JPS6324305B2 - - Google Patents
Info
- Publication number
- JPS6324305B2 JPS6324305B2 JP55109376A JP10937680A JPS6324305B2 JP S6324305 B2 JPS6324305 B2 JP S6324305B2 JP 55109376 A JP55109376 A JP 55109376A JP 10937680 A JP10937680 A JP 10937680A JP S6324305 B2 JPS6324305 B2 JP S6324305B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- positive electrode
- organic electrolyte
- electrolyte
- solute
- 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
Links
- 239000005486 organic electrolyte Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000203 mixture Substances 0.000 description 15
- 238000003860 storage Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
本発明は、正極活物質として、酸化銅、二酸化
マンガン、フツ化黒鉛等を使用し、リチウム、マ
グネシウム等の軽金属を負極活物質とし、γ−ブ
チロラクトン、テトラヒドロフラン、炭酸プロピ
レン、ジメトキシエタン、ジオキソラン等の単独
あるいは混合溶媒に、溶質として過塩素酸リチウ
ム、ホウフツ化リチウム等を溶解したいわゆる有
機電解液を用いる電池の製造法に係り、特に、電
池内部抵抗の減少、及び電池貯蔵性能を向上する
ことを目的とする。Detailed Description of the Invention The present invention uses copper oxide, manganese dioxide, graphite fluoride, etc. as the positive electrode active material, uses light metals such as lithium and magnesium as the negative electrode active material, and uses γ-butyrolactone, tetrahydrofuran, propylene carbonate, etc. , dimethoxyethane, dioxolane, etc., alone or in a mixed solvent, with lithium perchlorate, lithium borofluoride, etc. dissolved as a solute. The purpose is to improve storage performance.
非水の有機電解液を用いるこの種の電池は、正
極には、活物質となる金属酸化物などの粉末を導
電材としての炭素粉未と混合し、加圧成形した正
極合剤成形体を用いており、電解液は、電池構成
時に、負極、セパレータ、前記正極合剤成形体に
注入される。 This type of battery uses a nonaqueous organic electrolyte, and the positive electrode is a positive electrode mixture molded by mixing powder such as a metal oxide as an active material with carbon powder as a conductive material and press-molding the mixture. The electrolytic solution is injected into the negative electrode, the separator, and the positive electrode mixture molded body during battery construction.
この方法で用いられる電解液は、電池用として
最適な導電率を有するもので、通常１モル／付
近の溶質濃度のものであり、また正極合剤成形体
内へ電解液の浸透する速度の兼合いから、注入電
解液は、必ずしも十分といえない量で封口され、
完成電池とされていた。 The electrolyte used in this method has the optimum conductivity for batteries, and usually has a solute concentration of around 1 mol/mole/mole, and also has a balance between the speed at which the electrolyte penetrates into the positive electrode mixture molded body. Therefore, the injected electrolyte is sealed in an amount that is not necessarily sufficient.
It was considered a completed battery.
このようにして作られる現用電池は、一応の特
性を示すが、詳細に検討すると、予相以上に内部
抵抗が高く、また貯蔵に伴う劣化も大きいなどの
欠点を有していた。この原因は、電極内部に電解
液の入る余地が若干残されたままで封口電池とさ
れていること、また、電解液中の溶質の正極合剤
体への吸着から、電池封口後電解液中の溶質の濃
度分布が発生し、電解液バルクにおける溶質濃度
が不均一に希釈されていることなどによると考え
られる。従つて、電池封口後の電池の内部抵抗が
予想以上に高めになり、また貯蔵に伴う電池内部
抵抗の増大、あるいは、放電容量の減少となつて
現れる。この傾向は高温貯蔵時において著しく、
正極活物質による電解液の吸収、特に溶質の吸着
が性能劣化に大きく影響していることがわかつ
た。 Current batteries manufactured in this manner exhibit certain characteristics, but when examined in detail, they have drawbacks such as higher internal resistance than the pre-phase battery and greater deterioration during storage. This is due to the fact that the battery is sealed with some room left for the electrolyte to enter inside the electrode, and also because the solute in the electrolyte is adsorbed to the positive electrode mixture. This is thought to be due to the occurrence of solute concentration distribution, and the solute concentration in the electrolyte bulk being diluted non-uniformly. Therefore, the internal resistance of the battery after sealing becomes higher than expected, and the internal resistance of the battery increases or the discharge capacity decreases due to storage. This tendency is remarkable during high-temperature storage;
It was found that the absorption of electrolyte by the positive electrode active material, especially the adsorption of solute, has a large effect on performance deterioration.
本発明は、電池内部抵抗の減少、及び電池貯蔵
性能を向上させることを目的とし、正極合剤成形
体を、あらかじめ高濃度の溶質を含む電解液中に
十分含浸させた後、通常の電池構成を行うことを
特徴とする。 The present invention aims to reduce battery internal resistance and improve battery storage performance.The present invention aims to reduce battery internal resistance and improve battery storage performance.After a positive electrode mixture molded body is sufficiently immersed in an electrolytic solution containing a high concentration of solute, a normal battery configuration is used. It is characterized by doing the following.
本発明を実施するには、加圧成形した正極合剤
成形体を、その体積に対して十分な上記高濃度電
解液中に浸し、場合によつては、真空含浸を行
い、電解液が正極合剤成形体内部へ十分に浸透し
て平衝に達するまで放置する。そして、このよう
に十分に電解液が浸透した正極合剤成形体、負
極、及びセパレータで電池を構成し、通常濃度の
電解液を注入し、密封して完成電池とする。 To carry out the present invention, a pressure-molded positive electrode mixture molded body is immersed in the above-mentioned high-concentration electrolytic solution sufficient for its volume, and in some cases, vacuum impregnation is performed so that the electrolytic solution is absorbed into the positive electrode. The mixture is left until it has sufficiently penetrated into the molded body and reached equilibrium. Then, a battery is constructed from the positive electrode mixture molded body, the negative electrode, and the separator into which the electrolytic solution has sufficiently permeated, and the electrolytic solution of a normal concentration is injected and sealed to form a completed battery.
このように構成した電池では、この処理を施さ
ない電池と比較して電解液量を増すことができ、
かつ電池構成後に発生する電解質の正極合剤成形
体への吸着による濃度分布の偏よりも防ぎうるこ
とから、前記従来例で示したような欠点を補うこ
とができる。 In a battery configured in this way, the amount of electrolyte can be increased compared to a battery that is not subjected to this treatment.
In addition, since it is possible to prevent the concentration distribution from becoming uneven due to adsorption of the electrolyte to the positive electrode mixture molded body after battery construction, it is possible to compensate for the drawbacks shown in the conventional example.
以下、本発明を実施例のボタン型電池により説
明する。 Hereinafter, the present invention will be explained using a button type battery as an example.
第１図において、１はステンレス鋼板を打抜き
加工した電池ケース、２は同材質の封口板、３は
封口板の内側に圧着した負極リチウムシートであ
る。４は正極合剤成形体で、酸化銅を導電材の黒
鉛と混合して加圧成形したもので、ポリプロピレ
ン不織布からなるセパレータ５がかぶせてある。
６はポリエチレン製封口パツキングである。電解
液には炭酸プロピレンと１，２−ジメトキシエタ
ンとの等容積混合溶媒に１モル／の過塩素酸リ
チウムを溶解させたものを用い、これを注液後電
池を密封する。 In FIG. 1, 1 is a battery case made by punching a stainless steel plate, 2 is a sealing plate made of the same material, and 3 is a negative electrode lithium sheet crimped to the inside of the sealing plate. Reference numeral 4 denotes a positive electrode mixture molded body, which is formed by pressure molding a mixture of copper oxide and graphite as a conductive material, and is covered with a separator 5 made of a polypropylene nonwoven fabric.
6 is a polyethylene sealing packing. The electrolytic solution used was one obtained by dissolving 1 mole of lithium perchlorate in an equal volume mixed solvent of propylene carbonate and 1,2-dimethoxyethane, and after injecting this solution, the battery was sealed.
ここに用いた酸化銅正極合剤成形体は、前記混
合溶媒に過塩素酸リチウムを飽和（濃度約2.2モ
ル／）させた電解液中に１昼夜浸し、電池構成
時に取り出したものである。 The molded copper oxide positive electrode mixture used here was immersed in an electrolytic solution in which the mixed solvent was saturated with lithium perchlorate (concentration: about 2.2 mol/2) for one day and was taken out at the time of battery construction.
第２図は、上記の処理を施した合剤を用いた本
発明の電池Ａと、同サイズの上記の処理を施さな
い合剤を用いた従来の電池Ｂのそれぞれの電池封
口直後の内部抵抗と、60℃30日貯蔵後の内部抵抗
を比較したものである。これから、本発明による
浸漬処理を施した電池は、従来の方法による電池
と比較して、電池内部抵抗の３〜20％の減少がみ
られ、かつ電池貯蔵性能もかなり向上しているこ
とがわかる。 Figure 2 shows the internal resistance immediately after battery sealing of a battery A of the present invention using a mixture subjected to the above treatment and a conventional battery B of the same size using a mixture not subjected to the above treatment. This is a comparison of the internal resistance after storage at 60°C for 30 days. From this, it can be seen that the batteries subjected to the immersion treatment according to the present invention have a 3 to 20% reduction in battery internal resistance and a considerable improvement in battery storage performance compared to batteries treated with the conventional method. .
実施例では正極活物質として酸化銅を用いた
が、二酸化マンガン、フツ化黒鉛等についても、
上記と同様の効果が得られた。 In the examples, copper oxide was used as the positive electrode active material, but manganese dioxide, graphite fluoride, etc.
The same effect as above was obtained.
以上のように、本発明によれば、内部抵抗及び
貯蔵性能の優れた有機電解液電池を得ることがで
きる。 As described above, according to the present invention, an organic electrolyte battery with excellent internal resistance and storage performance can be obtained.
第１図は本発明の実施例におけるボタン型電池
の縦断面図、第２図は本発明の電池Ａと従来の電
池Ｂの電池封口直後の内部抵抗と60℃30日貯蔵後
の内部抵抗を比較した図である。
Fig. 1 is a longitudinal cross-sectional view of a button-type battery according to an embodiment of the present invention, and Fig. 2 shows the internal resistance of battery A of the present invention and conventional battery B immediately after the battery was sealed and after storage at 60°C for 30 days. This is a comparative diagram.
Claims (1)
機電解液とからなる電池の製造法であつて、前記
正極を電池構成前に高濃度の溶質を含む有機電解
液中で浸漬処理することを特徴とする有機電解液
電池の製造法。 ２ 前記浸漬処理に用いる有機電解液の溶質濃度
が、少なくとも電池用有機電解液よりも高いこと
を特徴とする特許請求の範囲第１項記載の有機電
解液電池の製造法。[Scope of Claims] 1. A method for manufacturing a battery comprising a negative electrode using a light metal as an active material, a positive electrode, and an organic electrolyte, the method comprising: placing the positive electrode in an organic electrolyte containing a high concentration of solute before constructing the battery; 1. A method for producing an organic electrolyte battery characterized by immersion treatment. 2. The method for manufacturing an organic electrolyte battery according to claim 1, wherein the solute concentration of the organic electrolyte used in the immersion treatment is at least higher than that of the organic electrolyte for batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10937680A JPS5734676A (en) | 1980-08-08 | 1980-08-08 | Manufacture of organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10937680A JPS5734676A (en) | 1980-08-08 | 1980-08-08 | Manufacture of organic electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5734676A JPS5734676A (en) | 1982-02-25 |
| JPS6324305B2 true JPS6324305B2 (en) | 1988-05-20 |
Family
ID=14508665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10937680A Granted JPS5734676A (en) | 1980-08-08 | 1980-08-08 | Manufacture of organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5734676A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0165794A3 (en) * | 1984-06-18 | 1987-05-13 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Light metal (cfx)n electrochemical cells having high current density and high power density |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5588266A (en) * | 1978-12-26 | 1980-07-03 | Hitachi Maxell Ltd | Method for preparing non-aqueous electrolyte cell |
-
1980
- 1980-08-08 JP JP10937680A patent/JPS5734676A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5588266A (en) * | 1978-12-26 | 1980-07-03 | Hitachi Maxell Ltd | Method for preparing non-aqueous electrolyte cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5734676A (en) | 1982-02-25 |
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