JPH04206476A - Organic electrolyte battery - Google Patents
Organic electrolyte batteryInfo
- Publication number
- JPH04206476A JPH04206476A JP2339553A JP33955390A JPH04206476A JP H04206476 A JPH04206476 A JP H04206476A JP 2339553 A JP2339553 A JP 2339553A JP 33955390 A JP33955390 A JP 33955390A JP H04206476 A JPH04206476 A JP H04206476A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- battery
- organic solvent
- organic
- acetonitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005486 organic electrolyte Substances 0.000 title claims abstract description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- LBKMJZAKWQTTHC-UHFFFAOYSA-N 4-methyldioxolane Chemical compound CC1COOC1 LBKMJZAKWQTTHC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- -1 lithium hexafluoroarsenate Chemical compound 0.000 claims description 11
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000008151 electrolyte solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000005843 Thiram Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- WMQDRXQOHUXCLT-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-arsane Chemical group [Li+].[Li+].[O-][As]([O-])(F)=O WMQDRXQOHUXCLT-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- VKJKOXNPYVUXNC-UHFFFAOYSA-K trilithium;trioxido(oxo)-$l^{5}-arsane Chemical compound [Li+].[Li+].[Li+].[O-][As]([O-])([O-])=O VKJKOXNPYVUXNC-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、有機電解液電池に関する。[Detailed description of the invention] Industrial applications The present invention relates to an organic electrolyte battery.
従来の技術とその課題
有機電解液電池は、電圧か高くエネルキー密度か高い点
て水溶液系電池より俊れている。Conventional technology and its challenges Organic electrolyte batteries are superior to aqueous batteries in terms of higher voltage and energy density.
しかし、従来の有機電解液電池は、電解液が負極で還元
分解、または正極で酸化分解され易いという問題があっ
た。また、従来の有機電解液電池は、電解液の導電率が
著しく低いので放電率を高くてきないという問題もあっ
た。すなわちプロピレンカーボネート（ｐｃ）とエチレ
ンカーボネ−１−（ＥＣ）との混合物からなる従来の電
解？？Ｚ］．５Ｍ Ｌ＋ＣＩＯＡ／ＰＣ＋ＥＣ（１：１
）では、５ｍＳ／ｃｍ程度の低い電導率しか得られなか
った。これは、水溶液電解液が数ｌｏｏｍｓ／ｃｍの導
電率を示すのに比較してきわめて低い値である。However, conventional organic electrolyte batteries have a problem in that the electrolyte tends to be reductively decomposed at the negative electrode or oxidatively decomposed at the positive electrode. In addition, conventional organic electrolyte batteries have the problem that the discharge rate cannot be increased because the electrolyte has extremely low conductivity. i.e. conventional electrolysis consisting of a mixture of propylene carbonate (PC) and ethylene carbonate-1-(EC)? ? Z]. 5M L+CIOA/PC+EC (1:1
), only a low conductivity of about 5 mS/cm was obtained. This is an extremely low value compared to the conductivity of aqueous electrolytes of several looms/cm.
したかっで、従来の有機電解液電池に代わって、耐還元
性能および耐酸化性能に優れしかも高い導電率を有する
有機電解液を備えた新しい有機電解７α電池が強く望ま
れていた。Therefore, in place of conventional organic electrolyte batteries, there has been a strong desire for a new organic electrolyte 7α battery that is equipped with an organic electrolyte that has excellent reduction and oxidation resistance as well as high electrical conductivity.
課題を解決するための方法
本発明は、リチウム塩が溶解した有機溶媒を電解液とし
て備えた有機電解液電池であって、該有機溶媒は４メチ
ルジオキソランとアセトニトリルとの混合物であること
を特徴とする有機電解液電池を用いて課題の解決を図る
ものである。また、６フッ化ヒ酸リチウム以外のリチウ
ム塩が溶解した有機溶媒を電解液として備えた有機電解
液電池であって、該有機溶媒は４メチルジオキソランと
アセトニトリルとジオキソランよりなることを特徴とす
る有機電解）後電池を用いて課題の解決をさらに容易に
せんとするものである。また、リチウム塩が溶解した有
機溶媒を電解液として備えた有機電解７夜電池であって
、該有機溶媒は４メチルジオキソランとアセＩ・ニトリ
ルとエチレンカーホイ、−トとの混合物であることを特
徴とずろ有機電解ｉα電池を用いて課題の解決をいっそ
う容易にするものである。さらに、リチウム塩が溶解し
た有機溶媒を電解液として備えた有機電解液電池であり
で、該有機溶媒は４メチルジオキソランとアセトニトリ
ルとジオキソランとエチレンカーホＳ、 −１・どの混
合物であることを特徴とずろ有機電解液電池を用いて課
題の解決を容易にするものである。Method for Solving the Problems The present invention is an organic electrolyte battery comprising an organic solvent in which a lithium salt is dissolved as an electrolyte, the organic solvent being a mixture of 4-methyldioxolane and acetonitrile. The aim is to solve this problem using an organic electrolyte battery. Also, an organic electrolyte battery comprising an organic solvent in which a lithium salt other than lithium hexafluoroarsenate is dissolved as an electrolyte, wherein the organic solvent is composed of 4-methyl dioxolane, acetonitrile, and dioxolane. The aim is to further facilitate the solution of the problem by using a post-electrolytic battery. In addition, it is an organic electrolytic 7-day battery equipped with an organic solvent in which a lithium salt is dissolved as an electrolyte, and the organic solvent is a mixture of 4-methyl dioxolane, acetal nitrile, and ethylene carbonate. This feature makes it easier to solve problems using organic electrolytic iα batteries. Furthermore, it is an organic electrolyte battery comprising an organic solvent in which a lithium salt is dissolved as an electrolyte, and the organic solvent is a mixture of 4-methyldioxolane, acetonitrile, dioxolane, ethylene carho-S, -1, etc. This makes it easier to solve the problem using organic electrolyte batteries.
作用
種々の有機電解液について電気化学的な安定性および導
電率を検討した。その結果、４メチルジオキソラン（４
Ｍｅ−ＤＯＬ）が優れた電気化学的安定性を有すること
、およびアセトニＩ・リル（ＡＮ）が高い導電率を有す
ることがわかった。これら両者は、耐酸化性能において
はいずれも優れているか、耐還元性能はアセトニトリル
において著しく劣っていた。The electrochemical stability and conductivity of various organic electrolytes were investigated. As a result, 4 methyldioxolane (4
It was found that Me-DOL) has excellent electrochemical stability and that acetonyl-lyl (AN) has high electrical conductivity. Both of these were excellent in oxidation resistance, but acetonitrile was significantly inferior in reduction resistance.
この両者を混合した電解液を用いて電池を作成したとこ
ろところ、あとの実施例に示すように電解）後の優れた
安定性を示唆する優れたサイクル寿命か得られた。また
、１．５Ｍ ＬｉＣｌ０ａ／４Ｍｅ−ＤＯＬ＋ＡＮ（１
：１）においては、１６ｍ５／ｃｍというきわめて高い
導電率か得られた。すなわち、混合することによってで
両者の短所をお互いに補償しあい長所か有効に生かされ
ることがわかった。When a battery was made using an electrolyte containing both of these, an excellent cycle life was obtained, indicating excellent stability after electrolysis, as shown in the Examples below. In addition, 1.5M LiCl0a/4Me-DOL+AN (1
:1), an extremely high conductivity of 16 m5/cm was obtained. In other words, it has been found that by mixing the two, the disadvantages of both can be compensated for and the advantages can be effectively utilized.
また、この新しい混合電解液についてさらに検討したと
ころ、あとの実施例に示すようにジオキソラン（ＤＯＬ
）を添加すると耐還元性能がざらに向上することかわか
った。この原因は明確ではないか次のように考えている
。すなわち、添加したジオキソランが還元分解されて負
極表面に被膜を形成しこの被膜が以後の電解液の分解を
抑制するものと思われる。なお、ジオキソランを添加混
合する場合には、電解質に６フッ化ヒ酸リチウムを用い
ることはできない。それは、ジオキソランと６フッ化ヒ
酸リチウムとが重合反応するためである。In addition, when we further investigated this new mixed electrolyte, we found that dioxolane (DOL
) was found to significantly improve reduction resistance. The reason for this is not clear, but I think it is as follows. That is, it seems that the added dioxolane is reductively decomposed to form a film on the surface of the negative electrode, and this film suppresses the subsequent decomposition of the electrolyte. Note that when dioxolane is added and mixed, lithium hexafluoroarsenate cannot be used as the electrolyte. This is because dioxolane and lithium hexafluoroarsenate undergo a polymerization reaction.
さらに電解液の安定性を向上させる方法について検討し
たところ、上記の電解液にエチレンカーホネ−１・を添
加すると電解液がざらに安定化することがわかった。こ
の原因は、現在のところ明確てないか、エチレンカーホ
ネ−１・自体のきわめて優れた電気化学的安定性に起因
しているものと考えられる。Furthermore, we investigated methods for improving the stability of the electrolytic solution and found that adding ethylene carbonate-1 to the electrolytic solution roughly stabilized the electrolytic solution. The cause of this is not clear at present, or it is thought to be due to the extremely excellent electrochemical stability of ethylene carbonate-1 itself.
実施例
繊維径か０．８μｍで、長さか４０７１ｍで、グラファ
イト屡の層間距離を示すｄ。。２面の平均面間距離が３
．４５Ａで、Ｌｃの平均値か３０Ａの炭素繊維を０．１
２ｇ採集し、３２５ ｍ ｅ ｓ ｂの５ＵＳ３１６金
網に包み込んで半径１０ｍ１ｎで厚さが２ ｍ ｍの円
板状に加圧成形し炭素電極（１）を得た。この炭素電極
は、約２０ ｍ Ａ ｈの充放電容量を有している。Example fiber diameter is 0.8 μm, length is 4071 m, and d indicates the interlayer distance of graphite. . The average distance between the two surfaces is 3
．． At 45A, the average value of Lc or 30A carbon fiber is 0.1
2 g was collected, wrapped in a 5US316 wire mesh of 325 m e s b, and press-molded into a disk shape with a radius of 10 ml and a thickness of 2 mm to obtain a carbon electrode (1). This carbon electrode has a charge/discharge capacity of about 20 mAh.
７０ ｗ ｔ％のＬ ｉ にｏ０２．２０ ｗ ｔ％の
アセチレンブラックおよび１０ｗｔ％のポリテトラフル
オロエチレン（、ＰＴＦＥ）を混合して正極合剤としこ
の正極合剤を０．５ｇ採集して３２５ ｍ ｅ ｓ ｈ
のステンレス製金網に包み込んで径か１２ｍｍで厚さが
２ｍｍの正極板ペレット（２）を試作した。この正極板
ペレットの放電容量は、０．５モルのりチラムか吸蔵放
出されろとした場合に約５０１ＴＩ Ａ ｂである。し
たかつて、上記の負極および正極の乳合せては、負極制
限の電池となる。A positive electrode mixture was prepared by mixing 02.20 wt% of acetylene black and 10 wt% of polytetrafluoroethylene (PTFE) with 70 wt% of Li. e s h
A positive electrode plate pellet (2) having a diameter of 12 mm and a thickness of 2 mm was produced by wrapping it in a stainless steel wire mesh. The discharge capacity of this positive electrode plate pellet is about 501 TI A b when 0.5 mole of thiram is occluded and released. However, the combination of the above-mentioned negative electrode and positive electrode results in a negative electrode limited battery.
葉脈状の無孔部および孔か３次元的に配列した有孔部を
有する平均厚さか２３ミクロンのポリエチレン製ｉＭ孔
膜を直径１４ｍｍｊこ打ち抜いて微孔性セパレーター（
３）を試作した。また、ポリプロピレンの不織布を１２
ｍ、ｍに打ち抜いて平均厚さか０．２ｍｍの不縁布セパ
レーター（４）を試作した。A microporous separator (
3) was prototyped. In addition, 12% polypropylene nonwoven fabric was used.
A non-woven fabric separator (4) with an average thickness of about 0.2 mm was made by punching it into pieces of m and m.
上記の電池構成材料に１．５Ｍ ＬｉＡｓＦ６／４Ｍｅ
−ＤＯＬ＋ＡＮ（１：ｌ）または１．５Ｍ ＬｉＣｌＯ
４／４Ｍｅ−ＤＯＬ＋ＡＮ（１：１）有機電解液を含浸
した。他の好適な電解質としては６フッ化リン酸リチウ
ム、４フッ化ホウ酸リチウムまたはトリフロロメタスル
フォン酸リチウムのそれぞれ単体または混合物等かある
。1.5M LiAsF6/4Me as the above battery constituent material
-DOL+AN (1:l) or 1.5M LiClO
It was impregnated with a 4/4Me-DOL+AN (1:1) organic electrolyte. Other suitable electrolytes include lithium hexafluorophosphate, lithium tetrafluoroborate, or lithium trifluorometasulfonate, each singly or as a mixture.
上記の電池構成物を耐食性ステンレス鋼板製の正極缶（
５）、負極缶（６）、およびポリプロピレン製の絶縁カ
スケラ１＝（７）からなる電池ケースに収納して第１図
に示したような径か１５．４ｍ １１１で厚さか４．８
Ｉｎｍの本発明の非水電解質電池を試作した。The above battery components are combined into a positive electrode can made of corrosion-resistant stainless steel plate (
5), a negative electrode can (6), and a polypropylene insulating case 1 = (7) are housed in a battery case with a diameter of 15.4 m and a thickness of 4.8 m as shown in Figure 1.
A prototype non-aqueous electrolyte battery of the present invention was manufactured by Inm.
ここで電解質に１．５Ｍ ＬｉＡｓＦ６（Ｇフッ化ヒ酸
リチウム）を用いた場合を本発明の電池（Ａ）、モして
］、５Ｍ ＬｉＣｌＯ４（過塩素酸リチウム）を用いた
場合を本発明の電池（Ｂ）とする。本発明の電池（Ａ）
、（Ｂ）では、負極に炭素繊維からなる炭素電極を用い
ているか、炭素繊維の径と長さの比（Ｄ／Ｌ）か１０以
下であるようなほぼ粒子状の炭素繊維や粒状炭素材ある
いは不定形の炭素材を用いて□もよい。また、炭素繊維
にＮ１、Ｃｕ、ＦｅもしくはＣｏまたはこれらの合金を
用いて被覆してもよい。さらに金属被覆を施した炭素電
極を焼結してもよい。Here, the case where 1.5M LiAsF6 (G lithium arsenate fluoride) is used as the electrolyte is the battery (A) of the present invention, and the case where 5M LiClO4 (lithium perchlorate) is used is the battery (A) of the present invention. Let it be a battery (B). Battery of the present invention (A)
In (B), a carbon electrode made of carbon fiber is used as the negative electrode, or a carbon fiber or granular carbon material in the form of almost particulates whose diameter-to-length ratio (D/L) of the carbon fiber is 10 or less is used. Alternatively, □ may be used using an irregularly shaped carbon material. Further, carbon fibers may be coated with N1, Cu, Fe, Co, or an alloy thereof. Furthermore, the metal-coated carbon electrode may be sintered.
平均粒径２０ミクロンのＡＬ（９０ｗｔ％）−Ｂ ｉ
（５） −Ｍｌｌ （３） −Ｎ ｉ、 （２）合金粉
末にβ−Ｌ ｉ Ａ １合金粉末５ｗｔ％およびｌＮＣ
ｏ社製Ｔｙｐｅ２５５Ｎｉ粉末５ ｗ ｔ％を添加した
ものを０．２５ｇ採集して３２５ ｍ ｅ ｓ ｂの５
ＵＳ３１６金網に包み込んで半径１０ｍｍで厚さが２Ｉ
ｎ Ｉｎの円板状に加圧成形してリチウム合金電極を得
た。このリチウム合金電極を負極ここ用いた以外は、電
池（Ａ）および電池（Ｂ）と同様の本発明の電池をそれ
ぞれ＜Ｃ＞および（Ｄ）とする。AL (90wt%) with an average particle size of 20 microns - B i
(5) -Mll (3) -N i, (2) 5 wt% β-L i A 1 alloy powder and lNC in the alloy powder
0.25g of Type 255Ni powder manufactured by Company O to which 5 wt% was added was collected and 5% of 325 m e s b.
Wrapped in US316 wire mesh with a radius of 10mm and a thickness of 2I
A lithium alloy electrode was obtained by pressure molding nIn into a disk shape. Batteries of the present invention which are similar to battery (A) and battery (B) except that this lithium alloy electrode was used here as a negative electrode are designated as <C> and (D), respectively.
また、電解）夜に１．５Ｍ ＬｉＣｌＯ４／４Ｍｅ−Ｄ
ＯＬ＋ＡＮ＋ＤＯＬ（１：ｌ：０．５）、１．５Ｍ Ｌ
ｉＣｌＯ４／４Ｍｅ−ＤＯＬ＋ＡＮ＋ＥＣ（１：ｌ：ｌ
）または］、５５ＭＬＩＣ１０４／４ト１ｅ−ＤＯＬ＋
ＡＮ＋ＤＯＬ＋ＥＣ（］：ｌ：０．５：ｌ）を用いた以
外は電池（Ａ）と同様の構成を有する電池を本発明の電
池（Ｅ）、 （Ｆ）または（Ｃ）とする。Also, electrolysis) 1.5M LiClO4/4Me-D at night
OL+AN+DOL (1:l:0.5), 1.5M L
iClO4/4Me-DOL+AN+EC (1:l:l
) or ], 55MLIC104/4t1e-DOL+
A battery having the same configuration as battery (A) except that AN+DOL+EC (]:l:0.5:l) was used is referred to as battery (E), (F) or (C) of the present invention.
゛・ また、１．５Ｍ Ｌｉ（、ｌＯａ／ＰＣ＋ＥＣ（
１：ｌ）を用いたこと以外は前記（Ａ）、（Ｂ）、（Ｃ
）および（Ｄ）と同様の構成を有する電池を比較のため
の有機電解）α電池（ａ）、（＋））、（Ｃ）および（
ｄ）を試作した。゛・ Also, 1.5M Li(, lOa/PC+EC(
The above (A), (B), (C
) and (D) and organic electrolyte for comparison) α batteries (a), (+)), (C) and (
d) was prototyped.
これら１１種類の電池を２０°Ｃの環境温度のもとて２
ｍＡ／ｃｍ２て４，０■まて充電したのち３゜０■まで
放電する容量確認試、験を最大５０サイクルおこなった
。その結果を第２図に示す。These 11 types of batteries were tested at an environmental temperature of 20°C.
A capacity confirmation test was conducted in which the battery was charged at 4.0 mm at mA/cm2 and then discharged to 3.0 mm for a maximum of 50 cycles. The results are shown in FIG.
本発明の電池（Ａ）、（Ｂ）、（ＣＬ （Ｄ）。Batteries (A), (B), (CL (D) of the present invention.
（Ｅ）、（Ｆ）および（Ｇ）は、従来の電池（ａ）、（
ｂ）、 （Ｃ）および（ｄ）に比較して長いサイクル
寿命を有する。(E), (F) and (G) are conventional batteries (a), (
b) has a long cycle life compared to (C) and (d).
また、６フッ化ヒ酸リチウムを電解質塩に用いた本発明
の電池（Ａ）、（Ｃ）は、過塩素酸リチウムを電解質に
用いた本発明の電池（Ｂ）、 （Ｄ）に比較して容量
の低下か少ない。これは、従来報告されているように６
フッ化ヒ酸リチウムが負極表面に保護被膜を形成し電解
液の安定性を向上させることに起因しているものと思わ
れる。Furthermore, the batteries (A) and (C) of the present invention using lithium hexafluoroarsenate as the electrolyte salt are better than the batteries (B) and (D) of the present invention using lithium perchlorate as the electrolyte. capacity decreases or decreases. This is due to the fact that 6
This is thought to be due to the fact that lithium fluoroarsenate forms a protective film on the surface of the negative electrode, improving the stability of the electrolyte.
また、ＤＯＬを追加混合した電解液を用いた電池（Ｅ）
は、電池（Ａ）よりもさらに優れたサイクル寿命を示し
ている。これは、作用の項で述へたようにＤＯＬの分解
生成物が電解液の分解を抑止する効果によるものと考え
られる。In addition, a battery (E) using an electrolyte solution additionally mixed with DOL
shows an even better cycle life than battery (A). This is thought to be due to the effect of the decomposition products of DOL in suppressing the decomposition of the electrolyte solution, as described in the section on action.
また、ＥＣを追加混合した電解液を用いた（Ｆ）。Further, an electrolyte solution additionally mixed with EC was used (F).
（Ｇ）の電池も、（Ａ）および（Ｅ）よりもさらに優れ
たサイクル性能を示す。この原因も作用の項で述べたよ
うにＥＣの優れた安定性に起因するものと考えられる。Battery (G) also exhibits even better cycle performance than (A) and (E). The reason for this is also considered to be due to the excellent stability of EC, as described in the section of action.
なお、前記の実施例に係る電池はいずれもボタン形電池
であるか、円筒形、角形またはベーパー形電池に本発明
を適用しても同様の効果か得られる。Note that the same effects can be obtained even if the batteries according to the above embodiments are all button-shaped batteries, or the present invention is applied to cylindrical, prismatic, or vapor-shaped batteries.
発明の効果
本発明により従来の電池に比較して電解液に起因する内
部抵抗か低くて、かつ優れたサイクル寿命性能を有する
有機電解液電池を提供することかできるものである。Effects of the Invention According to the present invention, it is possible to provide an organic electrolyte battery which has a lower internal resistance due to the electrolyte and excellent cycle life performance than conventional batteries.
第１図は、本発明の非水電解質電池の一例であるボタン
電池の内部構造を示した図。第２図（′ｉ、本発明の電
池および従来の電池のサイクル寿命性能を示した図であ
る。FIG. 1 is a diagram showing the internal structure of a button battery, which is an example of the nonaqueous electrolyte battery of the present invention. FIG. 2 ('i) is a diagram showing the cycle life performance of the battery of the present invention and the conventional battery.
Claims (1)
た有機電解液電池であって、 該有機溶媒は４メチルジオキソランとアセトニトリルと
の混合物であることを特徴とする有機電解液電池。 ２、６フッ化ヒ酸リチウム以外のリチウム塩が溶解した
有機溶媒を電解液として備えた有機電解液電池であつて
、 該有機溶媒は４メチルジオキソランとアセトニトリルと
ジオキソランよりなることを特徴とする有機電解液電池
。 ３、リチウム塩が溶解した有機溶媒を電解液として備え
た有機電解液電池であって、 該有機溶媒は４メチルジオキソランとアセトニトリルと
エチレンカーボネートとの混合物であることを特徴とす
る有機電解液電池。 ４、リチウム塩が溶解した有機溶媒を電解液として備え
た有機電解液電池であつて、 該有機溶媒は４メチルジオキソランとアセトニトリルと
ジオキソランとエチレンカーボネートとの混合物である
ことを特徴とする有機電解液電池。[Scope of Claims] 1. An organic electrolyte battery comprising an organic solvent in which a lithium salt is dissolved as an electrolyte, characterized in that the organic solvent is a mixture of 4-methyldioxolane and acetonitrile. liquid battery. An organic electrolyte battery comprising, as an electrolyte, an organic solvent in which a lithium salt other than lithium hexafluoroarsenate is dissolved, wherein the organic solvent is composed of 4-methyl dioxolane, acetonitrile, and dioxolane. electrolyte battery. 3. An organic electrolyte battery comprising an organic solvent in which a lithium salt is dissolved as an electrolyte, the organic solvent being a mixture of 4-methyldioxolane, acetonitrile, and ethylene carbonate. 4. An organic electrolyte battery comprising an organic solvent in which a lithium salt is dissolved as an electrolyte, wherein the organic solvent is a mixture of 4-methyldioxolane, acetonitrile, dioxolane, and ethylene carbonate. battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2339553A JP3049768B2 (en) | 1990-11-30 | 1990-11-30 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2339553A JP3049768B2 (en) | 1990-11-30 | 1990-11-30 | Organic electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04206476A true JPH04206476A (en) | 1992-07-28 |
| JP3049768B2 JP3049768B2 (en) | 2000-06-05 |
Family
ID=18328561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2339553A Expired - Lifetime JP3049768B2 (en) | 1990-11-30 | 1990-11-30 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3049768B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012109048A (en) * | 2010-11-15 | 2012-06-07 | Toyota Motor Corp | Regeneration method of nonaqueous electrolyte secondary battery |
| JP2017054822A (en) * | 2011-10-28 | 2017-03-16 | 旭化成株式会社 | Non-aqueous secondary battery |
-
1990
- 1990-11-30 JP JP2339553A patent/JP3049768B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012109048A (en) * | 2010-11-15 | 2012-06-07 | Toyota Motor Corp | Regeneration method of nonaqueous electrolyte secondary battery |
| JP2017054822A (en) * | 2011-10-28 | 2017-03-16 | 旭化成株式会社 | Non-aqueous secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3049768B2 (en) | 2000-06-05 |
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