JPH0340380A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH0340380A JPH0340380A JP1174694A JP17469489A JPH0340380A JP H0340380 A JPH0340380 A JP H0340380A JP 1174694 A JP1174694 A JP 1174694A JP 17469489 A JP17469489 A JP 17469489A JP H0340380 A JPH0340380 A JP H0340380A
- Authority
- JP
- Japan
- Prior art keywords
- dme
- lithium
- electrolyte
- charging
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 18
- 229910052744 lithium Inorganic materials 0.000 title claims description 18
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 5
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims abstract description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 7
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-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
- 239000011230 binding agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VKJKOXNPYVUXNC-UHFFFAOYSA-K trilithium;trioxido(oxo)-$l^{5}-arsane Chemical compound [Li+].[Li+].[Li+].[O-][As]([O-])([O-])=O VKJKOXNPYVUXNC-UHFFFAOYSA-K 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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】 産業上の利用分野 本発明は、リチウム二次電池に関するものである。[Detailed description of the invention] Industrial applications The present invention relates to a lithium secondary battery.
従来技術とその問題点
従来、リチウム二次電池は、正極活物質として二硫化モ
リブデン(MoS2)〜二酸化モリブデン(Mo03)
、二酸化マンガン(Mn02 )や五酸化バナジウム(
V2O3)等の無機物質、負極として金属リチウムやリ
チウムイオンな吸蔵、放出する合金、さらに電解液とし
て、過塩素酸リチウム、ホウフッ化すチウム、六フフ化
ヒ酸リチウム等のリチウム塩を溶かしたプロピレンカー
ボネートとジメトキシエタンの混合溶液等が知られてい
る。Conventional technology and its problems Conventionally, lithium secondary batteries use molybdenum disulfide (MoS2) to molybdenum dioxide (Mo03) as positive electrode active materials.
, manganese dioxide (Mn02) and vanadium pentoxide (
Inorganic substances such as V2O3), metal lithium and alloys that absorb and release lithium ions as negative electrodes, and propylene carbonate in which lithium salts such as lithium perchlorate, lithium borofluoride, and lithium arsenate hexafluoride are dissolved as electrolytes. Mixed solutions of dimethoxyethane and dimethoxyethane are known.
これらの正、負極及び電解液の組み合わせにより、非常
にたくさんの構成が考えられるが、電池のエネ〃ギー密
度を考慮した場合、金属リチウムを負極&用いた系が最
も有利と考えられるO
しかし、金属リチウムを負極に〜過塩素酸リチウムを溶
解したプロピレンカーボネートとジメトキシエタンの混
合溶液を電解液として用いた電池は、充放電をすると早
期にリチウムデンドライトが原因と考えられる充放電効
率の低下により、電池容量が減少するという問題が発生
した。A large number of configurations are possible depending on the combination of these positive and negative electrodes and electrolytes, but when considering the energy density of the battery, a system using metallic lithium as the negative electrode is considered to be the most advantageous. Batteries that use metallic lithium as the negative electrode - a mixed solution of propylene carbonate and dimethoxyethane in which lithium perchlorate is dissolved, as the electrolyte, quickly decrease in charging and discharging efficiency, which is thought to be caused by lithium dendrites, when charging and discharging. A problem occurred in which the battery capacity decreased.
また、上記の電解液を用いた電池は、低温での強負荷特
性が不十分であった。In addition, batteries using the above electrolyte had insufficient strong load characteristics at low temperatures.
発明の目的
本発明は、上記の間Q点Ic#iみ、充放電特性及び低
温における強負荷特性を改良したリチウム二次電池を提
供することを目的とする。OBJECTS OF THE INVENTION The object of the present invention is to provide a lithium secondary battery with improved Q point Ic#i, charge/discharge characteristics, and heavy load characteristics at low temperatures.
発明の構造
本発明は、上記目的を遺戒するぺ<、リチウムを活物質
とする負極と、正極と、リチウム塩を溶解した電解液の
有機溶媒が、プロピレンカーボネート(以下、PCと記
す。)、エチレンカーボネート(以下、ECと記す。)
、ジメトキシエタン(以下、DMEと記す。)、及び2
−メチルテトラヒドロフラン(以下、2Me−THFと
記す。)よりなる混合液の有I!溶媒からなる電解液を
用いたリチウム二次電池である。Structure of the Invention The present invention has a negative electrode containing lithium as an active material, a positive electrode, and an organic solvent of an electrolyte in which a lithium salt is dissolved in propylene carbonate (hereinafter referred to as PC). , ethylene carbonate (hereinafter referred to as EC)
, dimethoxyethane (hereinafter referred to as DME), and 2
-Presence of a mixed liquid consisting of methyltetrahydrofuran (hereinafter referred to as 2Me-THF)! This is a lithium secondary battery that uses an electrolyte consisting of a solvent.
作用 各種溶媒の特性を第1表に示す。action Table 1 shows the properties of various solvents.
一般的に、誘電率の高い溶媒はど、溶質のイオン解離度
が高いため、電解液の電導度も高くなるという特長があ
る。この点だけに着目すれば、PC/DI!系より誘電
率の高いEOを使用する、KO/DIE系の方が有利と
考えられる。Generally, a solvent with a high dielectric constant has a high degree of ionic dissociation of the solute, and therefore has the advantage that the conductivity of the electrolytic solution is also high. If you focus only on this point, PC/DI! The KO/DIE system, which uses EO having a higher dielectric constant than the KO/DIE system, is considered to be more advantageous.
ただし、]eO/DIE系は、低温でEOが凝固し用い
ることができない。そこで、PO,EC。However, the eO/DIE system cannot be used because EO solidifies at low temperatures. Therefore, PO, EC.
さらにDMEを混合することにより低温でも液状を保持
することをrIm詔し、電解液用溶媒として検討したと
ころ、PO/DIE系よりは電導度がさらに高くなり、
強負荷特性が向上することが判った。Furthermore, by mixing DME, it was proposed that it would maintain its liquid state even at low temperatures, and when it was investigated as a solvent for electrolyte solutions, it was found that the conductivity was even higher than that of the PO/DIE system.
It was found that the heavy load characteristics were improved.
さらに、POlICO及びDIEの混合溶媒に2Me−
THFを加え4種湯合とすると充放電効率が大きく向上
し、PO/DIE系に比べ、充放電による容量低下が抑
制されることが判った。Furthermore, 2Me-
It was found that when THF was added to form a four-type mixture, the charging and discharging efficiency was greatly improved, and the decrease in capacity due to charging and discharging was suppressed compared to the PO/DIE system.
実施例 以下、本発明の詳細について、実施例により説明する。Example Hereinafter, the details of the present invention will be explained with reference to Examples.
第1図は1正極に二酸化マンガン、負極に金属リチウム
、及び非水溶媒からなる電解液を用いたリチウム二次電
池の断面図を示す。1は正極端子を兼ねたケース、2は
負w1端子をなす封目板、3はケースと封口板を絶縁す
るポリプロピレン製ガスケット、4は正極であり、これ
は二酸化マンガン85重量部、導電材であるアセチレン
プフフク10!1量部、及び結着剤であるポリテトヲフ
〃オロエチレン5重量部を混練し、厚さ0.711mの
シート状に成形した後、直径15.0情に打ち抜いた。FIG. 1 shows a cross-sectional view of a lithium secondary battery using manganese dioxide as a positive electrode, metallic lithium as a negative electrode, and an electrolytic solution consisting of a nonaqueous solvent. 1 is a case that also serves as a positive electrode terminal, 2 is a sealing plate that forms a negative w1 terminal, 3 is a polypropylene gasket that insulates the case and the sealing plate, and 4 is a positive electrode, which is made of 85 parts by weight of manganese dioxide and a conductive material. 10.1 parts by weight of a certain acetylene powder and 5 parts by weight of polytethofluoroethylene as a binder were kneaded and formed into a sheet with a thickness of 0.711 m, which was then punched out to a diameter of 15.0 m.
その後、高温真空乾燥し、あらかじめケース1に溶接し
ておいた正極集電体5tC圧着した。6は金属リチウム
であり、厚さ0.4鵠、直径16mで負極集電体7に圧
着した。Thereafter, it was vacuum dried at high temperature, and the positive electrode current collector 5tC, which had been welded to case 1 in advance, was crimped. Reference numeral 6 denotes metallic lithium, which was crimped onto the negative electrode current collector 7 with a thickness of 0.4 m and a diameter of 16 m.
8はポリプロピレン製微孔膜からなるセパレータである
。8 is a separator made of a microporous membrane made of polypropylene.
電解液は、PC%EC,DIE、及び2Me−THFの
4種混合液とし、混合比率を1 +2:172とした。The electrolytic solution was a mixture of four types: PC%EC, DIE, and 2Me-THF, and the mixing ratio was 1 + 2:172.
これらに、溶質として過地素酸リチウム(LiO104
)を% 1モ/L//1溶解したものを用いた。These contain lithium peroxide (LiO104) as a solute.
) was dissolved at % 1 mo/L//1.
この様にして作製した電池ムについて、次の2m類の試
験を実施した。The following 2m type test was conducted on the battery thus produced.
サイクル試験
試験温度:25℃
充電=定電流 0.5*ム、終止電圧 3.5v放電:
定電流 1.0*ム、終止電圧 2.4v低温放電試験
試験温度:0℃
放t:定電流 10.0*ム
比較例
電解液の溶媒をPC,及びDIE、混合比率を1=1と
した以外は、すべて実施例と同様の電池Bを作製し、同
様の方法で試験を実施した。Cycle test Test temperature: 25°C Charging = constant current 0.5*mm, final voltage 3.5v Discharging:
Constant current 1.0*mm, final voltage 2.4v Low temperature discharge test Test temperature: 0°C Release t: Constant current 10.0*mu Comparative example The solvent of the electrolyte was PC and DIE, and the mixing ratio was 1=1. Battery B was manufactured in the same manner as in Example except for the above, and the test was conducted in the same manner.
第2図に、サイクル試験の結果を示す。図から明らかな
ように、電池ムは電池Bに比べ容量の低下が少なく本発
明の効果が発揮されているのがわかる。Figure 2 shows the results of the cycle test. As is clear from the figure, it can be seen that the effect of the present invention is exerted in Battery M with less decrease in capacity than Battery B.
第5図は、ot:tcおける電池ム及びBの放電時の電
圧降下を調査したものである。電池ムは、電池Bに比べ
低温での電圧降下が小さい。これは、本発明が低温にお
ける強負荷心強いことを示すものである。FIG. 5 shows an investigation of the voltage drop during discharge of battery M and B in ot:tc. Battery M has a smaller voltage drop than Battery B at low temperatures. This shows that the present invention is reliable under heavy loads at low temperatures.
発明の効果
上述した如く、本発明は充放電特性及び低温における強
負荷特性を改良したリチウム二次電池を提供することが
出来るので、その工業的価値は極めて大である。Effects of the Invention As described above, the present invention can provide a lithium secondary battery with improved charge/discharge characteristics and heavy load characteristics at low temperatures, and therefore has extremely great industrial value.
第1図は゛、本発明の実施例におけるリチウム二次電池
の縦断面図、第2図、第5図は、本発明及び従来の電池
の特性比較図である。
1・・・ケー7−2・・・封口板
3・・・ガスケット 4・・・正極
5・・・正極集電体 6・・・負極FIG. 1 is a longitudinal cross-sectional view of a lithium secondary battery according to an embodiment of the present invention, and FIGS. 2 and 5 are characteristic comparison diagrams of a battery of the present invention and a conventional battery. 1... Case 7-2... Sealing plate 3... Gasket 4... Positive electrode 5... Positive electrode current collector 6... Negative electrode
Claims (1)
溶解した有機溶媒からなる電解液とを備え、電解液の有
機溶媒がプロピレンカーボネート、エチレンカーボネー
ト、ジメトキシエタン、及び2−メチルテトラヒドロフ
ランよりなる混合液を用いたことを特徴とするリチウム
二次電池。A mixture comprising a negative electrode containing lithium as an active material, a positive electrode, and an electrolytic solution consisting of an organic solvent in which a lithium salt is dissolved, and the organic solvent of the electrolytic solution is composed of propylene carbonate, ethylene carbonate, dimethoxyethane, and 2-methyltetrahydrofuran. A lithium secondary battery characterized by using a liquid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1174694A JPH0340380A (en) | 1989-07-06 | 1989-07-06 | Lithium secondary battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1174694A JPH0340380A (en) | 1989-07-06 | 1989-07-06 | Lithium secondary battery |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0340380A true JPH0340380A (en) | 1991-02-21 |
Family
ID=15983043
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1174694A Pending JPH0340380A (en) | 1989-07-06 | 1989-07-06 | Lithium secondary battery |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0340380A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5983413A (en) * | 1994-12-28 | 1999-11-16 | Toto Ltd. | High performance flush toilet |
-
1989
- 1989-07-06 JP JP1174694A patent/JPH0340380A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5983413A (en) * | 1994-12-28 | 1999-11-16 | Toto Ltd. | High performance flush toilet |
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