JPH0564429B2 - - Google Patents
Info
- Publication number
- JPH0564429B2 JPH0564429B2 JP58188954A JP18895483A JPH0564429B2 JP H0564429 B2 JPH0564429 B2 JP H0564429B2 JP 58188954 A JP58188954 A JP 58188954A JP 18895483 A JP18895483 A JP 18895483A JP H0564429 B2 JPH0564429 B2 JP H0564429B2
- Authority
- JP
- Japan
- Prior art keywords
- pyrrole
- electrode
- electrolytic solution
- present
- lithium
- 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.)
- Expired - Lifetime
Links
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 239000008151 electrolyte solution Substances 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000007599 discharging Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- -1 CF 3 SO 3 Li Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013462 LiC104 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 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
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】
本発明はリチウム電池に用いる電解液に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrolyte for use in lithium 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、その二次化が大きな問題となつてい
る。 Batteries using lithium as a negative electrode active material are being researched as small-sized batteries with high energy density, but secondaryization has become a major problem.
二次化が可能な正極活物質として、V2O5、
V6O13等の金属酸化物、TiS2、VS2等の層状化合
物が、Liとの間でトポケミカルな反応をする化合
物として知られており、現在までチタン、ジルコ
ニウム、ハフニウム、ニオビウム、タンタル、バ
ナジウムの硫化物、セレン化物、テルル化物を用
いた電池（米国特許第4089052号明細書参照）等
が開示されている。 As a positive electrode active material that can be secondaryized, V 2 O 5 ,
Metal oxides such as V 6 O 13 and layered compounds such as TiS 2 and VS 2 are known as compounds that undergo topochemical reactions with Li. Batteries using vanadium sulfide, selenide, telluride (see US Pat. No. 4,089,052), etc. have been disclosed.
しかしながら、このような二次電池用正極活物
質の研究に比して、Li極の充放電特性に関する研
究は充分とはいえず、リチウム二次電池実現のた
めには、充放電効率及びサイクル寿命等の充放電
特性の良好な電解液の探査が重大な問題となつて
いる。Li極の充放電効率を向上させる試みとして
はLiC104／プロピレンカーボネイトにニトロメ
タン、SO2等の添加剤を加える試み
〔Electrochimica Acta.vol.22、第75頁〜85頁
（1977）〕等が行われているが、必ずしも充分とは
言えず、さらに特性の優れたリチウム二次電池用
電解液が求められている。 However, compared to such research on positive electrode active materials for secondary batteries, research on the charging and discharging characteristics of Li electrodes is not sufficient, and in order to realize lithium secondary batteries, charging and discharging efficiency and cycle life are The search for electrolytes with good charge-discharge characteristics has become a serious issue. Attempts to improve the charging and discharging efficiency of Li electrodes include adding additives such as nitromethane and SO 2 to LiC10 4 /propylene carbonate [Electrochimica Acta.vol. 22, pp. 75-85 (1977)]. However, this is not necessarily sufficient, and there is a need for an electrolyte for lithium secondary batteries with even better characteristics.
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、Li極の充放電特性の優れ
たリチウム二次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 a lithium secondary battery that has excellent charging and discharging characteristics of Li electrodes.
したがつて、本発明によるリチウム二次電池用
電解液は、リチウム塩を有機溶媒に溶解させてリ
チウム電池用電解液において、前記電解液の添加
材として最大0.2モル／のピロールを用いたこ
とを特徴とするものである。 Therefore, the electrolytic solution for lithium secondary 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 a maximum of 0.2 mol/pyrrole is used as an additive in the electrolytic solution. This is a characteristic feature.
本発明によれば、リチウム塩を有機溶媒に溶解
した電解液に、ピロールを添加することにより、
Li極の充放電特性が良好なリチウム二次電池を実
現しえる。 According to the present invention, by adding pyrrole to an electrolytic solution in which a lithium salt is dissolved in an organic solvent,
It is possible to realize a lithium secondary battery with good charge/discharge characteristics of the Li electrode.
本発明を更に詳しく説明する。 The present invention will be explained in more detail.
リチウム電池はリチウムを負極活物質とし、電
気化学的に活性で、かつLi+イオンと可逆的な電
気化学反応を行う物質を正極活物質とする電池で
あるが、本発明のよれば、リチウム塩を有機溶媒
に溶解した電解液の添加剤としてピロールを用い
る。 A lithium battery is a battery that uses lithium as a negative electrode active material and a positive electrode active material that is electrochemically active and undergoes a reversible electrochemical reaction with Li + ions.According to the present invention, lithium salt is used as a positive electrode active material. Pyrrole is used as an additive in an electrolytic solution prepared by dissolving pyrrole in an organic solvent.
ピロールの構造式を下記の式（）に示す。 The structural formula of pyrrole is shown in the following formula ().
本発明によるリチウム二次電池の非水電解液に
用いられる有機溶媒は、従来、この種の電解液に
用いられるものであればいかなるものでもよい。
例えば、プロピレンカーボネイト、テトラハイド
ロフラン、ジメチルスルホキシド、γ−ブチロラ
クトン、ジオキソラン、１，２−ジメトキシエタ
ン、２−メチルテトラハイドロフランから選択さ
れた１種以上の有機溶媒であることができる。 The organic solvent used in the non-aqueous electrolyte of the lithium secondary battery according to the present invention may be any organic solvent conventionally used in this type of electrolyte.
For example, one or more organic solvents selected from propylene carbonate, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, dioxolane, 1,2-dimethoxyethane, and 2-methyltetrahydrofuran can be used.
さらに、溶質であるリチウム塩は前述の有機溶
媒と同様限定されない。例えば、LiC104、
LiBF4、LiAsF6、LiPF6、LiAlCl4、CF3SO3Li、
CF3CO2Liから選択された１種以上のような、一
般に非水電解液の溶質として用いられるリチウム
塩を有効に用いることができる。 Furthermore, the lithium salt that is the solute is not limited to the above-mentioned organic solvent. For example, LiC104 ,
LiBF 4 , LiAsF 6 , LiPF 6 , LiAlCl 4 , CF 3 SO 3 Li,
Lithium salts commonly used as solutes in nonaqueous electrolytes, such as one or more selected from CF 3 CO 2 Li, can be effectively used.
本発明において前記非水電解液に添加される添
加剤はピロールである。 In the present invention, the additive added to the non-aqueous electrolyte is pyrrole.
ピロールを添加することにより、Li表面に吸着
し、このことが電解液構成物質とLiとの間の自己
放電的反応やLiの析出形態を変化させ、充放電効
率の向上が期待される。非水電解液に添加するピ
ロールの添加量は0.2モル／を上限とする。0.2
モル／を超えると、Liの充放電特性が劣化する
おそれがあるからである。 By adding pyrrole, it is adsorbed on the Li surface, which changes the self-discharge reaction between the electrolyte constituents and Li and the precipitation form of Li, and is expected to improve charge and discharge efficiency. The upper limit of the amount of pyrrole added to the non-aqueous electrolyte is 0.2 mol/. 0.2
This is because if the amount exceeds mol/, the charge/discharge characteristics of Li may deteriorate.
次ぎに、本発明の実施例を説明する。 Next, examples of the present invention will be described.
実施例 １
Pt極を作用極、対極にLiを参照電極としてLi
を用いた電池を組み、pt極上にLiを析出させるこ
とにより、Li極の充放電特性を測定した。電解液
には1.モル／のLiC104および0.1モル／１のピ
ロールをプロピレンカーボネイトに溶解させたも
のを用いた。Example 1 Pt electrode is used as a working electrode, Li is used as a counter electrode and Li is used as a reference electrode.
The charge and discharge characteristics of the Li electrode were measured by assembling a battery using the PT electrode and depositing Li on the PT electrode. The electrolytic solution used was one in which 1. mol/mol of LiC10 4 and 0.1 mol/1 pyrrole were dissolved in propylene carbonate.
測定は、まず0.5ｍＡ／cm2の定電流で20分間、
Pt極上にLiを析出させ充電した後、0.5ｍＡ／cm2
の定電流でPt極上に析出したLiをLi+イオンとし
て放電するサイクル試験を行つた。充放電効率は
Pt極の電位の変化より求め、Pt極上に析出した
LiをLi+イオンとして放電させるのに要した電気
量との比から算出した。 The measurement was first carried out for 20 minutes at a constant current of 0.5 mA/ cm2 .
After depositing Li on Pt electrode and charging, 0.5mA/cm 2
A cycle test was performed in which Li deposited on the Pt electrode was discharged as Li + ions at a constant current of . The charge/discharge efficiency is
Determined from the change in potential of the Pt electrode and deposited on the Pt electrode.
It was calculated from the ratio to the amount of electricity required to discharge Li as Li + ions.
第１図はLi極の充放電効率とサイクル数の関係
を示す図であり、図中、ａは本発明の上記電解液
を用いた場合であり、ｂは参考例の1MLiC104／
プロピレンカーボネイト中でのLi極の充放電特性
を示したものである。 FIG. 1 is a diagram showing the relationship between the charging and discharging efficiency of Li electrodes and the number of cycles. In the figure, a shows the case where the above-mentioned electrolyte of the present invention is used, and b shows the case where the above-mentioned electrolyte of the present invention is used, and b shows the case where the reference example 1MLiC10 4 /
This shows the charging and discharging characteristics of Li electrodes in propylene carbonate.
第１図から判る様に、ピロールを添加した電解
液を使用することにより、Li極の充放電特性は著
しく向上している。 As can be seen from FIG. 1, the use of an electrolytic solution containing pyrrole significantly improves the charging and discharging characteristics of the Li electrode.
実施例 ２
電解液として、LiC104および0.1Mピロールを
γ−ブチロラクトンにに溶解させたものを用いた
以外は実施例１と同様にしてLiの充放電特性を測
定した。Example 2 The charging and discharging characteristics of Li were measured in the same manner as in Example 1, except that LiC10 4 and 0.1M pyrrole dissolved in γ-butyrolactone were used as the electrolyte.
第２図はLi極の充放電効率とサイクル数の関係
を示す図であり、図中、ａは本発明の上記電解液
を用いた場合である。また、ｂは本発明の効果を
示すための参考例であり、1M LiC104／γ−ブ
チロラクトンを用いた場合の充放電特性を示した
ものである。 FIG. 2 is a diagram showing the relationship between the charge/discharge efficiency of Li electrodes and the number of cycles, and in the figure, a represents the case where the above-mentioned electrolytic solution of the present invention is used. Moreover, b is a reference example for demonstrating the effect of the present invention, and shows the charge/discharge characteristics when 1M LiC10 4 /γ-butyrolactone is used.
第２図から判る様に、ピロールを添加した電解
液を使用することにより、Li極の充放電特性は著
しく向上している。 As can be seen from FIG. 2, the use of an electrolytic solution containing pyrrole significantly improves the charging and discharging characteristics of the Li electrode.
以上の説明から明らかなように、本発明によれ
ば、リチウム塩を有機溶媒に溶解させた非水電解
液において、ピロールを添加剤として用いること
により、Li極の充放電特性の優れたリチウム二次
電池用非水電解液を提供する事ができる。 As is clear from the above description, according to the present invention, by using pyrrole as an additive in a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent, a lithium dielectric with excellent charge and discharge characteristics of a Li electrode can be obtained. It is possible to provide a non-aqueous electrolyte for next-generation batteries.
第１図及び第２図は本発明による電解液を用い
た場合のLi極の充放電効率とサイクル数の関係を
示す図である。
FIGS. 1 and 2 are diagrams showing the relationship between the charging/discharging efficiency of Li electrodes and the number of cycles when using the electrolytic solution according to the present invention.
Claims (1)
電池用電解液において、前記電解液の添加材とし
て最大0.2モル／のピロールを用いたことを特
徴とするリチウム二次電池用電解液。1. An electrolytic solution for a lithium secondary battery, characterized in that a lithium salt is dissolved in an organic solvent, and a maximum of 0.2 mol/pyrrole is used as an additive in the electrolytic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58188954A JPS6079677A (en) | 1983-10-07 | 1983-10-07 | Electrolyte for lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58188954A JPS6079677A (en) | 1983-10-07 | 1983-10-07 | Electrolyte for lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6079677A JPS6079677A (en) | 1985-05-07 |
| JPH0564429B2 true JPH0564429B2 (en) | 1993-09-14 |
Family
ID=16232824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58188954A Granted JPS6079677A (en) | 1983-10-07 | 1983-10-07 | Electrolyte for lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6079677A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3636528A1 (en) * | 1986-10-27 | 1988-04-28 | Basf Ag | ELECTROLYT FOR ELECTROCHEMICAL CELLS |
| JPH09204932A (en) * | 1996-01-25 | 1997-08-05 | Fujitsu Ltd | Electrolyte for lithium secondary battery, and lithium secondary battery |
| CN102569896B (en) * | 2010-12-10 | 2015-01-14 | 比亚迪股份有限公司 | Lithium ion secondary battery and preparation method thereof |
| CN102881862B (en) * | 2011-07-12 | 2015-03-25 | 中国科学院上海硅酸盐研究所 | Protective metal anode structure and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3778310A (en) * | 1972-05-01 | 1973-12-11 | Du Pont | High energy density battery having unsaturated heterocyclic solvent containing electrolyte |
-
1983
- 1983-10-07 JP JP58188954A patent/JPS6079677A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3778310A (en) * | 1972-05-01 | 1973-12-11 | Du Pont | High energy density battery having unsaturated heterocyclic solvent containing electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6079677A (en) | 1985-05-07 |
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