage characteristics are not good.
【０００４】本発明は、かかる問題を解決するべくなさ
れたものであって、その目的とするところは、非水系電
解液と正極活物質との反応を抑制することにより、保存
特性に優れた非水系電解液電池を提供するにある。The present invention has been made to solve the above problems, and an object of the present invention is to suppress the reaction between a non-aqueous electrolyte solution and a positive electrode active material, thereby providing a non-excellent storage property. An object is to provide an aqueous electrolyte battery.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
の本発明に係る非水系電解液電池（以下、「本発明電
池」と称する。）は、非水系電解液に、プロトカテク酸
エステル（３，４−ジヒドロキシ安息香酸エステル）、
没食子酸エステル（３，４，５−トリヒドロキシ安息香
酸エステル）、及びこれらの誘導体（以下、これらを総
称して「芳香族エステル」と称することがある。）より
なる群から選ばれた少なくとも一種の芳香族エステルが
添加されていることを特徴とする。A non-aqueous electrolyte battery according to the present invention for achieving the above object (hereinafter referred to as "the battery of the present invention") is prepared by adding a protocatechuic acid ester (3) to a non-aqueous electrolyte. , 4-dihydroxybenzoic acid ester),
At least one selected from the group consisting of gallic acid ester (3,4,5-trihydroxybenzoic acid ester) and derivatives thereof (hereinafter, these may be collectively referred to as “aromatic ester”). The aromatic ester is added.
【０００６】このように、本発明電池においては、非水
系電解液に特定の芳香族エステルが添加されているの
で、従来の非水系電解液電池において問題となっていた
非水系電解液と正極活物質とが反応することに起因して
保存特性が劣化するという問題が可及的に解消される。As described above, since the specific aromatic ester is added to the non-aqueous electrolyte solution in the battery of the present invention, the non-aqueous electrolyte solution and the positive electrode active material which have been problems in the conventional non-aqueous electrolyte solution battery. The problem that storage characteristics are deteriorated due to reaction with a substance is eliminated as much as possible.
【０００７】すなわち、本発明電池においては、還元力
の強い特定の芳香族エステルの還元作用により二酸化マ
ンガンなどの正極活物質の表面に存在する活性の高い−
ＭｎＯＯＨ等の官能基（表面官能基）が還元されて失活
（不活性化）し、これにより非水系電解液と正極活物質
との反応が抑制される。That is, in the battery of the present invention, the high activity existing on the surface of the positive electrode active material such as manganese dioxide is high due to the reducing action of the specific aromatic ester having a strong reducing power.
A functional group (surface functional group) such as MnOOH is reduced and inactivated (inactivated), and thereby the reaction between the non-aqueous electrolyte solution and the positive electrode active material is suppressed.
【０００８】下記の化１は、二酸化マンガンに存在する
表面官能基−ＭｎＯＯＨがプロトカテク酸メチルにより
還元されて失活する様子を反応式で表したものであり、
同反応式に示すように、二酸化マンガンの表面に存在す
る−ＭｎＯＯＨ中の水酸基はプロトカテク酸メチルから
脱離したメチルラジカルと反応して−ＯＣＨ3 となり、
また−ＭｎＯＯＨ中の＝Ｏはプロトカテク酸メチルの３
位又は４位の−ＯＨから引き抜かれた水素ラジカルと反
応して水酸基となる。このように、表面官能基の活性部
分がそれぞれより安定化するため失活するものと推察さ
れる。The following chemical formula 1 is a reaction formula showing how the surface functional group --MnOOH existing in manganese dioxide is reduced and deactivated by methyl protocatechuate.
As shown in the reaction formula becomes -OCH 3 hydroxyl groups in -MnOOH reacts with desorbed methyl radical protocatechuic acid methyl existing on the surface of the manganese dioxide,
Further, ═O in —MnOOH is 3 of methyl protocatechuate.
React with hydrogen radicals extracted from -OH at the 4-position or 4-position to form hydroxyl groups. As described above, it is presumed that the active portions of the surface functional groups are more stabilized and are deactivated.
【０００９】[0009]
【化１】 [Chemical 1]
【００１０】本発明におけるプロトカテク酸エステルと
しては、上記プロトカテク酸メチルの他、プロトカテク
酸エチル、プロトカテク酸プロピル、プロトカテク酸イ
ソアミルが例示され、また没食子酸エステルとしては、
没食子酸メチル、没食子酸エチル、没食子酸プロピル、
没食子酸イソアミルが好適なものとして例示される。Examples of the protocatechuic acid ester in the present invention include ethyl protocatechuate, propyl protocatechuate, and isoamyl protocatechuate in addition to the above methyl protocatechuate.
Methyl gallate, ethyl gallate, propyl gallate,
Isoamyl gallate is illustrated as a suitable example.
【００１１】これらのプロトカテク酸エステル、没食子
酸エステル、及びこれらの誘導体は、一種単独を使用し
てもよく、必要に応じて二種以上を併用してもよい。These protocatechuic acid esters, gallic acid esters, and their derivatives may be used alone or in combination of two or more if necessary.
【００１２】本発明における芳香族エステルの非水系電
解液への好適な添加比率は、非水系電解液の総重量に対
して０．０５重量％（５００ｐｐｍ）〜２重量％の範囲
である。芳香族エステルの添加比率が０．０５重量％未
満の場合は過少のため表面官能基を失活させる効果が充
分に発現されず、また添加比率が２重量％を越えた場合
は却って放電特性が低下する傾向があるので、ともに好
ましくない。The preferred addition ratio of the aromatic ester to the non-aqueous electrolytic solution in the present invention is in the range of 0.05% by weight (500 ppm) to 2% by weight based on the total weight of the non-aqueous electrolytic solution. When the addition ratio of the aromatic ester is less than 0.05% by weight, the effect of deactivating the surface functional group is not sufficiently exhibited because it is too small, and when the addition ratio exceeds 2% by weight, the discharge characteristics are rather rather deteriorated. Both of them are not preferable because they tend to decrease.
【００１３】本発明における非水系電解液の溶媒として
は、プロピレンカーボネート、エチレンカーボネート、
１，２−ブチレンカーボネートなどの有機溶媒や、これ
らとジメチルカーボネート、ジエチルカーボネート、
１，２−ジメトキエタン、１，２−ジエトキエタン、エ
トキシメトキシエタンなどの低沸点溶媒との混合溶媒が
例示され、また溶質としてはＬｉＰＦ6 、ＬｉＣｌ
Ｏ4 、ＬｉＣＦ3 ＳＯ3 が例示されるが、本発明におけ
る非水系電解液は、正極活物質と反応し易いものであれ
ば芳香族エステルを添加することにより本発明が企図す
る効果が奏されるので、これらに限定されない。Solvents for the non-aqueous electrolyte in the present invention include propylene carbonate, ethylene carbonate,
Organic solvents such as 1,2-butylene carbonate, these and dimethyl carbonate, diethyl carbonate,
A mixed solvent with a low boiling point solvent such as 1,2-dimethoethane, 1,2-dietoethane, and ethoxymethoxyethane is exemplified, and solutes such as LiPF 6 and LiCl
O 4 and LiCF 3 SO 3 are exemplified, but the non-aqueous electrolyte solution of the present invention exhibits the effect intended by the present invention by adding an aromatic ester as long as it easily reacts with the positive electrode active material. Therefore, it is not limited to these.
【００１４】本発明は、正極活物質と非水系電解液とが
反応することに起因する保存特性の劣化を、非水系電解
液に特定の芳香族エステルを添加混合することにより解
消したものであり、それゆえ電池を構成する他の部材に
ついては特に制限されず、従来非水系電解液電池用とし
て実用され、或いは提案されている種々の材料を使用す
ることが可能である。The present invention eliminates the deterioration of the storage characteristics caused by the reaction between the positive electrode active material and the non-aqueous electrolyte by adding and mixing a specific aromatic ester to the non-aqueous electrolyte. Therefore, other members constituting the battery are not particularly limited, and various materials that have been practically used or proposed for the conventional non-aqueous electrolyte battery can be used.
【００１５】たとえば、本発明における正極活物質とし
ては、金属酸化物（ＭｎＯ2 、改質ＭｎＯ2 、重質化Ｍ
ｎＯ2 、ＭｏＯ2 、ＣｕＯ、Ｃｒ2 Ｏ3 、ＣｒＯ3 、Ｖ
2 Ｏ5 、ＮｉＯＯＨなど）；金属硫化物（ＦｅＳ、Ｔｉ
Ｓ2 、又はＭｏＳ2 など）；金属セレン化物（ＴｉＳｅ
2 など）；クロム、マンガン、鉄、コバルト及びニッケ
ルよりなる群から選ばれた少なくとも一種の金属とＬｉ
との複合酸化物など、種々の材料を使用することができ
る。なかでも、マンガン酸化物、ニッケル酸化物及びコ
バルト酸化物は、活性の高い官能基を数多く有し、非水
系電解液と反応し易いので、本発明は、これらを正極活
物質とする非水系電解液電池に適用して特に好適であ
る。For example, as the positive electrode active material in the present invention, metal oxides (MnO 2 , modified MnO 2 , heavy M
nO 2 , MoO 2 , CuO, Cr 2 O 3 , CrO 3 , V
2 O 5 , NiOOH, etc.); metal sulfides (FeS, Ti
S 2 or MoS 2 ); Metal selenide (TiSe)
2 etc.); at least one metal selected from the group consisting of chromium, manganese, iron, cobalt and nickel, and Li
Various materials such as a complex oxide of Among them, manganese oxide, nickel oxide and cobalt oxide have a large number of highly active functional groups and easily react with a non-aqueous electrolyte solution. It is particularly suitable when applied to a liquid battery.
【００１６】また、本発明における負極材料としては、
リチウム金属又はリチウムを吸蔵放出可能な物質が例示
される。リチウムを吸蔵放出可能な物質としては、リチ
ウム合金、酸化物、炭素材料などが挙げられる。なお、
炭素材料などの粉末材料は、これをポリテトラフルオロ
エチレン等の結着剤と混練して負極合剤として使用す
る。Further, as the negative electrode material in the present invention,
Examples are lithium metal and substances capable of inserting and extracting lithium. Examples of the substance capable of inserting and extracting lithium include a lithium alloy, an oxide, and a carbon material. In addition,
A powder material such as a carbon material is kneaded with a binder such as polytetrafluoroethylene and used as a negative electrode mixture.
【００１７】[0017]
【作用】本発明電池においては、非水系電解液に特定の
芳香族エステルが添加され、当該芳香族エステルが正極
活物質の表面に存在する官能基を還元して失活させるの
で、正極活物質と非水系電解液との反応が抑制される。In the battery of the present invention, a specific aromatic ester is added to the non-aqueous electrolyte solution, and the aromatic ester reduces and deactivates the functional group present on the surface of the positive electrode active material. And the reaction with the non-aqueous electrolyte solution are suppressed.
【００１８】[0018]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例により何ら限定され
るものではなく、その要旨を変更しない範囲において適
宜変更して実施することが可能なものである。The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by the following examples, and various modifications can be made without departing from the scope of the invention. Is possible.
【００１９】（実施例１〜８）扁平型の非水系電解液一
次電池（本発明電池）を作製した。(Examples 1 to 8) Flat type non-aqueous electrolyte primary batteries (cells of the present invention) were produced.
【００２０】〔正極の作製〕活物質としての二酸化マン
ガンと、導電剤としてのカーボンブラックと、これら両
者の結着剤としてのフッ素樹脂とを、重量比８５：１
０：５で混合して正極合剤を得た。この正極合剤を鋳型
成形して、円板状の正極を作製した。なお、正極集電体
として、ステンレス鋼板（ＳＵＳ３０４）を使用した。[Preparation of Positive Electrode] Manganese dioxide as an active material, carbon black as a conductive agent, and a fluororesin as a binder for both of them were mixed at a weight ratio of 85: 1.
The mixture was mixed at 0: 5 to obtain a positive electrode mixture. This positive electrode mixture was molded into a disc-shaped positive electrode. A stainless steel plate (SUS304) was used as the positive electrode current collector.
【００２１】〔負極の作製〕圧延、打ち抜きによりリチ
ウム金属からなる円板状の負極を作製した。なお、負極
集電体として、ステンレス鋼板（ＳＵＳ３０４）を使用
した。[Production of Negative Electrode] A disk-shaped negative electrode made of lithium metal was produced by rolling and punching. A stainless steel plate (SUS304) was used as the negative electrode current collector.
【００２２】〔非水系電解液の調製〕プロピレンカーボ
ネート（ＰＣ）と１，２−ジメトキシエタン（ＤＭＥ）
との等体積混合溶媒にＬｉＣｌＯ4 （過塩素酸リチウ
ム）を１モル／リットル溶かした溶液に、さらに下記の
表１に示す芳香族エステルを非水系電解液の総重量に対
して０．１重量％（１０００ｐｐｍ）の比率で添加混合
して８種の非水系電解液を調製した。[Preparation of Non-Aqueous Electrolyte] Propylene carbonate (PC) and 1,2-dimethoxyethane (DME)
0.1% by weight based on the total weight of the non-aqueous electrolyte solution, in a solution in which 1 mol / liter of LiClO 4 (lithium perchlorate) is dissolved in an equal volume mixed solvent of % (1000 ppm) were added and mixed to prepare eight types of non-aqueous electrolyte solutions.
【００２３】[0023]
【表１】 [Table 1]
【００２４】〔電池の作製〕以上の正負両極及び８種の
非水系電解液を用いて８種の扁平型の本発明電池ＢＡ１
〜ＢＡ８（電池寸法：直径２０ｍｍ、厚み：２．５ｍ
ｍ）を作製した。セパレータとしては、ポリプロピレン
製の微孔性薄膜を用い、これに先に述べた各非水系電解
液を含浸させた。[Production of Battery] Using the above-mentioned positive and negative electrodes and eight types of non-aqueous electrolytes, eight types of flat type batteries of the present invention BA1
~ BA8 (Battery size: diameter 20mm, thickness: 2.5m
m) was prepared. As the separator, a microporous thin film made of polypropylene was used, which was impregnated with each of the above-mentioned non-aqueous electrolyte solutions.
【００２５】図１は作製した本発明電池ＢＡ１（〜ＢＡ
８）を模式的に示す断面図であり、同図に示す本発明電
池ＢＡ１は、正極１、負極２、これら両電極を離隔する
セパレータ３、正極缶４、負極缶５、正極集電体６、負
極集電体７及びポリプロピレン製の絶縁パッキング８な
どからなる。正極１及び負極２は、非水系電解質を含浸
したセパレータ３を介して対向して正負両極缶４、５が
形成する電池ケース内に収容されており、正極１は正極
集電体６を介して正極缶４に、また負極２は負極集電体
７を介して負極缶５に接続され、本発明電池ＢＡ１内部
で生じた化学エネルギーを正極缶４及び負極缶５の両端
子から電気エネルギーとして外部へ取り出し得るように
なっている。FIG. 1 shows the manufactured battery BA1 (to BA of the present invention).
8) is a cross-sectional view schematically showing a battery BA1 of the present invention shown in the same figure, which includes a positive electrode 1, a negative electrode 2, a separator 3 separating these electrodes, a positive electrode can 4, a negative electrode can 5, and a positive electrode current collector 6. , A negative electrode current collector 7, an insulating packing 8 made of polypropylene, and the like. The positive electrode 1 and the negative electrode 2 are housed in a battery case formed by positive and negative bipolar cans 4 and 5 facing each other with a separator 3 impregnated with a non-aqueous electrolyte interposed therebetween. The negative electrode 2 is connected to the positive electrode can 4 and the negative electrode 2 is connected to the negative electrode can 5 via the negative electrode current collector 7, and the chemical energy generated inside the battery BA1 of the present invention is output as electrical energy from both terminals of the positive electrode can 4 and the negative electrode can 5. You can take it out.
【００２６】（比較例１）非水系電解液の調製において
芳香族エステルを添加しなかったこと以外は実施例１〜
８と同様にして、比較電池ＢＣ１を作製した。Comparative Example 1 Examples 1 to 1 except that the aromatic ester was not added in the preparation of the non-aqueous electrolyte solution.
A comparative battery BC1 was prepared in the same manner as in Example 8.
【００２７】（初期の放電容量）本発明電池ＢＡ１〜Ｂ
Ａ８及び比較電池ＢＣ１のそれぞれについて、室温（２
５°Ｃ）下、２キロオームで定抵抗放電を行い初期の放
電容量を調べた。結果を、先の表１に示す。なお、放電
は、当初３．２Ｖあった電池電圧が２Ｖになるまで行っ
た。(Initial discharge capacity) Batteries BA1 to B of the present invention
For each of A8 and comparative battery BC1, room temperature (2
At 5 ° C.), constant resistance discharge was performed at 2 kOhm to examine the initial discharge capacity. The results are shown in Table 1 above. The discharging was continued until the battery voltage, which was 3.2 V at the beginning, became 2 V.
【００２８】（保存後の放電容量）６０°Ｃで３ヶ月保
存した後の本発明電池ＢＡ１〜ＢＡ８及び比較電池ＢＣ
１のそれぞれについて、室温下、２キロオームで定抵抗
放電を行い放電容量を調べた。結果を、先の表１に示
す。(Discharge capacity after storage) Inventive batteries BA1 to BA8 and comparative battery BC after storage at 60 ° C for 3 months
With respect to each of 1), a constant resistance discharge was performed at room temperature at 2 kOhm to examine the discharge capacity. The results are shown in Table 1 above.
【００２９】表１より、初期の放電容量については各電
池間に差異はないが、３ヶ月保存後の放電容量について
は、本発明電池ＢＡ１〜ＢＡ８では全く低下していない
のに対して、比較電池ＢＣ１では明らかに低下してお
り、本発明電池ＢＡ１〜ＢＡ８は比較電池ＢＣ１に比し
保存特性に優れていることが分かる。From Table 1, there is no difference in the initial discharge capacity among the batteries, but the discharge capacities after storage for 3 months are not lowered at all in the batteries BA1 to BA8 of the present invention. The battery BC1 has clearly decreased, and it is understood that the batteries BA1 to BA8 of the present invention have excellent storage characteristics as compared with the comparative battery BC1.
【００３０】叙上の実施例では本発明を扁平型の一次電
池に適用する場合の具体例について説明したが、一次か
二次かは問われず、また電池の形状も特に制限されず、
円筒型、角型など、本発明は種々の形状の非水系電解液
電池に適用することができる。In the above embodiment, a specific example in which the present invention is applied to a flat type primary battery has been described, but it does not matter whether it is a primary or secondary battery, and the shape of the battery is not particularly limited.
The present invention can be applied to various shapes of non-aqueous electrolyte batteries such as a cylindrical type and a rectangular type.
【００３１】[0031]
【発明の効果】本発明電池においては、正極活物質の表
面官能基を失活させる特定の芳香族エステルが非水系電
解液に添加されているので、非水系電解液と正極活物質
との反応が起こりにくく、このため保存特性に優れるな
ど、本発明は優れた特有の効果を奏する。In the battery of the present invention, since the specific aromatic ester which deactivates the surface functional group of the positive electrode active material is added to the non-aqueous electrolyte solution, the reaction between the non-aqueous electrolyte solution and the positive electrode active material. Is less likely to occur, and thus has excellent storage characteristics, and the present invention has excellent unique effects.
【図１】扁平型の本発明電池の模式的断面図である。FIG. 1 is a schematic cross-sectional view of a flat type battery of the present invention.
ＢＡ１ 本発明電池 １ 正極 ２ 負極 ３ セパレータ BA1 Inventive battery 1 Positive electrode 2 Negative electrode 3 Separator
Claims (3)
ル、没食子酸エステル、及びこれらの誘導体よりなる群
から選ばれた少なくとも一種の芳香族エステルが添加さ
れていることを特徴とする非水系電解液電池。1. A non-aqueous electrolytic solution, wherein at least one aromatic ester selected from the group consisting of protocatechuic acid ester, gallic acid ester, and derivatives thereof is added to the non-aqueous electrolytic solution. battery.
が０．０５〜２重量％添加されている請求項１記載の非
水系電解液電池。2. The non-aqueous electrolyte battery according to claim 1, wherein 0.05 to 2% by weight of the aromatic ester is added to the non-aqueous electrolyte solution.
化物又はコバルト酸化物である請求項１記載の非水系電
解液電池。3. The non-aqueous electrolyte battery according to claim 1, wherein the positive electrode active material is manganese oxide, nickel oxide or cobalt oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26075592A JPH0684525A (en) | 1992-09-02 | 1992-09-02 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26075592A JPH0684525A (en) | 1992-09-02 | 1992-09-02 | Nonaqueous electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0684525A true JPH0684525A (en) | 1994-03-25 |
Family
ID=17352284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26075592A Pending JPH0684525A (en) | 1992-09-02 | 1992-09-02 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0684525A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006100162A (en) * | 2004-09-30 | 2006-04-13 | Sanyo Electric Co Ltd | Non-aqueous electrolyte primary battery |
| KR20170096745A (en) * | 2016-02-17 | 2017-08-25 | 주식회사 엘지화학 | Electrode Slurry Comprising Additive Preventing Gelation of Electrolyte and Secondary Battery Comprising the Same |
-
1992
- 1992-09-02 JP JP26075592A patent/JPH0684525A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006100162A (en) * | 2004-09-30 | 2006-04-13 | Sanyo Electric Co Ltd | Non-aqueous electrolyte primary battery |
| KR20170096745A (en) * | 2016-02-17 | 2017-08-25 | 주식회사 엘지화학 | Electrode Slurry Comprising Additive Preventing Gelation of Electrolyte and Secondary Battery Comprising the Same |
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