JPH053112B2 - - Google Patents
Info
- Publication number
- JPH053112B2 JPH053112B2 JP58138776A JP13877683A JPH053112B2 JP H053112 B2 JPH053112 B2 JP H053112B2 JP 58138776 A JP58138776 A JP 58138776A JP 13877683 A JP13877683 A JP 13877683A JP H053112 B2 JPH053112 B2 JP H053112B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- charge
- liclo
- charging
- propylene carbonate
- 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
- 239000008151 electrolyte solution Substances 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 24
- 238000007599 discharging Methods 0.000 description 23
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 22
- 239000003792 electrolyte Substances 0.000 description 13
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- QLRKASHXFNIPLZ-UHFFFAOYSA-M benzyl-dimethyl-phenylazanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[N+](C)(C)CC1=CC=CC=C1 QLRKASHXFNIPLZ-UHFFFAOYSA-M 0.000 description 7
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 4
- 150000003839 salts Chemical class 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
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 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
- NJQFCQXFOHVYQJ-PMACEKPBSA-N BF 4 Chemical compound C1([C@@H]2CC(=O)C=3C(O)=C(C)C4=C(C=3O2)[C@H](C(C)C)C2=C(O4)C(C)=C(C(C2=O)(C)C)OC)=CC=CC=C1 NJQFCQXFOHVYQJ-PMACEKPBSA-N 0.000 description 1
- -1 CF 3 SO 3 Li Inorganic materials 0.000 description 1
- 229910020366 ClO 4 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
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 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
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- ICXXXLGATNSZAV-UHFFFAOYSA-N butylazanium;chloride Chemical compound [Cl-].CCCC[NH3+] ICXXXLGATNSZAV-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 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
- 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
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-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LiClO4／プロピレンカーボネイトにテトラ−
ｎ−ブチルアンモニウムクロライドとテトラグラ
イムを混合する試み〔Power Sources 5661頁、
アカデミツクプレス、1975〕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. In an attempt to improve the charging and discharging efficiency of Li electrodes, LiClO 4 /propylene carbonate and tetra-
Attempt to mix n-butylammonium chloride and tetraglyme [Power Sources page 5661,
Academic Press, 1975], but these are 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たリ
チウム電池用電解液において、前記電解液の添加
剤として、少なくとも１個の芳香環を有する四級
アンモニウム塩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. It is characterized by the use of ammonium salt.
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、少なくとも１個の芳香環を有する
アンモニウム塩を用いることにより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 using an ammonium salt having at least one aromatic ring in an electrolytic solution in which a lithium salt is dissolved in an organic solvent, a lithium secondary battery with good charge/discharge characteristics of the Li electrode can be realized.
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、本発明によれば、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少なくとも１個
の芳香環を有する四級アンモニウム塩が用いられ
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. A quaternary ammonium salt having at least one aromatic ring is used as an additive for an electrolytic solution prepared by dissolving the above in an organic solvent.
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LiClO4、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, LiClO 4 , 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
加剤は少なくとも１個の芳香環を有する四級アン
モニウム塩である。このような四級アンモニウム
塩としては、例えばトリメチルフエニルアンモニ
ウム、トリメチルベンジルアンモニウム、ジメチ
ルフエニルアンモニウム等のハロゲン化塩、BF4
塩、ClO4塩等の群から選択された一種以上を挙
げることができる。前述の四級アンモニウム塩の
具体例としては、たとえばトリメチルフエニルア
オニウムクロライド、トリメチルベンジルアンモ
ニウムクロライド及びジメチルベンジルフエニル
アンモニウムクロライドからなる群より選択され
た一種以上を挙げることができる。 In the present invention, the additive added to the non-aqueous electrolyte is a quaternary ammonium salt having at least one aromatic ring. Examples of such quaternary ammonium salts include halogenated salts such as trimethylphenylammonium, trimethylbenzylammonium, and dimethylphenylammonium, BF 4
Examples include one or more selected from the group of salts, ClO 4 salts, and the like. Specific examples of the above-mentioned quaternary ammonium salt include one or more selected from the group consisting of trimethylphenylammonium chloride, trimethylbenzylammonium chloride, and dimethylbenzylphenylammonium chloride.
非水電解液に添加する四級アンモニウム塩の量
は0.2Mを上限とするのが好ましい。0.2Mを超え
ると、Liの充放電特性が劣化する虞があるからで
ある。 The upper limit of the amount of quaternary ammonium salt added to the non-aqueous electrolyte is preferably 0.2M. This is because if it exceeds 0.2M, 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0.1Mのトリメチルベンジルアンモニウム
クロライド〔（CH3）3C6H5CH2NCl〕と1M
LiClO4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.
We assembled a battery using Pt and deposited Li on the Pt electrode to measure the charge/discharge characteristics of the Li electrode. The electrolyte contains 0.1M trimethylbenzylammonium chloride [(CH 3 ) 3 C 6 H 5 CH 2 NCl] and 1M
LiClO dissolved in propylene carbonate was used.
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、1M
LiClO4／0.1Mトリメチルベンジルアンモニウム
クロライド／プロピレンカーボネイトを用いた場
合の充放電特性を示したものであり、(b)は参考例
の1M LiClO4／プロピレンカーボネイトを用い
た場合の充放電特性を示したものである。 Figure 1 is a diagram showing the relationship between the charge/discharge efficiency of Li electrodes and the number of cycles.
The figure shows the charge-discharge characteristics when using LiClO 4 /0.1M trimethylbenzylammonium chloride/propylene carbonate, and (b) shows the charge-discharge characteristics when using the reference example 1M LiClO 4 /propylene carbonate. It is something that
第１図から判る様に、トリメチルベンジルアン
モニウムクロライド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 trimethylbenzylammonium chloride significantly improves the charging and discharging characteristics of the Li electrode.
実施例 ２
電解液として1Mトリメチルフエニルアンモニ
ウムクロライド〔（CH3）3C6H5NCl〕と1M
LiClO4をプロピレンカーボネイトに溶解させた
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 1M trimethylphenylammonium chloride [(CH 3 ) 3 C 6 H 5 NCl] and 1M as electrolytes
The charge and discharge characteristics of Li were measured in the same manner as in Example 1, except that LiClO 4 dissolved in propylene carbonate was used.
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、1M
LiClO4／0.1Mトリメチルフエニルアンモニウム
クロライド／プロピレンカーボネイトを用いた場
合の充放電特性を示したものであり、(b)は参考例
の1M LiClO4／プロピレンカーボネイトを用い
た場合の充放電特性を示したものである。 Figure 2 is a diagram showing the relationship between the charge/discharge efficiency of Li electrodes and the number of cycles.
It shows the charge-discharge characteristics when using LiClO 4 /0.1M trimethylphenylammonium chloride/propylene carbonate, and (b) shows the charge-discharge characteristics when using the reference example 1M LiClO 4 /propylene carbonate. This is what is shown.
第２図から判る様に、トリメチルフエニルアン
モニウムクロライド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 trimethylphenylammonium chloride significantly improves the charging and discharging characteristics of the Li electrode.
実施例 ３
電解液として、1Mジメチルベンジルフエニル
アンモニウムクロライド
〔（CH3）2C6H5C6H5CH2NCl〕と1M LiClO4をプ
ロピレンカーボネイト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 3 The same procedure was carried out except that 1M dimethylbenzylphenyl ammonium chloride [(CH 3 ) 2 C 6 H 5 C 6 H 5 CH 2 NCl] and 1M LiClO 4 dissolved in propylene carbonate were used as the electrolyte. The charging and discharging characteristics of Li were measured in the same manner as in Example 1.
第３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、1M
LiClO4／0.1Mジメチルベンジルフエニルアンモ
ニウムクロライド／プロピレンカーボネイトを用
いた場合の充放電特性を示したものであり、(b)は
参考例の1M LiClO4／プロピレンカーボネイト
を用いた場合の充放電特性を示したものである。 Figure 3 is a diagram showing the relationship between the charge/discharge efficiency of Li electrodes and the number of cycles.
Charging and discharging characteristics when using LiClO 4 /0.1M dimethylbenzylphenyl ammonium chloride / propylene carbonate are shown, and (b) shows the charging and discharging characteristics when using 1M LiClO 4 /propylene carbonate as a reference example. This is what is shown.
第３図から判る様に、ジメチルベンジルフエニ
ルアンモニウムクロライド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. 3, the use of an electrolytic solution containing dimethylbenzylphenylammonium chloride significantly improves the charging and discharging characteristics of the Li electrode.
実施例 ４
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0.1Mのトリメチルベンジルアンモニウム
クロライドと1M LiClO4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 4 Pt electrode is used as a working electrode, Li is used as a counter electrode and Li is used as a reference electrode.
We assembled a battery using Pt and deposited Li on the Pt electrode to measure the charge/discharge characteristics of the Li electrode. The electrolyte used was 0.1M trimethylbenzylammonium chloride and 1M LiClO 4 dissolved in propylene carbonate.
測定は、まず５ｍＡ／cm2の定電流で１分間、
Pt極上にLiを析出させ充電した後、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 at a constant current of 5 mA/cm 2 for 1 minute.
After depositing Li on Pt electrode and charging, 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 was determined from the change in the potential of the Pt electrode, and calculated from the ratio to the amount of electricity required to discharge Li deposited on the Pt electrode as Li + ions.
第４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、1M
LiClO4／0.1Mトリメチルベンジルアンモニウム
クロライド／プロピレンカーボネイトを用いた場
合の充放電特性を示したものであり、(b)は参考例
の1M LiClO4／プロピレンカーボネイトを用い
た場合の充放電特性を示したものである。 Figure 4 is a diagram showing the relationship between the charge/discharge efficiency of Li electrodes and the number of cycles.
The figure shows the charge-discharge characteristics when using LiClO 4 /0.1M trimethylbenzylammonium chloride/propylene carbonate, and (b) shows the charge-discharge characteristics when using the reference example 1M LiClO 4 /propylene carbonate. It is something that
第４図から判る様に、トリメチルベンジルアン
モニウムクロライド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. 4, the use of an electrolytic solution containing trimethylbenzylammonium chloride significantly improves the charging and discharging characteristics of the Li electrode.
実施例 ５
電解液として、0.1Mトリメチルフエニルアン
モニウムクロライドと1M LiClO4をプロピレン
カーボネイト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 5 The charging and discharging characteristics of Li were measured in the same manner as in Example 1 except that 0.1M trimethylphenylammonium chloride and 1M LiClO 4 dissolved in propylene carbonate were used as the electrolyte.
第５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、1M
LiClO4／0.1Mトリメチルフエニルアンモニウム
クロライド／プロピレンカーボネイトを用いた場
合の充放電特性を示したものであり、(b)は参考例
の1M LiClO4／プロピレンカーボネイトを用い
た場合の充放電特性を示したものである。 Figure 5 is a diagram showing the relationship between the charge/discharge efficiency of Li electrodes and the number of cycles; in the figure, (a) is the 1M
It shows the charge-discharge characteristics when using LiClO 4 /0.1M trimethylphenylammonium chloride/propylene carbonate, and (b) shows the charge-discharge characteristics when using the reference example 1M LiClO 4 /propylene carbonate. This is what is shown.
第５図から判る様に、トリメチルフエニルアン
モニウムクロライド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. 5, the use of an electrolytic solution containing trimethylphenylammonium chloride significantly improves the charging and discharging characteristics of the Li electrode.
実施例 ６
電解液として、0.1Mジメチルベンジルフエニ
ルアンモニウムクロライドと1MのLiClO4をプロ
ピレンカーボネイトに溶解させたものを用いた以
外は実施例４と同様にして、Liの充放電特性を測
定した。Example 6 The charging and discharging characteristics of Li were measured in the same manner as in Example 4 except that 0.1M dimethylbenzylphenylammonium chloride and 1M LiClO 4 dissolved in propylene carbonate were used as the electrolyte.
第６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、1M
LiClO4／0.1Mジメチルベンジルフエニルアンモ
ニウムクロライド／プロピレンカーボネイトを用
いた場合の充放電特性を示したものであり、図中
(b)は参考例の1M LiClO4／プロピレンカーボネ
イトを用いた場合の充放電特性を示したものであ
る。 FIG. 6 is a diagram showing the relationship between the charging/discharging efficiency of Li electrodes and the number of cycles. In the figure, (a) is the 1M
This figure shows the charge/discharge characteristics when using LiClO 4 /0.1M dimethylbenzylphenylammonium chloride/propylene carbonate.
(b) shows the charge/discharge characteristics when using 1M LiClO 4 /propylene carbonate as a reference example.
第６図から判る様に、ジメチルベンジルフエニ
ルアンモニウムクロライド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. 6, the use of an electrolytic solution containing dimethylbenzylphenylammonium chloride significantly improves the charging and discharging characteristics of the Li electrode.
参考例
本発明の効果を明らかにするため、参考例とし
て以下の実験を行つた。Reference Example In order to clarify the effects of the present invention, the following experiment was conducted as a reference example.
電解液として、0.1Mのテトラｎ−ブチルアン
モニウムクロライドと1MのLiClO4をプロピレン
カーボネイトに溶解させたものを用いた以外は実
施例と同様にして、Li極の充放電特性を測定し
た。 The charging and discharging characteristics of the Li electrode were measured in the same manner as in the example except that 0.1M tetra n-butylammonium chloride and 1M LiClO 4 dissolved in propylene carbonate were used as the electrolyte.
第７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)は上記電解液を用いた
場合の充放電特性を示したものであり、(b)は1M
LiClO4／プロピレンカーボネイト中での充放電
特性を示したものである。第７図より明らかなよ
うに、テトラｎ−ブチルアンモニウムクロライド
を添加した系では、無添加に比して特性は向上し
ているが、芳香環を有する四級アンモニウム塩を
添加した場合より、特性は劣つていることが判
る。 Figure 7 is a diagram showing the relationship between the charging and discharging efficiency of Li electrodes and the number of cycles, in which (a) shows the charging and discharging characteristics when the above electrolyte is used, and (b) 1M
This figure shows the charge/discharge characteristics in LiClO 4 /propylene carbonate. As is clear from Figure 7, in the system to which tetra-n-butylammonium chloride is added, the properties are improved compared to the system without the addition, but the properties are better than in the case where quaternary ammonium salt having an aromatic ring is added. is found to be inferior.
実施例 ７
電解液として、0.1Mトリメチルベンジルアン
モニウムクロライドと0.75MのLiClO4をγ−ブチ
ロラクトンに溶解させたものを用いた以外は実施
例４と同様にしてLiの充放電特性を測定した。Example 7 The charging and discharging characteristics of Li were measured in the same manner as in Example 4 except that 0.1M trimethylbenzylammonium chloride and 0.75M LiClO 4 dissolved in γ-butyrolactone were used as the electrolyte.
第８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、0.75M
LiClO4／0.1Mトリメチルベンジルアンモニウム
クロライド／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り、(b)は参考例の
0.75M LiClO4／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. 8 is a diagram showing the relationship between the charge/discharge efficiency of Li electrodes and the number of cycles. In the figure, (a) is the 0.75M
It shows the charge/discharge characteristics when using LiClO 4 /0.1M trimethylbenzylammonium chloride/γ-butyrolactone, and (b) is the reference example.
This figure shows the charge/discharge characteristics when using 0.75M LiClO 4 /γ-butyrolactone.
第５図から判る様に、トリメチルベンジルアン
モニウムクロライド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. 5, the use of an electrolytic solution containing trimethylbenzylammonium chloride 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、少なくとも１個の芳香環を有する四
級アンモニウム塩を添加剤として用いる事によ
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 a quaternary ammonium salt having at least one aromatic ring as an additive in a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent, It is possible to provide a non-aqueous electrolyte for lithium secondary batteries that has excellent charging and discharging characteristics for Li electrodes.
第１図から第６図及び第８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り、第７図は参考例のLi極
の充放電効率とサイクル数の関係を示す図であ
る。
Figures 1 to 6 and Figure 8 are diagrams showing the relationship between the charge/discharge efficiency of Li electrodes and the number of cycles when using the electrolyte solution according to the present invention, and Figure 7 is a diagram showing the relationship between charging and discharging efficiency of Li electrodes and the number of cycles when the electrolyte solution according to the present invention is used. It is a figure showing the relationship between discharge efficiency and number of cycles.
Claims (1)
電池用電解液において、前記電解液の添加剤とし
て少なくとも１個の芳香環を有する四級アンモニ
ウム塩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 lithium secondary batteries, characterized in that a quaternary ammonium salt having at least one aromatic ring is used as an additive in an electrolytic solution for lithium batteries in which a lithium salt is dissolved in an organic solvent. liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58138776A JPS6030065A (en) | 1983-07-29 | 1983-07-29 | Electrolyte for lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58138776A JPS6030065A (en) | 1983-07-29 | 1983-07-29 | Electrolyte for lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6030065A JPS6030065A (en) | 1985-02-15 |
| JPH053112B2 true JPH053112B2 (en) | 1993-01-14 |
Family
ID=15229924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58138776A Granted JPS6030065A (en) | 1983-07-29 | 1983-07-29 | Electrolyte for lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6030065A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5634590U (en) * | 1979-08-27 | 1981-04-04 | ||
| JPS63184269A (en) * | 1987-01-27 | 1988-07-29 | Nippon Telegr & Teleph Corp <Ntt> | Lithium battery electrolyte |
| US4764440A (en) * | 1987-05-05 | 1988-08-16 | Eveready Battery Company | Low temperature molten compositions |
| JP2761212B2 (en) * | 1988-04-08 | 1998-06-04 | 旭硝子株式会社 | Energy storage device using non-aqueous electrolyte |
| JPH02281572A (en) * | 1989-04-24 | 1990-11-19 | Matsushita Electric Ind Co Ltd | Electrolyte for lithium secondary battery |
| US5188914A (en) * | 1991-10-09 | 1993-02-23 | Eveready Battery Company, Inc. | Low temperature molten compositions comprised of quaternary alkyl phosphonium salts |
| JP2004146346A (en) * | 2002-08-28 | 2004-05-20 | Nisshinbo Ind Inc | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery |
| WO2004051784A1 (en) * | 2002-11-29 | 2004-06-17 | Yuasa Corporation | Nonaqueous electrolyte and nonaqueous electrolyte battery |
-
1983
- 1983-07-29 JP JP58138776A patent/JPS6030065A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6030065A (en) | 1985-02-15 |
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