JPS6155740B2 - - Google Patents
Info
- Publication number
- JPS6155740B2 JPS6155740B2 JP53130183A JP13018378A JPS6155740B2 JP S6155740 B2 JPS6155740 B2 JP S6155740B2 JP 53130183 A JP53130183 A JP 53130183A JP 13018378 A JP13018378 A JP 13018378A JP S6155740 B2 JPS6155740 B2 JP S6155740B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- batteries
- battery
- cuo
- discharge
- 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
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 27
- 229960004643 cupric oxide Drugs 0.000 claims description 13
- 239000011149 active material Substances 0.000 claims description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 229940112669 cuprous oxide Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000010949 copper Substances 0.000 description 14
- 238000003860 storage Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 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
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (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第二銅を用いた
非水電解液電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-aqueous electrolyte battery using cupric oxide as a positive electrode active material.
非水電解液電池の正極活物質として、二酸化マ
ンガン、フツ化炭素、クロム酸銀、塩化チオニ
ル、亜硫酸ガスなどを用いた電池は、その作動電
圧が3Vと高く3V系電池と云はれているに対し、
酸化第二銅（CuO），三酸化ビスマス（Bi2O3）、
四三酸化鉛（Pb3O4）などを用いた電池は、作動
電圧が1.5Vと低いため1.5V系電池と云われ、従
来汎用されている酸化銀電池や水銀電池と互換使
用し得る特徴がある。 Nonaqueous electrolyte batteries that use manganese dioxide, carbon fluoride, silver chromate, thionyl chloride, sulfur dioxide gas, etc. as positive electrode active materials have operating voltages as high as 3V, and are called 3V batteries. For,
Cupric oxide (CuO), bismuth trioxide (Bi 2 O 3 ),
Batteries using trilead tetroxide (Pb 3 O 4 ), etc., are called 1.5V batteries because their operating voltage is as low as 1.5V, and they have the characteristic that they can be used interchangeably with conventionally widely used silver oxide batteries and mercury batteries. There is.
しかし前記酸化第二銅を正極活物質とする電池
は、保存特性が従来の乾電池に比して劣るという
欠点があつた。 However, batteries using cupric oxide as a positive electrode active material have a disadvantage in that storage characteristics are inferior to conventional dry batteries.
本発明は酸化第二銅を活物質とする正極中に少
量の酸化第一銅（Cu2O）を添加することにより
保存特性を改善するものである。 The present invention improves storage characteristics by adding a small amount of cuprous oxide (Cu 2 O) to a positive electrode containing cupric oxide as an active material.
以下本発明の実施例を説明する。 Examples of the present invention will be described below.
正極は市販のCuO粉末85ｇに、CuO2O粉末５
ｇ，炭素粉末７ｇ，フツ素樹脂粉末３ｇを混合
し、この混合粉末材を極板寸法に加圧成型後減圧
乾燥する。従来品はCu2Oを混入することなく同
様の方法で正極を作成した。 The positive electrode was 85g of commercially available CuO powder, and 5g of CuO 2 O powder.
g, 7 g of carbon powder, and 3 g of fluororesin powder are mixed, and this mixed powder material is pressure-molded to the size of an electrode plate and then dried under reduced pressure. The positive electrode of the conventional product was created using the same method without mixing Cu 2 O.
負極はリチウム圧延板を極板寸法に打抜いて作
成し、電解液はプロピレンカーボネイトとジメト
キシエタンの混合溶媒に1M濃度の過塩素酸リチ
ウムを溶解したものを、又セパレータはポリプロ
ピレン不織布を用いた。 The negative electrode was made by punching a rolled lithium plate to the plate size, the electrolyte was a solution of 1M lithium perchlorate in a mixed solvent of propylene carbonate and dimethoxyethane, and the separator was made of polypropylene nonwoven fabric.
図面は上記で作成した扁平電池（容量
500mAH）の放電特性を製造直後（実線）及び60
℃１ケ月保存後（点線）に分けて示したもので、
イは本発明電池ロは従来電池の場合である。 The drawing shows the flat battery (capacity) created above.
500mAH) immediately after manufacturing (solid line) and 60mAH)
After storage for 1 month at °C (dotted line),
A is a case of a battery according to the present invention B is a case of a conventional battery.
この特性図からわかるように本発明電池と従来
電池とは製造直後の放電曲線に有意差は認めがた
いが、60℃１ケ月保存後の特性には明らかに差が
見られ、放電容量で約15〜25％、作動電圧で0.05
〜0.08V本発明が優れている。 As can be seen from this characteristic diagram, there is no significant difference in the discharge curves between the battery of the present invention and the conventional battery immediately after manufacture, but there is a clear difference in the characteristics after storage at 60°C for one month, with a discharge capacity of approximately 15-25%, 0.05 at working voltage
~0.08V The present invention is superior.
このような保存特性の改善が見られるのは正極
に起因するものと考えられる。 This improvement in storage characteristics is considered to be due to the positive electrode.
即ちLi―CuO系電池の放電反応は
2Li＋CuO→Cu＋Li2O
であつて、CuOは金属Cuまで還元されてその過
程で１価のCu2Oを生成しないのに対し、保存中
の自己放電による反応は、下記のようにCuOが
次第に分解してO2を放出しながら１価のCu2Oに
一部変化する。 In other words, the discharge reaction of a Li-CuO battery is 2Li + CuO → Cu + Li 2 O, and CuO is reduced to metal Cu and does not produce monovalent Cu 2 O in the process, whereas the reaction due to self-discharge during storage is As shown below, CuO gradually decomposes and partially changes to monovalent Cu 2 O while releasing O 2 .
2CuO→Cu2O＋1/2O2 ……(1)
1/2O2＋2Li→Li2O
このCu2Oは正極活物質となり得ないのでこの
量が自己放電量となると共に分離したO2が拡散
して対極のLiを放電反応生成物であるLi2Oに酸
化する。 2CuO→Cu 2 O+1/2O 2 ...(1) 1/2O 2 +2Li→Li 2 O Since this Cu 2 O cannot be used as a positive electrode active material, this amount becomes the self-discharge amount and the separated O 2 diffuses. The Li on the counter electrode is oxidized to Li 2 O, which is a discharge reaction product.
本発明では正極中に最初からCu2Oを適量添加
しているので(1)の反応式の平衡定数が変化して→
方向の反応が抑制され、活物質となりえない
Cu2Oの生成即ち自己放電量が低下し、更に分離
O2の減少によりLi極の自己放電（Li2Oの生成）
及びLi極における酸化被膜の形成（電池内部抵抗
の増大）が抑制され、保存特性の改善が達成され
る。尚、添加するCu2Oの量は10％以下が適当で
これを越えると正極の充てん密度（mAH／cc）
が減少する。又Cu2Oは粉末で添加する代りに銅
塩の形で合剤中に混し熱分解によりCu2Oに変え
ることも可能である。 In the present invention, since an appropriate amount of Cu 2 O is added to the positive electrode from the beginning, the equilibrium constant of the reaction equation (1) changes →
The directional reaction is suppressed and it cannot become an active material.
The generation of Cu 2 O, that is, the amount of self-discharge, decreases and further separation occurs.
Self-discharge of Li electrode due to decrease in O2 (generation of Li2O )
Also, the formation of an oxide film on the Li electrode (increase in battery internal resistance) is suppressed, and storage characteristics are improved. The amount of Cu 2 O to be added is preferably 10% or less; if it exceeds this, the filling density of the positive electrode (mAH/cc) will decrease.
decreases. Moreover, instead of adding Cu 2 O in powder form, it is also possible to mix it into the mixture in the form of a copper salt and convert it into Cu 2 O by thermal decomposition.
上述の如く本発明は酸化第二銅（CuO）を活
物質とする正極合剤中に少量の酸化第一銅
（Cu2O）を添加することにより保存特性を改善す
るもので、酸化銀電池や水銀電池と互換使用可能
な非水電解液電池の性能向上に資する所大なるも
のがある。 As mentioned above, the present invention improves storage characteristics by adding a small amount of cuprous oxide (Cu 2 O) to a positive electrode mixture containing cupric oxide (CuO) as an active material. There are many things that contribute to improving the performance of non-aqueous electrolyte batteries that can be used interchangeably with mercury batteries and mercury batteries.
図面は本発明電池の製造直後及び60℃１ケ月保
存後の放電特性を従来電池と比較して示すもので
ある。
The drawing shows the discharge characteristics of the battery of the present invention immediately after manufacture and after storage at 60°C for one month in comparison with a conventional battery.
Claims (1)
の酸化第一銅を添加したことを特徴とする非水電
解液電池。1. A non-aqueous electrolyte battery characterized in that a small amount of cuprous oxide is added to a positive electrode mixture containing cupric oxide as an active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13018378A JPS5556367A (en) | 1978-10-20 | 1978-10-20 | Non-aqueous electrolyte cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13018378A JPS5556367A (en) | 1978-10-20 | 1978-10-20 | Non-aqueous electrolyte cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5556367A JPS5556367A (en) | 1980-04-25 |
| JPS6155740B2 true JPS6155740B2 (en) | 1986-11-28 |
Family
ID=15028044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13018378A Granted JPS5556367A (en) | 1978-10-20 | 1978-10-20 | Non-aqueous electrolyte cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5556367A (en) |
-
1978
- 1978-10-20 JP JP13018378A patent/JPS5556367A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5556367A (en) | 1980-04-25 |
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