JPH02265171A - Electrolyte for lithium battery - Google Patents
Electrolyte for lithium batteryInfo
- Publication number
- JPH02265171A JPH02265171A JP1087195A JP8719589A JPH02265171A JP H02265171 A JPH02265171 A JP H02265171A JP 1087195 A JP1087195 A JP 1087195A JP 8719589 A JP8719589 A JP 8719589A JP H02265171 A JPH02265171 A JP H02265171A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- electrolytic solution
- electrolyte
- batteries
- lipf6
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003792 electrolyte Substances 0.000 title description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 23
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001290 LiPF6 Inorganic materials 0.000 abstract description 7
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 abstract description 7
- 239000007774 positive electrode material Substances 0.000 abstract description 5
- 229920001940 conductive polymer Polymers 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 abstract 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract 2
- 239000011149 active material Substances 0.000 abstract 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 11
- 238000007599 discharging Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 229910001558 CF3SO3Li Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013888 LiPF5 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- -1 jetoxyethane Chemical compound 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000417 polynaphthalene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- 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
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
童来上段札肛分災
本発明は、リチウム電池用電解液に関し、更に詳述する
と充電により再使用可能なリチウム二次電池用電解液と
して好適に使用し得る電解液に関する。[Detailed Description of the Invention] The present invention relates to an electrolytic solution for lithium batteries, and more specifically, an electrolytic solution that can be suitably used as an electrolytic solution for lithium secondary batteries that can be reused by charging. Regarding.
電池は、軽量、小型、高エネルギー密度等の利点を有す
る高性能電池として種々の用途に使用されている。しか
し、その二次電池化は一部商品化されているものの、良
好なサイクル寿命が得難い等、未だ困難な問題点を多く
有している。特に、高エネルギー密度のリチウム電池を
得るためには、負極活物質としてリチウム金属のみを使
用することが有利であるが、リチウム金属のみを負極活
物質とする二次電池を構成する場合、そのサイクル寿命
は電解液の選択により著しく異なることが知られており
、良好なサイクル寿命を有するリチウム二次電池を得る
ためには、高い導電率を有すると共に、高いリチウム充
放電効率を有する電解液が望まれる。Batteries are used in a variety of applications as high-performance batteries that have advantages such as light weight, small size, and high energy density. However, although some secondary batteries have been commercialized, they still have many problems, such as difficulty in achieving a good cycle life. In particular, in order to obtain a lithium battery with high energy density, it is advantageous to use only lithium metal as the negative electrode active material, but when constructing a secondary battery using only lithium metal as the negative electrode active material, the cycle It is known that the lifespan varies significantly depending on the choice of electrolyte, and in order to obtain a lithium secondary battery with a good cycle life, it is desirable to have an electrolyte that has high conductivity and high lithium charge/discharge efficiency. It will be done.
ここで、充放電の繰り返しによりリチウム充放電効率が
減少する主な原因としては、析出したリチウムと溶媒と
の反応により、リチウムが電気化学的に不活性化し、放
電の際にリチウムイオンとして放出できないためや、充
電時のリチウム析出の際に溶媒和している溶媒分子の分
解によりリチラムが充電電気量から推定される量よりも
少なく析出しているためと考えられる。The main reason why lithium charge/discharge efficiency decreases due to repeated charging and discharging is that lithium becomes electrochemically inactive due to the reaction between precipitated lithium and the solvent, and cannot be released as lithium ions during discharge. This is considered to be because less lithium is precipitated than estimated from the amount of charge electricity due to decomposition of solvent molecules solvated during lithium precipitation during charging.
従って、リチウムの充放電効率を向上させるためには、
リチウムと溶媒との反応を抑制することが効果的と考え
られ、従来このようなリチウムと溶媒との反応を抑制す
る方法として、電解質としてＬ ｉ Ａ ｓ Ｆ、を用
いることにより、リチウム表面にＡｓを含む高分子膜を
形成させ、該高分子膜でリチウムと溶媒との反応を抑制
することが提案されている。Therefore, in order to improve the charging and discharging efficiency of lithium,
Suppressing the reaction between lithium and solvent is considered to be effective. Conventionally, as a method for suppressing such a reaction between lithium and solvent, As is applied to the lithium surface by using LiAsF as an electrolyte. It has been proposed to form a polymer film containing lithium and to suppress the reaction between lithium and a solvent using the polymer film.
しかしながら、電解質としてＬｉＡｓＦｃを用いること
は、Ｌ ｉ Ａ ｓ Ｆ Ｇ自体の毒性は低いものの、
これを廃棄した場合に分解して有毒な化合物を生成する
おそれがあり、使用上問題がある。However, using LiAsFc as an electrolyte means that although the toxicity of LiAsFG itself is low,
If this is disposed of, it may decompose and produce toxic compounds, which poses a problem in use.
また、従来からリチウム電池に使われている電解質とし
てＬｉＣＱＯ４，ＬｉＢＦ４．ＬｉＰＦ、等があるが、
これらの電解液のリチウム充放電効率は溶媒の影響を受
け、実用に際しては単独の溶媒を用いるよりも混合溶媒
を用いることが一般的である。しかしながら混合溶媒の
選定はリチウム負極との反応に加えて正極活物質との反
応性も考慮しなくてはならず、使用しすらいという欠点
がある。In addition, LiCQO4, LiBF4. There are LiPF, etc.
The lithium charge/discharge efficiency of these electrolytes is affected by the solvent, and in practical use, it is more common to use a mixed solvent than to use a single solvent. However, when selecting a mixed solvent, it is necessary to consider the reactivity with the positive electrode active material in addition to the reaction with the lithium negative electrode, and there is a drawback that it is difficult to use.
本発明は、上記事情に鑑みなされたもので、リチウムの
充放電効率が高く、かつ取り扱い性に優れ、リチウム二
次電池の電解液として良好に適応するリチウム電池用電
解液を提供することを目的とする。The present invention was made in view of the above circumstances, and an object of the present invention is to provide an electrolytic solution for lithium batteries that has high lithium charging/discharging efficiency, is easy to handle, and is well suited as an electrolytic solution for lithium secondary batteries. shall be.
題を するための手 び
本発明者は、上記目的を達成するため、リチウム電池用
電解液を構成する溶質と溶媒について種々検討した結果
、溶質としてＬｉＰＦ、とＬｉＣＱＯ４゜ＬｉＢＦ４．
ＬｉＡｆｌＣＱ４等のＬｉＰＦ、以外のリチウム塩の１
種又は２種以上との混合物を用い、これをプロピレンカ
ーボネートとエチレンカーボネートとを含む混合溶媒に
溶解した電解液が高いリチウム充放電効率を示し、これ
をリチウムを吸蔵・放出することのできる物質を負極活
物質とし、リチウムイオン又は対アニオンと可逆的な電
気化学反応を行なうことのできる物質を正極活物質とす
る電池、特に負極活物質にリチウム金属のみを用いた二
次電池の電解液として用いることにより、高エネルギー
密度でサイクル特性に優れるリチウム二次電池が得られ
ることを知見し、本発明を完成したものである。In order to achieve the above object, the inventor of the present invention has conducted various studies on solutes and solvents constituting the electrolyte solution for lithium batteries, and has found that LiPF, LiCQO4°LiBF4.
1 of lithium salts other than LiPF such as LiAflCQ4
An electrolytic solution obtained by dissolving a species or a mixture of two or more species in a mixed solvent containing propylene carbonate and ethylene carbonate exhibits high lithium charging and discharging efficiency. Used as an electrolyte in batteries whose negative electrode active material is a material that can undergo a reversible electrochemical reaction with lithium ions or counteranions, especially in secondary batteries that use only lithium metal as the negative electrode active material. The present invention was completed based on the finding that a lithium secondary battery with high energy density and excellent cycle characteristics could be obtained by doing so.
従って、本発明は、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、上記リチウム塩として
ＬｉＰＦ５と他のリチウム塩の１種又は２種以上との混
合物を用いると共に、上記有機溶媒としてプロピレンカ
ーボネートとエチレンカーボネートとを含む混合溶媒を
用いたことを特徴とするリチウム電池用電解液を提供す
るものである。Therefore, the present invention uses a mixture of LiPF5 and one or more other lithium salts as the lithium salt in an electrolytic solution for a lithium battery in which a lithium salt is dissolved in an organic solvent; The present invention provides an electrolytic solution for lithium batteries characterized by using a mixed solvent containing propylene carbonate and ethylene carbonate.
以下、本発明につき更に詳しく説明する。The present invention will be explained in more detail below.
本発明のリチウム電池用電解液中のリチウム塩は、Ｌｉ
ＰＦ、とＬｉＰＦ６以外のリチウム塩の１種又は２種以
上を混合したものであるが、ＬｉＰ Ｆ。The lithium salt in the electrolyte for lithium batteries of the present invention is Li
LiPF is a mixture of PF and one or more lithium salts other than LiPF6.
に混合する他のリチウム塩としては、基本的には従来か
ら知られているリチウム電池用電解質を自由に用いるこ
とができる。具体的にはＬｉＣＱＯ４゜ＬｉＢＦ、、
ＬｉＡＱＣＱ、、 ＣＦ３ＳＯ３Ｌｉ、 ＣＦ３ＣＯ２
Ｌｉなどを挙げることができるが、これらの中でも特に
正極活物質として金属酸化物を用いた電池にはＬｉＣΩ
０４が好ましく、正極活物質に導電性高分子物質を用い
た電池にはＬｉＢＦ４が特に好ましく用いられる。なお
、ＬｉＰＦ６とこれらの他のリチウム塩との混合比は１
：９〜９：１（モル比）、特に４：６〜８：２とするこ
とが好ましい。As the other lithium salt to be mixed in, basically any conventionally known electrolyte for lithium batteries can be freely used. Specifically, LiCQO4゜LiBF,,
LiAQCQ,, CF3SO3Li, CF3CO2
Among them, LiCΩ is particularly suitable for batteries using metal oxides as positive electrode active materials.
04 is preferred, and LiBF4 is particularly preferably used for batteries using a conductive polymer material as the positive electrode active material. Note that the mixing ratio of LiPF6 and these other lithium salts is 1
:9 to 9:1 (molar ratio), particularly preferably 4:6 to 8:2.
上記リチウム塩の混合物を溶解させる有機溶媒は、プロ
ピレンカーボネートとエチレンカーボネートとを含む混
合溶媒であり、その混合比は２：８〜９：１（容量比）
、特に３ニア〜６：４とすることが好ましい。The organic solvent in which the mixture of lithium salts is dissolved is a mixed solvent containing propylene carbonate and ethylene carbonate, and the mixing ratio thereof is 2:8 to 9:1 (volume ratio).
It is particularly preferable that the ratio be 3:4 to 6:4.
本発明の電解液は、上記リチウム塩の混合物よりなる溶
質をこの混合溶媒に溶解して得られるが、この場合リチ
ウム塩濃度は０．５〜３モル／Ｑとすることができ、ま
た必要に応じてジェトキシカーボネート、ジメトキシメ
タン、ジェトキシエタン、γ−ブチロラクトン等のリチ
ウム及びリチウムイオンに不活性な溶媒を添加してもよ
いが、この場合、添加する溶媒の割合は、重量比で５０
％以下とすることが望ましく、これが５０％を超えると
本発明の効果が良好に発揮されない場合がある。The electrolytic solution of the present invention is obtained by dissolving a solute consisting of a mixture of lithium salts in this mixed solvent. In this case, the lithium salt concentration can be 0.5 to 3 mol/Q, and the Depending on the situation, an inert solvent may be added to lithium and lithium ions such as jetoxy carbonate, dimethoxymethane, jetoxyethane, γ-butyrolactone, etc. In this case, the proportion of the solvent added is 50% by weight.
% or less, and if it exceeds 50%, the effects of the present invention may not be exhibited satisfactorily.
本発明の電解液は、リチウム電池の電解液として使用さ
れるものであり、この場合リチウム電池は一次電池でも
二次電池でもよいが、特に二次電池の電解液として使用
した場合にその効果をより有効に発揮する。The electrolytic solution of the present invention is used as an electrolytic solution for a lithium battery, and in this case, the lithium battery may be a primary battery or a secondary battery, but it is particularly effective when used as an electrolytic solution for a secondary battery. Demonstrate more effectively.
なお、リチウム電池の構成は、従来のリチウム電池と同
様の構成とすることができ、例えば正極活物質としては
、ポリアニリン、ポリアセチレン。Note that the configuration of the lithium battery can be similar to that of conventional lithium batteries, and for example, the positive electrode active material is polyaniline or polyacetylene.
ポリ−ｐ−フェニレン、ポリベンゼン、ポリピリジン、
ポリチオフェン、ポリフラン、ポリピロール、アントラ
セン、ポリナフタレン及びこれらの誘導体等の有機導電
性高分子物質又はフッ化炭素やＭｎＯ２，ｖ２０５．Ｍ
ｏＯ２，Ｃｒ２０１．ＣｕＯ等の金属酸化物、ＭｏＳ２
．’ｒｉｓ２．ＦｅＳ２等の金属硫化物などを用いるこ
とができる。また、負極活物質としては、リチウム又は
リチウム合金を用いることができ、この場合リチウム合
金としては、リアー
チウムとアルミニウム、マグネシウム、インジウム、水
銀、亜鉛、カドミウム、鉛、ビスマス、錫。Poly-p-phenylene, polybenzene, polypyridine,
Organic conductive polymer substances such as polythiophene, polyfuran, polypyrrole, anthracene, polynaphthalene, and derivatives thereof, or fluorocarbon, MnO2, v205. M
oO2, Cr201. Metal oxides such as CuO, MoS2
．． 'ris2. Metal sulfides such as FeS2 can be used. Further, as the negative electrode active material, lithium or a lithium alloy can be used. In this case, the lithium alloy includes lithium, aluminum, magnesium, indium, mercury, zinc, cadmium, lead, bismuth, and tin.
アンチモン等の１種又は２種以上との合金などが挙げら
れる。Examples include alloys with one or more of antimony and the like.
光艷叫羞末
本発明のリチウム電池用電解液は、リチウムの充放電効
率に優れ、特にリチウム二次電池の電解液として用いる
ことにより、高エネルギー密度でサイクル特性に優れる
リチウム二次電池が得られるものである。The electrolytic solution for lithium batteries of the present invention has excellent lithium charging and discharging efficiency, and in particular, when used as an electrolytic solution for lithium secondary batteries, a lithium secondary battery with high energy density and excellent cycle characteristics can be obtained. It is something.
以下、実施例及び比較例を示し、本発明を具体的に説明
するが、本発明は下記実施例に制限されるものではない
。EXAMPLES Hereinafter, the present invention will be specifically explained by showing examples and comparative examples, but the present invention is not limited to the following examples.
〔実施例１〕
エチレンカーボネートとプロピレンカーボネートとの混
合溶媒（体積混合比１：１）に１モル／ＱのＬｉＰＦ６
とＬｉＣｕｏ４とを種々の混合割合で溶解し、リチウム
電池用電解液を調製した。この電解液を用いてリチウム
の充放電効率（Ｅ＃、１０）を測定した。測定方法は、
第１図に示したようにビ−カー１内に上記電解液２を入
れ、この電解液中に作用極としてニッケル板３（面積１
ｄ／片面）、対極としてリチウム板４（面積１ｃＪ／片
面）を対面状態に浸漬し、この作用極・対極３，４間に
参照極としてリチウム片５を浸漬し、まず２ ’ｍ Ａ
の定電流でニッケル板３上にリチウムを４００秒析出（
０，４Ｃ／ｄ）させた後、同じ＜ ２ ｍ Ａの定電流
でリチウムを溶解させる充放電サイクルを１０サイクル
繰り返し、これらのサイクルにおけるリチウムの充放電
効率の平均Ｅｆｚ、１０を求めた。なお、充放電の際の
溶解終止点は０．８ＶｖｓＬｉ／Ｌｉ”とした。この実
験により得られた１モル／ＱＬｉＰＦ。[Example 1] 1 mol/Q LiPF6 in a mixed solvent of ethylene carbonate and propylene carbonate (volume mixing ratio 1:1)
and LiCuo4 were dissolved at various mixing ratios to prepare electrolyte solutions for lithium batteries. Using this electrolytic solution, the lithium charge/discharge efficiency (E#, 10) was measured. The measurement method is
As shown in FIG. 1, the electrolytic solution 2 is placed in a beaker 1, and a nickel plate 3 (with an area of 1
d/one side), a lithium plate 4 (area 1 cJ/one side) was immersed as a counter electrode in a facing state, and a lithium piece 5 was immersed as a reference electrode between the working and counter electrodes 3 and 4.
Lithium was deposited on the nickel plate 3 for 400 seconds at a constant current of (
0.4 C/d), 10 charge/discharge cycles were repeated in which lithium was dissolved at the same constant current of <2 mA, and the average Efz, 10, of the lithium charge/discharge efficiency in these cycles was determined. In addition, the dissolution end point during charging and discharging was set to 0.8VvsLi/Li''.1 mol/QLiPF obtained by this experiment.
Ｌ Ｉ Ｃｎ Ｏ４／エチレンカーボネート・プロピレ
ンカーボネート系におけるＥ＃、１０と、ＬｉＰ Ｆ６
とＬｉＣＱＯ４とのモル混合比との関係について第２図
に示す。E#, 10 in L I Cn O4/ethylene carbonate/propylene carbonate system and LiP F6
The relationship between the molar mixing ratio of LiCQO4 and LiCQO4 is shown in FIG.
第２図に示した結果から、ＬｉＰ Ｆ、とＬｉＣｆ１Ｏ
４とを混合することにより、個々の単独の溶質を用いた
場合よりも高いリチウムの充放電効率を示すことが認め
られた。From the results shown in Figure 2, it can be seen that LiP F and LiCf1O
It was found that by mixing 4 and 4, higher lithium charge/discharge efficiency was exhibited than when each solute was used alone.
〔実施例２〕
溶質としてＬｉＰＦ、とＬｉＢＦ４とを種々の混合割合
で混合した溶質を用いた以外は上記実施例１と同様にし
てリチウム電池用電解液を調製した。[Example 2] An electrolytic solution for a lithium battery was prepared in the same manner as in Example 1 above, except that a solute containing LiPF and LiBF4 mixed at various mixing ratios was used as the solute.
この電解液につき実施例１と同様の実験を行なった。１
モル／ Ｑ Ｌ ｘ Ｐ Ｆ ｓ Ｌ Ｉ Ｂ Ｆ
４ ／エチレンカーボネート・プロピレンカーボネート
系におけるＥｆｆ、１０と、ＬｉＰＦ６とＬｉＢＦ４と
のモル混合比との関係を第３図に示す。The same experiment as in Example 1 was conducted using this electrolyte. 1
Mol/Q L x P F s L I B F
FIG. 3 shows the relationship between Eff, 10 and the molar mixing ratio of LiPF6 and LiBF4 in the 4/ethylene carbonate/propylene carbonate system.
第３図に示した結果からも、Ｌ ｘ Ｐ Ｆ ＧとＬｉ
Ｂ Ｆ４とを混合することにより個々の単独の溶質を用
いた場合よりも高いリチウムの充放電効率を示すことが
確認された。From the results shown in Figure 3, it can be seen that L x P F G and Li
It was confirmed that by mixing B 2 F4, higher lithium charging and discharging efficiency was exhibited than when each solute was used alone.
溶媒としてエチレンカーボネートとジエチルカーボネー
トとの混合溶媒（体積混合比１：１）を用いた以外は実
施例１と同様に混合溶質として１モル／ Ｑ Ｌ ｉＰ
Ｆ ｓとＬｉＣＱＯ４を用いてリチウム電池用電解液
を調製した。この電解液について実施例１と同様の実験
を行なった結果を第４図に示す。1 mol/Q L iP as the mixed solute in the same manner as in Example 1 except that a mixed solvent of ethylene carbonate and diethyl carbonate (volume mixing ratio 1:1) was used as the solvent.
An electrolytic solution for lithium batteries was prepared using Fs and LiCQO4. FIG. 4 shows the results of an experiment similar to that of Example 1 performed on this electrolytic solution.
第４図かられかるように溶媒としてエチレンカーボネー
トとジエチルカーボネートどの混合溶媒を用いた場合は
溶質を混合してもリチウムの充電効率の向上は認められ
なかった。As can be seen from FIG. 4, when a mixed solvent of ethylene carbonate and diethyl carbonate was used as the solvent, no improvement in lithium charging efficiency was observed even if the solute was mixed.
第１図は実施例及び比較例の電解液を用いて行なった充
放電効率試験の実験装置を示す概略断面図、第２〜４図
はそれぞれ実施例及び比較例で行なった実験により得ら
れたリチウムの充放電効率を示すグラフである。
１・・・ビーカー ２・・・電解液３・・・
作用極にッケル板） ４・・・対極（リチウム板）５・
・・参照極（リチウム片）Figure 1 is a schematic cross-sectional view showing the experimental equipment for charge/discharge efficiency tests conducted using the electrolytes of Examples and Comparative Examples, and Figures 2 to 4 are the results obtained from experiments conducted in Examples and Comparative Examples, respectively. It is a graph showing charging and discharging efficiency of lithium. 1... Beaker 2... Electrolyte 3...
Working electrode is a nickel plate) 4... Counter electrode (lithium plate) 5.
・Reference electrode (lithium piece)
Claims (1)
電解液において、上記リチウム塩としてＬｉＰＦ＿６と
他のリチウム塩の１種又は２種以上との混合物を用いる
と共に、上記有機溶媒としてプロピレンカーボネートと
エチレンカーボネートとを含む混合溶媒を用いたことを
特徴とするリチウム電池用電解液。1. In a lithium battery electrolyte solution in which a lithium salt is dissolved in an organic solvent, a mixture of LiPF_6 and one or more other lithium salts is used as the lithium salt, and propylene carbonate and ethylene are used as the organic solvent. An electrolytic solution for lithium batteries characterized by using a mixed solvent containing carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087195A JPH02265171A (en) | 1989-04-05 | 1989-04-05 | Electrolyte for lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087195A JPH02265171A (en) | 1989-04-05 | 1989-04-05 | Electrolyte for lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02265171A true JPH02265171A (en) | 1990-10-29 |
Family
ID=13908203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1087195A Pending JPH02265171A (en) | 1989-04-05 | 1989-04-05 | Electrolyte for lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02265171A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010013673A (en) * | 2008-07-01 | 2010-01-21 | Hokkaido Univ | Method of producing alkali metal and apparatus for producing alkali metal |
-
1989
- 1989-04-05 JP JP1087195A patent/JPH02265171A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010013673A (en) * | 2008-07-01 | 2010-01-21 | Hokkaido Univ | Method of producing alkali metal and apparatus for producing alkali metal |
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