JPH01163968A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH01163968A JPH01163968A JP62322532A JP32253287A JPH01163968A JP H01163968 A JPH01163968 A JP H01163968A JP 62322532 A JP62322532 A JP 62322532A JP 32253287 A JP32253287 A JP 32253287A JP H01163968 A JPH01163968 A JP H01163968A
- Authority
- JP
- Japan
- Prior art keywords
- licuo
- positive electrode
- open circuit
- battery
- circuit voltage
- 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 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229960004643 cupric oxide Drugs 0.000 claims description 7
- 229910000733 Li alloy Inorganic materials 0.000 claims description 6
- 239000001989 lithium alloy Substances 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 2
- 230000002860 competitive effect Effects 0.000 abstract description 2
- 208000028659 discharge Diseases 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 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
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 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
- -1 polypropylene Polymers 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
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 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
- 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)
Abstract
Description
【発明の詳細な説明】
イ６ 産業上の利用分野
本発明はリチウム又はリチウム合金からなる負極と、酸
化第二銅を活物質とする正極とを備えた非水電解液電池
に関するものである。DETAILED DESCRIPTION OF THE INVENTION A6 Field of Industrial Application The present invention relates to a non-aqueous electrolyte battery comprising a negative electrode made of lithium or a lithium alloy and a positive electrode made of cupric oxide as an active material.
口、 従来の技術
リチウム又はリチウム合金からなる負極を用いた非水電
解液電池は高エネルギー密度を有し、且自己放電が少な
いという利点がある。そして、例えば特公昭５９−３３
９３５号公報に開示されているように正極活物質として
酸化第二銅を用いると電池電圧は約１．５ｖ程度となり
、既存のアルカリ乾電池、水銀電池、銀電池などと互換
使用しうる利点があるので注目されている。BACKGROUND OF THE INVENTION Non-aqueous electrolyte batteries using negative electrodes made of lithium or lithium alloys have the advantage of having high energy density and low self-discharge. For example,
As disclosed in Publication No. 935, when cupric oxide is used as the positive electrode active material, the battery voltage becomes approximately 1.5V, which has the advantage of being compatible with existing alkaline batteries, mercury batteries, silver batteries, etc. Therefore, it is attracting attention.
ハ、 発明が解決しようとする問題点
ところで、リチウム又はリチウム合金からなる負極と酸
化第二銅正極とを組合せた非水電解液電池は組立後の開
回路電圧（ＯＣＶ）が３Ｖ程度と高電位を示し、この高
電位のために使用機器に組込んだ回路が破壊されるとい
う懸念がある。C. Problems to be solved by the invention By the way, a non-aqueous electrolyte battery that combines a negative electrode made of lithium or a lithium alloy and a cupric oxide positive electrode has a high potential open circuit voltage (OCV) of about 3V after assembly. There is a concern that this high potential will destroy the circuits installed in the equipment used.
その対策として電池組立後に予備放電処理することが行
なわれている。この予備放電により初期の高い開回路電
圧は除去されるのであるが、この種電池では保存中に侵
入する水分や正極中の活性な部分との反応に°よって、
開回路電圧が、また上昇するという問題を有し、この点
については予備放電では解決できない。As a countermeasure against this problem, preliminary discharge treatment is carried out after battery assembly. This pre-discharge removes the initial high open circuit voltage, but in this type of battery, water enters during storage and reacts with active parts in the positive electrode.
There is also the problem that the open circuit voltage increases, which cannot be solved by pre-discharge.
本発明は上記せる保存時における問題点に鑑みなきれた
ものであり、保存時の開回路ｔｆｆ：の上昇が抑制され
た電池の提供を目的とするものである。The present invention was developed in view of the above-mentioned problems during storage, and it is an object of the present invention to provide a battery in which an increase in open circuit tff: during storage is suppressed.
二、 問題点を解決するための手段
本発明はリチウム又はリチウム合金からなる負極と、非
水電解液と、酸化第二銅を活物質とする正極とを備えた
非水電解液電池において、正極にＬｉＣｕＯを添加した
ことを特徴とするものである。2. Means for Solving the Problems The present invention provides a non-aqueous electrolyte battery comprising a negative electrode made of lithium or a lithium alloy, a non-aqueous electrolyte, and a positive electrode containing cupric oxide as an active material. It is characterized by the addition of LiCuO.
尚、ＬｉＣｕＱの添加量としては正極に対して１〜１０
重量％の範囲が好ましい。The amount of LiCuQ added is 1 to 10% relative to the positive electrode.
A weight percent range is preferred.
ホ、 作用
酸化第二銅（Ｃｕｏ ）を活物質とする正極に、ＬｉＣ
ｕＯを添加すると、ＣｕＯとＬｉＣｕＯの競争反応が進
行し、開回路電圧はＣｕＯとＬｉＣｕＯの混成電位とな
る。ここで、ＣｕＯ単独では２．２Ｖ。E. LiC is used as a positive electrode containing cupric oxide (Cuo) as an active material.
When uO is added, a competitive reaction between CuO and LiCuO proceeds, and the open circuit voltage becomes a hybrid potential of CuO and LiCuO. Here, the voltage of CuO alone is 2.2V.
ＬｉＣｕＱ単独では１．６ｖであるため開回路電圧はＣ
ｕＯ単独の場合に比して低下する。そのため、例え保存
時に開回路電圧が上昇したとしてもＣｕＯ単独の場合に
比して低く抑えることができる。Since LiCuQ alone is 1.6V, the open circuit voltage is C
This is lower than when uO is used alone. Therefore, even if the open circuit voltage increases during storage, it can be suppressed to a lower level than in the case of CuO alone.
へ、 実施例
正極は市販特級のＣｕ０８５重量％、ＬｉＣｕＯ３重量
％に導電剤としての黒鉛５１ｉ量％、結着剤としてのフ
ッ素樹脂粉末５重量％を加えて混合した後、この混合物
を約２トン／■２の圧力で加圧成型して径１５．Ｑｆｆ
ｌｌ、厚み１．１Ｗ＋の成型体を得、この成型体を２０
０〜３００℃の温度で熱処理したものである。The positive electrode of the example was prepared by mixing 85% by weight of commercially available special grade Cu0 and 3% by weight of LiCuO with 51% by weight of graphite as a conductive agent and 5% by weight of fluororesin powder as a binder, and then mixing this mixture into approximately 2 tons. / ■ Pressure molded at a pressure of 2 to a diameter of 15. Qff
A molded body with a thickness of 1.1W+ was obtained, and this molded body was
It is heat-treated at a temperature of 0 to 300°C.
負極はリチウム板を約０．６１１０の厚みに圧延し、こ
のリチウム圧延板を径１５．０■に打抜いたものである
。The negative electrode was made by rolling a lithium plate to a thickness of about 0.6110 mm, and punching out the rolled lithium plate to a diameter of 15.0 cm.
そして、これら正負極及びポリプロピレン製不織布より
なるセパレータとを組合せて径２０．ｇｍｍ。These positive and negative electrodes and a separator made of polypropylene nonwoven fabric are combined to form a 20mm diameter. gmm.
厚み２．５ｍの本発明電池（Ａ）を作製した。A battery (A) of the present invention having a thickness of 2.5 m was produced.
尚、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を１モル／Ｐ
溶解させた溶液を用いた。The electrolyte is a mixed solvent of propylene carbonate and 1.2 dimethoxyethane containing 1 mol/P of lithium perchlorate.
A dissolved solution was used.
次いで、本発明電池の優位性を調べるために、正極にＬ
ｉＣｕＯを添加しないことを除いて他は本発明電池と同
様の比較電池（Ｂ）を作製した。Next, in order to investigate the superiority of the battery of the present invention, L was added to the positive electrode.
A comparative battery (B) was produced which was the same as the battery of the present invention except that iCuO was not added.
第１図はこれら電池を温度６０℃、湿度９０％の条件下
で保存した時の開回路電圧の経時変化を示し、又第２図
は本発明電池において温度６０°Ｃ５湿度９０％の条件
で３０日間保存した時のＬｉＣｕＯの添加量と開回路電
圧、および温度２５°Ｃ１負荷１０にΩでの放電容量と
の関係を示す、尚、試験電池はいずれも予じめ理論容量
の５％を予備放電した。Figure 1 shows the change in open circuit voltage over time when these batteries were stored at a temperature of 60°C and a humidity of 90%, and Figure 2 shows the change in open circuit voltage over time when these batteries were stored at a temperature of 60°C and a humidity of 90%. The relationship between the amount of LiCuO added, the open circuit voltage, and the discharge capacity in Ω at 25°C and 10 Ω after storage for 30 days is shown. All test batteries had 5% of their theoretical capacity in advance. Pre-discharged.
第１図から本発明電池（Ａ）は、比較電池（Ｂ）と同様
に保存期間に伴い開回路電圧が上昇するものの、その電
位は低く抑えられていることがわかる。 。It can be seen from FIG. 1 that in the battery of the present invention (A), like the comparative battery (B), the open circuit voltage increases with the storage period, but the potential is kept low. .
又、第２図から開回路電圧および放電容量の推移を考慮
するとＬｉＣｕＯの添加量としては１〜１０重量％の範
囲が好ましいことがわかる。Further, from FIG. 2, it can be seen that when considering the changes in open circuit voltage and discharge capacity, the amount of LiCuO added is preferably in the range of 1 to 10% by weight.
ト、 発明の効果
上述した如く、リチウム又はリチウム合金からなる負極
と、非水電解液と、酸化第二銅を活物質とする正極とを
備えた非水電解液電池において、正極にＬｉＣｕＯを添
加することにより、この種電池の保存時における開回路
電圧の上昇を抑制することができるものであり、その工
業的価値は極めて犬である。G. Effects of the invention As described above, in a non-aqueous electrolyte battery comprising a negative electrode made of lithium or a lithium alloy, a non-aqueous electrolyte, and a positive electrode containing cupric oxide as an active material, LiCuO is added to the positive electrode. By doing so, it is possible to suppress the increase in open circuit voltage during storage of this type of battery, and its industrial value is extremely high.
第１＠は高温、高湿下における電池の開回路電圧の経時
変化を示す図、第２図はＬｉＣｕＯの添加量と開回路電
圧および放電容量との関係を示す図である。
（Ａ）・・・本発明電池、（Ｂ）（Ｃ）・・・比較電池
。Fig. 1 is a diagram showing the change over time in the open circuit voltage of a battery under high temperature and high humidity conditions, and Fig. 2 is a diagram showing the relationship between the amount of LiCuO added, the open circuit voltage, and the discharge capacity. (A)...Battery of the present invention, (B) (C)...Comparison battery.
Claims (2)
電解液と、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、前記正極にＬｉＣｕＯを添加したことを特
徴とする非水電解液電池。(1) A non-aqueous device comprising a negative electrode made of lithium or a lithium alloy, a non-aqueous electrolyte, and a positive electrode made of cupric oxide as an active material, characterized in that LiCuO is added to the positive electrode. electrolyte battery.
重量％であることを特徴とする特許請求の範囲第（１）
項記載の非水電解液電池。(2) The amount of LiCuO added is 1 to 10% relative to the positive electrode.
Claim No. (1) characterized in that it is % by weight.
The non-aqueous electrolyte battery described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62322532A JPH01163968A (en) | 1987-12-18 | 1987-12-18 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62322532A JPH01163968A (en) | 1987-12-18 | 1987-12-18 | Nonaqueous electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01163968A true JPH01163968A (en) | 1989-06-28 |
Family
ID=18144716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62322532A Pending JPH01163968A (en) | 1987-12-18 | 1987-12-18 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01163968A (en) |
-
1987
- 1987-12-18 JP JP62322532A patent/JPH01163968A/en active Pending
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