JPS63307668A - Nonaqueous electrolyte cell - Google Patents
Nonaqueous electrolyte cellInfo
- Publication number
- JPS63307668A JPS63307668A JP14264287A JP14264287A JPS63307668A JP S63307668 A JPS63307668 A JP S63307668A JP 14264287 A JP14264287 A JP 14264287A JP 14264287 A JP14264287 A JP 14264287A JP S63307668 A JPS63307668 A JP S63307668A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- lithium
- aluminum
- active material
- battery
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 9
- -1 acetylacetone aluminum Chemical compound 0.000 claims abstract description 8
- 239000011149 active material Substances 0.000 claims abstract description 7
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- 239000007773 negative electrode material Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
イ、産業上の利用分野
本発明はリチウムを活物質とする負極と、非水電解液と
、酸化第二銅を活物質とする正極とを備える非水電解液
電池に関するものである。Detailed Description of the Invention A. Field of Industrial Application The present invention relates to a nonaqueous electrolyte battery comprising a negative electrode using lithium as an active material, a nonaqueous electrolyte, and a positive electrode using cupric oxide as an active material. It is related to.
口、従来の技術
リチウムを活物質とする非水電解液電池は高エネルギー
密度を有し且自己放電が少なめと−う利点t−NL、更
に例えば特開昭55−137669号会報に開示されて
−るように酸化第二銅を正極活物質に用−れば電a電圧
は約tsva度となプ、既存のアルカリ乾電池、水銀電
池、銀電池等と互換使用しうる利点があるので注目され
ている。Conventional technology Non-aqueous electrolyte batteries using lithium as an active material have the advantage of having high energy density and low self-discharge. If cupric oxide is used as the positive electrode active material, the electric voltage will be reduced to about TSVA, and it has the advantage of being compatible with existing alkaline batteries, mercury batteries, silver batteries, etc., which is attracting attention. ing.
ところが、この種電池は保存時において電池内に水分が
侵入しリチウム負極表面に酸化被膜が生成したり、又電
解液中に溶解した正極反応生成物としての金属銅がリチ
ウム負極表面に析出して内部抵抗が上昇し、電池容量が
低下するという問題かめる。However, when this type of battery is stored, moisture enters the battery and an oxide film is formed on the surface of the lithium negative electrode, and metal copper, which is a reaction product of the positive electrode dissolved in the electrolyte, is deposited on the surface of the lithium negative electrode. The problem is that internal resistance increases and battery capacity decreases.
ハ0発明が解決しようとする問題点
本発明はリチウムを負極活物質とし、酸化第二銅を正極
活物質とする非水電解液電池の保存特性を改善すること
を目的とする。Problems to be Solved by the Invention The present invention aims to improve the storage characteristics of a nonaqueous electrolyte battery that uses lithium as a negative electrode active material and cupric oxide as a positive electrode active material.
二0問題点を解決するための手段
非水電解液にアセチルアセトンアルミニウムを添加する
。アセチルアセトンアルミニウムの添2FJImとして
は非水電解液に対して001〜CL50モル/lの範囲
が好ましい。20 Means for Solving the Problems Aluminum acetylacetonate is added to the non-aqueous electrolyte. The amount of aluminum acetylacetonate added is preferably in the range of 001 to CL50 mol/l based on the non-aqueous electrolyte.
ホ0作 用
電解液中にアセチルアセトンアルミニウムを溶解すると
、アル建二りムイオンがリチウム負極表面に析出してア
ルミニウム被膜を形成し、このアルミニウム被膜の存在
によシリチウム負極と水分との反応が抑制されると共に
金属銅のリチウム負極表面への析出が抑制され内部抵抗
の上昇が抑えられる。When aluminum acetylacetonate is dissolved in an electrolytic solution, aluminum ions precipitate on the surface of the lithium negative electrode to form an aluminum film, and the presence of this aluminum film suppresses the reaction between the silium negative electrode and water. At the same time, precipitation of metallic copper on the surface of the lithium negative electrode is suppressed, and an increase in internal resistance is suppressed.
へ、実施例
正極は市販特級の酸化第二@90重量優に導電剤と°し
ての黒鉛5重量%及び結着剤としてのフッ素樹脂粉末5
重量*を夫々加え混合した後、この混合物を約2トン/
−の圧力で加圧底置して径15、QW、厚みtllsの
成型体を得、この成型体を200〜500℃の温度で熱
処塩したものである。The positive electrode of the example was made of commercially available special grade 2nd oxide @90% by weight, approximately 5% by weight of graphite as a conductive agent, and 5% by weight of fluororesin powder as a binder.
After adding and mixing the respective weights*, this mixture is weighed approximately 2 tons/
A molded body having a diameter of 15, QW, and thickness tlls was obtained by placing the molded body under pressure at a pressure of -, and this molded body was heat-treated at a temperature of 200 to 500°C.
負極はリテクム板を約α6Mの厚みに圧嬌しこのリチウ
ム圧延板を径15.01!lに打抜iたものである。For the negative electrode, a lithium plate was compressed to a thickness of about α6M, and this lithium rolled plate was made with a diameter of 15.01 mm. It is a punched piece.
而して、電解液はプロピレンカーボネートと1・ 2ジ
メトキシエタンとの混合溶媒に過塩素酸リチウムt−1
−etblI!溶解し、更にアセチルアセトンアルミニ
ウムをα1モル/is姦加したものを用i、又セパレー
タとしてポリプ四ビレン不織布ヲ用−て直径2α01l
l、厚み2.5Mの本発明電池(4)を作成した。The electrolyte was a mixed solvent of propylene carbonate and 1.2 dimethoxyethane with t-1 lithium perchlorate.
-etblI! A polypropylene nonwoven fabric was used as a separator, and the diameter was 2α01L.
A battery (4) of the present invention having a thickness of 2.5M and a thickness of 2.5M was prepared.
第1図は本発明電池の縦断面図を示し、(11は酸化第
二銅正極であって正極集電体(2)を介して正極ffr
(31の内底面に圧接されて−る。(4)はリチウム
負極でありて負極集電体(5)を介して負極缶(6)の
内底面に圧着されている。(7)はセパレータ、(81
は絶縁バッキング、(91は正極内借である。FIG. 1 shows a longitudinal cross-sectional view of the battery of the present invention (11 is a cupric oxide positive electrode, and the positive electrode ffr is connected through a positive electrode current collector (2).
(It is pressed to the inner bottom surface of the negative electrode can (6). (4) is a lithium negative electrode, which is pressed to the inner bottom surface of the negative electrode can (6) via the negative electrode current collector (5). (7) is a separator. , (81
is an insulating backing, (91 is a positive electrode inner layer.
ついで本発明電池の優位性f:調べるために、電解液に
アセチルアセトンアルミニウムを添加しなめことを除い
て他は本発明電池と同様の比較電池の)を作成した。尚
、本発明電池及び比較電池ともIE池戚立任、予じめ放
電容量の約5%を放電して完成電池とした。Next, in order to investigate the superiority f of the battery of the present invention, a comparative battery (f) which was the same as the battery of the present invention except that aluminum acetylacetonate was added to the electrolytic solution was prepared. The battery of the present invention and the comparative battery were prepared by IE Ikeaki, and were pre-discharged to about 5% of the discharge capacity to form completed batteries.
8g2図はこれらの電池を温区60°C1湿度90%の
条件下で保存した時の内部抵抗の経時変化を示す。Figure 8g2 shows the change in internal resistance over time when these batteries were stored at a temperature of 60° C. and a humidity of 90%.
第2図より本発明電池(A)は比較電池の)に比して保
存後の内部抵抗の上昇が抑制されて−るのがわかる。It can be seen from FIG. 2 that the increase in internal resistance after storage in the battery (A) of the present invention is suppressed compared to the comparative battery (A).
この理由は本発明電池の場合、電解液中に添加したアセ
チルアセトンアルミニウムにより、リチウム負極表面に
アルミニウム被膜が形成されこのアルミニウム被膜の存
在によって、リチウム負極と水分との反応或いは金属銅
のリチウム負極表面への析出が抑制されるためであると
考えられる。The reason for this is that in the case of the battery of the present invention, aluminum film acetylacetonate added to the electrolyte solution forms an aluminum film on the surface of the lithium negative electrode, and the presence of this aluminum film causes a reaction between the lithium negative electrode and moisture or a reaction between the lithium negative electrode and the surface of the lithium negative electrode made of metallic copper. This is thought to be because the precipitation of is suppressed.
尚、リチウム負極表面のアルミニウム被膜は放電時には
容易に除去されるため通常の放電反応には何ら支r4は
ない。Incidentally, since the aluminum film on the surface of the lithium negative electrode is easily removed during discharging, there is no problem in the normal discharging reaction.
又、第3図はアセチルアセトンアルミニウムの添加量を
変化させ、温度60℃、m度90%の条件下で1ケ月保
存した後の電池の内部抵抗を示し、第4図よりアセチル
アセトンアルミニウムの添加量としては(LO1〜0.
50の範囲が好まじりことがわかる。In addition, Figure 3 shows the internal resistance of the battery after changing the amount of aluminum acetylacetone added and storing it for one month at a temperature of 60°C and 90% m. From Figure 4, the amount of aluminum acetylacetone added is (LO1~0.
It can be seen that a range of 50 is preferable.
尚、リチウム負極の表面にアルミニウム被膜を形成する
手段として例えば特開昭61−294756号会報に開
示されているようにセパレータにアルミニウムを蒸着し
たり、或いは米国特許第4゜05へ886号に開示され
ているように負極表面にアル建ニウム箔を配置する方法
が提案されているが、これらは製造工程が煩雑であり、
又アルミニウム被膜の均一性に誰がある。As a means of forming an aluminum film on the surface of the lithium negative electrode, for example, aluminum may be vapor-deposited on a separator as disclosed in JP-A No. 61-294756, or as disclosed in U.S. Pat. No. 4.05-886. Methods have been proposed in which aluminum foil is placed on the surface of the negative electrode, but the manufacturing process for these is complicated;
Also, there is no question about the uniformity of the aluminum coating.
これに対して、本発明電池では単に非水電解液中に添加
するのみで均一性に優れたアルミニウム被膜を形成する
ことができるものである。In contrast, in the battery of the present invention, an aluminum coating with excellent uniformity can be formed simply by adding it to a non-aqueous electrolyte.
又、添加剤としてのアセチルアセトンアルミニウムの無
水塩は分節されに(匹ため十分な脱水処理&施すことが
でき、特に非水電解液電池において有益である。In addition, the anhydrous salt of acetylacetonaluminum as an additive can be sufficiently dehydrated and subjected to segmentation, and is particularly useful in non-aqueous electrolyte batteries.
ト0発明の効果
上述した如く、リチウムを負極活物質とし、酸化第二銅
を正極活@質とする非水電解液電池において、非水電解
液にアセチルアセトンアルミニウムを添加することによ
り、保存後の内部抵抗の上昇を抑制することができるも
のであり、その工業的価値は極めて大である。Effects of the Invention As mentioned above, in a non-aqueous electrolyte battery that uses lithium as a negative electrode active material and cupric oxide as a positive electrode active material, by adding acetylacetonaluminum to the non-aqueous electrolyte, the It is possible to suppress the increase in internal resistance, and its industrial value is extremely large.
第1図は本発明電池の縦断面図、第2図は電池の内部抵
抗と保存期間との関係を示す図、第5図はアセチルアセ
トンアルミニウムの添加室と電池の内部抵抗との関係を
示す図である。
はト・・酸化第二銅正極、 (2;・・・正極集電体。
(訃・・正極缶、(41・・・リチウム負極、 (51
・・・負極集電体、(6)・・・負極前、 (7)・・
・セパレータ、 (8)・・・絶縁バッキング、 囚・
・・本発明電池、 但)・・・比較電池。Figure 1 is a longitudinal cross-sectional view of the battery of the present invention, Figure 2 is a diagram showing the relationship between the internal resistance of the battery and storage period, and Figure 5 is a diagram showing the relationship between the addition chamber of aluminum acetylacetonate and the internal resistance of the battery. It is. Hato... Cupric oxide positive electrode, (2;... Positive electrode current collector. (Fan... Positive electrode can, (41... Lithium negative electrode, (51
... Negative electrode current collector, (6)... Before negative electrode, (7)...
・Separator, (8)...Insulating backing, prisoner・
...Battery of the present invention, however)...Comparison battery.
Claims (2)
酸化第二銅を活物質とする正極とを備えるものであって
、前記非水電解液にアセチルアセトンアルミニウムを添
加したことを特徴とする非水電解液電池。(1) A negative electrode using lithium as an active material, a non-aqueous electrolyte,
1. A non-aqueous electrolyte battery comprising a positive electrode containing cupric oxide as an active material, the non-aqueous electrolyte comprising aluminum acetylacetonate added to the non-aqueous electrolyte.
解液に対して0.01〜0.50モル/lの範囲である
特許請求の範囲第(1)項記載の非水電解液電池。(2) The non-aqueous electrolyte battery according to claim (1), wherein the amount of aluminum acetylacetone added is in the range of 0.01 to 0.50 mol/l relative to the non-aqueous electrolyte.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14264287A JPS63307668A (en) | 1987-06-08 | 1987-06-08 | Nonaqueous electrolyte cell |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14264287A JPS63307668A (en) | 1987-06-08 | 1987-06-08 | Nonaqueous electrolyte cell |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63307668A true JPS63307668A (en) | 1988-12-15 |
Family
ID=15320098
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14264287A Pending JPS63307668A (en) | 1987-06-08 | 1987-06-08 | Nonaqueous electrolyte cell |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63307668A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7049030B2 (en) | 2003-03-06 | 2006-05-23 | The Gillette Company | Battery |
-
1987
- 1987-06-08 JP JP14264287A patent/JPS63307668A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7049030B2 (en) | 2003-03-06 | 2006-05-23 | The Gillette Company | Battery |
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