JPS62271370A - Electrolyte for lithium battery - Google Patents
Electrolyte for lithium batteryInfo
- Publication number
- JPS62271370A JPS62271370A JP61112085A JP11208586A JPS62271370A JP S62271370 A JPS62271370 A JP S62271370A JP 61112085 A JP61112085 A JP 61112085A JP 11208586 A JP11208586 A JP 11208586A JP S62271370 A JPS62271370 A JP S62271370A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- electrolyte
- liasf6
- liasf
- conductivity
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- 239000003792 electrolyte Substances 0.000 title abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 21
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 1
- 229910015013 LiAsF Inorganic materials 0.000 description 19
- 238000007599 discharging Methods 0.000 description 11
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- OXMIDRBAFOEOQT-UHFFFAOYSA-N 2,5-dimethyloxolane Chemical compound CC1CCC(C)O1 OXMIDRBAFOEOQT-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910013888 LiPF5 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- -1 L i5bF s Inorganic materials 0.000 description 1
- 229910015040 LiAsFe Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZHGDJTMNXSOQDT-UHFFFAOYSA-N NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O Chemical compound NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O ZHGDJTMNXSOQDT-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明はリチウム電池用電解液、さらに詳細にはりチウ
ム−次および二次電池に用いる電解液に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an electrolyte for lithium batteries, and more particularly to an electrolyte for use in lithium secondary and secondary batteries.
リチウムを負極活物質として用いる電池は、小型・高エ
ネルギ密度を有する電池として研究されているが、その
二次電池化が大きな問題点となっている。Batteries using lithium as a negative electrode active material are being researched as small-sized batteries with high energy density, but converting them into secondary batteries has become a major problem.
リチウム電池を二次電池化するためには、正捲活物質の
選択、電池構成法など、多くの問題点がある。特に電解
液の選択は重要な課題である。In order to convert a lithium battery into a secondary battery, there are many issues such as the selection of a normally wound active material and the battery construction method. In particular, the selection of electrolyte is an important issue.
電解液は、■高いリチウム充放電効率を有すること、■
高い導電率を有することの二点を同時に充足する必要が
ある。そして、二次電池化では、特に高いリチウムの充
放電効率を有することが重要である。The electrolyte should have ■high lithium charging and discharging efficiency,■
It is necessary to satisfy the two requirements of having high conductivity at the same time. In the production of secondary batteries, it is particularly important to have high lithium charging and discharging efficiency.
リチウムの充放電効率減少の主要因として、析出リチウ
ムと溶媒の反応により、リチウムが電気化学的に不活性
化し、Ｌビを放電できない化合物に変化することが指摘
されている（Ｊ、 Ｐｏｗｅｒ ５ｏｕｃｅｓ 、第６
巻、 ３５７〜３７０頁、１９８１年）。It has been pointed out that the main reason for the decrease in lithium charging and discharging efficiency is that lithium is electrochemically inactivated by the reaction between precipitated lithium and the solvent, and turns into a compound that cannot discharge lithium (J, Power 5uces, 6th
Vol., pp. 357-370, 1981).
したがって、リチウムの充放電効率を向上させるために
は、リチウムと溶媒の反応を抑制することが効果的であ
ると考えられる。溶質（つまり電解質）としてＬｉＡｓ
Ｆ ｓを、溶媒として酸素を含む化合物を用いた場合、
リチウムの表面に（＞Ａｓ−０−Ａｓ＜）を単位とする
高分子膜が形成され、溶媒とリチウムの反応を抑制する
可能性が指摘されている（Ｊ、［ｉｌｅｃｔｒｏｃｈｅ
ｍ Ｓａｃ、、第１２７ Ｓ、１４６１〜１４６７頁
、１９７９年）。しかしながらＬｉＡｓＦ ６を使用し
た電解液の導電率は必ずしも充分ではない。Therefore, in order to improve the charging and discharging efficiency of lithium, it is considered effective to suppress the reaction between lithium and the solvent. LiAs as solute (i.e. electrolyte)
When F s is used as a solvent and a compound containing oxygen,
It has been pointed out that a polymer film with units of (>As-0-As<) is formed on the surface of lithium, which may suppress the reaction between the solvent and lithium (J, [electroche
m Sac, 127 S, pp. 1461-1467, 1979). However, the conductivity of electrolytes using LiAsF 6 is not always sufficient.
また、ＬｉＡｓＦ ｓ自体の毒性はＬＤｓ ｏ ＝９２
５ ｍｇ／にｇと低く問題とならないが（リチウム−次
電池に多用されているＬｉＣｌ０ｊはＬＤｓ ｏ ＝１
１６０ｍｇ／Ｋｇ）、高い充放電容量での長い充放電サ
イクルを繰り返し、かつ分解生成物が１１２０と接触す
るような条件下では、ＬｉＡｓＦ Ｈに比較して毒性の
高い化合物が生成する危惧がある。本来、リチウム電池
の場合、リチウムが空気中の水分、酸素、炭酸ガスなど
と反応するため、消費者に電池を提供する際には、電池
は完全に密閉された状態になっているので、上記のよう
な毒性に関する問題は、消費者に関することより主とし
て廃液処理に関する問題になる。このような仮定より、
リチウム二次電池用電解質としてのＬｉＡｓＦ ｓの利
点を生かしながら、その使用量を低減することができる
ならば、ＬｉＡｓＦ ｓの使用方法としては、より望ま
しいものとなると考えられるが、具体的な提案がなされ
ていないのが現状である。In addition, the toxicity of LiAsF s itself is LDs o =92
Although it is low at 5 mg/g and not a problem (LiCl0j, which is often used in lithium-ion batteries, LDs o = 1
160 mg/Kg), repeating long charge/discharge cycles at a high charge/discharge capacity, and under conditions where decomposition products come into contact with 1120, there is a risk that compounds with higher toxicity than LiAsF H may be produced. Normally, in the case of lithium batteries, lithium reacts with moisture, oxygen, carbon dioxide, etc. in the air, so when batteries are provided to consumers, they are in a completely sealed state, so the above-mentioned Toxicity issues such as these are primarily a waste disposal issue rather than a consumer issue. From such an assumption,
If LiAsFs can be used as an electrolyte for lithium secondary batteries while taking advantage of its advantages while reducing its usage, it would be a more desirable way to use LiAsFs, but there are no concrete proposals. The current situation is that this has not been done.
本発明は、このような現状に鑑みてなされたものであり
、その目的はリチウムの充放電効率が高く、かつできる
限り、導電性が高いリチウム電池用電解液を提供するこ
とにある。The present invention has been made in view of the current situation, and its purpose is to provide an electrolytic solution for lithium batteries that has high lithium charging and discharging efficiency and has as high conductivity as possible.
したがって本発明によるリチウム電池用電解液は、リチ
ウム塩を有機溶媒に溶解させたリチウム電池用電解液に
おいて、前記電解液のリチウム塩としてＬｉＡｓＦ ｓ
とＬｉＡｓＦ ｓ以外のリチウム塩の一種以上を混合し
たことを特徴とするものである。Therefore, the electrolytic solution for lithium batteries according to the present invention is an electrolytic solution for lithium batteries in which a lithium salt is dissolved in an organic solvent.
and one or more types of lithium salts other than LiAsFs.
本発明によれば、リチウム電池の電解液としてＬｉＡｓ
Ｆ ６とＬｉＡｓＦ ６以外のＬｉＡｓＦ ｓ塩を一種
以上混合したものを用いることにより、リチウム極の充
放電特性が優秀で、かつ導電率が高いリチウム電池用非
水電解液を提供することができる。According to the present invention, LiAs is used as an electrolyte for a lithium battery.
By using a mixture of F 6 and one or more LiAsF s salts other than LiAsF 6 , it is possible to provide a nonaqueous electrolyte for lithium batteries that has excellent charging and discharging characteristics of the lithium electrode and high conductivity.
本発明を更に詳しく説明する。 The present invention will be explained in more detail.
リチウム二次電池は、リチウムを負極活物質とし、Ｌｉ
”イオンと可逆的な電気化学的反応を行う物質を正極活
物質とし、さらにリチウム塩を有機溶媒に溶解させた非
水電解液を用いたものであるが、このようなリチウム二
次電池用非水電解液のリチウム塩として、本発明におい
てはＬｉＡｓＦ ｓとＬｉＡｓＦ ６以外のリチウム塩
を一種以上混合したものを用いている。この混合溶質に
よって、ＬｉＡｓＦ６とリチウムの反応によりリチウム
表面に保護膜が形成され、リチウムの充放電効率が高い
値を示すと同時に、ＬｉＡｓＦ ｓ以外のリチウム塩と
ＬｉＡｓＦ６の混合効果により保護膜形成のためＬｉＡ
ｓＦ ６が一部分解し、導電率が低下するのを補うのみ
ならず、高い導電率が実現できることが期待される。Lithium secondary batteries use lithium as a negative electrode active material, and Li
``The cathode active material is a substance that undergoes a reversible electrochemical reaction with ions, and a non-aqueous electrolyte in which lithium salt is dissolved in an organic solvent is used. In the present invention, a mixture of one or more lithium salts other than LiAsF s and LiAsF 6 is used as the lithium salt in the aqueous electrolyte. This mixed solute forms a protective film on the lithium surface due to the reaction between LiAsF 6 and lithium. At the same time, due to the mixing effect of lithium salt other than LiAsF s and LiAsF6, LiAs is used to form a protective film.
It is expected that this will not only compensate for the decrease in conductivity due to partial decomposition of sF 6 but also realize high conductivity.
また、この保護膜により、リチウムと溶媒の反応が抑制
され、電池の自己放電による放電容量の低下を抑制し、
電池の保存性能を高めるとともに、混合溶質による導電
率の向上により電池取得電流値も向上することも期待さ
れる。このようなことから、本発明によるリチウム電池
用非水電解液は二次電池のみならず一次電池用としても
優れた性能を有することがわかる。In addition, this protective film suppresses the reaction between lithium and the solvent, suppressing the decrease in discharge capacity due to self-discharge of the battery,
In addition to improving the storage performance of the battery, it is also expected that the current value obtained by the battery will also improve due to the improvement in conductivity due to the mixed solute. From these facts, it can be seen that the non-aqueous electrolyte for lithium batteries according to the present invention has excellent performance not only for secondary batteries but also for primary batteries.
本発明による電解液に用いられるリチウム塩はＬｉＡｓ
Ｆ ａとＬｉＡｓＦ ６以外のリチウム塩を一種以上混
合したものであるが、ＬｉＡｓＦ ｅに混合する溶質は
、基本的には、従来この種の電池に用いられる溶質を自
由に用いることができる。特に、単独溶質でＬｉＡｓＦ
ｓより高い導電率を示すものが効果的である。たとえ
ば、ＬｉＣｌ０ ａ 、ＬｉＢＦａ 、ＬｉＰＦ５、Ｌ
ｉ５ｂＦ ｓ 、ＬｉＡｌＣｌ４、ＣＦ３ Ｓ０３ Ｌ
ｉ、、ＣＩ’３ ＣＯ２Ｌｉ。The lithium salt used in the electrolyte according to the present invention is LiAs
Although it is a mixture of F a and one or more lithium salts other than LiAsF 6 , the solute to be mixed with LiAsF e can basically be any solute conventionally used in this type of battery. In particular, LiAsF as a single solute
Those exhibiting higher conductivity than s are effective. For example, LiCl0 a , LiBFa , LiPF5, L
i5bF s , LiAlCl4, CF3 S03 L
i,, CI'3 CO2Li.
Ｌｉ２ Ｂ １ｏｃＩｔｏなどの一種以上のリチウム塩
を有効に用いることができる。One or more lithium salts such as Li2B 1ocIto can be used effectively.
このような混合溶質は、有機溶媒に０．５〜２．５モル
／ｌ （Ｍ）添加するのがよい。０．５門未満であると
、リチウムの充放電特性が著しく低下し、また２、５Ｍ
を超えると溶質の溶解が困難になる恐れがあるからであ
る。また、ＬｉＡｓＦ ６と他のリチウム塩のモル混合
比は、好ましくは１ 二９〜９ ：１、最も好ましくは
、３ ニア〜１ ：１である。１：９未満の混合比であ
ると、両者を混合した意味が薄くなり、単独系の充放電
特性あるいは導電率特性に近づき充放電特性が悪化する
からである。Such a mixed solute is preferably added to the organic solvent in an amount of 0.5 to 2.5 mol/l (M). If it is less than 0.5 M, the charging and discharging characteristics of lithium will deteriorate significantly, and if it is less than 2.5 M
This is because if the amount exceeds 100%, it may become difficult to dissolve the solute. Further, the molar mixing ratio of LiAsF 6 and other lithium salts is preferably 129 to 9:1, most preferably 3 to 1:1. This is because if the mixing ratio is less than 1:9, the meaning of mixing the two becomes weak, and the charge-discharge characteristics or conductivity characteristics approach those of a single system, and the charge-discharge characteristics deteriorate.
また、上記のリチウム塩を溶解させる有機溶媒は、従来
この種の電池に用いられる溶媒を自由に用いることがで
きる。たとえば、プロピレンカーボネイト、エチレンカ
ーボネイト、スルホラン、３−メチルスルホラン、ジメ
チルスルホキシド、γ−ブチロラクトン、γ−バレロラ
クオン、γ−オクタノイフクラクトン、テトラヒドロフ
ラン、２−メチルテトラヒドロフラン、２，５−ジメチ
ルテトラヒドロフラン、１．３−ジオキソラン、２−メ
チル−１，３−ジオキソラン、４−メチル−１，３−ジ
オキソラン、１．２−ジメトキシエタン、１，２−ジェ
トキシエタン、酢酸メチル、ギ酸メチル、アセト、アセ
トニトリル、Ｎ、Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−
テトラメチルエチレンジアミン、ヘキサりん酸トリアミ
ド、１２−クラウン−４、ジグライム、トリグライム、
テトラグライムなどのなかから選択された１種以上の溶
媒を用いることができる。Further, as the organic solvent for dissolving the above-mentioned lithium salt, any solvent conventionally used in this type of battery can be freely used. For example, propylene carbonate, ethylene carbonate, sulfolane, 3-methylsulfolane, dimethylsulfoxide, γ-butyrolactone, γ-valerolacone, γ-octanoifuclactone, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1.3 -dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-dimethoxyethane, 1,2-jethoxyethane, methyl acetate, methyl formate, acetate, acetonitrile, N, N- dimethylformamide, N, N-
Tetramethylethylenediamine, hexaphosphoric acid triamide, 12-crown-4, diglyme, triglyme,
One or more solvents selected from tetraglyme and the like can be used.
以下実施例について説明する。Examples will be described below.
実施例１
電解液として、エチレンカーボネイトと２−メチルテト
ラヒドロフランの体積混合比１／１の混合溶媒に１．５
ＭのＬｉＡｓＦ ６とＬｉＰ Ｆ′６を溶解させたもの
を用いて、リチウムの充放電効率ＣＨａ）を測定した。Example 1 As an electrolyte, a mixed solvent of ethylene carbonate and 2-methyltetrahydrofuran with a volume mixing ratio of 1/1 was mixed with 1.5
The lithium charge/discharge efficiency CHa) was measured using a solution of M LiAsF 6 and LiP F'6.
Ｅａは作用極に白金極を、対極にリチウムを、参照電極
としてリチウムを用いた電池を組、以下のように測定し
た。測定は、まず、０．５ｍＡ／−の定電流で１６０分
間、白金極上にリチウムを析出させた後（４，８Ｃ／ｃ
ｎｌ） 、この析出させたリチウムの一部（１，２Ｃ／
ｃｄ）をＬｉ“イオンとして放電し、再びさらに１．２
Ｃ／ｃｎＴの容量で放電するサイクル試験を繰り返した
。Ea was measured as follows using a battery using a platinum electrode as a working electrode, lithium as a counter electrode, and lithium as a reference electrode. The measurement was carried out by depositing lithium on a platinum electrode for 160 minutes at a constant current of 0.5 mA/- (4,8 C/c).
nl), a part of this precipitated lithium (1,2C/
cd) as Li“ ions, and again further 1.2
A cycle test of discharging at a capacity of C/cnT was repeated.
充放電効率（Ｅａ）は、白金極の電位の変化より求め、
見掛は上１００％の効率を示すサイクル数をｎとすると
、下記の式（１）より、前記Ｅａを求めることができる
。The charge/discharge efficiency (Ea) is determined from the change in potential of the platinum electrode,
Assuming that the number of cycles showing an apparent efficiency of 100% is n, the above Ea can be determined from the following equation (1).
第１図に、１．５ Ｍ ＬｉＡｓＦ ｅ ／ＬｉＰ Ｆ
ｓ ／／エチレンカーボネイト／２−メチルテトラヒ
ドロフラン中でのＥａとＬｉＡｓＦ ６モル混合量との
関係を示す。In FIG. 1, 1.5 M LiAsF e /LiP F
s // shows the relationship between Ea in ethylene carbonate/2-methyltetrahydrofuran and the amount of 6 moles of LiAsF mixed.
１．５ Ｍ ＬｉＰ Ｆ ｓ単独にＬｉＡｓＦ ６を混
合することによってＥａは向上し、ＬｉＡｓＦ ６混合
量が３０％以上でほぼＬｉＡｓＦ ｅ単独のＥａと同等
のＥａを示すことがわかる。つまり、ＬｉＡｓＦ ｓ
／ＬｉＰ Ｆ ｓ ＝３ ／７でＬｉＰＦ５単独より約
６％充放電効率が向上することがわかった。It can be seen that Ea is improved by mixing LiAsF 6 with 1.5 M LiP F s alone, and when the amount of LiAsF 6 mixed is 30% or more, Ea is almost equivalent to that of LiAsF e alone. In other words, LiAsF s
It was found that when /LiPF s =3 /7, the charge/discharge efficiency was improved by about 6% compared to LiPF5 alone.
実施例２
電解液として、１．５ Ｍ ＬｉＡｓＦ ｅ ／ＬｉＰ
Ｆ ｓ （体１ｍ ンｍ 合、３ ／７ ） ／／
エチレンカーボネイト／２−メチルテトラヒドロフラン
（体積混合比１／１）を用いて、この電解液の導電率を
測定した。Example 2 1.5 M LiAsF e /LiP as electrolyte
F s (body 1 m m combination, 3 /7) //
The conductivity of this electrolytic solution was measured using ethylene carbonate/2-methyltetrahydrofuran (volume mixing ratio 1/1).
第２図（Ａ ）に−２０〜＋３０℃の範囲における上記
電解液の導電率を示す。第２図（Ｂ ’）は本発明の効
果を示すための比較例として、１．５ Ｍ ＬｉＡｓＦ
Ｇ−エチレンカーボネイト／２−メチルテトラヒドロフ
ラン（体積混合比１／１）単独溶質系電解液の導電率を
示しである。第２図より明らかなように、−２０〜＋３
０℃の範囲において、本発明によるＬｉＡｓＦ ｓ ／
ＬｉＰ Ｆ ｅ混合溶質系は、ＬｉＡｓＦ ６より高い
導電率を示すことがわかった。FIG. 2(A) shows the conductivity of the electrolytic solution in the range of -20 to +30°C. FIG. 2 (B') shows a comparative example of 1.5 M LiAsF to show the effect of the present invention.
The graph shows the conductivity of a single solute electrolyte containing G-ethylene carbonate/2-methyltetrahydrofuran (volume mixing ratio 1/1). As is clear from Figure 2, -20 to +3
In the range of 0°C, LiAsF s /
The LiP Fe mixed solute system was found to exhibit higher conductivity than LiAsF6.
実施例３
溶媒として、エチレンカーボネイト／２−メチルテトラ
ヒドロフラン（体１ａ ？Ｗ、合比１／１）を使用し、
溶質として■Ｉ Ｍ ＬｉＡｓＦ ｓ ／ ＬｉＣｌ０
４（モル混合比、３／７ ）あるいは■Ｉ Ｍ ＬｉＡ
ｓＦ Ｇ ／ＬｉＢＦ４（モル混合比、３／７ ）を溶
解させたものを用いた以外は、実施例１と同様にして、
リチウムの充放電効率を測定した。Example 3 Using ethylene carbonate/2-methyltetrahydrofuran (body 1a?W, combined ratio 1/1) as a solvent,
■I M LiAsF s / LiCl0 as solute
4 (molar mixing ratio, 3/7) or ■I M LiA
The same procedure as in Example 1 was carried out, except that a solution of sF G /LiBF4 (molar mixing ratio, 3/7) was used.
The charging and discharging efficiency of lithium was measured.
結果を第１表に示す。この第１表より明らかなように、
ＬｉＡｓＦ ６ ／ ＬｉＣＩＯ４およびＬｉＡｓＦ
６ ／ＬｉＢＦａの混合溶質系は、それぞれＬｉＣＩＯ
４およびＬｉＢ Ｆ ４単独系より高い充放電効率を示
すことがわかった。The results are shown in Table 1. As is clear from this Table 1,
LiAsF6/LiCIO4 and LiAsF
The mixed solute systems of 6/LiBFa are each LiCIO
4 and LiB F 4 alone.
また上記混合溶質系電解液の導電率の測定結果を第２表
に示す。第２表より明らかなように、本発明による上記
混合溶質系電解液は、ＬｉＡｓＦ ａ単独溶質系電解液
よりたいあい導電率を示すことがわかる。Further, Table 2 shows the measurement results of the electrical conductivity of the mixed solute electrolyte. As is clear from Table 2, the mixed solute electrolyte according to the present invention exhibits higher conductivity than the LiAsFa single solute electrolyte.
実施例４
溶媒としてプロピレンカーボネイトを溶質としてＩ Ｍ
ＬｉＡｓＦ ｓ ／ ＬｉＣＩＯ４を用いて電解液を
作製い、導電率を測定した。結果を第２表に合わせてし
めす。本発明による上記混合溶質系電解液はＬｉＡｓＦ
ｅ単独溶質系電解液よりも高い導電率を示すことがわ
かった。Example 4 Propylene carbonate as a solvent and IM as a solute
An electrolytic solution was prepared using LiAsFs/LiCIO4, and the conductivity was measured. The results are shown in Table 2. The mixed solute electrolyte according to the present invention is LiAsF
It was found that the conductivity was higher than that of a single solute electrolyte.
以上の説明より明らかなように、本発明によれば、リチ
ウム塩を有機溶媒に溶解させたリチウム電池用非水電解
液において、前記リチウム塩として、ＬｉＡｓＦ ｅと
前記ＬｉＡｓＦ ｓ以外のＬｉＡｓＦ ｓ塩を一４以上
混合したものを用いることにより、ＬｉＡｓＦ６の充放
電効率が高く、導電率も高いリチウム−次および二次電
池用非水電解液を提供することが可能になるという利点
がある。As is clear from the above description, according to the present invention, in a nonaqueous electrolyte for lithium batteries in which a lithium salt is dissolved in an organic solvent, a LiAsF s salt other than LiAsFe and the LiAsF s is used as the lithium salt. The use of a mixture of 14 or more has the advantage that it is possible to provide a non-aqueous electrolyte for lithium-primary and secondary batteries with high LiAsF6 charging/discharging efficiency and high conductivity.
図面の簡単な説明
第１図は本発明による電解液を用いた場合のリチウムの
充放電効率を示した図、第２図は本発明による電解液の
導電率を示した図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the charging and discharging efficiency of lithium when using the electrolytic solution according to the present invention, and FIG. 2 is a diagram showing the electrical conductivity of the electrolytic solution according to the present invention.
出願人代理人 雨 宮 正 季 第１図Applicant's representative Masashi Ame Miya Figure 1
Claims (1)
用電解液において、前記電解液のリチウム塩としてＬｉ
ＡｓＦ＿６とＬｉＡｓＦ＿６以外のリチウム塩の一種以
上を混合したことを特徴とするリチウム電池用電解液。(1) In an electrolytic solution for lithium batteries in which a lithium salt is dissolved in an organic solvent, Li is used as the lithium salt in the electrolytic solution.
An electrolytic solution for a lithium battery, characterized in that it contains a mixture of AsF_6 and one or more types of lithium salts other than LiAsF_6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61112085A JPS62271370A (en) | 1986-05-16 | 1986-05-16 | Electrolyte for lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61112085A JPS62271370A (en) | 1986-05-16 | 1986-05-16 | Electrolyte for lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62271370A true JPS62271370A (en) | 1987-11-25 |
Family
ID=14577712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61112085A Pending JPS62271370A (en) | 1986-05-16 | 1986-05-16 | Electrolyte for lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62271370A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63148569A (en) * | 1986-12-10 | 1988-06-21 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte cell |
| JPH01281677A (en) * | 1988-05-09 | 1989-11-13 | Fuji Elelctrochem Co Ltd | Battery of nonaqueous electrolyte |
| EP0397248A2 (en) * | 1989-05-08 | 1990-11-14 | Eastman Kodak Company | Electrochemical cell modules |
| US7939201B2 (en) | 2005-08-08 | 2011-05-10 | A123 Systems, Inc. | Nanoscale ion storage materials including co-existing phases or solid solutions |
| US8158090B2 (en) | 2005-08-08 | 2012-04-17 | A123 Systems, Inc. | Amorphous and partially amorphous nanoscale ion storage materials |
| US8323832B2 (en) | 2005-08-08 | 2012-12-04 | A123 Systems, Inc. | Nanoscale ion storage materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58106771A (en) * | 1981-12-18 | 1983-06-25 | Nippon Telegr & Teleph Corp <Ntt> | Nonaqueous electrolyte for lithium secondary battery |
| JPS60175380A (en) * | 1984-02-20 | 1985-09-09 | Hitachi Maxell Ltd | Lithium organic cell |
| JPS6168864A (en) * | 1984-09-11 | 1986-04-09 | Bridgestone Corp | Battery |
-
1986
- 1986-05-16 JP JP61112085A patent/JPS62271370A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58106771A (en) * | 1981-12-18 | 1983-06-25 | Nippon Telegr & Teleph Corp <Ntt> | Nonaqueous electrolyte for lithium secondary battery |
| JPS60175380A (en) * | 1984-02-20 | 1985-09-09 | Hitachi Maxell Ltd | Lithium organic cell |
| JPS6168864A (en) * | 1984-09-11 | 1986-04-09 | Bridgestone Corp | Battery |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63148569A (en) * | 1986-12-10 | 1988-06-21 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte cell |
| JPH01281677A (en) * | 1988-05-09 | 1989-11-13 | Fuji Elelctrochem Co Ltd | Battery of nonaqueous electrolyte |
| EP0397248A2 (en) * | 1989-05-08 | 1990-11-14 | Eastman Kodak Company | Electrochemical cell modules |
| EP0397248A3 (en) * | 1989-05-08 | 1992-05-20 | Eastman Kodak Company | Electrochemical cell modules |
| US7939201B2 (en) | 2005-08-08 | 2011-05-10 | A123 Systems, Inc. | Nanoscale ion storage materials including co-existing phases or solid solutions |
| US8057936B2 (en) | 2005-08-08 | 2011-11-15 | A123 Systems, Inc. | Nanoscale ion storage materials including co-existing phases or solid solutions |
| US8158090B2 (en) | 2005-08-08 | 2012-04-17 | A123 Systems, Inc. | Amorphous and partially amorphous nanoscale ion storage materials |
| US8323832B2 (en) | 2005-08-08 | 2012-12-04 | A123 Systems, Inc. | Nanoscale ion storage materials |
| US8617430B2 (en) | 2005-08-08 | 2013-12-31 | A123 Systems Llc | Amorphous and partially amorphous nanoscale ion storage materials |
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