JPH0355769A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH0355769A JPH0355769A JP1190331A JP19033189A JPH0355769A JP H0355769 A JPH0355769 A JP H0355769A JP 1190331 A JP1190331 A JP 1190331A JP 19033189 A JP19033189 A JP 19033189A JP H0355769 A JPH0355769 A JP H0355769A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- secondary battery
- organic solvent
- lithium secondary
- 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.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 4
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011149 active material Substances 0.000 claims abstract description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 3
- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 abstract description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- -1 lithium fluoroborate Chemical compound 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 238000010586 diagram Methods 0.000 description 1
- WMQDRXQOHUXCLT-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-arsane Chemical compound [Li+].[Li+].[O-][As]([O-])(F)=O WMQDRXQOHUXCLT-UHFFFAOYSA-L 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid 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
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〇
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
リグデン（ＭｏＳ２）、二酸化モリプダン（Ｍｏ０５）
、二酸化ｆｆ冫ガン（Ｍｎ０２）や五酸化バナジウム
（Ｖ２０５）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、過塩素酸リチウふ、ホウフッ化リチウム、六フッ
化ヒ酸リチウム等のリチウム塩を溶かしたプロビレンカ
ーボネートｌ＃液等が知られている。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a lithium secondary battery.〇Prior art and its problems Conventionally, a lithium secondary battery uses molygdenum disulfide (MoS2) as a positive electrode active material, Molypdan dioxide (Mo05)
, inorganic materials such as FF powder dioxide (Mn02) and vanadium pentoxide (V205), metal lithium and alloys that absorb and release lithium ions as negative electrodes, and lithium perchlorate, lithium fluoroborate, hexafluoride, etc. as electrolytes. A propylene carbonate l# solution in which a lithium salt such as lithium fluoroarsenate is dissolved is 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Ｗ４ｇ．が考えられるが、電池の二ネ〃ギ
ー密度を考慮した場合、金属リチウムを負極に用いた系
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
解したグロピレンカーボネートの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フィ
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。With these combinations of positive and negative electrodes and electrolytes, a large amount of W4g. However, when considering the two-energy density of the battery, a system using metallic lithium as the negative electrode is considered to be the most advantageous. Batteries using this solution as an electrolyte had a problem in that during charging and discharging, the battery capacity decreased early due to a decrease in charging and discharging efficiency, which was thought to be caused by lithium dendophytes.
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、上記の問題点に鑑み、充放電特性及び強負荷
特性を改良したリチウム二次電池を提供する二とを目的
とする。OBJECTS OF THE INVENTION In view of the above problems, the second object of the present invention is to provide a lithium secondary battery with improved charge/discharge characteristics and heavy load characteristics.
発明の構造
本発明は、上記目的を達或するべく、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、デロビレンカーボネート（以下、ＰＯと記
す。）、エチレンカーボネート（以下、ＥＯと記す。）
、及びジエチレンカーボネート（以下、ＤＥＯと記す。Structure of the Invention In order to achieve the above object, the present invention provides a negative electrode containing lithium as an active material, a positive electrode, and an organic solvent of an electrolytic solution in which a lithium salt is dissolved, delobylene carbonate (hereinafter referred to as PO). , ethylene carbonate (hereinafter referred to as EO)
, and diethylene carbonate (hereinafter referred to as DEO).
）よりなる混合液の有機溶媒からなる電解液を用いたリ
チウム二次電池である。) is a lithium secondary battery using an electrolyte solution consisting of an organic solvent mixture.
作用 各ａｌ溶媒の特性を第１表に示す。action Table 1 shows the characteristics of each Al solvent.
第 １ 表
一般的に、誘電率の高い溶媒ほど、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＃ｆｖ−着目すれば、ＰＯより誘電率の高
いＥＯを使用する方が有利と考えられる。Table 1 In general, the higher the dielectric constant of a solvent, the higher the degree of ionic dissociation of the solute, and therefore the higher the conductivity of the electrolyte. If we pay attention to this point #fv, it is considered more advantageous to use EO, which has a higher dielectric constant than PO.
ただし．ＫＯは、常温で固体てあるので１単独では用い
ることができない０そこでＳＰ○と混合することにより
常温でも液状を保持することを確詔し、電解液用溶媒と
して検討したところ、ＰＣ単独よりは電導度が高くなる
ことが判った０
また、この混合溶媒に、ＰＯ，ＫＯより粘度の低いＤＥ
Ｏを添加すること１こより、電導度がさら會こ高くなり
、リチウム負極の充放電効率もＰ Ｏ／Ｅ Ｏ系に比べ
大きく向上することが判った〇
実施例
以下、本発明の詳細について、寮施倒により説明する。however. Since KO is solid at room temperature, it cannot be used alone. Therefore, we determined that it would remain liquid even at room temperature by mixing it with SP○, and when we investigated it as a solvent for electrolytes, we found that it was better than PC alone. It was found that the conductivity increased.0 In addition, DE, which has a lower viscosity than PO and KO, was added to this mixed solvent.
It was found that by adding O, the electrical conductivity becomes much higher, and the charging and discharging efficiency of the lithium negative electrode is also greatly improved compared to the P O / E O system.The details of the present invention are as follows: This will be explained by the dormitory.
第１図は、正極に二酸化マンガン、負極に金（２）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は負極端子をなす封口板、３はケースと封口板を絶縁
するポリデ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
ンブラック１０重量部、及び結着剤であるボリテトラフ
μオロエチレン５重量部を混練し、厚さ０．７闘のシー
ト状に戒形した後、直径１５．ＯＵに打ち抜いた。その
後、？ｋＪ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５に圧着した。６は金属リチウムで
ありへ厚さ０．４ｗ，ｍ径１６報で負極集電体７に圧着
した。FIG. 1 shows a cross-sectional view of a lithium secondary battery using manganese dioxide as a positive electrode, gold(2) lithium as a negative electrode, and an electrolytic solution consisting of a nonaqueous solvent. 1 is a case that also serves as a positive terminal,
2 is a sealing plate that forms a negative electrode terminal, 3 is a polyderopylene gasket that insulates the case and the sealing plate, and 4 is a positive electrode, which contains 85 parts by weight of manganese dioxide, 10 parts by weight of acetylene black as a conductive material, and a binder. After kneading 5 parts by weight of borotetrafluoroethylene and forming it into a sheet with a thickness of 0.7mm, it was made into a sheet with a diameter of 15mm. It was punched out by OU. after that,? It was vacuum dried at kJ temperature and crimped onto the positive electrode current collector 5 which had been welded to the case 1 in advance. Reference numeral 6 is metal lithium, which has a thickness of 0.4 w and a diameter of 16 m, and is pressure-bonded to the negative electrode current collector 7.
８はポリプロピレン製氷孔膜からなるセパレータである
。8 is a separator made of a polypropylene ice-making hole membrane.
電解ａは、ＰＯ、ＥＯ、及ヒＤ Ｅ （１）３ｍ混合液
とし、混合比率を１＋２＋１とした。これらに、溶質と
して過塩素酸リチウム（Ｌｉ０１０４）を、１屹ｌｖ／
ｌ溶解したものを用いた●この様にして作製した電池▲
について、次の２積類の試験な夾施した。Electrolysis a was a 3 m mixture of PO, EO, and D E (1), with a mixing ratio of 1+2+1. To these, lithium perchlorate (Li0104) was added as a solute at 1 lv/
●Battery made in this way using melted material▲
Regarding this, the following two types of tests were conducted.
サイク／％／試験
試ｈ温度８２５℃
充電１走電流 ０．５Ｍ▲、終止電圧３．５ｖ放電：定
電流 １．０ ＃ｌＡ、終止電圧２．５ｖ低温放電拭験
賦験温ｉ１２５℃
放電二定電流 １０．Ｏｊｊｌ▲
比較例
電解液の溶媒をＰＯのみとした以外は、すべて実施例と
同様の電池Ｂを作製し、同様の方法て試験を実施した。Cycle/%/Test h Temperature 825℃ Charging 1 Running current 0.5M▲, Final voltage 3.5V Discharge: Constant current 1.0 #lA, Final voltage 2.5V Low temperature discharge wiping test Temperature i 125℃ Discharge 2 Constant current 10. Ojjl▲ Comparative Example Battery B was prepared in the same manner as in the example except that only PO was used as the solvent for the electrolytic solution, and tests were conducted in the same manner.
第２図に、サイクル試験の結果を示す。第２図から明ら
かなように、電池▲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 FIG. 2, it can be seen that the battery ▲ exhibits the effect of the present invention with less decrease in capacity than battery B.
第６図は、２５℃における電池Ａ及びＢの放電時の電圧
降下を釉査したものである●電池Ａは、電池Ｂに比べ電
圧降下が小さい。これは一本発明が強負荷に強いことを
示すものである。Figure 6 shows the voltage drop during discharge of batteries A and B at 25°C. ●Battery A has a smaller voltage drop than battery B. This shows that the present invention is resistant to heavy loads.
発明の効果
上述した如く、本発明は充放電特性及び低温ｔこおける
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.
【図面の簡単な説明】
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３図は、本発明及び従来の電池の
特性比較図である。BRIEF DESCRIPTION OF THE DRAWINGS 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 3 are characteristic comparison diagrams of a battery of the present invention and a conventional battery.
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、及びジエチルカーボネート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 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 a mixed solution consisting of propylene carbonate, ethylene carbonate, and diethyl carbonate. A lithium secondary battery featuring:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1190331A JPH0355769A (en) | 1989-07-21 | 1989-07-21 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1190331A JPH0355769A (en) | 1989-07-21 | 1989-07-21 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0355769A true JPH0355769A (en) | 1991-03-11 |
Family
ID=16256414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1190331A Pending JPH0355769A (en) | 1989-07-21 | 1989-07-21 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0355769A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0614240A1 (en) * | 1993-03-02 | 1994-09-07 | Saft | Rechargeable lithium containing electrochemical generator |
| JP2012204155A (en) * | 2011-03-25 | 2012-10-22 | Seiko Instruments Inc | Nonaqueous electrolyte secondary battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0212777A (en) * | 1988-06-29 | 1990-01-17 | Matsushita Electric Ind Co Ltd | Organic electrolyte secondary battery |
| JPH02172163A (en) * | 1988-12-23 | 1990-07-03 | Bridgestone Corp | Nonaqueous electrolyte battery |
-
1989
- 1989-07-21 JP JP1190331A patent/JPH0355769A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0212777A (en) * | 1988-06-29 | 1990-01-17 | Matsushita Electric Ind Co Ltd | Organic electrolyte secondary battery |
| JPH02172163A (en) * | 1988-12-23 | 1990-07-03 | Bridgestone Corp | Nonaqueous electrolyte battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0614240A1 (en) * | 1993-03-02 | 1994-09-07 | Saft | Rechargeable lithium containing electrochemical generator |
| FR2702311A1 (en) * | 1993-03-02 | 1994-09-09 | Accumulateurs Fixes | Electrolyte for rechargeable lithium generator. |
| WO1994020999A1 (en) * | 1993-03-02 | 1994-09-15 | Saft | Lithium rechargeable electrochemical generator |
| JP2012204155A (en) * | 2011-03-25 | 2012-10-22 | Seiko Instruments Inc | Nonaqueous electrolyte secondary battery |
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