JPH01159971A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH01159971A JPH01159971A JP62318109A JP31810987A JPH01159971A JP H01159971 A JPH01159971 A JP H01159971A JP 62318109 A JP62318109 A JP 62318109A JP 31810987 A JP31810987 A JP 31810987A JP H01159971 A JPH01159971 A JP H01159971A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- secondary battery
- lithium secondary
- carbonate
- aqueous 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
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 8
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 7
- 229910052738 indium Inorganic materials 0.000 claims abstract description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 125000005587 carbonate group Chemical group 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910020159 Pb—Cd Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-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
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000743 fusible alloy Inorganic materials 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 239000008188 pellet Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
２・＼−ノ
本発明は、移動用直流電源、バックアップ電源などに用
いるリチウム二次電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application 2.\-The present invention relates to a lithium secondary battery used for a mobile DC power source, a backup power source, and the like.
従来の技術
リチウムを負極として用いる二次電池は、高密度エネル
ギー、高信頼性を有することが期待され、近年多くの研
究機関で開発されている。たとえば、正極としてクロム
酸化物、マンガン酸化物、あるいは２硫化チタン、２硫
化モリブデンなどのカルコゲン化合物、さらには、ポリ
アセチレン、ポリアニリンなどの導電性ポリマー々ど、
数多ぐの物質が検討されている。壕だ負極としては、ア
ルミニウム合金、あるいは鉛、ビスマス、カドミウム。BACKGROUND OF THE INVENTION Secondary batteries using lithium as a negative electrode are expected to have high energy density and high reliability, and have been developed by many research institutes in recent years. For example, as a positive electrode, chromium oxide, manganese oxide, chalcogen compounds such as titanium disulfide and molybdenum disulfide, and conductive polymers such as polyacetylene and polyaniline, etc.
A large number of substances are being considered. For the negative electrode, use aluminum alloy, lead, bismuth, or cadmium.
インジウム、スズかどの可融合金が検討１れている。Fusible metals such as indium and tin are being considered.
発明が解決しようとする問題点
しかし、これらの材料は必ずしも十分に生かされておら
ず、リチウム二次電池の技術としては、まだまだこれか
らの段階であり、良い組み合わせが望まれている。Problems to be Solved by the Invention However, these materials are not always fully utilized, and lithium secondary battery technology is still in its infancy, and a good combination is desired.
３・＼−・
本発明では、正極に五酸化ニオブを用いる系で、充放電
特性や、放電々圧々どから適切な電解液や負極合金々ど
の組み合わせ条件を選定するものである。3.\-- In the present invention, the system uses niobium pentoxide for the positive electrode, and the combination conditions such as an appropriate electrolytic solution and negative electrode alloy are selected based on charge/discharge characteristics, discharge pressure, etc.
問題点全解決するだめの手段
正極に五酸化ニオブ、負極にアルミニウム合金を用い、
電解液として、過塩素酸リチウムを溶解した非水溶媒を
用いるものである。非水溶媒としては、プロピレンカー
ボネート（ＰＣ；）やプチレンカーボネー）（ＢＣ）、
エチレンカーボネート（［；）などカーボネート基を有
する脂肪族炭化水素を用いる。さらに１，２−ジメトキ
シエタン（ＤＭＥ）、１．２−ジエトキシエタン（ＩＩ
ＥＥ）１．２−エトキシメトキシエタン（ＥＭＫ ）な
どを補助溶媒として用いることができる。The only way to solve all the problems is to use niobium pentoxide for the positive electrode and aluminum alloy for the negative electrode.
A non-aqueous solvent in which lithium perchlorate is dissolved is used as the electrolyte. Examples of non-aqueous solvents include propylene carbonate (PC) and butylene carbonate (BC),
An aliphatic hydrocarbon having a carbonate group such as ethylene carbonate ([;) is used. Furthermore, 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (II
EE) 1,2-ethoxymethoxyethane (EMK) etc. can be used as a co-solvent.
才だ、アルミニウム合金としては、アルミニウムの強度
やリチウムのアルミニウム固相拡散ケ向よさせるだめに
、マンガン、銀、マグネシウム。However, as aluminum alloys, manganese, silver, and magnesium are used because they interfere with the strength of aluminum and the solid phase diffusion of lithium into aluminum.
インジウムなどを添加したものを用いることができる。A material to which indium or the like is added can be used.
作用
上記の組み合わせにより、五酸化ニオブの充放電性能を
向上はせることができる。種々横割したところ、たとえ
ば電解液として、ＬｉＧ１０４ｆ浴解したγブチロラク
トン（γＢＬ）’７５用いた場合や、ホウフッ化リチウ
ム（ＬＩＢＦ ４） ｆ溶解したＰＣを用いた場合、良
好な充放電特性を得ることができず、上記した様に、電
解質にＬｉＧｇ０４ｉ溶解したｐｃやＥＣあるいはＤＭ
ＥやＤＥＥ 、ＥＭＥを添加したもののみ良好な充放電
特性を示すことがわかった。理由はさだがではないが、
五酸化ニオブのような酸化物へのリチウムの充放電反応
に対して過塩素酸塩とカーボネート基を有する脂肪族炭
化水素やグライム類が副反応を起こさず、促進作用をも
つものと考えられる。Effect: The above combination can improve the charging and discharging performance of niobium pentoxide. After various cross-sections, it was found that, for example, when using γ-butyrolactone (γBL) '75 dissolved in LiG104f as the electrolyte, or when using PC dissolved in lithium borofluoride (LIBF4), good charge-discharge characteristics were obtained. As mentioned above, PC, EC, or DM dissolved in LiGg04i in the electrolyte
It was found that only those to which E, DEE, and EME were added showed good charge/discharge characteristics. The reason is not Sadaga, but
It is thought that aliphatic hydrocarbons and glymes with perchlorate and carbonate groups have a promoting effect on the charging and discharging reaction of lithium to oxides such as niobium pentoxide without causing side reactions.
１だ、負極合金としてはＢ１−Ｐｂ −０６合金などの
可融合金も可能であるが、純リチウムに対しｏ、Ｂｙ付
近の電位で、電池電圧がやや低く、さらに高温中で過放
電などをくり返した場合鉛、カドミウムイオンが電解液
中に溶解し充放電性能を劣５・＼−／
化させてし甘うことがある。これらの点でアルミニウム
合金の場合電位が純リチウムに対し０．３ｖ付近で、電
池電圧がｐｂ −ｃａ金合金較べ約０．５Ｖ近く高くな
る土、耐腐食性に強く、高電位をかけても、アルミニウ
ムは、分解や溶解はせず安定である。これらのことよシ
アルミニウム合金負極ヲ対極とした場合、高い信頼性を
得ることができる。1. B1-Pb-06 alloy and other fusible alloys are also possible as negative electrode alloys, but the battery voltage is somewhat low at potentials near o and By compared to pure lithium, and over-discharging at high temperatures is also possible. If this is repeated, lead and cadmium ions may dissolve in the electrolyte, resulting in poor charge/discharge performance. In these respects, in the case of aluminum alloy, the potential is around 0.3V compared to pure lithium, and the battery voltage is about 0.5V higher than that of PB-CA gold alloy. , aluminum is stable and does not decompose or dissolve. For these reasons, high reliability can be obtained when a sialuminium alloy negative electrode is used as the counter electrode.
実施例
実施例１
第１図は正極に五酸化ニオブ、負極にリチウム・アルミ
ニウム合金及び、過塩素酸リチウム全溶解した非水溶媒
を電解液として用いた本発明のリチウム二次電池の縦断
面図である。図中１は正極端子を兼ねたケース、２はケ
ースと同じ材料を打ち抜き加工した負極端子を兼ねた封
口板、３はケースと封口板とを絶縁するポリプロピレン
製ガスケットである。４は正極であり、五酸化ニオブ８
５重量部、導電剤であるカーボンブラック５重量部、フ
ッ素樹脂ディスバージョン固形分１０重量部を混練し乾
燥したあと粉砕し、直径１４゜０ｍｍ、厚さ６・・−７
０、ｓ ｍｍのペレットに成形したものである。６はカ
ーボン塗布層よりなる正極集電体である。６はり１４．
０ｍｍ、厚さ○ｊｍｍの大きさである。７は負極集電体
であり、線径０．１ｍｍで６０メツシユのステンレス鋼
のネットヲ用いた。８はポリプロピレン製微孔膜からな
るセパレータテアル。Examples Example 1 Figure 1 is a longitudinal cross-sectional view of a lithium secondary battery of the present invention using niobium pentoxide as a positive electrode, a lithium-aluminum alloy as a negative electrode, and a non-aqueous solvent in which lithium perchlorate is completely dissolved as an electrolyte. It is. In the figure, 1 is a case that also serves as a positive electrode terminal, 2 is a sealing plate that is punched out of the same material as the case and also serves as a negative electrode terminal, and 3 is a polypropylene gasket that insulates the case and the sealing plate. 4 is the positive electrode, niobium pentoxide 8
5 parts by weight of carbon black, which is a conductive agent, and 10 parts by weight of fluororesin dispersion solid content are kneaded, dried, and crushed to form pellets with a diameter of 14°0 mm and a thickness of 6...-70, s mm. It is molded into. 6 is a positive electrode current collector made of a carbon coating layer. 6 beams 14.
It has a size of 0mm and a thickness of ○jmm. 7 is a negative electrode current collector, and a 60-mesh stainless steel net with a wire diameter of 0.1 mm was used. 8 is a separator seal made of a microporous membrane made of polypropylene.
電解液は第１表の如く調整したものを用いた。The electrolyte solution prepared as shown in Table 1 was used.
第 １ 表
７へ−７
これらの電解液を用いた電池について以下に示す条件で
充放電をした。To Table 1-7 Batteries using these electrolytes were charged and discharged under the conditions shown below.
各サイクルでえられた放電々気容量を第２図に示しだ。Figure 2 shows the discharge capacity obtained in each cycle.
実施例２
電解液全第１表のＮｏ、 １とし、リチウム合金負極組
成を第２表の如く調整し、他は実施例１とまったく同じ
とした。Example 2 The electrolytic solution was set to No. 1 in Table 1, the lithium alloy negative electrode composition was adjusted as shown in Table 2, and the other conditions were exactly the same as in Example 1.
第 ２ 表
これらの電池について、実施例１と同じ条件で充放電を
し、初期サイクルの平均維持電圧（ｖ）及び各サイクル
の容量変化を調べた。この結果を第３〜４図に示しだ。Table 2 These batteries were charged and discharged under the same conditions as in Example 1, and the average maintenance voltage (v) in the initial cycle and the change in capacity in each cycle were examined. The results are shown in Figures 3 and 4.
第２図の結果より明らか々ように、電解液が、ＬｉＣβ
０４を溶解したＰＣ，１Ｇ、ＥＣ系は充放電サイクルが
３ｏ○サイクル前後得られているが、γＢＬやＬｉＢＦ
４を用いたものは１つたく充放電ができない。さらに、
Ｎ（１１，２，３より補助溶媒としてＤＭＥ、ＤＥＪＥ
ＭＥは用いても問題が々い。これらの補助溶媒は粘度が
低く、製造時や、強負荷特性に役立つものである。As is clear from the results shown in Figure 2, the electrolyte is LiCβ
PC, 1G, and EC systems in which 04 was dissolved have a charge/discharge cycle of around 3o○ cycles, but γBL and LiBF
4 cannot be charged and discharged one by one. moreover,
N (DME, DEJE as co-solvents from 11,2,3)
Even if ME is used, there are many problems. These co-solvents have a low viscosity and are useful during manufacturing and for high load characteristics.
一方、第３〜４図から、Ｂｉ −Ｐｂ−Ｃｄ合金では平
均電圧が低く、２〜１ｖでは得られる電気容量も小さく
、サイクル寿命も小さい。捷だ、アルミニウム合金系に
おいても、Ｎｏ、 ９〜１１にみられるように、マンガ
ン、銀、マグネシウムのいずれかとインジウムを添加し
たものはサイクル寿命が伸びている。これは、マンガン
、銀、マグネシウムなどはアルミニウムの強度全向上さ
せ、インジウムはアルミニウム中のリチウムの固相拡散
’に促９′＼−７
進させる作用があるだめと考えられる。On the other hand, from FIGS. 3 and 4, in the Bi-Pb-Cd alloy, the average voltage is low, the obtained electric capacity is small at 2 to 1 V, and the cycle life is also short. Even among aluminum alloys, as seen in Nos. 9 to 11, those containing manganese, silver, or magnesium and indium have a longer cycle life. This is thought to be because manganese, silver, magnesium, etc. have the effect of improving the overall strength of aluminum, and indium has the effect of accelerating the solid phase diffusion of lithium in aluminum.
発明の効果
以上のように、本発明は充放電サイクル寿命にすぐれる
リチウム二次電池を提供するものである。Effects of the Invention As described above, the present invention provides a lithium secondary battery with excellent charge/discharge cycle life.
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図及び第４図は実施例におけるリ
チウム二次電池の特性比較図である。
４・・・・・正極、６・・・・・・負極、８・・・・・
セパレータ。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名４−
正 極
第２図
ナイクル歎FIG. 1 is a longitudinal cross-sectional view of a lithium secondary battery in an example of the present invention, and FIGS. 2, 3, and 4 are characteristic comparison diagrams of lithium secondary batteries in an example. 4...Positive pole, 6...Negative pole, 8...
Separator. Name of agent: Patent attorney Toshio Nakao and 1 other person 4-
Positive pole 2
Claims (3)
ルミニウム合金負極と、電解液とからなり、前記電解液
が、溶質として過塩素酸リチウム、溶媒としてカーボネ
ート基を有する脂肪族炭化水素を含有する非水溶媒を用
いることを特徴としたリチウム二次電池。(1) Consisting of a positive electrode mainly made of niobium pentoxide, a lithium-absorbing aluminum alloy negative electrode, and an electrolytic solution, the electrolytic solution contains lithium perchlorate as a solute and an aliphatic hydrocarbon having a carbonate group as a solvent. A lithium secondary battery characterized by using a non-aqueous solvent.
インジウム及びマグネシウムよりなる群から選んだ少な
くとも１種を含有する特許請求の範囲第１項記載のリチ
ウム二次電池。(2) Lithium storage aluminum alloy is manganese, silver,
The lithium secondary battery according to claim 1, which contains at least one member selected from the group consisting of indium and magnesium.
、１．２−ジエトキシエタンあるいは１、２−エトキシ
メトキシエタンを含有する特許請求の範囲第１項記載の
リチウム二次電池。(3) The lithium secondary battery according to claim 1, wherein the electrolytic solution contains 1,2-dimethoxyethane, 1,2-diethoxyethane, or 1,2-ethoxymethoxyethane as a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62318109A JPH01159971A (en) | 1987-12-16 | 1987-12-16 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62318109A JPH01159971A (en) | 1987-12-16 | 1987-12-16 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01159971A true JPH01159971A (en) | 1989-06-22 |
Family
ID=18095592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62318109A Pending JPH01159971A (en) | 1987-12-16 | 1987-12-16 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01159971A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01200562A (en) * | 1988-02-05 | 1989-08-11 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte cell |
-
1987
- 1987-12-16 JP JP62318109A patent/JPH01159971A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01200562A (en) * | 1988-02-05 | 1989-08-11 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte cell |
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