JPS6366849A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPS6366849A JPS6366849A JP21003786A JP21003786A JPS6366849A JP S6366849 A JPS6366849 A JP S6366849A JP 21003786 A JP21003786 A JP 21003786A JP 21003786 A JP21003786 A JP 21003786A JP S6366849 A JPS6366849 A JP S6366849A
- Authority
- JP
- Japan
- Prior art keywords
- indium
- positive electrode
- battery
- lithium
- indium compound
- 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 7
- 150000002472 indium compounds Chemical class 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052738 indium Inorganic materials 0.000 claims abstract description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 14
- 239000011149 active material Substances 0.000 claims description 7
- 229960004643 cupric oxide Drugs 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 239000010949 copper Substances 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- 241001185311 Lyticum Species 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000007774 positive electrode material Substances 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
- HAOKAUSLWSQQKU-UHFFFAOYSA-N [C].[In] Chemical compound [C].[In] HAOKAUSLWSQQKU-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 150000002471 indium Chemical class 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 239000000843 powder Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 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
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
- H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）Ｍ梁上の利用分野
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響二関するものである。Detailed Description of the Invention (a) Field of Application on M Beam The present invention comprises 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. This is related to non-aqueous electrolyte battery Hibiki II.
回 従来の技術
リチウム又はリチウム合金を活物質とする負極を用いた
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を有する。そして例えば特公昭５
９−５５９３５号公報に開示されているように酸化第二
銅を正極活物質Ｃｍｍいれば電池電圧が約１５ｖ程度と
なり、既存のアルカリ乾電池、水銀電池、銀電池等と互
換使用できるので注目されている。BACKGROUND ART A non-aqueous electrolyte battery using a negative electrode containing lithium or a lithium alloy as an active material has the advantages of high energy density and low self-discharge. For example, Tokuko Sho 5
As disclosed in Publication No. 9-55935, if cupric oxide is used as the positive electrode active material, the battery voltage will be approximately 15V, and it is attracting attention because it can be used interchangeably with existing alkaline batteries, mercury batteries, silver batteries, etc. There is.
（ハ）発明が解決しようとする問題点
酸化第二銅−リチウム系電池は保存時、正極活物質とし
ての酸化第二銅が分解して電解液中に金属銅が溶解し、
リチウム負極表面に析出して銅の緻密な被１１Ｌｄ！形
成される。この被成によりリチウムの放電反応（Ｌｉ→
Ｌ１＋θ〕が阻害され、電荷移動が低下することに起因
して内部抵抗が上昇し、電池の放電容量が低下するとい
う問題がある。(c) Problems to be solved by the invention When cupric oxide-lithium batteries are stored, cupric oxide as a positive electrode active material decomposes and metal copper dissolves in the electrolyte.
A dense coating of copper is deposited on the surface of the lithium negative electrode! It is formed. This formation causes a lithium discharge reaction (Li→
L1+θ] is inhibited and charge transfer is reduced, resulting in an increase in internal resistance and a problem in that the discharge capacity of the battery is reduced.
本発明はこの種電池の保存特性を改善しようとするもの
である。The present invention seeks to improve the storage characteristics of this type of battery.
に）問題点を解決するための手段
本発明は正極にインジウム化合物を浄加することを特徴
とする。B) Means for solving the problems The present invention is characterized in that an indium compound is added to the positive electrode.
インジウム化合物としては二硫化インジウム層いは三酸
化インジクムが挙げられ、添刀口量としては正極合剤Ｃ
二対して５〜４０重量％が好ましい。Examples of the indium compound include indium disulfide layer or indicum trioxide, and the amount of addition is positive electrode mixture C.
5 to 40% by weight is preferred.
ボ）作 用 インジウム化合物を添加した正極を用いると。b) Production When a positive electrode containing an indium compound is used.
インジウム化合物の一部がイオンとして電解液中Ｃ二溶
解し、そしてリチウム負極表面にインジウム層が形成さ
れる。このインジウム層は銅の場合とは異なりリチクム
との合金を生成するように形成されると共に、放電反応
によってインジウム層は容易に除去されるため放電反応
を阻害する（二は至らない。又このインジウム層（＝よ
って銅被膜の形成が抑制される。この結果、内部抵抗の
上昇は抑制されることＣ二なる。A part of the indium compound is dissolved as ions in the electrolytic solution, and an indium layer is formed on the surface of the lithium negative electrode. Unlike the case of copper, this indium layer is formed to form an alloy with lithicum, and the indium layer is easily removed by the discharge reaction, so it inhibits the discharge reaction (the second is not possible). Therefore, the formation of the copper film is suppressed. As a result, the increase in internal resistance is suppressed.C2.
尚、インジウム化合物の添加↑よが正極合剤Ｃ一対して
４０重量％以上１：なるとリチウム負極表面へのインジ
クムの析出礒が多量となってインジウム層が緻密となり
、リチクム負極の放電が円滑に進まず内部抵抗が上昇す
ること（二なるため添加量の上限は４０重量％とするの
が好ましい。In addition, if the addition of an indium compound is ↑ 40% by weight or more based on the positive electrode mixture C, a large amount of indicum will be deposited on the surface of the lithium negative electrode, making the indium layer dense, and the discharge of the lithium negative electrode will be smooth. The upper limit of the amount added is preferably 40% by weight, since the internal resistance will increase without progressing.
（へ）実施例 以下本発明の実施例（二ついて詳述する。(f) Example Hereinafter, two embodiments of the present invention will be described in detail.
市販特級の酸化第二銅（ＣｕＯ）７０重量％。Commercially available special grade cupric oxide (CuO) 70% by weight.
市販特級の三硫化インジクム（ｘｎ２ｓ５）２０重鼠チ
、導電剤としての黒鉛５重量％及び結看剤としてのフッ
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／ｃＩ１１の圧力で加圧成型して径１虻、Ｏｗ
ｍ、厚み１１ｍの成型体を得、この成型体を２００〜６
００℃の温度で熱処理して工種とする。After adding and mixing 20 weight percent of commercially available special grade indicum trisulfide (xn2s5), 5% by weight of graphite as a conductive agent, and 5% by weight of fluororesin powder as a binding agent, this mixture was mixed at a rate of about 2 tons/cI11. Pressure molded to 1 diameter, Ow
A molded body with a thickness of 11 m and a thickness of 11 m was obtained, and this molded body was
Heat treated at a temperature of 00°C to form a workpiece.
負極は厚み約０．６ ｍのリチクム圧延仮を径１５゜Ｑ
ｓ＠ｌ−打抜いたものであり、′電解液はプロピレンカ
ーボネートとｔ２ジメトキシエタンとの混合溶媒【二過
塩素酸すチクムを１モル／ｌ溶解させｔものを用い、父
セパレータとしてポリプロピレン不織布を用いて直径２
Ｑ、Ｑｍ、厚み２．５ｍ＠の本発明電池体を作成した。The negative electrode is made of rolled lyticum with a thickness of about 0.6 m and a diameter of 15°Q.
The electrolytic solution was a mixed solvent of propylene carbonate and dimethoxyethane [1 mol/l of diperchlorate dissolved therein], and a polypropylene nonwoven fabric was used as the main separator. diameter 2
A battery body of the present invention with Q, Qm, and thickness of 2.5 m was created.
ついで１本発明電池の優位性を畠べるために正極中Ｃニ
インジウム化合物を添加しない従来の電池（Ｂｌを作成
した。Next, in order to demonstrate the superiority of the battery of the present invention, a conventional battery (Bl) was prepared in which no carbon indium compound was added in the positive electrode.
第１図はこれら電池の温度６０℃、湿度９０％下での内
部抵抗と保存期間との関係を示し、第２因は三硫化イン
ジクムの正極合剤（：対する添加量と、温度６０’Ｃ，
湿度９０％で５０日保存後の内部抵抗との関係を示す。Figure 1 shows the relationship between the internal resistance and storage period of these batteries at a temperature of 60°C and a humidity of 90%. ，
The relationship with internal resistance after storage for 50 days at 90% humidity is shown.
第１図より本発明電池体）は従来電池ＩＢＩに比して保
存期間に伴う内部抵抗の上昇が抑制されているのがわか
る。又、第２図よりインジウム化合物の添加量としては
５〜４０重量％の範囲が好ましいことがわかる。From FIG. 1, it can be seen that the increase in internal resistance associated with the storage period is suppressed in the battery body of the present invention as compared to the conventional battery IBI. Further, from FIG. 2, it can be seen that the amount of the indium compound added is preferably in the range of 5 to 40% by weight.
（ト） 発明の効果
上述した如く、リテワム又はリチクム合金を活物質とす
る負極と酸化第二銅を活物質とする正掻とを備えた非水
電解ｇ電池ｔ；おいて、工種監；インジクム化合物を添
加することにより保存後の内部抵抗の上昇を抑制でき保
存特性を改善しうるものであり、この種電池の用途拡大
（＝資するところ極めて犬である。(g) Effects of the invention As mentioned above, a non-aqueous electrolytic battery equipped with a negative electrode using lithium or lyticum alloy as an active material and a positive electrode using cupric oxide as an active material; By adding a compound, it is possible to suppress the increase in internal resistance after storage and improve storage characteristics, which is extremely helpful in expanding the applications of this type of battery.
第１図は電池の内部抵抗と保存期間との関係を示す図、
第２図は高温、高湿下で５０日保存後の電池の内部抵抗
と二硫化インジウムの添加量との関係を示す図である。
囚・・・本発明電池、（Ｂ）・・・従来電池。Figure 1 is a diagram showing the relationship between battery internal resistance and storage period.
FIG. 2 is a diagram showing the relationship between the internal resistance of the battery and the amount of indium disulfide added after storage for 50 days at high temperature and high humidity. Prisoner: Battery of the present invention, (B): Conventional battery.
Claims (3)
、非水電解液と、酸化第二銅を活物質とする正極とを備
え、前記正極にインジウム化合物を添加したことを特徴
とする非水電解液電池。(1) A non-aqueous product 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, and an indium compound added to the positive electrode. electrolyte battery.
化インジウム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 non-aqueous electrolyte battery according to claim (1), wherein the indium compound is indium trisulfide or indium trioxide.
〜４０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。(3) The amount of indium compound added is 5% to the positive electrode mixture.
40% by weight of the non-aqueous electrolyte battery according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21003786A JPS6366849A (en) | 1986-09-05 | 1986-09-05 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21003786A JPS6366849A (en) | 1986-09-05 | 1986-09-05 | Nonaqueous electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6366849A true JPS6366849A (en) | 1988-03-25 |
Family
ID=16582760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21003786A Pending JPS6366849A (en) | 1986-09-05 | 1986-09-05 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6366849A (en) |
-
1986
- 1986-09-05 JP JP21003786A patent/JPS6366849A/en active Pending
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