JPS62168344A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPS62168344A JPS62168344A JP61009344A JP934486A JPS62168344A JP S62168344 A JPS62168344 A JP S62168344A JP 61009344 A JP61009344 A JP 61009344A JP 934486 A JP934486 A JP 934486A JP S62168344 A JPS62168344 A JP S62168344A
- Authority
- JP
- Japan
- Prior art keywords
- cupric oxide
- battery
- treated
- nonaqueous electrolyte
- sulfite
- 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.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- 239000006258 conductive agent Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [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 description 1
- 238000005259 measurement 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material 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
- 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
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 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)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
イ 産業上の利用分野
本発明はリチウム又はリチウム合金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
備えた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 is a non-aqueous device comprising a negative electrode using lithium or a lithium alloy as an active material, a non-aqueous electrolyte, and a positive electrode using cupric oxide as an active material. It relates to electrolyte batteries.
口 従来の技術 リチウム又はリチウム合金を負極活物質とし。Mouth Conventional technology Use lithium or lithium alloy as the negative electrode active material.
酸化第二銅を正極活物質とする非水電解液電池は例えば
特公昭５２−３１３２６号公報に開示されており、その
電池電圧は約１５ Ｖ８度であるので電子機器の電源に
汎用されている酸化銀電池や水銀電池と互換使用しつる
利点がある。A nonaqueous electrolyte battery using cupric oxide as a positive electrode active material is disclosed, for example, in Japanese Patent Publication No. 52-31326, and since its battery voltage is approximately 15 V8 degrees, it is widely used as a power source for electronic devices. It has the advantage of being compatible with silver oxide batteries and mercury batteries.
ハ 発明が解決しようとする問題点 この種電池においては正極中の不純物例えば鉄。C. Problems that the invention attempts to solve In this type of battery, impurities in the positive electrode, such as iron.
ケイ素、マンガンなど、又活性な部分（−より放電初期
（：は高電圧を示す。その念め予じめ予備放電して対処
しているものの保存中ｌ二徐々１：開回路電圧が上昇す
るという問題がある。Active parts such as silicon and manganese (-) indicate high voltage at the early stage of discharge.Although we take precautions against this by pre-discharging, the open circuit voltage gradually increases during storage. There is a problem.
又、 ｎ＊１記不純物或いは活性な部分が電解液に溶解
し負極上に析出して保存）：伴ない内部抵抗が上昇する
という問題がある。In addition, there is a problem that n*1 impurities or active parts are dissolved in the electrolytic solution and deposited on the negative electrode (storage), resulting in an increase in internal resistance.
二 問題点を解決するための手段
正極活物質として亜硫酸塩で処理した酸化第二銅を用い
る。亜硫酸塩の代表例としては亜硫酸ナトリクム（Ｎａ
２Ｓ０５）或いは亜硫酸水素ナトリクム（ＮａＨ３Ｏ＆
）が挙げられる。2. Means for solving the problem: Cupric oxide treated with sulfite is used as the positive electrode active material. A typical example of sulfite is sodium sulfite (Na
2S05) or sodium bisulfite (NaH3O&
).
ホ作 用
正極中の不純物或いは活性な部分によって高電圧を示す
メカニズムは次のように考えられる。！Ｕち、不純物例
えば鉄、ケイ素、マンガン等の金属が酸化物の形態とな
る時或いは活性な部分１例えばＣｕ２Ｏ３の如き過酸化
鋼の浮石である。本発明によれば酸化第二銅を処理する
亜硫酸塩が脱酸素還元剤であるため不純物の酸化物への
変化を抑えることができ、且活性な部分を低活性にする
。The mechanism of high voltage caused by impurities or active parts in the positive electrode is thought to be as follows. ! When impurities such as metals such as iron, silicon, manganese, etc. are in the form of oxides, or active parts 1 are floating stones of peroxidized steel such as Cu2O3. According to the present invention, since the sulfite used to treat cupric oxide is a deoxidizing and reducing agent, it is possible to suppress the change of impurities into oxides, and to reduce the activity of active parts.
又、理由は詳かではないが亜硫酸塩は不純物が電解液中
に溶解するのを抑制でき、不純物がリチウム負極上に析
出することを因とする内部抵抗の上昇を抑えることがで
きる。Further, although the reason is not clear, sulfite can suppress impurities from dissolving in the electrolytic solution, and can suppress an increase in internal resistance caused by impurities depositing on the lithium negative electrode.
へ実施例 以下本発明の実施例について詳述する。Examples Examples of the present invention will be described in detail below.
市販特級の酸化第二銅を１モル／ｌのＮａ２ＳＯ３水溶
液中に７２時間浸漬し、その後水洗、乾燥する。この処
理済酸化第二銅８５重量％Ｃ：今電剤としての黒鉛１０
重漬チ、結着剤としてのフッ素樹脂粉末５重槽％を加え
て充分混合した後、この混合物を約２トン／−の圧力で
加圧成型して径１５．０１ｍ１．厚み１．１調の成型体
を得、この成型体を２００〜３００℃の温度で熱処理し
て正極とする。Commercially available special grade cupric oxide is immersed in a 1 mol/l Na2SO3 aqueous solution for 72 hours, then washed with water and dried. This treated cupric oxide 85% by weight C: Now graphite as an electric agent 10
After adding 5% of fluororesin powder as a binder and mixing thoroughly, this mixture was pressure molded at a pressure of about 2 tons/- to form a diameter of 15.01 m1. A molded body with a thickness of 1.1 is obtained, and this molded body is heat-treated at a temperature of 200 to 300°C to form a positive electrode.
負極はリチウム板を約０．６閤の厚み（：圧延しこのリ
チウム圧延板を径１５．０調に打抜いたものである。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！＝過３１ｉｉ素酸リチウムを１モル
／ｌ溶解させたものを用い、又セパレータはポリプロピ
レン不織布を用いて面径２０．０ｍ、厚み２．５１１１
の電池（Ａｌを作成した。The negative electrode is made by rolling a lithium plate to a thickness of approximately 0.6 mm and punching the rolled lithium plate to a diameter of 15.0 mm.The electrolyte is a mixed solvent of propylene carbonate and 1,2-dimethoxyethane. !=Lithium peroxide dissolved at 1 mol/l was used, and the separator was made of polypropylene nonwoven fabric with a surface diameter of 20.0 m and a thickness of 2.5111.
A battery (Al) was prepared.
ついで本発明電池の優位性を調べるためＣ二酸化第二鋼
を亜硫酸塩で処理しないことを除いて他は本発明電池と
同様の比較電池ｔＢｌを作成した。Next, in order to investigate the superiority of the battery of the present invention, a comparative battery tBl was prepared which was the same as the battery of the present invention except that the C steel dioxide was not treated with sulfite.
第１図はこれら電池を予め理論容量の５％を放電した後
、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、第１図より本発明電池は高温
、高湿下における保存特性が改Ｓされているのがわかる
。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% after being discharged to 5% of their theoretical capacity. It can be seen that the storage characteristics under high temperature and high humidity conditions have been improved.
又、第２図及び第３図は夫々亜硫酸塩としてのＮ１２８
０！１及びＮ６２８０ｇの濃度と開回路電圧との関係を
示し、第４図及び第５図は同様ｆ：１ｔｌｌａ ２８０
５及びＮ！Ｌｌ（ＳＯ３の濃度と内部抵抗との関係を示
す。Also, Figures 2 and 3 show N128 as sulfite, respectively.
0!1 and N6280g concentration and the open circuit voltage, and FIGS. 4 and 5 show the same f:1tlla 280
5 and N! Ll (represents the relationship between SO3 concentration and internal resistance).
第２図乃至第５図よりＮ６２８０ｇの濃度としては１〜
３モル／Ｊ、ＮａＨ８Ｏ５の濃度としては１〜４モル／
ｌの範囲が好ましいことがわかる。From Figures 2 to 5, the concentration of N6280g is 1~
3 mol/J, the concentration of NaH8O5 is 1 to 4 mol/J.
It can be seen that a range of 1 is preferable.
尚、第２図乃至第５図は温１？６０℃、湿９９０％。In Figures 2 to 5, the temperature is 1-60°C and the humidity is 990%.
の条件で５０日間保存した後の測定結果である。These are the measurement results after storage for 50 days under these conditions.
ト 発明の効果
上述した如く、リチウムはリチウム合金を頁枠活物質と
し酸化第二銅を正極活物質とする非水電解液電池（＝お
いて、亜硫酸塩で処理した酸化第二銅を用いることによ
りこの種電池の保存特性を改善しつるものでありその工
業的価値は極めて大である。G. Effects of the Invention As mentioned above, lithium can be used in a non-aqueous electrolyte battery that uses a lithium alloy as a page frame active material and cupric oxide as a positive electrode active material (= in which cupric oxide treated with sulfite is used). As a result, the storage characteristics of this type of battery can be improved, and its industrial value is extremely large.
第１■は電池の開回路電圧と保存期間との関係を示す図
、第２図及び第３図は亜硫酸塩濃度と電池の開［山路電
圧との関係を示す因、々′Ｊ４図及び第５図は亜硫酸塩
濃度と電池の内部抵抗との関係を示す図であみ。
囚・・・本発明電池、（Ｂ）・・・比較電池。Figures 1 and 3 are diagrams showing the relationship between the open circuit voltage and storage period of the battery, and Figures 2 and 3 are the factors showing the relationship between the sulfite concentration and the battery open circuit voltage. Figure 5 shows the relationship between sulfite concentration and battery internal resistance. (B)...Battery of the present invention, (B)...Comparison battery.
Claims (2)
、非水電解液と、亜硫酸塩で処理した酸化第二銅を活物
質とする正極とを備えた非水電解液電池。(1) A nonaqueous electrolyte battery comprising a negative electrode using lithium or a lithium alloy as an active material, a nonaqueous electrolyte, and a positive electrode using cupric oxide treated with sulfite as an active material.
トリウム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 sulfite is sodium sulfite or sodium bisulfite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61009344A JPH0675399B2 (en) | 1986-01-20 | 1986-01-20 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61009344A JPH0675399B2 (en) | 1986-01-20 | 1986-01-20 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62168344A true JPS62168344A (en) | 1987-07-24 |
| JPH0675399B2 JPH0675399B2 (en) | 1994-09-21 |
Family
ID=11717852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61009344A Expired - Fee Related JPH0675399B2 (en) | 1986-01-20 | 1986-01-20 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0675399B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0317960A (en) * | 1989-06-14 | 1991-01-25 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery and manufacture thereof |
| WO2018179935A1 (en) * | 2017-03-30 | 2018-10-04 | パナソニックＩｐマネジメント株式会社 | Lithium primary cell |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5210521A (en) * | 1975-07-16 | 1977-01-26 | Matsushita Electric Ind Co Ltd | Organic electrolyte battery |
-
1986
- 1986-01-20 JP JP61009344A patent/JPH0675399B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5210521A (en) * | 1975-07-16 | 1977-01-26 | Matsushita Electric Ind Co Ltd | Organic electrolyte battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0317960A (en) * | 1989-06-14 | 1991-01-25 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery and manufacture thereof |
| WO2018179935A1 (en) * | 2017-03-30 | 2018-10-04 | パナソニックＩｐマネジメント株式会社 | Lithium primary cell |
| CN110036511A (en) * | 2017-03-30 | 2019-07-19 | 松下知识产权经营株式会社 | Lithium primary battery |
| CN110036511B (en) * | 2017-03-30 | 2021-10-08 | 松下知识产权经营株式会社 | Lithium primary battery |
| US11329268B2 (en) | 2017-03-30 | 2022-05-10 | Panasonic Intellectual Property Management Co., Ltd. | Lithium primary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0675399B2 (en) | 1994-09-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |