JPH0922722A - Electrolyte for lithium-ion battery - Google Patents
Electrolyte for lithium-ion batteryInfo
- Publication number
- JPH0922722A JPH0922722A JP7170844A JP17084495A JPH0922722A JP H0922722 A JPH0922722 A JP H0922722A JP 7170844 A JP7170844 A JP 7170844A JP 17084495 A JP17084495 A JP 17084495A JP H0922722 A JPH0922722 A JP H0922722A
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic solution
- carbonate
- organic solvent
- lithium
- volume
- 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 239000003792 electrolyte Substances 0.000 title description 6
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 42
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- 150000002170 ethers Chemical class 0.000 claims abstract description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 23
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 13
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 10
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 claims description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- HCYKRYCBNLVXJW-UHFFFAOYSA-N (2-propylphenyl) hydrogen carbonate Chemical compound CCCC1=CC=CC=C1OC(O)=O HCYKRYCBNLVXJW-UHFFFAOYSA-N 0.000 claims description 2
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 claims description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- CMIUEWSUNAYXCG-UHFFFAOYSA-N butyl phenyl carbonate Chemical compound CCCCOC(=O)OC1=CC=CC=C1 CMIUEWSUNAYXCG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- YCNSGSUGQPDYTK-UHFFFAOYSA-N ethyl phenyl carbonate Chemical compound CCOC(=O)OC1=CC=CC=C1 YCNSGSUGQPDYTK-UHFFFAOYSA-N 0.000 claims description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 2
- 229940049953 phenylacetate Drugs 0.000 claims description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 2
- 229950009215 phenylbutanoic acid Drugs 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 2
- 159000000002 lithium salts Chemical class 0.000 abstract description 2
- 239000012046 mixed solvent Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002023 wood Substances 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
(57)【要約】
【構成】 正極、炭素質材料よりなる負極、及び電解液
を基本構成とする電池用の電解液であって、該電解液
が、（ａ）分子量が１０８〜２２０であって、該電解液
が、フェニル基を有するエステル類、エーテル類、カー
ボネート類より選ばれた液状有機溶媒１〜５０モル％
と、前記（ａ）以外の有機溶媒（ｂ）９９〜５０容量％
よりなる有機溶媒に、溶質としてリチウム塩（ｃ）を溶
解してなるものである、リチウムイオン電池用電解液。
【効果】 炭素電極との親和性に優れた非水系電解液で
ある。(57) [Summary] [Structure] An electrolytic solution for a battery, which basically comprises a positive electrode, a negative electrode made of a carbonaceous material, and an electrolytic solution, wherein the electrolytic solution has (a) a molecular weight of 108 to 220. The electrolytic solution is a liquid organic solvent selected from esters having phenyl groups, ethers, and carbonates in an amount of 1 to 50 mol%.
And an organic solvent (b) other than the above (a) 99 to 50% by volume
An electrolyte solution for a lithium ion battery, which is obtained by dissolving a lithium salt (c) as a solute in an organic solvent consisting of [Effect] A non-aqueous electrolyte solution having excellent affinity with a carbon electrode.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、持続性の良好なリチウ
ムイオン電池用の電解液に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolyte solution for a lithium ion battery having good durability.
【０００２】[0002]
【従来の技術】電気化学素子は、正極、負電極、電解
液、セパレーター等によって構成されている。この中で
電解液は、電極表面での電気化学反応を速やかに進行さ
せることが目的であるため、イオンの移動を円滑に行う
性能が要求される。電解液の選択には、用いる電極との
反応性、使用電位範囲、使用温度範囲が重要な必要条件
となるため、例えばリチウム一次電池、リチウムイオン
電池、アルミ電解コンデンサー等には非水系電解液が一
般に用いられている。2. Description of the Related Art An electrochemical device is composed of a positive electrode, a negative electrode, an electrolytic solution, a separator and the like. Among them, the electrolytic solution has a purpose of promptly promoting an electrochemical reaction on the electrode surface, and therefore is required to have a property of smoothly moving ions. For the selection of the electrolytic solution, the reactivity with the electrode to be used, the working potential range, and the working temperature range are important necessary conditions. It is commonly used.
【０００３】例えば、リチウムイオン電池は使用電位幅
が３Ｖ以上であり、極めて活性の高いリチウムを用いる
ことから、エチレンカーボネート、プロピレンカーボネ
ートなどの安定性の高い有機溶媒を用いることによっ
て、電池性能が向上することが報告されている（「機能
材料」ｖｏｌ．１５、４月号、４８頁（１９９５年
刊））。For example, since a lithium-ion battery has a working potential range of 3 V or more and uses highly active lithium, battery performance is improved by using a highly stable organic solvent such as ethylene carbonate or propylene carbonate. It has been reported (“Functional Material” vol. 15, April issue, p. 48 (published in 1995)).
【０００４】従来用いられているリチウムイオン電池用
非水系電解液の有機溶媒はジメトキシエタン等の脂肪族
エーテル、プロピレンカーボネート等の脂肪族カーボネ
ート、γ−ブチロラクトン等である。これら脂肪族系の
有機溶媒を用いた電解液は初期特性は良好であるが、サ
イクル特性に問題があり、長期使用に際して電池容量の
低下が見られる。この問題点を解決するために、フルフ
ラール類を添加することが提案されている（特開平６−
３３８３４６号）。これら化合物の作用は、負極側で生
成する活性なデンドライトと反応し、有機薄膜層を生成
することにより、電極表面を保護するものである。しか
し、これら化合物はアルデヒド基を有しているため、分
解、重合等の可能性がある。また、電気化学的に生成し
たデンドライトと反応するため、充放電効率が低下する
という問題点がある。Conventionally used organic solvents for non-aqueous electrolytes for lithium ion batteries are aliphatic ethers such as dimethoxyethane, aliphatic carbonates such as propylene carbonate, and γ-butyrolactone. The electrolytic solution using these aliphatic organic solvents has good initial characteristics, but has a problem in cycle characteristics, and the battery capacity is reduced when used for a long period of time. In order to solve this problem, it has been proposed to add furfurals (JP-A-6-
338346). The action of these compounds is to protect the electrode surface by reacting with the active dendrite generated on the negative electrode side to form an organic thin film layer. However, since these compounds have an aldehyde group, they may be decomposed or polymerized. Further, since it reacts with the electrochemically generated dendrite, there is a problem that the charge / discharge efficiency is reduced.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、前記問題点
を鑑みてなされたものであり、サイクル特性を向上させ
たリチウムイオン電池用電解液の提供を目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide an electrolytic solution for a lithium ion battery having improved cycle characteristics.
【０００６】[0006]
【課題を解決するための手段】本発明は、正極、炭素質
材料よりなる負極、及び電解液を基本構成とする電池用
の電解液であって、該電解液が、（ａ）分子量が１０８
〜２２０であって、次式（Ｉ）、（II）または（III)で
示されるフェニル基を有するエステル類、エーテル類、
カーボネート類より選ばれた液状有機溶媒１〜３０容量
％と、（ｂ）エチレンカーボネートとジエチルカーボネ
ートの混合物９９〜７０容量％（但し、エチレンカーボ
ネートとジエチルカーボネートの容量比は１：８〜１：
０．１５の範囲である）よりなる有機溶媒に溶質の六フ
ッ化リン酸リチウムが０．５〜２．０モル／リットルの
モル濃度で溶解されたものである、リチウムイオン電池
用電解液を提供するものである。The present invention provides an electrolytic solution for a battery, which basically comprises a positive electrode, a negative electrode made of a carbonaceous material, and an electrolytic solution, the electrolytic solution having a molecular weight (a) of 108.
To 220 and has a phenyl group represented by the following formula (I), (II) or (III), an ether,
1 to 30% by volume of a liquid organic solvent selected from carbonates, and (b) a mixture of ethylene carbonate and diethyl carbonate 99 to 70% by volume (provided that the volume ratio of ethylene carbonate and diethyl carbonate is 1: 8 to 1: 1).
An electrolyte solution for a lithium-ion battery, wherein a solute of lithium hexafluorophosphate is dissolved at a molar concentration of 0.5 to 2.0 mol / liter in an organic solvent consisting of 0.15). It is provided.
【０００７】[0007]
【化２】 Embedded image
【０００８】（式中、Ｒは炭素数が１〜４のアルキル基
である。）(In the formula, R is an alkyl group having 1 to 4 carbon atoms.)
【０００９】（発明の概要）リチウムイオン電池 リチウムイオン電池は、正極、炭素質材料の負極、電解
液を基本構成としている。図１と図２にその構造の１例
を示す。図１、図２において、１は正電極、２は炭素質
材料の負電極、３はセパレータ、４は電池缶、５は封口
蓋、６は正極端子、７は絶縁体である。(Outline of the Invention) Lithium Ion Battery A lithium ion battery basically comprises a positive electrode, a negative electrode made of a carbonaceous material, and an electrolytic solution. 1 and 2 show an example of the structure. 1 and 2, 1 is a positive electrode, 2 is a negative electrode of carbonaceous material, 3 is a separator, 4 is a battery can, 5 is a sealing lid, 6 is a positive electrode terminal, and 7 is an insulator.
【００１０】正極 正極としては特に限定されるものではないが、例えば、
ＴｉＳ2 、ＴｉＳ3 、ＭｏＳ2 ，ＦｅＳ2 等の金属硫化
物、Ｖ2 Ｏ5 ，Ｖ6 Ｏ13、ＭｏＯ3 等の金属酸化物、Ｌ
ｉ(1-x) ＭｎＯ2 、Ｌｉ(1-x) ＣｏＯ2 、Ｌｉ(1-x) Ｎ
ｉＯ2 、Ｌｉ(1 -x) Ｃｏy Ｓｎ2 Ｏ2 等のアルカリ金属
特にリチウム含有複合金属酸化物等が挙げられる。The positive electrode is not particularly limited, but for example,
Metal sulfides such as TiS 2 , TiS 3 , MoS 2 and FeS 2 , metal oxides such as V 2 O 5 , V 6 O 13 and MoO 3 , L
i (1-x) MnO 2 , Li (1-x) CoO 2 , Li (1-x) N
Examples thereof include alkali metals such as iO 2 , Li (1- x) Co y Sn 2 O 2 and the like, and particularly lithium-containing composite metal oxides.
【００１１】負極 本発明で負極として用いられる炭素質材料は特に限定さ
れるものではないが、有機高分子化合物、ピッチ、石
炭、木材等を焼成炭化して得られるもの、有機物質の気
相炭化成長反応により得られるもの、天然黒鉛等の天然
産出炭素質材料等を例示することができる。Negative Electrode The carbonaceous material used as the negative electrode in the present invention is not particularly limited, but it is obtained by calcining and carbonizing an organic polymer compound, pitch, coal, wood, or gas phase carbonization of an organic substance. Examples thereof include those obtained by the growth reaction and naturally occurring carbonaceous materials such as natural graphite.
【００１２】電解液 電解液は、（ａ）分子量が１０８〜２２０のフェニル基
を有する前述の式（Ｉ）、（II）および（III)のエステ
ル類、エーテル類、カーボネート類より一種または二種
以上選ばれた有機溶媒１〜３０容量％と、（ｂ）エチレ
ンカーボネートとジエチルカーボネートの混合物９９〜
７０容量％（但し、エチレンカーボネートとジエチルカ
ーボネートの容量比は１：８〜１：０．１５の範囲であ
る。）よりなる有機溶媒に、溶質として六フッ化リン酸
リチウムを溶解してなるものである。 Electrolyte Solution The electrolyte solution is (a) one or two kinds selected from the esters, ethers and carbonates of the above formulas (I), (II) and (III) having a phenyl group having a molecular weight of 108 to 220. 1 to 30% by volume of the above-selected organic solvent, and (b) a mixture of ethylene carbonate and diethyl carbonate 99 to
Dissolved lithium hexafluorophosphate as a solute in an organic solvent composed of 70% by volume (however, the volume ratio of ethylene carbonate and diethyl carbonate is in the range of 1: 8 to 1: 0.15). Is.
【００１３】（ａ）有機溶媒：かかるフェニル基を有す
る分子量が１０８〜２２０の有機化合物（ａ）として
は、（ａ1 ）メチルフェニルカーボネート、エチルフェ
ニルカーボネート、プロピルフェニルカーボネート、ブ
チルフェニルカーボネートなどのカーボネート類；（ａ
2 ）アニソール、フェネトールなどのエーテル類；（ａ
3 ）酢酸フェニル、プロピオン酸フェニル、酪酸フェニ
ルなどのエステル類などが挙げられる。これらフェニル
基を有する有機溶媒は単独で、または二種以上混合して
用いられる。このフェニル基を有する液状有機溶媒
（ａ）は、後述する他の有機溶媒（ｂ）との溶媒の容量
和の１〜３０容量％、好ましくは４．５〜２０容量％の
割合で用いられる。溶媒中に占める割合が１容量％未満
ではサイクル特性の向上が期待できない。３０容量％を
越えて用いると電気伝導度が低下する。 (A) Organic solvent: Examples of the organic compound (a) having a phenyl group and a molecular weight of 108 to 220 include (a 1 ) methylphenyl carbonate, ethylphenyl carbonate, propylphenyl carbonate, butylphenyl carbonate, and other carbonates. Kind; (a
2 ) Ethers such as anisole and phenetole; (a
3 ) Esters such as phenyl acetate, phenyl propionate and phenyl butyrate. These organic solvents having a phenyl group may be used alone or in combination of two or more. The liquid organic solvent (a) having a phenyl group is used in a proportion of 1 to 30% by volume, preferably 4.5 to 20% by volume of the total volume of the solvent with the other organic solvent (b) described later. If the proportion in the solvent is less than 1% by volume, improvement in cycle characteristics cannot be expected. If it is used in excess of 30% by volume, the electric conductivity will decrease.
【００１４】（ｂ）エチレンカーボネートとジエチルカ
ーボネートの混合溶媒エチレンカーボネートとジエチル
カーボネートの混合割合は、エチレンカーボネート１容
量に対し、ジエチルカーボネート８〜０．１５容量であ
る。この範囲であると電気伝導度が高く、かつ、サイク
ル特性の良好な電解液となる。かかる混合比は、エチレ
ンカーボネートが有機溶媒〔（ａ）＋（ｂ）〕中の１０
〜８０容量％、ジエチルカーボネートが有機溶媒
〔（ａ）＋（ｂ）〕中の１０〜６０容量％の範囲で好適
に選ばれる。(B) Mixed solvent of ethylene carbonate and diethyl carbonate The mixing ratio of ethylene carbonate and diethyl carbonate is 8 to 0.15 volume of diethyl carbonate to 1 volume of ethylene carbonate. Within this range, the electrolyte has high electric conductivity and good cycle characteristics. Such a mixing ratio is such that ethylene carbonate is 10 in the organic solvent [(a) + (b)].
˜80% by volume and diethyl carbonate are preferably selected within the range of 10 to 60% by volume in the organic solvent [(a) + (b)].
【００１５】（ｃ）電解質 成分（ａ）と成分（ｂ）の有機溶媒に溶解される電解質
のリチウム塩は六フッ化リン酸リチウムである。電解液
中の電解質（ｃ）六フッ化リン酸リチウムのモル濃度
は、０．５〜２．０モル／リットルである。 (C) The lithium salt of the electrolyte dissolved in the organic solvent of the electrolyte component (a) and the component (b) is lithium hexafluorophosphate. The molar concentration of the electrolyte (c) lithium hexafluorophosphate in the electrolytic solution is 0.5 to 2.0 mol / liter.
【００１６】他の素材：リチウムイオン電池を組み立て
る場合、更にセパレーターが挙げられる。セパレーター
としては織布、不織布、ガラス織布、合成樹脂微多孔膜
等が挙げられる。更に要すれば、集電体、端子、絶縁板
等の部品を用いて電池が構成される。電池の構造として
は、正極、負極、更に要すればセパレーターを単層又は
複層としたペーパー型電池、積層型電池、又は正極、負
極、更に要すればセパレーターをロール状に巻いた円筒
状電池等の形態が挙げられる。 Other materials: In the case of assembling a lithium-ion battery, a separator is further included. Examples of the separator include woven cloth, non-woven cloth, glass woven cloth, and synthetic resin microporous film. If necessary, a battery is configured using components such as a current collector, a terminal, and an insulating plate. As the structure of the battery, a positive electrode, a negative electrode, if necessary, a paper-type battery in which a separator is a single layer or multiple layers, a laminated battery, or a positive electrode, a negative electrode, and if necessary, a cylindrical battery in which a separator is rolled And the like.
【００１７】[0017]
【実施例】以下に、実施例を挙げて、本発明を更に具体
的に説明する。 実施例１ 乾燥アルゴン雰囲気下で、充分に乾燥を行った六フッ化
リン酸リチウム１５２ｇ（１モル）をエチレンカーボネ
ート（ＥＣ）６２７ｇ（４７５ｃｃ）、ジエチルカーボ
ネート（ＤＥＣ）４６３ｇ（４７５ｃｃ）、メチルフェ
ニルカーボネート（ＭＰｈＣ）５７ｇ（５０ｃｃ）から
なる混合溶媒に溶かし、全量を１０００ｃｃとした電解
液を調製した。The present invention will be described more specifically with reference to the following examples. Example 1 152 g (1 mol) of lithium hexafluorophosphate that had been sufficiently dried under a dry argon atmosphere, 627 g (475 cc) of ethylene carbonate (EC), 463 g (475 cc) of diethyl carbonate (DEC), methylphenyl carbonate (MPhC) was dissolved in a mixed solvent of 57 g (50 cc) to prepare an electrolytic solution having a total amount of 1000 cc.
【００１８】このものの２５℃での電気伝導度は７．８
ｍＳ／ｃｍであった。ＮＧ−７（天然黒鉛粉末、関西熱
化学社製、商品名）を塗布したシート状電極、コバルト
酸リチウム、ポリプロピレン製セパレータによって構成
されたコインセルを用いて、５０回の充放電試験（０．
２ｍＡ定電流）を行い、炭素質材料からの充電容量のサ
イクル変化および充放電効率（放電容量／充電容量）を
測定した。結果を図３と図４に示す。The electrical conductivity of this product at 25 ° C. is 7.8.
It was mS / cm. A charge-discharge test (0 ..
2 mA constant current) was performed, and the cycle change of the charge capacity from the carbonaceous material and the charge / discharge efficiency (discharge capacity / charge capacity) were measured. The results are shown in FIGS.
【００１９】実施例２ 実施例１において、電解液を六フッ化リン酸リチウム１
５２ｇ（１モル）をＥＣ６２７ｇ（４７５ｃｃ）、ＤＥ
Ｃ４６３ｇ（４７５ｃｃ）、ＭＰｈＣ５７ｇ（５０ｃ
ｃ）からなる混合溶媒に溶かし、全量を１０００ｃｃと
したものから、六フッ化リン酸リチウム１５２ｇ（１モ
ル）をＥＣ６２７ｇ（４７５ｃｃ）、ＤＥＣ４６３ｇ
（４７５ｃｃ）、アニソール（ＭＯＢ）５０ｇ（５０ｃ
ｃ）からなる混合溶媒に溶かし、全量を１０００ｃｃと
したものに変更した以外は同様な操作を行った。結果を
図３と図４に示す。なお、電解液の２５℃における電気
伝導度は８．０ｍＳ／ｃｍであった。Example 2 In Example 1, the electrolytic solution was changed to lithium hexafluorophosphate 1
52 g (1 mol) of EC627 g (475 cc), DE
C463g (475cc), MPhC57g (50c
Dissolved in a mixed solvent consisting of c) and adjusting the total amount to 1000 cc, 152 g (1 mol) of lithium hexafluorophosphate was added to EC627 g (475 cc), DEC463 g
(475cc), Anisole (MOB) 50g (50c
The same operation was performed except that the solvent was dissolved in the mixed solvent consisting of c) and the total amount was changed to 1000 cc. The results are shown in FIGS. The electric conductivity of the electrolytic solution at 25 ° C. was 8.0 mS / cm.
【００２０】実施例３ 実施例１において、電解液を六フッ化リン酸リチウム１
５２ｇ（１モル）をＥＣ６２７ｇ（４７５ｃｃ）、ＤＥ
Ｃ４６３ｇ（４７５ｃｃ）、ＭＰｈＣ５７ｇ（５０ｃ
ｃ）からなる混合溶媒に溶かし、全量を１０００ｃｃと
したものから、六フッ化リン酸リチウム１５２ｇ（１モ
ル）をＥＣ６２７ｇ（４７５ｃｃ）、ＤＥＣ４６３ｇ
（４７５ｃｃ）、プロピオン酸フェニル（ＰｈＰ）５３
ｇ（５０ｃｃ）からなる混合溶媒に溶かし、全量を１０
００ｃｃとしたものに変更した以外は同様な操作を行っ
た。結果を図３と図４に示す。なお、電解液の２５℃に
おける電気伝導度は７．８ｍＳ／ｃｍであった。Example 3 In Example 1, the electrolytic solution was changed to lithium hexafluorophosphate 1
52 g (1 mol) of EC627 g (475 cc), DE
C463g (475cc), MPhC57g (50c
Dissolved in a mixed solvent consisting of c) and adjusting the total amount to 1000 cc, 152 g (1 mol) of lithium hexafluorophosphate was added to EC627 g (475 cc) and DEC463 g.
(475 cc), phenyl propionate (PhP) 53
Dissolve in a mixed solvent consisting of g (50 cc) and add 10
The same operation was performed except that the value was changed to 00cc. The results are shown in FIGS. The electric conductivity of the electrolytic solution at 25 ° C. was 7.8 mS / cm.
【００２１】比較例１ 実施例１において、電解液を六フッ化リン酸リチウム１
５２ｇ（１モル）をＥＣ６２７ｇ（４７５ｃｃ）、ＤＥ
Ｃ４６３ｇ（４７５ｃｃ）、ＭＰｈＣ５７ｇ（５０ｃ
ｃ）からなる混合溶媒に溶かし、全量を１０００ｃｃと
したものから、六フッ化リン酸リチウム１５２ｇ（１モ
ル）をＥＣ６６１ｇ（５００ｃｃ）、ＤＥＣ４８８ｇ
（５００ｃｃ）からなる混合溶媒に溶かし、全量を１０
００ｃｃとしたものに変更した以外は同様な操作を行っ
た。結果を図３と図４に示す。Comparative Example 1 In Example 1, the electrolytic solution was changed to lithium hexafluorophosphate 1
52 g (1 mol) of EC627 g (475 cc), DE
C463g (475cc), MPhC57g (50c
Dissolved in a mixed solvent consisting of c) and making the total amount 1000 cc, 152 g (1 mol) of lithium hexafluorophosphate was EC661 g (500 cc), DEC 488 g
Dissolve in a mixed solvent consisting of (500 cc),
The same operation was performed except that the value was changed to 00cc. The results are shown in FIGS.
【００２２】実施例４ 実施例１において、シート状電極をＮＧ−７を塗布した
ものから、ＫＳ−４４（人造黒鉛粉末、ＬＯＮＺＡ社
製、商品名）を塗布したものに変更した以外は同様な操
作を行った。結果を図５と図６に示す。Example 4 Similar to Example 1 except that the sheet electrode coated with NG-7 was changed to the one coated with KS-44 (artificial graphite powder, manufactured by LONZA, trade name). The operation was performed. The results are shown in FIGS.
【００２３】実施例５ 実施例４において、電解液を六フッ化リン酸リチウム１
５２ｇ（１モル）をＥＣ６２７ｇ（４７５ｃｃ）、ＤＥ
Ｃ４６３ｇ（４７５ｃｃ）、ＭＰｈＣ５７ｇ（５０ｃ
ｃ）からなる混合溶媒に溶かし、全量を１０００ｃｃと
したものから、六フッ化リン酸リチウム１５２ｇ（１モ
ル）をＥＣ６２７ｇ（４７５ｃｃ）、ＤＥＣ４６３ｇ
（４７５ｃｃ）、アニソール（ＭＯＢ）５０ｇ（５０ｃ
ｃ）からなる混合溶媒に溶かし、全量を１０００ｃｃと
したものに変更した以外は同様な操作を行った。結果を
図５と図６に示す。電解液の電気伝導度は８．０ｍＳ／
ｃｍであった。Example 5 In Example 4, the electrolytic solution was changed to lithium hexafluorophosphate 1
52 g (1 mol) of EC627 g (475 cc), DE
C463g (475cc), MPhC57g (50c
Dissolved in a mixed solvent consisting of c) and adjusting the total amount to 1000 cc, 152 g (1 mol) of lithium hexafluorophosphate was added to EC627 g (475 cc), DEC463 g
(475cc), Anisole (MOB) 50g (50c
The same operation was performed except that the solvent was dissolved in the mixed solvent consisting of c) and the total amount was changed to 1000 cc. The results are shown in FIGS. The electric conductivity of the electrolyte is 8.0 mS /
cm.
【００２４】実施例６ 実施例４において、電解液を六フッ化リン酸リチウム１
５２ｇ（１モル）をＥＣ６２７ｇ（４７５ｃｃ）、ＤＥ
Ｃ４６３ｇ（４７５ｃｃ）、ＭＰｈＣ５７ｇ（５０ｃ
ｃ）からなる混合溶媒に溶かし、全量を１０００ｃｃと
したものから、六フッ化リン酸リチウム１５２ｇ（１モ
ル）をＥＣ６２７ｇ（４７５ｃｃ）、ＤＥＣ４６３ｇ
（４７５ｃｃ）、プロピオン酸フェニル（ＰｈＰ）５３
ｇ（５０ｃｃ）からなる混合溶媒に溶かし、全量を１０
００ｃｃとしたものに変更した以外は同様な操作を行っ
た。結果を図５と図６に示す。電解液の電気伝導度は
７．８ｍＳ／ｃｍであった。Example 6 In Example 4, the electrolytic solution was changed to lithium hexafluorophosphate 1
52 g (1 mol) of EC627 g (475 cc), DE
C463g (475cc), MPhC57g (50c
Dissolved in a mixed solvent consisting of c) and adjusting the total amount to 1000 cc, 152 g (1 mol) of lithium hexafluorophosphate was added to EC627 g (475 cc) and DEC463 g.
(475 cc), phenyl propionate (PhP) 53
Dissolve in a mixed solvent consisting of g (50 cc) and add 10
The same operation was performed except that the value was changed to 00cc. The results are shown in FIGS. The electric conductivity of the electrolytic solution was 7.8 mS / cm.
【００２５】比較例２ 実施例４において、電解液を六フッ化リン酸リチウム１
５２ｇ（１モル）をＥＣ６２７ｇ（４７５ｃｃ）、ＤＥ
Ｃ４６３ｇ（４７５ｃｃ）、ＭＰｈＣ５７ｇ（５０ｃ
ｃ）からなる混合溶媒に溶かし、全量を１０００ｃｃと
したものから、六フッ化リン酸リチウム１５２ｇ（１モ
ル）をＥＣ６６１ｇ（５００ｃｃ）、ＤＥＣ４８８ｇ
（５００ｃｃ）からなる混合溶媒に溶かし、全量を１０
００ｃｃとしたものに変更した以外は同様な操作を行っ
た。結果を図５と図６に示す。Comparative Example 2 In Example 4, the electrolytic solution was changed to lithium hexafluorophosphate 1
52 g (1 mol) of EC627 g (475 cc), DE
C463g (475cc), MPhC57g (50c
Dissolved in a mixed solvent consisting of c) and adjusting the total amount to 1000 cc, 152 g (1 mol) of lithium hexafluorophosphate was EC661 g (500 cc), DEC 488 g
Dissolve in a mixed solvent consisting of (500 cc),
The same operation was performed except that the value was changed to 00cc. The results are shown in FIGS.
【００２６】[0026]
【発明の効果】充放電効率の低下がなく、サイクル特性
を向上させたリチウムイオン電池用非水系電解液であ
り、リチウムイオンの電池の小型化、高性能化に寄与す
ることができる。EFFECTS OF THE INVENTION A non-aqueous electrolyte for a lithium-ion battery that has improved charge / discharge efficiency and improved cycle characteristics, and can contribute to miniaturization and higher performance of lithium-ion batteries.
【図１】筒状型リチウムイオン電池の一部を切り欠いた
斜視図である。FIG. 1 is a perspective view in which a cylindrical lithium ion battery is partially cut away.
【図２】コイン型リチウムイオン電池の一部を切り欠い
た斜視図である。FIG. 2 is a perspective view in which a coin-type lithium-ion battery is partially cut away.
【図３】負極に天然黒鉛を用いた場合の本発明の電解液
と従来の電解液の充放電サイクル特性図である。FIG. 3 is a charge / discharge cycle characteristic diagram of an electrolytic solution of the present invention and a conventional electrolytic solution when natural graphite is used for a negative electrode.
【図４】負極に天然黒鉛を用いた場合の本発明の電解液
と従来の電解液の充放電効率特性図である。FIG. 4 is a charge / discharge efficiency characteristic diagram of an electrolytic solution of the present invention and a conventional electrolytic solution when natural graphite is used for a negative electrode.
【図５】負極に人造黒鉛を用いた場合の本発明の電解液
と従来の電解液の充放電サイクル特性図である。FIG. 5 is a charge / discharge cycle characteristic diagram of an electrolytic solution of the present invention and a conventional electrolytic solution when artificial graphite is used for a negative electrode.
【図６】負極に人造黒鉛を用いた場合の本発明の電解液
と従来の電解液の充放電効率特性図である。FIG. 6 is a charge / discharge efficiency characteristic diagram of the electrolytic solution of the present invention and the conventional electrolytic solution when artificial graphite is used for the negative electrode.
１ 炭素電極 ２ 対極 ３ セパレータ ４ 電池缶 ５ ふた ６ 端子 ７ 絶縁体 1 carbon electrode 2 counter electrode 3 separator 4 battery can 5 lid 6 terminal 7 insulator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石垣 憲一 茨城県稲敷郡阿見町中央八丁目３番１号 三菱化学株式会社筑波研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenichi Ishigaki 3-1, Chuo 8-chome, Ami-cho, Inashiki-gun, Ibaraki Mitsubishi Chemical Corporation Tsukuba Research Center
Claims (2)
解液を基本構成とする電池用の電解液であって、該電解
液が、 （ａ）分子量が１０８〜２２０であって、次式（Ｉ）、
（II）または（III)で示されるフェニル基を有するエス
テル類、エーテル類、カーボネート類より選ばれた液状
有機溶媒１〜３０容量％と、（ｂ）エチレンカーボネー
トとジエチルカーボネートの混合物９９〜７０容量％
（但し、エチレンカーボネートとジエチルカーボネート
の容量比は１：８〜１：０．１５の範囲である）よりな
る有機溶媒に溶質の六フッ化リン酸リチウムが０．５〜
２．０モル／リットルのモル濃度で溶解されたものであ
る、リチウムイオン電池用電解液。 【化１】 （式中、Ｒは炭素数が１〜４のアルキル基である。）1. An electrolytic solution for a battery, comprising a positive electrode, a negative electrode made of a carbonaceous material, and an electrolytic solution as a basic component, wherein the electrolytic solution has the following formula: (I),
1 to 30% by volume of a liquid organic solvent selected from esters, ethers and carbonates having a phenyl group represented by (II) or (III), and (b) a mixture of ethylene carbonate and diethyl carbonate 99 to 70% by volume. %
(However, the volume ratio of ethylene carbonate and diethyl carbonate is in the range of 1: 8 to 1: 0.15), the solute of lithium hexafluorophosphate is 0.5 to
An electrolytic solution for a lithium ion battery, which is dissolved at a molar concentration of 2.0 mol / liter. Embedded image (In the formula, R is an alkyl group having 1 to 4 carbon atoms.)
カーボネート、エチルフェニルカーボネート、プロピル
フェニルカーボネート、ブチルフェニルカーボネート、
アニソール、フェネトール、酢酸フェニル、プロピオン
酸フェニル、酪酸フェニルより選ばれた有機溶媒である
請求項１記載のリチウムイオン電池用電解液。2. The liquid organic solvent (a) is methylphenyl carbonate, ethylphenyl carbonate, propylphenyl carbonate, butylphenyl carbonate,
The electrolytic solution for a lithium ion battery according to claim 1, which is an organic solvent selected from anisole, phenetole, phenyl acetate, phenyl propionate, and phenyl butyrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7170844A JPH0922722A (en) | 1995-07-06 | 1995-07-06 | Electrolyte for lithium-ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7170844A JPH0922722A (en) | 1995-07-06 | 1995-07-06 | Electrolyte for lithium-ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0922722A true JPH0922722A (en) | 1997-01-21 |
Family
ID=15912382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7170844A Pending JPH0922722A (en) | 1995-07-06 | 1995-07-06 | Electrolyte for lithium-ion battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0922722A (en) |
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| JP2014017258A (en) * | 2008-02-29 | 2014-01-30 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte and nonaqueous electrolyte battery |
| US8889302B2 (en) | 2008-02-29 | 2014-11-18 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous-electrolyte battery |
| US9083058B2 (en) | 2008-02-29 | 2015-07-14 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous-electrolyte battery |
| JP2011023160A (en) * | 2009-07-14 | 2011-02-03 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte solution and nonaqueous electrolyte battery |
| KR20170094424A (en) | 2015-01-14 | 2017-08-17 | 고쿠리츠다이가쿠호우진 도쿄다이가쿠 | Aqueous electrolyte solution for electrical storage device, and electrical storage device including said aqueous electrolyte solution |
| US10629958B2 (en) | 2015-01-14 | 2020-04-21 | The University Of Tokyo | Aqueous electrolytic solution for power storage device and power storage device including said aqueous electrolytic solution |
| US10658706B2 (en) | 2016-01-14 | 2020-05-19 | The University Of Tokyo | Aqueous electrolytic solution for power storage device and power storage device including said aqueous electrolytic solution |
| JP2019102428A (en) * | 2017-12-05 | 2019-06-24 | 寧徳時代新能源科技股▲分▼有限公司Ｃｏｎｔｅｍｐｏｒａｒｙ Ａｍｐｅｒｅｘ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｉｍｉｔｅｄ | battery |
| US10658673B2 (en) | 2017-12-05 | 2020-05-19 | Contemporary Amperex Technology Co., Limited | Battery |
| US10749184B2 (en) | 2017-12-05 | 2020-08-18 | Contemporary Amperex Technology Co., Limited | Battery |
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